Patent Document

CROSS-REFERENCE TO RELATED APPLICATIONS 
       [0001]    This application is a continuation of International Patent Application No. PCT/CN2007/070957 with an international filing date of Oct. 25, 2007, designating the United States, now pending, and further claims priority benefits to Chinese Patent Application No. 200710052179.5 filed May 14, 2007. The contents of all of the aforementioned applications, including any intervening amendments thereto, are incorporated herein by reference. 
     
    
     BACKGROUND OF THE INVENTION 
       [0002]    1. Field of the Invention 
         [0003]    The invention relates to an isocyanate trimer and a method of preparing the same, and more particularly an isocyanate trimer modified with silane or functional polysiloxane and a method of preparing the same. 
         [0004]    2. Description of the Related Art 
         [0005]    Nowadays, silicone-modified polyurethane has aroused more and more attention in academy and industry. While maintaining the original excellent performance, silicone-modified polyurethane exhibits improved properties such as adhesion, wear resistance, chemical resistance, heat resistance, weather resistance, electrical insulation, fire retardancy, and hydrophobicity, and can be cured at room temperature. However, the above-mentioned silicone-modified polyurethane mainly focuses on the modification of an isocyanate prepolymer. There are few reports on silicone-modified isocyanate trimer. 
         [0006]    The study on preparation and application of isocyanate trimers has been very active. U.S. Pat. Nos. 2,801,244, 5,264,572, 0,109,665, 6,515,125, and 3,996,223 separately discloses a method of preparing an isocyanate trimer, all of which have different yield under different catalytic system. Isocyanate trimers have a high application value and are mainly used in coatings, adhesives, sealants, elastomers, foam plastics and so on, particularly for current production of quick-drying and highly decorative furniture and automobile. However, most isocyanate trimers are solid at room temperature, except that hexamethylene diisocyanate (HDI) trimer is liquid. Therefore, to develop an isocyanate trimer with high compatibility is of great significance. 
       SUMMARY OF THE INVENTION 
       [0007]    In view of the above-described problems, it is one objective of the invention to provide a modified isocyanate trimer featuring high compatibility. Polyurethane or other polymers (for example, epoxy resins, polymethacrylate, polyacrylamide, and phenolic resin) prepared by the modified isocyanate trimer can improve the heat resistance, weather resistance, electrical insulation, fire retardancy, and hydrophobicity. 
         [0008]    It is another objective of the invention to provide a method of preparing the modified isocyanate trimer featuring high compatibility. 
         [0009]    To achieve the above objectives, in accordance with one embodiment of the invention, there is provided a modified isocyanate trimer featuring high compatibility, the isocyanate trimer being modified with silane or functional polysiloxane and having formula of 
         [0000]    
       
                 
         
             
             
         
       
     
         [0010]    wherein 
         [0011]    R represents tolyl, ethylphenyl, diphenylmethyl, 1,5-naphthyl, hexamethylene, isophorone, 2,2,6-trimethylcyclohexyl, 4,4-dicyclohexylmethyl; 
         [0012]    R 1  is saturated or unsaturated and linear or branched C 1-8  alkyl, cycloalkyl, aryl, or a homologue of aromatic hydrocarbon; 
         [0013]    R 2  and R 3  at each occurrence separately represents C 1-6  alkyl, aryl, trialkylsilyl, or methoxyalkoxyl; 
         [0014]    a is an integer from 0 to 3; 
         [0015]    R 1 , R 2 , R 3 , R 4 , and R 5  at each occurrence separately represents saturated or unsaturated and linear or branched C 1-12  alkyl, cycloalkyl, alkoxyl, aryl, or cycloalkoxyl; 
         [0016]    X represents —NH—, —NHCH 2 CH 2 NH—, —NHCH 2 CH 2 NHCH 2 CH 2 NH—, —N—, —NHCONH—, 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    and 
         [0017]    n is an integer which is ≧0. 
         [0018]    In accordance with another embodiment of the invention, there is provided a method of preparing the modified isocyanate trimer represented by formula (1) or (2) featuring high compatibility, the method comprising steps of:
       a) dissolving an isocyanate trimer into an inert solvent;   b) adding dropwise to a mixture of silane or functional polysiloxane and a catalyst;   c) stirring the resultant solution of b) at room temperature and in a dry environment; and   d) removing said inert solvent with reduced pressure distillation.       
 
         [0023]    In a class of this embodiment, the isocyanate trimer has a formula of 
         [0000]    
       
                 
         
             
             
         
       
     
         [0024]    wherein R represents tolyl, ethylphenyl, diphenylmethyl, 1,5-naphthyl, hexamethylene, isophorone, 2,2,6-trimethylcyclohexyl, or 4,4-dicyclohexylmethyl. 
         [0025]    In a class of this embodiment, the isocyanate is toluene diisocyanate (TDI), ethylbenzene diisocyanate (EDI), methylene diphenyl diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 1,4-diisocyanate-2,2,6-trimethyl cyclohexane (TMCDI), or 4,4-bis(isocyanatecyclohexyl)methane (HMDI). 
         [0026]    In a class of this embodiment, the silane or functional polysiloxane has a formula of 
         [0000]    
       
                 
         
             
             
         
       
