Patent Publication Number: US-2023159719-A1

Title: Method of forming foam material

Description:
CROSS REFERENCE TO RELATED APPLICATIONS 
     This application is a Divisional of pending U.S. patent application Ser. No. 16/731,772, filed on Dec. 31, 2019 and entitled “Foaming composition and method of forming foam material”. 
    
    
     TECHNICAL FIELD 
     The technical field relates to a foam material, and in particular it relates to a foaming composition for forming the foam material. 
     BACKGROUND 
     There are a great number of applications for foam materials, among which polyurethane foam materials have excellent chemical resistance, solvent resistance, abrasion resistance, and the like. They are therefore widely used in industry, especially in furniture, bedding, transportation, refrigerated construction, thermal insulation, and the like. In global polyurethane application fields and product distribution, lightweight foam products account for about 65% of all polyurethane markets, which is very alarming. The foaming agent used in the general foaming process refers to an additive that can form a porous structure in plastic, that is, the additive to produce foam structure. They can generate a large amount of gas under certain conditions to form porous structure materials with continuous or discontinuous pores (such as open or closed pores). 
     Currently, isocyanate foaming compositions in common use are toxic, and a novel foaming composition is called for to replace the isocyanates in foaming materials. 
     SUMMARY 
     One embodiment of the disclosure provides a foaming composition that includes: 100 parts by weight of a compound having cyclic carbonate groups; and a foaming agent, wherein the foaming agent includes: 3 to 13 parts by weight of carbamate salt; and 15 to 65 parts by weight of amino compound. 
     One embodiment of the disclosure provides a method of forming foam material, including: mixing 100 parts by weight of a compound having cyclic carbonate groups and a foaming agent to form a foaming composition, wherein the foaming agent includes 3 to 13 parts by weight of carbamate salt and 15 to 65 parts by weight of amino compound; in addition, heating the foaming composition to 100° C. to 170° C. for decomposing the carbamate salt into CO 2  and the amino compound, and the amino compound is reacted with the compound having cyclic carbonate groups to form a foam material. 
    
    
     DETAILED DESCRIPTION 
     One embodiment of the disclosure provides a foaming composition, including: 100 parts by weight of a compound having cyclic carbonate groups and a foaming agent. The foaming agent includes 3 to 13 parts by weight of carbamate salt and 15 to 65 parts by weight of amino compound. If the carbamate salt ratio is too low, the foaming effect will be insufficient. If the carbamate salt ratio is too high, the foam product will easily collapse and stick. If the amino compound ratio is too low, the foam product will be sticky. If the amino compound ratio is too high, the foam product will also be sticky. In some embodiments, the compound having cyclic carbonate groups includes compound having aliphatic cyclic carbonate groups, compound having alicyclic cyclic carbonate groups, compound having aromatic cyclic carbonate groups, or a combination thereof. 
     For example, the compound having cyclic carbonate groups may have a chemical structure of 
     
       
         
         
             
             
         
       
     
     wherein n is an integer of 1 to 6; R 1  is aliphatic compound, alicyclic compound, aromatic compound, alkyl substituted aromatic compound, polyether oligomer, polyester oligomer, or a combination thereof; and R 2  is H, aliphatic compound, aliphatic compound containing cyclic carbonate groups, or a combination thereof. 
     In some embodiments, the compound having cyclic carbonate groups can be 1,4-butanediol diglycidyl cyclic carbonate ether (BDCE), resorcinol diglycidyl cyclic carbonate ether (RDCE), bisphenol A diglycidyl cyclic carbonate ether (DABCE), polypropylene glycol diglycidyl cyclic carbonate ether (PPGDCE), diglycidyl cyclic carbonate 1,2-cyclohexanedicarboxylate (DCCDC), 1,4-cycloexanedimethanol diglycidyl cyclic carbonate ether (CDCE), trimethylolpropane triglycidyl cyclic carbonate ether (PE300C, Mn=250 to 10000), cyclic carbonated soybean oil (CSBO) or a combination. 
     In some embodiments, the carbamate salt is formed by reacting the amino compound and CO 2  and has a chemical structure of 
     
       
         
         
             
             
         
       
     
     R 3  is C 1-12  polyether amine, alkylamine, cyclic alkyl amine, aromatic amine, or a combination thereof. In one embodiment, the amino compound includes polyether amine, alkyl amine, cyclic alkyl amine, aromatic amine, or a combination thereof. For example, the amino compound includes triethylenetetramine (TETA), trimethylhexamethylene diamine (TMD), polyethylenimine (branched, PEI300), 1,3-bis(aminomethyl)cyclohexane (1,3-BAC), m-xylene diamine (mXDA), polyoxypropylenediamine (Mn=200 to 4000), polyetheramine (Mn=100 to 200), ethylenediamine (EDA), or a combination thereof. 
     In some embodiment, the foaming composition further includes 0.1 to 10 parts by weight of epoxy compound having a chemical structure of: 
     
       
         
         
             
             
         