     
         [0027]    wherein R 2  and R 3  at each occurrence separately represents C 1-6  alkyl, aryl, trialkylsilyl, or methoxylalkoxyl and a is an integer from 0 to 3; R 1 , R 2 , R 3 , R 4 , and R 5  at each occurrence separately represents saturated or unsaturated and linear or branched C 1-12  alkyl, aryl, cycloalkyl, alkoxyl, or cycloalkoxyl; X represents —NH—, —NHCH 2 CH 2 NH—, —NHCH 2 CH 2 NHCH 2 CH 2 NH—, —N—, —NHCONH—, 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    —S—, or —O—, and m is an integer from 0 to 30. 
         [0028]    In a class of this embodiment, the catalyst is an organic tin compound including but not limited to dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dilaurylmercaptan, and dimethyltin dichloride. 
         [0029]    In a class of this embodiment, the amount of the catalyst is between 0.01 and 0.5 weight % of the total amount of the trimer and silicon compound. 
         [0030]    In a class of this embodiment, the inert organic solvent which does not react with the reactants is hydrocarbon, chlorinated hydrocarbon, ester, or ether. 
         [0031]    In a class of this embodiment, the hydrocarbon solvent is petroleum ether, linear or branched hydrocarbon with low boiling point, benzene, toluene, or xylene; the chlorinated hydrocarbon is chloroform, chlorobenzene, dichloromethane, or dichloroethane; ester is ethyl acetate; and ether is aether or tetrahydrofuran. 
         [0032]    In a class of this embodiment, a molar ratio of the isocyanate trimer to the active hydrogen of silane or polysiloxane is 1:1. 
         [0033]    Advantages of this invention are summarized below:
       1. The isocyanate trimer modified with silanes or functional polysiloxanes has low viscosity, low volatile, low toxicity, high functionality, and high tolerance against xylene due to reduced isocyanate polarity, so that the compatibility of trimer with hydroxy resin has been improved significantly. In addition, heat resistance, weather resistance, and adhesion of isocyanate trimer have been further increased due to the introduction of organic silicon.   2. For the isocyanate trimer modified with silanes or functional polysiloxanes of the invention, isocyanate as a reactive functional group can react with polyester diols, polyether diols, hydroxy resins, and other polyols, and siloxane as another reactive functional group can react with inorganic materials or hydroxyl resins to form chemical bonds. In addition, the isocyanate trimer modified with silane or functional polysiloxane can be designed properly in accordance with the type of a polyol or polyol resin, which benefits the combination thereof.   3. For the reaction between isocyanate and active hydrogen of silanes or functional polysiloxanes to prepare carbamate, the introduction of an organometallic catalyst such as dibutyltin dilaurate can help obtain a high yield of product at low temperature (between −50° C. and 30° C.). Particularly, in case it is difficult for isocyanate trimer to react with active hydrogen of silanes or functional polysiloxanes due to space block, or the occurrence of a large amount of by-products at high temperature, the introduction of organic tin catalysts can smooth the reaction.       
 
         [0037]    A monomer of the isocyanate trimer is selected from toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 1,4-diisocyanate-2,2,6-trimethyl cyclohexane (TMCDI), 4,4-bis(isocyanatecyclohexyl)methane (HMDI), etc. 
         [0038]    The silanes or functional polysiloxanes of the invention optionally have sulfhydryl, amino, diamino, triamino, secondary amino, hydroxy, hydroxyalkylamino, phenylamino, ureaalkyl, epoxy, N-alkyl amino, and N,N,N′,N′-tetraalkyl guanidine with hydroxyl. 
         [0039]    Particularly, a molar ratio of isocyanate trimer to the active hydrogen of silane or polysiloxane is 1:1. 
         [0040]    In one embodiment of the invention, dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dilaurylmercaptan, and dimethyltin dichloride is used as catalyst. 
         [0041]    The reaction can be completed in a chlorinated alkyl solvent such as chloroform, cholorbenzene, dichloromethane, and dichloroethane, in an ether solvent such as aether, tetrahydrofuran, and cycloether, and in a hydrocarbon solvent such as petroleum ether, benzene, toluene, and xylene. 
         [0042]    The isocyanate trimers of the invention have good compatibility with acrylic resin. As additives, the isocyanate trimers make acrylic resin with good gloss, scratching and wear resistance, water resistance, solvent resistance, chemical resistance, weather resistance, heat resistance, gloss retention, and good flexibility. In addition, it is also an important modifier of polyurethanes, epoxy resins, polyacrylamides, phenolic resins, etc. 
     
    
     DETAILED DESCRIPTION OF THE EMBODIMENTS 
       [0043]    For further illustrating the invention, experiments detailing a modified isocyanate trimer featuring high compatibility and a method of preparing the same are described below. It should be noted that the following examples are intended to describe and not to limit the invention. 
       Example 1 
     Compound A 
       [0044]    52.2 g of TDI trimer was dissolved in 400 mL of anhydrous tetrahydrofuran (THF), and the solution was added to a mixture of 22.1 g of γ-aminopropyl triethoxysilane and 0.07 g of dibutyltin dilaurate (DBTDL). The resultant solution was stirred for 5 hs at room temperature under a dry environment. Subsequently, THF was removed with reduced pressure distillation and 68.36 g of compound A was obtained, with a yield of 92%. The compound A has a formula of 
         [0000]    
       
                 
         
             
             
         
       
     
         [0045]    Elemental analysis of C 36 H 41 N 7 O 9 Si: measured value (calculated value) %: C, 58.02 (58.14); H, 5.43 (5.52); N 13.07 (13.19); O, 19.29 (19.38); Si 3.68 (3.77).  1 HNMR (δ/ppm): 0.58 (t, 2H), 1.22 (q, 3H), 1.6 (q, 2H), 2.0 (m, 2H), 2.35 (m, 3H), 2.65 (q, 2H), 3.83 (q, 2H), 6.9 (t, 1H), 7.0 (q, 1H), 7.26 (m, 1H), 7.5 (m, 2H), 7.9 (s, 1H). 
       Example 2 
     Compound B 
       [0046]    52.2 g of TDI trimer was dissolved in 400 mL of anhydrous tetrahydrofuran (THF), and the solution was added to a mixture of 44 g of bis[γ-(triethoxysilyl) propyl]amine and 0.07 g of dibutyltin dilaurate (DBTDL). The resultant solution was stirred for 5 hs at room temperature under a dry environment. Subsequently, THF was removed with reduced pressure distillation and 80.5 g of compound B was obtained, with a yield of 85%. The compound B has a formula of 
         [0000]    
       
                 
         
             
             
         
       
     
         [0047]    Elemental analysis of C 45 H 61 N 7 O 12 Si 2 : measured value (calculated value) %: C, 56.89 (57.02); H, 6.33 (6.44); N, 10.26 (10.35); O, 20.16 (20.27); Si, 5.79 (5.91). 
         [0048]      1 HNMR (δ/ppm): 0.58 (t, 2H), 1.22 (q, 3H), 1.6 (q, 2H), 2.0 (m, 2H), 2.35 (m, 3H), 2.65 (q, 2H), 3.83 (q, 2H), 6.9 (t, 1H), 7.0 (q, 1H), 7.26 (m, 1H), 7.5 (m, 2H), 7.9 (s, 1H). 
       Example 3 
     Compound C 
       [0049]    52.2 g of TDI trimer was dissolved in 400 mL of anhydrous tetrahydrofuran (THF), and the solution was added to a mixture of 22.2 g of γ-(β-amino-ethylamino) propyltrimethoxysilane and 0.07 g of dibutyltin dilaurate (DBTDL) The resultant solution was stirred for 5 hs at room temperature under a dry environment. Subsequently, THF was removed with reduced pressure distillation and 70.68 g of compound C was obtained, with a yield of 95%. The compound C has a formula of 
         [0000]    
       
                 
         
             
             
         
       
     
         [0050]    Elemental analysis of C 35 H 40 N 8 O 9 Si: measured value (calculated value) %: C, 56.32 (56.45); H, 5.26 (5.38); N, 14.97 (15.05); O, 19.28 (19.35); Si, 3.69 (3.76).  1 HNMR (δ/ppm): 1.22 (q, 3H), 1.6 (q, 2H), 2.0 (m, 2H), 2.35 (m, 3H), 2.65 (q, 2H), 3.83 (q, 2H), 6.0 (s, 1H), 6.9 (t, 1H), 7.0 (q, 1H), 7.26 (m, 1H), 7.5 (m, 2H), 7.9 (s, 1H). 
       Example 4 
     Compound D 
       [0051]    52.2 g of TDI trimer was dissolved in 400 mL of anhydrous tetrahydrofuran (THF), and the solution was added to a mixture of 26.5 g of γ-(aminoethyl-aminoethylamino)propyltrimethoxysilane and 0.07 g of dibutyltin dilaurate (DBTDL). The resultant solution was stirred for 5 hs at room temperature under a dry environment. Subsequently, THF was removed with reduced pressure distillation and 75.5 g of compound D was obtained, with a yield of 96%. The compound D has a formula of 
         [0000]    
       
                 
         
             
             
         
       
     
         [0052]    Elemental analysis of C 37 H 45 N 9 O 9 Si: measured value (calculated value) %: C, 56.34 (56.42); H, 5.64 (5.72); N, 15.94 (16.01); O, 16.21 (16.30); Si, 3.42 (3.56). 
         [0053]      1 HNMR (δ/ppm): 0.58 (q, 2H), 1.50 (q, 2H), 2.0 (q, 1H), 2.35 (m, 1H), 2.55 (q, 2H), 2.67 (m, 2H), 2.81 (q, 2H), 3.28 (q, 2H), 3.55 (s, 3H), 6.0 (s, 1H), 6.9 (m, 1H), 7.0 (q, 1H), 7.5 (s, 1H), 7.9 (m, 1H). 
       Example 5 
     Compound E 
       [0054]    52.2 g of TDI trimer was dissolved in 400 mL of anhydrous tetrahydrofuran (THF), and the solution was added to a mixture of 22.7 g of anilinomethyltrimethoxysilane and 0.08 g of dibutyltin dilaurate (DBTDL). The resultant solution was stirred for 8 hs at room temperature under a dry environment. Subsequently, THF was removed with reduced pressure distillation and 66.6 g of compound E was obtained, with a yield of 89%. The compound E has a formula of 
         [0000]    
       
                 
         
             
             
         
       
     
         [0055]    Elemental analysis of C 37 H 35 N 7 O 9 Si: measured value (calculated value) %: C, 59.19 (59.28); H, 4.54 (4.67); N, 12.94 (13.06); O, 19.11 (19.23); Si, 3.66 (3.74). 
         [0056]      1 HNMR (δ/ppm): 2.35 (m, 1H), 5 (s, 2H, 2.4), 3.55 (s, 3H), 6.0 (s, 1H), 6.9 (m, 1H), 7.0 (q, 1H), 7.4 (q, 1H), 7.5 (s, 1H), 7.64 (m, 1H), 7.9 (s, 1H). 
       Example 6 
     Compound F 
       [0057]    52.2 g of TDI trimer was dissolved in 400 mL of anhydrous tetrahydrofuran (THF), and the solution was added to a mixture of 21.3 g of p-aminophenyl-trimethoxysilane and 0.08 g of dibutyltin dilaurate (DBTDL). The resultant solution was stirred for 8 hs at room temperature under a dry environment. Subsequently, THF was removed with reduced pressure distillation and 63.0 g of compound F was obtained, with a yield of 86%. The compound F has a formula of 
         [0000]    
       
                 
         
             
             
         
       