       
     
     wherein in is an integer of 1 to 6; R 4  is aliphatic compound, alicyclic compound, aromatic compound, alkyl substituted aromatic compound, polyether oligomer, polyester oligomer, or a combination thereof; and R 5  is H, aliphatic compound, aliphatic compound containing cyclic carbonate groups, or a combination thereof. In one embodiment, the epoxy compound includes aliphatic epoxy compound, alicyclic epoxy compound, aromatic epoxy compound, or a combination thereof. The epoxy compound can improve the tensile strength and tear strength of the foam material. If the epoxy compound ratio is too high, the foam material will not be soft enough. 
     For example, the epoxy compound includes 1,4-butanediol diglycidyl ether (BDGE), resorcinol diglycidyl ether (RDGE), bisphenol A diglycidyl ether (DABGE), polypropylene glycol diglycidyl ether (PPGDGE), diglycidyl 1,2 -cyclohexanedicarboxylate (DGCDC), 1,4-cycloexanedimethanol diglycidylether (CDGE), trimethylolpropane triglycidyl ether (PE300), epoxidized soybean oil (ESBO), or a combination thereof. 
     In some embodiments, the foaming composition further includes 2 to 10 parts by weight of filler, and the filler includes hollow beads, vermiculite, or a combination thereof. The hollow beads can be composed of plastic, ceramic, or glass. The filler may support the foam to prevent collapse. If the filler amount is too high, the foam will be too dense. 
     One embodiment of the disclosure provides a method of forming foam material, including: mixing 100 parts by weight of a compound having cyclic carbonate groups and a foaming agent to form a foaming composition. The foaming agent includes 3 to 13 parts by weight of carbamate salt and 15 to 65 parts by weight of amino compound. The composition and ratio of the foaming composition are described as above and not repeated here. 
     The foaming composition is then heated to 100° C. to 170° C. for decomposing the carbamate salt into CO 2  and the amino compound, and the amino compound is reacted with the compound having cyclic carbonate groups to form a foam material. If the heating temperature of the foaming composition is too low, the carbamate salt will not decompose into CO 2  and the amino compound, and the foaming effect cannot be achieved. If the heating temperature of the foaming composition is too high, bubbles in the foam product will break. 
     Accordingly, the carbamate salt may provide CO 2  (serving as the foaming agent) and react with cyclic carbonate groups through ring-opening reaction. Due to the foaming composition is free of halogen and isocyanate, the demands for environmental protection and low toxicity are met. 
     Below, exemplary embodiments will be described in detail so as to be easily realized by a person having ordinary knowledge in the art. The inventive concept may be embodied in various forms without being limited to the exemplary embodiments set forth herein. Descriptions of well-known parts are omitted for clarity, and like reference numerals refer to like elements throughout. 
     EXAMPLES 
     Synthesis Example 1 (CA-TETA) 
     TETA (150 g) was put into a jacketed glass reactor (2 L) and mechanically stirred , while CO 2  (20 Kg/cm 2 ) was introduced into TETA with a sprayer. The reactor was cooled and kept at 30° C. with cold water from circulating cooling tank for 1 hour in a first stage, and then heated to 60 ° C. and kept at 60° C. for 2 hours in a second stage. CO 2  was continuously introduced into and reacted with TETA in the first stage and the second stage. After the above reaction of CO 2  and TETA, a viscous liquid CA-TETA containing carbamate salt was obtained. CA-TETA was weighted to calculate its CO 2  content (15.19%), and analyzed by thermogravimetric analyzer (TGA) to calculate its CO 2  content (16.86%). Accordingly, the viscosity liquid contained 16.86 wt % of the carbamate salt. The viscosity liquid was analyzed by differential scanning calorimetry (DSC) to obtain its maximum foaming temperature (148.6° C.). 
     Synthesis Example 2 (CA-PEI300) 
     PEI300 (150 g) was put into a jacketed glass reactor (2 L) and mechanically stirred, while CO 2  (20 Kg/cm 2 ) was introduced into PEI300 with a sprayer. The reactor was cooled and kept at 30° C. with cold water from circulating cooling tank for 1 hour in a first stage, and then heated to 60° C. and kept at 60° C. for 2 hours in a second stage. CO 2  was continuously introduced into and reacted with PEI300 in the first stage and the second stage. After the above reaction of CO 2  and PEI300, a viscous liquid CA-PEI300 containing carbamate salt was obtained. CA-PEI300 was weighted to calculate its CO 2  content (9.98%), and analyzed by TGA to calculate its CO 2  content (9.78%). Accordingly, the viscosity liquid contained 9.78 wt % of the carbamate salt. The viscosity liquid was analyzed by DSC to obtain its maximum foaming temperature (155.7° C.). 
     Synthesis Example 3 (CA-TMD) 
     TMD (150 g) was put into a jacketed glass reactor (2 L) and mechanically stirred, while CO 2  (20 Kg/cm 2 ) was introduced into TMD with a sprayer. The reactor was cooled and kept at 30° C. with cold water from circulating cooling tank for 1 hour in a first stage, and then heated to 60° C. and kept at 60° C. for 2 hours in a second stage. CO 2  was continuously introduced into and reacted with TMD in the first stage and the second stage. After the above reaction of CO 2  and TMD, a viscous liquid CA-TMD containing carbamate salt was obtained. CA-TMD was weighted to calculate its CO 2  content (14.23%), and analyzed by TGA to calculate its CO 2  content (14.23%). Accordingly, the viscosity liquid contained 14.23 wt % of the carbamate salt. The viscosity liquid was analyzed by DSC to obtain its maximum foaming temperature (130.2° C.). 
     Synthesis Example 4 (CA-BAC) 
     BAC (150 g) was put into a jacketed glass reactor (2 L) and mechanically stirred, while CO 2  (20 Kg/cm 2 ) was introduced into BAC with a sprayer. The reactor was cooled and kept at 30° C. with cold water from circulating cooling tank for 1 hour in a first stage, and then heated to 60° C. and kept at 60° C. for 2 hours in a second stage. CO 2  was continuously introduced into and reacted with BAC in the first stage and the second stage. After the above reaction of CO 2  and BAC, a viscous liquid CA-BAC containing carbamate salt was obtained. CA-BAC was weighted to calculate its CO 2  content (11.96%), and analyzed by TGA to calculate its CO 2  content (12.67%). Accordingly, the viscosity liquid contained 12.67 wt % of the carbamate salt. The viscosity liquid was analyzed by DSC to obtain its maximum foaming temperature (135.7° C.). 
     Synthesis Example 5 (CA-mXDA) 
     mXDA (150 g) was put into a jacketed glass reactor (2 L) and mechanically stirred, while CO 2  (20 Kg/cm 2 ) was introduced into mXDA with a sprayer. The reactor was cooled and kept at 30° C. with cold water from circulating cooling tank for 1 hour in a first stage, and then heated to 60° C. and kept at 60° C. for 2 hours in a second stage. CO 2  was continuously introduced into and reacted with mXDA in the first stage and the second stage. After the above reaction of CO 2  and mXDA, a viscous liquid CA-mXDA containing carbamate salt was obtained. CA-mXDA was weighted to calculate its CO 2  content (12.75%), and analyzed by TGA to calculate its CO 2  content (13.02%). Accordingly, the viscosity liquid contained 13.02 wt % of the carbamate salt. The viscosity liquid was analyzed by DSC to obtain its maximum foaming temperature (152.3° C.). 
     Synthesis Example 6 (CSBO) 
     Epoxidized soybean oil (150 g) and catalyst tetrabutylammonium bromide (TBAB, 1.5 g, 2 wt %) were put into a reaction tank, while CO 2  (20 Kg/cm 2 ) was introduced into the reaction tank, and the mixture in the reaction tank was heated to 140° C. and continuously stirred to react for 24 hours to obtain CSBO. The conversion ratio (99%) of the above reaction was determined by  1 H NMR. 
     Example 1 
     CSBO (100 parts by weight) and CA-TETA (36.4 parts by weight, containing 16.86% of carbamate salt, such as 6.1 parts by weight of carbamate salt and 30.3 parts by weight of TETA) were stirred to mix well, and then put into an oven at 130° C. for 20 minutes to obtain a product. The product had a density of 107 Kg/m 3 , a tensile strength of 0.11 Kgf/cm 2 , an elongation of 24.2%, and a tear strength of 0.33 Kgf/cm. In this example and following examples, the density was measured by the standard ASTM D3574, the tensile strength was measured by the standard ASTM D3574, the elongation ratio was measured by the standard ASTM D3574, and the tear strength was measured by the standard ASTM D3574. 
     Example 2 
     CSBO (100 parts by weight), CA-TETA (36.4 parts by weight, containing 16.86% of carbamate salt, such as 6.1 parts by weight of carbamate salt and 30.3 parts by weight of TETA), and filler 031DU40 (commercially available from AkzoNobel, 5% of the total weight of CSBO and CA-TETA) were stirred to mix well, and then put into an oven at 130° C. for 30 minutes to obtain a product. The product had a density of 103 Kg/m 3 , a tensile strength of 0.15 Kgf/cm 2 , an elongation of 36.7%, and a tear strength of 0.22 Kgf/cm. 
     Example 3 
     CSBO (100 parts by weight), CA-TETA (36.4 parts by weight, containing 16.86% of carbamate salt, such as 6.1 parts by weight of carbamate salt and 30.3 parts by weight of TETA), and filler 031DU40 (commercially available from AkzoNobel, 5% of the total weight of CSBO and CA-TETA) were stirred to mix well, and then put into an oven at 150° C. for 30 minutes to obtain a product. The product had a density of 95 Kg/m 3 , a tensile strength of 0.17 Kgf/cm 2 , an elongation of 31.8%, and a tear strength of 0.24 Kgf/cm. 