     
         [0058]    Elemental analysis of C 36 H 33 N 7 O 8 Si: measured value (calculated value) %: C, 69.88 (70.1); H, 4.44 (4.59); N, 13.53 (13.63); O, 17.69 (17.8); Si, 3.76 (3.89). 
         [0059]      1 HNMR (δ/ppm): 0.66 (m, 3H), 2.35 (s, 1H), 5 (s, 3H, 3.5), 6.0 (s, 1H), 6.9 (q, 1H), 7.0 (q, 1H), 7.26 (q, 1H), 7.5 (s, 1H), 7.6 (m, 1H), 7.9 (m, 1H). 
       Example 7 
     Compound G 
       [0060]    52.2 g of TDI trimer was dissolved in 400 mL of anhydrous tetrahydrofuran (THF), and the solution was added to a mixture of 23.5 g of n-butylamino-propyltrimethoxysilane and 0.07 g of dibutyltin dilaurate (DBTDL). The resultant solution was stirred for 6 hs at room temperature under a dry environment. Subsequently, THF was removed with reduced pressure distillation and 71.2 g of compound G was obtained, with a yield of 94%. The compound G has a formula of 
         [0000]    
       
                 
         
             
             
         
       
     
         [0061]    Elemental analysis of C 37 H 43 N 7 O 9 Si: measured value (calculated value) %: C, 58.56 (58.65); H, 5.59 (5.68); N, 12.86 (12.95); O, 18.89 (19.02); Si, 3.62 (3.70). 
         [0062]      1 HNMR (δ/ppm): 0.96 (q, 3H), 1.33 (q, 2H), 1.55 (q, 2H), 2.1 (q, 2H), 2.35 (m, 1H), 3.16 (q, 2H), 3.55 (s, 3H), 6.0 (s, 1H), 6.9 (q, 1H), 7.0 (q, 1H), 7.26 (q, 1H), 7.5 (s, 1H), 7.9 (s, 1H). 
       Example 8 
     Compound H 
       [0063]    52.2 g of TDI trimer was dissolved in 400 mL of anhydrous tetrahydrofuran (THF), and the solution was added to a mixture of 22.2 g of γ-ureido-propyltrimethoxysilane and 0.07 g of dibutyltin dilaurate (DBTDL). The resultant solution was stirred for 5 hs at room temperature under a dry environment. Subsequently, THF was removed with reduced pressure distillation and 70.7 g of compound H was obtained, with a yield of 95%. The compound H has a formula of 
         [0000]    
       
                 
         
             
             
         
       
     
         [0064]    Elemental analysis of C 34 H 36 N 8 O 10 Si: measured value (calculated value) %: C, 54.73 (54.84); H, 4.75 (4.84); N, 14.96 (15.05); O, 21.39 (21.50); Si, 3.63 (3.76).  1 HNMR (δ/ppm): 2.1 (q, 2H), 2.35 (m, 1H), 3.55 (m, 3H), 4.19 (m, 2H), 6.0 (s, 1H), 6.9 (t, 1H), 7.0 (t, 1H), 7.26 (t, 1H), 7.5 (s, 1H), 7.9 (s, 1H), 10 (s, 1H). 
       Example 9 
     Compound I 
       [0065]    52.2 g of TDI trimer was dissolved in 400 mL of anhydrous tetrahydrofuran (THF), and the solution was added to a mixture of 19.6 g of γ-mercapto-propyltrimethoxysilane and 0.07 g of dibutyltin dilaurate (DBTDL). The resultant solution was stirred for 8 hs at room temperature under a dry environment. Subsequently, THF was removed with reduced pressure distillation and 66.77 g of compound I was obtained, with a yield of 93%. The compound I has a formula of 
         [0000]    
       
                 
         
             
             
         
       
     
         [0066]    Elemental analysis of C 33 H 34 N 6 O 9 SSi: measured value (calculated value) %: C, 55.03 (55.15); H, 4.65 (4.74); N, 11.59 (11.70); O, 19.92 (20.05); S, 4.35 (4.46); Si, 3.79 (3.90). 1HNMR (δ/ppm): 2.35 (m, 1H), 2.8 (q, 2H), 3.2 (q, 2H), 3.55 (s, 1H), 6.9 (t, 1H), 7.02 (q, 1H), 7.26 (m, 1H), 7.5 (m, 1H), 7.9 (s, 1H), 8.0 (s, 1H). 
       Example 10 
     Compound J 
       [0067]    52.2 g of TDI trimer was dissolved in 400 mL of anhydrous tetrahydrofuran (THF), and the solution was added to a mixture of 18.0 g of γ-hydroxyl-propyltrimethoxysilane and 0.07 g of dibutyltin dilaurate (DBTDL). The resultant solution was stirred for 5 hs at room temperature under a dry environment. Subsequently, THF was removed with reduced pressure distillation and 65.98 g of compound J was obtained, with a yield of 94%. The compound J has a formula of 
         [0000]    
       
                 
         
             
             
         
       
     
         [0068]    Elemental analysis of C 33 H 34 N 6 O 10 Si: measured value (calculated value) %: C, 56.39 (56.41); H, 4.69 (4.84); N, 11.83 (11.97); O, 22.68 (22.79); Si, 3.89 (3.99). 
         [0069]      1 HNMR (δ/ppm): 0.58 (t, 2H), 1.6 (q, 2H), 2.35 (m, 1H), 3.55 (s, 3H), 4.08 (t, 2H), 6.9 (q, 1H), 7.0 (q, 1H), 7.26 (m, 1H), 7.5 (s, 1H), 7.9 (s, 1H), 8.0 (s, 1H). 
       Example 11 
     Compound K 
       [0070]    52.2 g of TDI trimer was dissolved in 400 mL of anhydrous tetrahydrofuran (THF), and the solution was added to a mixture of 35.1 g of N″-[2-hydroxy-3-[(3-trimethoxylsilyl) propoxyl]propyl]-N,N,N′,N′-Tetra-methyl guanidine and 0.08 g of dibutyltin dilaurate (DBTDL). The resultant solution was stirred for 8 hs at room temperature under a dry environment. Subsequently, THF was removed with reduced pressure distillation and 78.57 g of compound K was obtained, with a yield of 90%. The compound K has a formula of 
         [0000]    
       