     Example 4 
     CSBO (100 parts by weight), CA-TETA (36.9 parts by weight, containing 16.86% of carbamate salt, such as 6.2 parts by weight of carbamate salt and 30.7 parts by weight of TETA), epoxy resin BDGE (1.8 parts by weight), and filler 031DU40 (commercially available from AkzoNobel, 5% of the total weight of CSBO, CA-TETA, and BDGE) were stirred to mix well, and then put into an oven at 130° C. for 30 minutes to obtain a product. The product had a density of 122 Kg/m 3 , a tensile strength of 0.15 Kgf/cm 2 , an elongation of 38.8%, and a tear strength of 0.21 Kgf/cm. 
     Example 5 
     CSBO (100 parts by weight), CA-TETA (37.8 parts by weight, containing 16.86% of carbamate salt, such as 6.4 parts by weight of carbamate salt and 31.4 parts by weight of TETA), epoxy resin BDGE (3.7 parts by weight), filler 031DU40 (commercially available from AkzoNobel, 5% of the total weight of CSBO, CA-TETA, and BDGE) were stirred to mix well, and then put into an oven at 130° C. for 30 minutes to obtain a product. The product had a density of 114 Kg/m 3 , a tensile strength of 0.57 Kgf/cm 2 , an elongation of 39.5%, and a tear strength of 0.45 Kgf/cm. 
     Example 6 
     CSBO (100 parts by weight), CA-TETA (36.8 parts by weight, containing 16.86% of carbamate salt, such as 6.2 parts by weight of carbamate salt and 30.6 parts by weight of TETA), epoxy resin RDGE (2.1 parts by weight), filler 031DU40 (commercially available from AkzoNobel, 5% of the total weight of CSBO, CA-TETA, and RDGE) were stirred to mix well, and then put into an oven at 130° C. for 30 minutes to obtain a product. The product had a density of 106 Kg/m 3 , a tensile strength of 0.19 Kgf/cm 2 , an elongation of 35.5%, and a tear strength of 0.20 Kgf/cm 2 . 
     Example 7 
     CSBO (100 parts by weight), CA-TETA (37.6 parts by weight, containing 16.86% of carbamate salt, such as 6.3 parts by weight of carbamate salt and 31.3 parts by weight of TETA), epoxy resin RDGE (4.3 parts by weight), filler 031DU40 (commercially available from AkzoNobel, 5% of the total weight of CSBO, CA-TETA, and RDGE) were stirred to mix well, and then put into an oven at 130° C. for 30 minutes to obtain a product. The product had a density of 97 Kg/m 3 , a tensile strength of 0.70 Kgf/cm 2 , an elongation of 40.3%, and a tear strength of 0.36 Kgf/cm. 
     Example 8 
     CSBO (100 parts by weight), CA-TETA (36.8 parts by weight, containing 16.86% of carbamate salt, such as 6.2 parts by weight of carbamate salt and 30.6 parts by weight of TETA), epoxy resin DABGE (3.2 parts by weight), filler 031DU40 (commercially available from AkzoNobel, 5% of the total weight of CSBO, CA-TETA, and DABGE) were stirred to mix well, and then put into an oven at 130° C. for 30 minutes to obtain a product. The product had a density of 96 Kg/m 3 , a tensile strength of 0.16 Kgf/cm 2 , an elongation of 38.3%, and a tear strength of 0.22 Kgf/cm. 
     Example 9 
     CSBO (100 parts by weight), CA-TETA (37.7 parts by weight, containing 16.86% of carbamate salt, such as 6.4 parts by weight of carbamate salt and 31.3 parts by weight of TETA), epoxy resin DABGE (6.6 parts by weight), and filler 031DU40 (commercially available from AkzoNobel, 5% of the total weight of CSBO, CA-TETA, and DABGE) were stirred to mix well, and then put into an oven at 130° C. for 30 minutes to obtain a product. The product had a density of 101 Kg/m 3 , a tensile strength of 0.82 Kgf/cm 2 , an elongation of 31.1%, and a tear strength of 0.55 Kgf/cm. 
     Example 10 
     CSBO (100 parts by weight), CA-TETA (36.4 parts by weight, containing 16.86% of carbamate salt, such as 6.1 parts by weight of carbamate salt and 30.3 parts by weight of TETA), filler 031DU40 (commercially available from AkzoNobel, 2.5% of the total weight of CSBO and CA-TETA), and filler 920DU40 (commercially available from AkzoNobel, 2.5% of the total weight of CSBO and CA-TETA) were stirred to mix well, and then put into an oven at 150° C. for 30 minutes to obtain a product. The product had a density of 82 Kg/m 3 , a tensile strength of 0.15 Kgf/cm 2 , an elongation of 32.2%, and a tear strength of 0.26 Kgf/cm. 
     Example 11 
     CSBO (100 parts by weight), CA-TETA (36.4 parts by weight, containing 16.86% of carbamate salt, such as 6.1 parts by weight of carbamate salt and 30.3 parts by weight of TETA), and filler 920DU40 (commercially available from AkzoNobel, 2.5% of the total weight of CSBO and CA-TETA) were stirred to mix well, and then put into an oven at 150° C. for 30 minutes to obtain a product. The product had a density of 157 Kg/m 3 , a tensile strength of 0.39 Kgf/cm 2 , an elongation of 25.1%, and a tear strength of 0.40 Kgf/cm. 
     
       
         
           
               
               
               
               
               
               
               
               
             
               
                 TABLE 1 
               
               
                   
               
               
                   
                 Compound 
                   
                 Foaming agent 
                   
                   
                   
                   
               
               
                   
                 having cyclic 
                   
                 (carbamate 
                   
                 Tensile 
                   
                 Tear 
               
               
                   
                 carbonate 
                 Epoxy 
                 salt/amino 
                 Density 
                 strength 
                 Elongation 
                 strength 
               
               
                 Example 
                 groups 
                 resin 
                 compound) 
                 (Kg/m 3 ) 
                 (Kgf/cm 2 ) 
                 (%) 
                 (Kgf/cm) 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 1 
                 CSBO 
                 None 
                 CA-TETA 
                 107 
                 0.11 
                 24.2 
                 0.33 
               
               
                   
                 (100) 
                   
                 (6.1/30.3) 
               
               
                 2 
                 CSBO 
                 None 
                 CA-TETA 
                 103 
                 0.15 
                 36.7 
                 0.22 
               
               
                   
                 (100) 
                   
                 (6.1/30.3) 
               
               
                 3 
                 CSBO 
                 None 
                 CA-TETA 
                 95 
                 0.17 
                 31.8 
                 0.24 
               
               
                   
                 (100) 
                   
                 (6.1/30.3) 
               
               
                 4 
                 CSBO 
                 BDGE 
                 CA-TETA 
                 122 
                 0.15 
                 38.8 
                 0.21 
               
               
                   
                 (100) 
                 (1.8) 
                 (6.2/30.7) 
               
               
                 5 
                 CSBO 
                 BDGE 
                 CA-TETA 
                 114 
                 0.57 
                 39.5 
                 0.45 
               
               
                   
                 (100) 
                 (3.7) 
                 (6.4/31.4) 
               
               
                 6 
                 CSBO 
                 RDGE 
                 CA-TETA 
                 106 
                 0.19 
                 35.5 
                 0.20 
               
               
                   
                 (100) 
                 (2.1) 
                 (6.2/30.6) 
               
               
                 7 
                 CSBO 
                 RDGE 
                 CA-TETA 
                 97 
                 0.70 
                 40.3 
                 0.36 
               
               
                   
                 (100) 
                 (4.3) 
                 (6.3/31.3) 
               
               
                 8 
                 CSBO 
                 DABGE 
                 CA-TETA 
                 96 
                 0.16 
                 38.3 
                 0.22 
               
               
                   
                 (100) 
                 (3.2) 
                 (6.2/30.6) 
               
               
                 9 
                 CSBO 
                 DABGE 
                 CA-TETA 
                 101 
                 0.82 
                 31.1 
                 0.55 
               
               
                   
                 (100) 
                 (6.6) 
                 (6.4/31.3) 
               
               
                 10 
                 CSBO 
                 None 
                 CA-TETA 
                 82 
                 0.15 
                 32.2 
                 0.26 
               
               
                   
                 (100) 
                   
                 (6.1/30.3) 
               
               
                 11 
                 CSBO 
                 None 
                 CA-TETA 
                 157 
                 0.39 
                 25.1 
                 0.40 
               
               
                   
                 (100) 
                   
                 (6.1/30.3) 
               
               
                   
               
            
           
         
       
     
     As seen from Table 1, the epoxy resin (serving as crosslinking agent) could help to increase the tensile strength and tear strength of the foam material. 
     Example 12 
     CSBO (100 parts by weight), CA-TETA (18.2 parts by weight, containing 16.86% of carbamate salt, such as 3.1 parts by weight of carbamate salt and 15.1 parts by weight of TETA), filler 031DU40 (commercially available from AkzoNobel, 2.5% of the total weight of CSBO and CA-TETA), and filler 920DU40 (commercially available from AkzoNobel, 2.5% of the total weight of CSBO and CA-TETA) were stirred to mix well, and then put into an oven at 150° C. for 60 minutes to obtain a product. The product had a density of 92 Kg/m 3 , a tensile strength of 0.12 Kgf/cm 2 , and an elongation of 75.6%. 
     Example 13 
     CSBO (100 parts by weight), CA-TETA (72.7 parts by weight, containing 16.86% of carbamate salt, such as 12.2 parts by weight of carbamate salt and 60.5 parts by weight of TETA), filler 031DU40 (commercially available from AkzoNobel, 2.5% of the total weight of CSBO and CA-TETA), and filler 920DU40 (commercially available from AkzoNobel, 2.5% of the total weight of CSBO and CA-TETA) were stirred to mix well, and then put into an oven at 150° C. for 60 minutes to obtain a product. The product had a density of 80 Kg/m 3 , a tensile strength of 0.10 Kgf/cm 2 , and an elongation of 94.7%. 
     Example 14 
     CSBO (100 parts by weight), CA-TETA (28.8 parts by weight, containing 16.86% of carbamate salt, such as 4.8 parts by weight of carbamate salt and 24.0 parts by weight of TETA), CA-TMD (7.6 parts by weight, containing 14.23 wt % of carbamate salt, such as 1.1 parts by weight of carbamate salt and 6.5 parts by weight of TMD), filler 031DU40 (commercially available from AkzoNobel, 2.5% of the total weight of CSBO, CA-TETA, and CA-TMD), and filler 920DU40 (commercially available from AkzoNobel, 2.5% of the total weight of CSBO, CA-TETA, and CA-TMD) were stirred to mix well, and then put into an oven at 150° C. for 30 minutes to obtain a product. The product had a density of 109 Kg/m 3 , a tensile strength of 0.31 Kgf/cm 2 , an elongation of 67.2%, and a tear strength of 0.53 Kgf/cm. 
     Example 15 
     CSBO (100 parts by weight), CA-TETA (28.9 parts by weight, containing 16.86% of carbamate salt, such as 4.9 parts by weight of carbamate salt and 24.0 parts by weight of TETA), CA-BAC (6.8 parts by weight, containing 12.67wt % of carbamate salt, such as 0.8 parts by weight of carbamate salt and 6.0 parts by weight of BAC), filler 031DU40 (commercially available from AkzoNobel, 2.5% of the total weight of CSBO, CA-TETA, and CA-BAC), and filler 920DU40 (commercially available from AkzoNobel, 2.5% of the total weight of CSBO, CA-TETA, and CA-BAC) were stirred to mix well, and then put into an oven at 150° C. for 30 minutes to obtain a product. The product had a density of 112 Kg/m 3 , a tensile strength of 0.35 Kgf/cm 2 , an elongation of 47.1%, and a tear strength of 0.68 Kgf/cm. 
     Example 16 
     CSBO (100 parts by weight), CA-TETA (28.9 parts by weight, containing 16.86% of carbamate salt, such as 4.9 parts by weight of carbamate salt and 24.0 parts by weight of TETA), CA-PEI300 (6.8 parts by weight, containing 9.78 wt % of carbamate salt, such as 0.7 parts by weight of carbamate salt and 6.1 parts by weight of PEI300), filler 031DU40 (commercially available from AkzoNobel, 2.5% of the total weight of CSBO, CA-TETA, and CA-PEI300), and filler 920DU40 (commercially available from AkzoNobel, 2.5% of the total weight of CSBO, CA-TETA, and CA-PEI300) were stirred to mix well, and then put into an oven at 150° C. for 30 minutes to obtain a product. The product had a density of 118 Kg/m 3 , a tensile strength of 0.44 Kgf/cm 2 , an elongation of 33.9%, and a tear strength of 0.46 Kgf/cm. 
     Example 17 
     CSBO (100 parts by weight), CA-TETA (28.8 parts by weight, containing 16.86% of carbamate salt, such as 4.8 parts by weight of carbamate salt and 24.0 parts by weight of TETA), CA-mXDA (8.2 parts by weight, containing 13.02% of carbamate salt, such as 1.1 parts by weight of carbamate salt and 7.1 parts by weight of mXDA), filler 031DU40 (commercially available from AkzoNobel, 2.5% of the total weight of CSBO, CA-TETA, and CA-mXDA), and filler 920DU40 (commercially available from AkzoNobel, 2.5% of the total weight of CSBO, CA-TETA, and CA-mXDA) were stirred to mix well, and then put into an oven at 150° C. for 30 minutes to obtain a product. The product had a density of 120 Kg/m 3 , a tensile strength of 0.47 Kgf/cm 2 , an elongation of 52.6%, and a tear strength of 0.51 Kgf/cm. 
     