                 
         
             
             
         
       
     
         [0071]    Elemental analysis of C 41 H 5 1N 9 O 11 Si: measured value (calculated value) %: C, 65.72 (65.75); H, 5.74 (5.84); N, 14.33 (14.43); O, 20.03 (20.16); Si, 3.09 (3.2). 1HNMR (δ/ppm): 1.4 (t, 2H), 1.57 (q, 2H), 1.96 (q, 2H), 2.35 (s, 1H), 2.47 (s, 3H), 3.55 (s, 3H), 4.0 (q, 2H), 5.0 (m, 2H), 6.9 (t, 1H), 7.0 (q, 1H), 7.5 (m, 1H), 7.9 (s, 1H), 8.0 (s, 1H). 
       Example 12 
     Compound L 
       [0072]    104.4 g of TDI trimer was dissolved in 400 mL of anhydrous tetrahydrofuran (THF) and the solution was added to a mixture of 42 g of 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    and 0.14 g of dibutyltin dilaurate (DBTDL). The resultant solution was stirred for 8 hs at room temperature under a dry environment. Subsequently, THF was removed with reduced pressure distillation and 135 g of compound L was obtained, with a yield of 92%. The compound L has a formula of 
         [0000]    
       
                 
         
             
             
         
       
     
         [0073]    wherein R is 
         [0000]    
       
                 
         
             
             
         
       
     
       and R 1  is —CH 2 CH 2 CH 2 —. 
       [0074]    Elemental analysis of C 66 H 50 N 12 O 18 S 2 Si 2 : measured value (calculated value) %: C, 55.76 (55.85); H, 3.44 (3.53); N, 11.74 (11.85); O, 20.22 (20.31); S, 4.42 (4.51); Si, 3.86 (3.95). 1HNMR (δ/ppm): 2.35 (m, 1H), 2.8 (q, 2H), 3.2 (q, 2H), 3.55 (s, 1H), 6.9 (t, 1H), 7.02 (q, 1H), 7.26 (m, 1H), 7.5 (m, 1H), 7.9 (s, 1H), 8.0 (s, 1H). 
         [0075]    Other derivatives can be prepared by methods similar to the above mentioned. Some derivatives of the invention are listed in Tables 1 and 2. 
         [0076]    In different compounds, the group represented by R has a formula of 
         [0000]    
       
         
               
               
               
             
           
               
                   
                   
               
             
             
               
                   
                 TDI 3   
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
                   
               
               
                   
                 NDI 3   
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
                   
               
               
                   
                 IPDI 3   
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
                   
               
               
                   
                 HMDI 3   
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
                   
               
               
                   
                 MDI 3   
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
                   
               
               
                   
                 HDI 3   
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
                   
               
               
                   
                 TMCDI 3   
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
                   
               
             
          
         
       
     
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Derivatives represented by formula (1) of the invention 
               
             
          
           
               
                 No. 
                 R 
                 X 
                 R 1   
                 R 2   
                 R 3   
                 a 
               
               
                   
               
             
          
           
               
                 1 
                 TDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 2 
                 TDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 3 
                 TDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 4 
                 TDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 5 
                 TDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 6 
                 TDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 7 
                 TDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 8 
                 TDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 9 
                 TDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 10 
                 TDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 11 
                 TDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 12 
                 TDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 13 
                 TDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 14 
                 TDI 3   
                 NHCONHCH 2 CH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 15 
                 TDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 16 
                 TDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 17 
                 TDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 18 
                 TDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 19 
                 TDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 20 
                 TDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 21 
                 MDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 22 
                 MDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 23 
                 MDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 24 
                 MDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 25 
                 MDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 26 
                 MDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 27 
                 MDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 28 
                 MDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 29 
                 MDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 30 
                 MDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 31 
                 MDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 32 
                 MDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 33 
                 MDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 34 
                 MDI 3   
                 NHCONHCH 2 CH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 35 
                 MDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 36 
                 MDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 37 
                 MDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 38 
                 MDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 39 
                 MDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 40 
                 MDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 41 
                 NDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 42 
                 NDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 43 
                 NDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 44 
                 NDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 45 
                 NDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 46 
                 NDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 47 
                 NDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 48 
                 NDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 49 
                 NDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 50 
                 NDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 51 
                 NDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 52 
                 NDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 53 
                 NDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 54 
                 NDI 3   
                 NHCONHCH 2 CH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 55 
                 NDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 56 
                 NDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 57 
                 NDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 58 
                 NDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 59 
                 NDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 60 
                 NDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 61 
                 HDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 62 
                 HDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 63 
                 HDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 64 
                 HDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 65 
                 HDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 66 
                 HDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 67 
                 HDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 68 
                 HDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 69 
                 HDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 70 
                 HDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 71 
                 HDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 72 
                 HDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 73 
                 HDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 74 
                 HDI 3   
                 NHCONHCH 2 CH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 75 
                 HDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 76 
                 HDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 77 
                 HDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 78 
                 HDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 79 
                 HDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 80 
                 HDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 81 
                 IPDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 82 
                 IPDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 83 
                 IPDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 84 
                 IPDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 85 
                 IPDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 86 
                 IPDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 87 
                 IPDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 88 
                 IPDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 89 
                 IPDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 90 
                 IPDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 91 
                 IPDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                   
                 1 
               