       
         
           
               
               
               
               
               
               
               
             
               
                 TABLE 2 
               
               
                   
               
               
                   
                 Compound 
                 Foaming agent 
                   
                   
                   
                   
               
               
                   
                 having cyclic 
                 (carbamate 
                   
                 Tensile 
                   
                 Tear 
               
               
                   
                 carbonate 
                 salt/amino 
                 Density 
                 strength 
                 Elongation 
                 strength 
               
               
                 Example 
                 groups 
                 compound) 
                 (Kg/m 3 ) 
                 (kgf/cm 2 ) 
                 (%) 
                 (Kgf/cm) 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 10 
                 CSBO 
                 CA-TETA 
                 82 
                 0.15 
                 32.2 
                 0.26 
               
               
                   
                 (100) 
                 (6.1/30.3) 
               
               
                 12 
                 CSBO 
                 CA-TETA 
                 92 
                 0.12 
                 75.6 
                 Not 
               
               
                   
                 (100) 
                 (3.1/15.1) 
                   
                   
                   
                 measured 
               
               
                 13 
                 CSBO 
                 CA-TETA 
                 80 
                 0.10 
                 94.7 
                 Not 
               
               
                   
                 (100) 
                 (12.2/60.5) 
                   
                   
                   
                 measured 
               
               
                 14 
                 CSBO 
                 CA-TETA 
                 109 
                 0.31 
                 67.2 
                 0.53 
               
               
                   
                 (100) 
                 (4.8/24.0) + 
               
               
                   
                   
                 CA-TMD 
               
               
                   
                   
                 (1.1/6.5) 
               
               
                 15 
                 CSBO 
                 CA-TETA 
                 112 
                 0.35 
                 47.1 
                 0.68 
               
               
                   
                 (100) 
                 (4.9/24.0) + 
               
               
                   
                   
                 CA-BAC 
               
               
                   
                   
                 (0.8/6.0) 
               
               
                 16 
                 CSBO 
                 CA-TETA 
                 118 
                 0.44 
                 33.9 
                 0.46 
               
               
                   
                 (100) 
                 (4.9/24.0) + 
               
               
                   
                   
                 CA-PEI300 
               
               
                   
                   
                 (0.7/6.1) 
               
               
                 17 
                 CSBO 
                 CA-TETA 
                 120 
                 0.47 
                 52.6 
                 0.51 
               
               
                   
                 (100) 
                 (4.8/24.0) + 
               
               
                   
                   
                 CA-mXDA 
               
               
                   
                   
                 (1.1/7.1) 
               
               
                   
               
            
           
         
       
     
     As shown in Table 2, the foaming composition could be adjusted to enhance the tensile strength and density of the foam materials. 
     Example 18 
     CDCE (100 parts by weight), CA-TETA (54.6 parts by weight, containing 16.86% of carbamate salt, such as 9.2 parts by weight of carbamate salt and 45.4 parts by weight of TETA), filler 031DU40 (commercially available from AkzoNobel, 2.5% of the total weight of CDCE and CA-TETA) and filler 920DU40 (commercially available from AkzoNobel, 2.5% of the total weight of CDCE and CA-TETA) were stirred to mix well, and then put into an oven at 150° C. for 30 minutes to obtain a product. The product had a density of 139 Kg/m 3 , a tensile strength of 1.06 Kgf/cm 2 , and an elongation of 8.2%. 
     Example 19 
     PE300C (100 parts by weight), CA-TETA (59.7 parts by weight, containing 16.86% of carbamate salt, such as 10.1 parts by weight of carbamate salt and 49.6 parts by weight of TETA), filler 031DU40 (commercially available from AkzoNobel, 2.5% of the total weight of PE300C and CA-TETA) and filler 920DU40 (commercially available from AkzoNobel, 2.5% of the total weight of PE300C and CA-TETA) were stirred to mix well, and then put into an oven at 150° C. for 30 minutes to obtain a product. The product had a density of 142 Kg/m 3 , a tensile strength of 0.88 Kgf/cm 2 , and an elongation of 15.1%. 
     Example 20 
     RDCE (100 parts by weight), CA-TETA (53.6 parts by weight, containing 16.86% of carbamate salt, such as 9.0 parts by weight of carbamate salt and 44.6 parts by weight of TETA), filler 031DU40 (commercially available from AkzoNobel, 2.5% of the total weight of RDCE and CA-TETA), and filler 920DU40 (commercially available from AkzoNobel, 2.5% of the total weight of RDCE and CA-TETA) were stirred to mix well, and then put into an oven at 150° C. for 30 minutes to obtain a product. The product had a density of 138 Kg/m 3 , a tensile strength of 1.24 Kgf/cm 2 , and an elongation of 9.5%. 
     Example 21 
     CSBO (100 parts by weight), CDCE (28.6 parts by weight), CA-TETA (50.3 parts by weight, containing 16.86% of carbamate salt, such as 8.5 parts by weight of carbamate salt and 41.8 parts by weight of TETA), filler 031DU40 (commercially available from AkzoNobel, 2.5% of the total weight of CSBO, CDCE, and CA-TETA), and filler 920DU40 (commercially available from AkzoNobel, 2.5% of the total weight of CSBO, CDCE, and CA-TETA) were stirred to mix well, and then put into an oven at 150° C. for 30 minutes to obtain a product. The product had a density of 94 Kg/m 3 , a tensile strength of 0.51 Kgf/cm 2 , an elongation of 27.4%, and a tear strength of 0.45 Kgf/cm. 
     Example 22 
     CSBO (100 parts by weight), PE300C (36.1 parts by weight), CA-TETA (50.1 parts by weight, containing 16.86% of carbamate salt, such as 8.4 parts by weight of carbamate salt and 41.7 parts by weight of TETA), filler 031DU40 (commercially available from AkzoNobel, 2.5% of the total weight of CSBO, PE300C, and CA-TETA), and filler 920DU40 (commercially available from AkzoNobel, 2.5% of the total weight of CSBO, PE300C, and CA-TETA) were stirred to mix well, and then put into an oven at 150° C. for 30 minutes to obtain a product. The product had a density of 93 Kg/m 3 , a tensile strength of 0.28 Kgf/cm 2 , an elongation of 35.9%, and a tear strength of 0.26 Kgf/cm. 
     Example 23 
     CSBO (100 parts by weight), RDCE (25.9 parts by weight), CA-TETA (50.2 parts by weight, containing 16.86% of carbamate salt, such as 8.5 parts by weight of carbamate salt and 41.7 parts by weight of TETA), filler 031DU40 (commercially available from AkzoNobel, 2.5% of the total weight of CSBO, RDCE, and CA-TETA), and filler 920DU40 (commercially available from AkzoNobel, 2.5% of the total weight of CSBO, RDCE, and CA-TETA) were stirred to mix well, and then put into an oven at 150° C. for 30 minutes to obtain a product. The product had a density of 99 Kg/m 3 , a tensile strength of 0.56 Kgf/cm 2 , an elongation of 25.5%, and a tear strength of 0.58 Kgf/cm. 
     
       
         
           
               
               
               
               
               
               
               
             
               
                 TABLE 3 
               
               
                   
               
               
                   
                 Compound 
                 Foaming agent 
                   
                   
                   
                   
               
               
                   
                 having cyclic 
                 (carbamate 
                   
                 Tensile 
                   
                 Tear 
               
               
                   
                 carbonate 
                 salt/amino 
                 Density 
                 strength 
                 Elongation 
                 strength 
               
               
                 Example 
                 groups 
                 compound) 
                 (Kg/m 3 ) 
                 (Kgf/cm 2 ) 
                 (%) 
                 (Kgf/cm) 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 10 
                 CSBO 
                 CA-TETA 
                 82 
                 0.15 
                 32.2 
                 0.26 
               
               
                   
                 (100) 
                 (6.1/30.3) 
               
               
                 18 
                 CDCE 
                 CA-TETA 
                 139 
                 1.06 
                 8.2 
                 Not 
               
               
                   
                 (100) 
                 (9.2/45.4) 
                   
                   
                   
                 measured 
               
               
                 19 
                 PE300C 
                 CA-TETA 
                 142 
                 0.88 
                 15.1 
                 Not 
               