               
                 92 
                 IPDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 93 
                 IPDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                   
                 1 
               
               
                 94 
                 IPDI 3   
                 NHCONHCH 2 CH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 95 
                 IPDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 96 
                 IPDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 97 
                 IPDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 98 
                 IPDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 99 
                 IPDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 100 
                 IPDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 101 
                 TMCDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 102 
                 TMCDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 103 
                 TMCDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 104 
                 TMCDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 105 
                 TMCDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 106 
                 TMCDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 107 
                 TMCDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 108 
                 TMCDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 109 
                 TMCDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 110 
                 TMCDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 111 
                 TMCDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 112 
                 TMCDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 113 
                 TMCDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 114 
                 TMCDI 3   
                 NHCONHCH 2 CH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 115 
                 TMCDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 116 
                 TMCDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 117 
                 TMCDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 118 
                 TMCDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 119 
                 TMCDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 120 
                 TMCDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 121 
                 HMDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 122 
                 HMDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 123 
                 HMDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 124 
                 HMDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 125 
                 HMDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 126 
                 HMDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 127 
                 HMDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 128 
                 HMDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 129 
                 HMDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 130 
                 HMDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 131 
                 HMDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 132 
                 HMDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 133 
                 HMDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 134 
                 HMDI 3   
                 NHCONHCH 2 CH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 135 
                 HMDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 136 
                 HMDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                 137 
                 HMDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 138 
                 HMDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 1 
               
               
                 139 
                 HMDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 CH 2 O 
                 1 
               
               
                 140 
                 HMDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 2 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Derivatives represented by formula (2) of the invention 
               
             
          
           
               
                 No. 
                 R 
                 X 
                 R 1   
                 R 2  = R 4   
                 R 3  = R 5   
                 m 
               
               
                   
               
               
                 141 
                 TDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 142 
                 TDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 143 
                 TDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 144 
                 TDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 145 
                 TDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 146 
                 TDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 147 
                 TDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 148 
                 TDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 149 
                 TDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 150 
                 TDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 151 
                 TDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 152 
                 TDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 153 
                 TDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 154 
                 TDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 155 
                 TDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 156 
                 TDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 157 
                 TDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 158 
                 TDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 159 
                 TDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 160 
                 TDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 161 
                 TDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 162 
                 TDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 163 
                 TDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 164 
                 TDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 165 
                 MDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 166 
                 MDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 167 
                 MDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 168 
                 MDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                  1-10 
               
               
                 169 
                 MDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 10-20 
               
               
                 170 
                 MDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 20-30 
               
               
                 171 
                 MDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 172 
                 MDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 173 
                 MDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 174 
                 MDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 175 
                 MDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 176 
                 MDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 177 
                 MDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                  1-10 
               
               
                 178 
                 MDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 10-20 
               
               
                 179 
                 MDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 20-30 
               
               
                 180 
                 MDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 181 
                 MDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 182 
                 MDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 183 
                 MDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                  1-10 
               
               
                 184 
                 MDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 10-20 
               
               
                 185 
                 MDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 20-30 
               
               
                 186 
                 MDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 187 
                 MDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 188 
                 MDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 189 
                 NDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 190 
                 NDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 191 
                 NDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 192 
                 NDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                  1-10 
               
               
                 193 
                 NDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 10-20 
               
               
                 194 
                 NDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 20-30 
               
               
                 195 
                 NDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 196 
                 NDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 197 
                 NDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 198 
                 NDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                  1-10 
               
               
                 199 
                 NDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 10-20 
               
               
                 200 
                 NDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 20-30 
               
               
                 201 
                 NDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 202 
                 NDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 203 
                 NDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 204 
                 NDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                  1-10 
               
               
                 205 
                 NDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 10-20 
               
               
                 206 
                 NDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 20-30 
               
               
                 207 
                 NDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 208 
                 NDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 209 
                 NDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 210 
                 NDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                  1-10 
               
               
                 211 
                 NDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 10-20 
               
               
                 212 
                 NDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 20-30 
               
               
                 213 
                 HDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH3O 
                  1-10 
               
               
                 214 
                 HDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 215 
                 HDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 216 
                 HDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                  1-10 
               
               
                 217 
                 HDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 10-20 
               
               
                 218 
                 HDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 20-30 
               
               
                 219 
                 HDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 220 
                 HDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 221 
                 HDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 222 
                 HDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                  1-10 
               
               
                 223 
                 HDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 10-20 
               
               
                 224 
                 HDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 20-30 
               
               
                 225 
                 HDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 226 
                 HDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 227 
                 HDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 228 
                 HDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                  1-10 
               
               
                 229 
                 HDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 10-20 
               
               
                 230 
                 HDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 20-30 
               
               
                 231 
                 HDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 232 
                 HDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 233 
                 HDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 234 
                 HDI 3   
                 OH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                  1-10 
               
               
                 235 
                 HDI 3   
                 OH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 10-20 
               
               
                 236 
                 HDI 3   
                 OH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 20-30 
               
               
                 237 
                 IPDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 238 
                 IPDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 239 
                 IPDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 240 
                 IPDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                  1-10 
               
               
                 241 
                 IPDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 10-20 
               
               
                 242 
                 IPDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 20-30 
               
               
                 243 
                 IPDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 244 
                 IPDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 245 
                 IPDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 246 
                 IPDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                  1-10 
               
               
                 247 
                 IPDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 10-20 
               
               
                 248 
                 IPDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 20-30 
               
               
                 249 
                 IPDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 250 
                 IPDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 251 
                 IPDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 252 
                 IPDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                  1-10 
               