               
                   
                 (100) 
                 (10.1/49.6) 
                   
                   
                   
                 measured 
               
               
                 20 
                 RDCE 
                 CA-TETA 
                 138 
                 1.24 
                 9.5 
                 Not 
               
               
                   
                 (100) 
                 (9.0/44.6) 
                   
                   
                   
                 measured 
               
               
                 21 
                 CSBO 
                 CA-TETA 
                 94 
                 0.51 
                 27.4 
                 0.45 
               
               
                   
                 (100)/ 
                 (8.5/41.8) 
               
               
                   
                 CDCE 
               
               
                   
                 (28.6) 
               
               
                 22 
                 CSBO 
                 CA-TETA 
                 93 
                 0.28 
                 35.9 
                 0.26 
               
               
                   
                 (100)/ 
                 (8.4/41.7) 
               
               
                   
                 PE300C 
               
               
                   
                 (36.1) 
               
               
                 23 
                 CSBO 
                 CA-TETA 
                 99 
                 0.56 
                 25.5 
                 0.58 
               
               
                   
                 (100)/ 
                 (8.5/41.7) 
               
               
                   
                 RDCE 
               
               
                   
                 (25.9) 
               
               
                   
               
            
           
         
       
     
     As known from Table 3, the foam material of the rigid compounds having cyclic carbonate groups (e.g. CDCD or RDCE) had a higher tensile strength, and their rigid properties were favorable for rigid foam. 
     Comparative Example 1 
     CSBO (100 parts by weight), TETA (30.4 parts by weight), filler 031DU40 (commercially available from AkzoNobel, 2.5% of the total weight of CSBO and TETA), and filler 920DU40 (commercially available from AkzoNobel, 2.5% of the total weight of CSBO and TETA) were stirred to mix well, and then put into an oven at 150° C. for 30 minutes to obtain a product. The product had a density of 572 Kg/m 3 , a tensile strength of 0.77 Kgf/cm 2 , an elongation of 28.9%, and a tear strength of 0.54 Kgf/cm. The product was obviously not foamed. 
     Comparative Example 2 
     CSBO (100 parts by weight), TETA (15.3 parts by weight), TMD (16.5 parts by weight), filler 031DU40 (commercially available from AkzoNobel, 2.5% of the total weight of CSBO, TETA, and TMD), and filler 920DU40 (commercially available from AkzoNobel, 2.5% of the total weight of CSBO, TETA, and TMD) were stirred to mix well, and then put into an oven at 150° C. for 30 minutes to obtain a product. The product had a density of 601 Kg/m 3 , a tensile strength of 1.49 Kgf/cm 2 , an elongation of 56.3%, and a tear strength of 0.75 Kgf/cm. The product was obviously not foamed. 
     
       
         
           
               
               
               
               
               
               
               
             
               
                   
                 TABLE 4 
               
               
                   
                   
               
               
                   
                   
                 Foaming agent 
                   
                   
                   
                   
               
               
                   
                 Compound 
                 (carbamate 
               
               
                   
                 having cyclic 
                 salt/amino 
                   
                 Tensile 
                   
                 Tear 
               
               
                   
                 carbonate 
                 compound) or 
                 Density 
                 strength 
                 Elongation 
                 strength 
               
               
                   
                 groups 
                 amino compound 
                 (Kg/m3) 
                 (kgf/cm 2 ) 
                 (%) 
                 (Kgf/cm) 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Example 10 
                 CSBO 
                 CA-TETA 
                 82 
                 0.15 
                 32.2 
                 0.26 
               
               
                   
                 (100) 
                 (6.1/30.3) 
               
               
                 Comparative 
                 CSBO 
                 TETA 
                 572 
                 0.77 
                 28.9 
                 0.54 
               
               
                 Example 1 
                 (100) 
                 (30.4) 
               
               
                 Comparative 
                 CSBO 
                 TETA 
                 601 
                 1.49 
                 56.3 
                 0.75 
               
               
                 Example 2 
                 (100) 
                 (15.3)/ 
               
               
                   
                   
                 TMD 
               
               
                   
                   
                 (16.5) 
               
               
                   
               
            
           
         
       
     
     As shown in Table 4, the foam product with a low density could not be obtained without the carbamate salt. 
     Comparative Example 3 
     CSBO (100 parts by weight), CA-TETA (36.4 parts by weight), and filler 031DU40 (commercially available from AkzoNobel, 5% of the total weight of CSBO and CA-TETA) were stirred to mix well, and then put into an oven at 100° C. for 30 minutes to obtain a product. The product had a density of 860 Kg/m 3 , which was obviously not foamed. 
     Comparative Example 4 
     CSBO (100 parts by weight), CA-TETA (36.4 parts by weight), and filler 031DU40 (commercially available from AkzoNobel, 5% of the total weight of CSBO and CA-TETA) were stirred to mix well, and then put into an oven at 170° C. for 30 minutes to obtain a product. The product had a density of 320 Kg/m 3 . The bubbles in the product were broken. As known from Comparative Examples 3 and 4, the properties of the foam products would be deteriorated if the heating temperature of the foaming composition was too high or too low. 
     It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed methods and materials. It is intended that the specification and examples be considered as exemplary only, with the true scope of the disclosure being indicated by the following claims and their equivalents.