               
                 253 
                 IPDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 10-20 
               
               
                 254 
                 IPDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 20-30 
               
               
                 255 
                 IPDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 256 
                 IPDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 257 
                 IPDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 258 
                 IPDI 3   
                 OH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                  1-10 
               
               
                 259 
                 IPDI 3   
                 OH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 10-20 
               
               
                 260 
                 IPDI 3   
                 OH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 20-30 
               
               
                 261 
                 TMCDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 262 
                 TMCDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 263 
                 TMCDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 264 
                 TMCDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                  1-10 
               
               
                 265 
                 TMCDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 10-20 
               
               
                 266 
                 TMCDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 20-30 
               
               
                 267 
                 TMCDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 268 
                 TMCDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 269 
                 TMCDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 270 
                 TMCDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                  1-10 
               
               
                 271 
                 TMCDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 10-20 
               
               
                 272 
                 TMCDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 20-30 
               
               
                 273 
                 TMCDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 274 
                 TMCDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 275 
                 TMCDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 276 
                 TMCDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                  1-10 
               
               
                 277 
                 TMCDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 10-20 
               
               
                 278 
                 TMCDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 20-30 
               
               
                 279 
                 TMCDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 280 
                 TMCDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 281 
                 TMCDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 282 
                 TMCDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                  1-10 
               
               
                 283 
                 TMCDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 10-20 
               
               
                 284 
                 TMCDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 20-30 
               
               
                 285 
                 HMDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 286 
                 HMDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 287 
                 HMDI 3   
                 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 288 
                 HMDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                  1-10 
               
               
                 289 
                 HMDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 10-20 
               
               
                 290 
                 HMDI 3   
                 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 20-30 
               
               
                 291 
                 HMDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 292 
                 HMDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 293 
                 HMDI 3   
                 (C 6 H 6 )N 
                 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 294 
                 HMDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                  1-10 
               
               
                 295 
                 HMDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 10-20 
               
               
                 296 
                 HMDI 3   
                 NHCH 2 CH 2 NHCH 2 CH 2 NH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 20-30 
               
               
                 297 
                 HMDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 298 
                 HMDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 299 
                 HMDI 3   
                 CH 3 CH 2 CH 2 CH 2 N 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 300 
                 HMDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                  1-10 
               
               
                 301 
                 HMDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 10-20 
               
               
                 302 
                 HMDI 3   
                 NHCONH 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 20-30 
               
               
                 303 
                 HMDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                  1-10 
               
               
                 304 
                 HMDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 10-20 
               
               
                 305 
                 HMDI 3   
                 HS 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 20-30 
               
               
                 306 
                 HMDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                  1-10 
               
               
                 307 
                 HMDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3   
                 CH 3 O 
                 10-20 
               
               
                 308 
                 HMDI 3   
                 HO 
                 CH 2 CH 2 CH 2   
                 CH 3 O 
                 CH 3   
                 20-30 
               
               
                   
               
             
          
         
       
     
       Example 13 
       [0077]    To a four necked flask (500 mL) equipped with a thermometer, a reflux condenser, a stirrer, and a funnel, 128 g of the compound 89, 46.5 g of polycarbonate diol (Mn=1000), 6 g of polyethyleneglycol adipate (Mn=2000), 6 g of dimethyopropionic acid, 14 g of N-methylpyrrolidone, 0.4 g of DBTDL, and 10 g of acetone were separately added. The mixture was allowed to react at 70° C. until the amount of free isocyanate was less than 0.5 weight %, and thereby a polyurethane prepolymer was obtained. The prepolymer was cooled to 40° C., and then 6 g of triethylamine was added dropwise for neutralizing, 120 g of deionized water added for shearing, and 2 g of ethyldiamine added for chain extension. Finally, acetone was removed under reduced pressure distillation to yield a polyurethane emulsion with solid content of 42 weight %. 
       Example 14 
       [0078]    To a four necked flask (500 mL) equipped with a thermometer, a reflux condenser, a stirrer, and a funnel, 32 g of IPDI, 46.5 g of polycarbonate diol (Mn=1000), 6 g of polyethyleneglycol adipate (Mn=2000), 6 g of dimethyopropionic acid, 14 g of N-methylpyrrolidone, 0.4 g of DBTDL, and 10 g of acetone were separately added. The mixture was allowed to react at 70° C. until the amount of free isocyanate was less than 0.5 weight %, and thereby a polyurethane prepolymer was obtained. The prepolymer was cooled to 40° C., and then 6 g of triethylamine was added dropwise for neutralizing, 120 g of deionized water added for shearing, and 2 g of ethyldiamine added for chain extension. Finally, acetone was removed under reduced pressure distillation to yield a polyurethane emulsion with solid content of 40 weight %. 
       Example 15 
     Performance Measurement 
       [0079]    To evaluate the effectiveness of polyurethane (PU), epoxy resin, polymethacrylate (PMA), polyacrylamide (PAM), or phenolic resingloss prepared by isocyanate trimers modified with silane or functional polysiloxane, the gross, contact angle, surface drying time (h), adhesion, hardness, and flexibility of a coating of waterborne polyurethane prepared by isocyanate trimers modified with silane or functional polysiloxane were measured, and part of results were listed in Table 3. 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 3 
               
             
             
               
                   
               
               
                 Performance index of waterborne polyurethane prepared by isocyanate 
               
               
                 trimer modified with silane or functional polysiloxane 
               
             
          
           
               
                   
                   
                   
                   
                 Surface 
                   
                   
                   
               
               
                   
                   
                   
                 Contact 
                 drying time 
                   
                   
                 Flexibility 
               
               
                 No. 
                 Si-compound 
                 Gloss 
                 angle(θ) 
                 (min, 25° C.) 
                 Hardness 
                 Adhesion 
                 (mm) 
               
               
                   
               
               
                 309(b) 
                 — 
                 82 
                 55 
                 60 
                 0.4 
                 3 
                 4 
               
               
                 310 
                 81 
                 90 
                 72 
                 25 
                 0.6 
                 1 
                 2 
               
               
                 311 
                 82 
                 90 
                 72 
                 24 
                 0.6 
                 1 
                 2 
               
               
                 312 
                 83 
                 90 
                 72 
                 24 
                 0.6 
                 1 
                 2 
               
               
                 313 
                 84 
                 92 
                 72 
                 24 
                 0.6 
                 1 
                 2 
               
               
                 314 
                 85 
                 91 
                 70 
                 24 
                 0.6 
                 2 
                 2 
               
               
                 315 
                 86 
                 90 
                 70 
                 23 
                 0.6 
                 2 
                 2 
               
               
                 316 
                 87 
                 90 
                 71 
                 22 
                 0.6 
                 1 
                 2 
               
               
                 317 
                 88 
                 90 
                 71 
                 23 
                 0.6 
                 1 
                 2 
               
               
                 318 
                 89 
                 90 
                 71 
                 24 
                 0.6 
                 1 
                 2 
               
               
                 319 
                 90 
                 91 
                 72 
                 20 
                 0.6 
                 1 
                 2 
               
               
                 320 
                 91 
                 93 
                 72 
                 20 
                 0.6 
                 1 
                 2 
               
               
                 321 
                 92 
                 93 
                 72 
                 19 
                 0.6 
                 1 
                 2 
               
               
                 322 
                 93 
                 94 
                 72 
                 19 
                 0.6 
                 1 
                 2 
               
               
                 323 
                 94 
                 94 
                 72 
                 19 
                 0.6 
                 1 
                 2 
               
               
                 324 
                 95 
                 90 
                 72 
                 22 
                 0.6 
                 1 
                 2 
               
               
                 325 
                 96 
                 90 
                 72 
                 22 
                 0.6 
                 1 
                 2 
               
               
                 326 
                 97 
                 90 
                 72 
                 22 
                 0.6 
                 1 
                 2 
               
               
                 327 
                 98 
                 90 
                 72 
                 24 
                 0.6 
                 1 
                 2 
               
               
                 328 
                 99 
                 90 
                 71 
                 25 
                 0.6 
                 2 
                 2 
               
               
                 329 
                 100 
                 90 
                 71 
                 25 
                 0.6 
                 2 
                 2 
               
               
                 330 
                 237 
                 98 
                 77 
                 21 
                 0.7 
                 1 
                 1 
               
               
                 331 
                 238 
                 97 
                 77 
                 21 
                 0.7 
                 0 
                 1 
               
               
                 332 
                 239 
                 98 
                 77 
                 22 
                 0.7 
                 0 
                 1 
               
               
                 333 
                 240 
                 99 
                 77 
                 19 
                 0.7 
                 1 
                 1 
               
               
                 334 
                 241 
                 98 
                 77 
                 19 
                 0.7 
                 1 
                 1 
               
               
                 335 
                 242 
                 98 
                 78 
                 19 
                 0.7 
                 0 
                 1 
               
               
                 336 
                 243 
                 97 
                 78 
                 20 
                 0.7 
                 1 
                 1 
               
               
                 337 
                 244 
                 98 
                 78 
                 20 
                 0.7 
                 1 
                 1 
               
               
                 338 
                 245 
                 99 
                 78 
                 20 
                 0.7 
                 1 
                 1 
               
               
                 339 
                 246 
                 98 
                 78 
                 20 
                 0.7 
                 1 
                 1 
               
               
                 340 
                 247 
                 97 
                 78 
                 20 
                 0.7 
                 0 
                 1 
               
               
                 341 
                 248 
                 99 
                 78 
                 20 
                 0.7 
                 0 
                 1 
               
               
                 342 
                 249 
                 97 
                 78 
                 19 
                 0.7 
                 1 
                 1 
               
               
                 343 
                 250 
                 97 
                 78 
                 21 
                 0.7 
                 0 
                 1 
               
               
                 344 
                 251 
                 97 
                 78 
                 21 
                 0.7 
                 0 
                 1 
               
               
                 345 
                 252 
                 98 
                 78 
                 21 
                 0.7 
                 1 
                 1 
               
               
                 346 
                 253 
                 98 
                 78 
                 22 
                 0.7 
                 0 
                 1 
               
               
                 347 
                 254 
                 98 
                 77 
                 22 
                 0.7 
                 0 
                 1 
               
               
                 348 
                 255 
                 99 
                 77 
                 21 
                 0.7 
                 1 
                 1 
               
               
                 349 
                 256 
                 98 
                 78 
                 21 
                 0.7 
                 0 
                 1 
               
               
                 350 
                 257 
                 99 
                 77 
                 21 
                 0.7 
                 0 
                 1 
               
               
                 351 
                 258 
                 98 
                 77 
                 21 
                 0.7 
                 1 
                 1 
               
               
                 352 
                 259 
                 99 
                 77 
                 22 
                 0.7 
                 0 
                 1 
               
               
                   
               
             
          
         
       
     
         [0080]    The invention provides an isocyanate trimer modified with silane or functional polysiloxane and a method preparing the same. Waterborne polyurethane prepared by the modified isocyanate trimer has higher gloss, larger contact angle, greater hardness, drying faster, better adhesion, and better flexibility. 
         [0081]    While particular embodiments of the invention have been shown and described, it will be obvious to those skilled in the art that changes and modifications may be made without departing from the invention in its broader aspects, and therefore, the aim in the appended claims is to cover all such changes and modifications as fall within the true spirit and scope of the invention.

Technology Category: 8