Abstract:
Hydrazides of the formula ##STR1## are good curing agents for epoxy resin, wherein in the formula, X is an aromatic hydrocarbon residue of dihydric phenol, ##STR2## The curing agents are useful in formulating novel storable one-package, heat-curable epoxy resin-based compositions.

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to certain novel hydrazides and the use thereof as curing agents for epoxy resins. 
     2. Description of the Prior Art 
     Epoxy resins are widely employed as electric insulating materials, various moulded products, adhesives or coatings because they give valuable cured resins having excellent mechanical, electrical and chemical properties when cured with suitable curing agents, for example acid anhydride and amine curing agents. However, epoxy resin composition incorporating amine curing agents are cured rapidly at ordinary temperature and at elevated temperature, and hence they lack storage stability. Also, epoxy resin compositions incorporating acid anhydride curing agents are stable at ordinary temperature, but heating for a long period of time at elevated temperature is required for full curing. Usually, tertiary amines, quaternary ammonium compounds or organo metal complexes are further added to the composition for the purpose of accelerating curing rate. However, the addition of such cure accelerator impairs storage stability markedly. 
     So-called latent curing agents which are compatible with epoxy resins to form a composition which is stable at relatively low temperature and which is rapidly cured when heated to elevated temperature are eagerly desired. In the field of coating, particularly, curing agents are desired which give colorless and transparent cured epoxy resin, from the view of tone of color. Representative compounds which have been heretofore proposed as latent curing agents are dicyandiamide, dibasic acid hydrazide, boron trifluoride-amine adduct, guanamine and melamine. Among these compounds, dicyandiamide, dibasic acid hydrazide and quanamine are useful in formulating epoxy resin compositions having excellent storage stability, but full curing by means of these compounds could be achieved only by heating at higher temperature than 150° C. for a long time. Also, boron trifluoride-amine adduct is hard to treat owing to its high hygroscopic property, and it affects the physical properties of the cured resin adversely. 
     There has been heretofore known almost no latent epoxy curing agent which causes rapid curing at moderate elevated temperature (that is 100° C.-150° C.) and which gives an epoxy resin composition having excellent storage stability at ordinary temperature. 
     SUMMARY OF THE INVENTION 
     An object of the present invention is to provide novel hydrazide-type curing agents which are useful in making storable one-package curable epoxy resin compositions. 
     Another object of the present invention is to provide hydrazide-type curing agents which alone or together with other curing agents can activate a rapid curing of epoxy resin composition at relatively low temperatures and yet be extraordinarily resistant to gelling at 40° C. for three or more weeks. 
     A further object of the present invention is to provide hydrazide-type curing agents which give cured epoxy resin having excellent transparency and water resistance. 
     The above objects of the present invention may be substantially achieved by providing as a curing agent a hydrazide compound having the following general formula (I): ##STR3## wherein X is an aromatic hydrocarbon residue of a dihydric phenol, ##STR4## 
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     The hydrazides which may be represented by the above general formula (I) may be readily prepared by reacting an adduct of 1 mole of aromatic diol represented by the general formula OH--X--OH wherein X has the meanings set forth above and 2 moles of alkyl acrylate having the general formula CH 2  ═CHCOOR wherein R is alkyl group, with hydrazine hydrate, said adduct of aromatic diol and bimolecular alkyl acrylate being represented by the following general formula (a) ##STR5## wherein X has the meanings set forth above and R is alkyl group having 1-4 carbon atoms. 
     Although the aromatic diol-bimolecular alkyl acrylate adduct may be directly prepared by the addition reaction between an aromatic diol and alkyl acrylate, it may also be prepared by the following two-step reaction. That is, 1 mole of aromatic diol is reacted with 2 moles of acrylonitrile to form an aromatic diol-bimolecular acrylonitrile adduct, which is then subjected to alcoholysis whereby the nitrile group in the adduct is converted into a carboalkoxy group, said aromatic diol-bimolecular acrylonitrile adduct being represented by the general formula (b) 
     
         NCCH.sub.2 CH.sub.2 --O--X--O--CH.sub.2 CH.sub.2 CN        (b) 
    
     wherein X has the meanings set forth above. 
     Preferred specific examples of the aromatic diols are catechol, resorcinol, hydroquinone, bisphenol A and bisphenol F. 
     The preparation of the aromatic diol-bimolecular alkyl acrylate may be carried out by heating an aromatic diol and an alkyl acrylate in the presence of a basic catalyst such as potassium hydroxide in the absence or presence of solvents such as methanol and ethanol at reflux temperature for several hours, the amount of alkyl acrylate being at least 2 times the amount of the aromatic diol (mole basis). 
     The preparation of the aromatic diol-bimolecular alkyl acrylate adduct starting from an aromatic diol and acrylonitrile may be accomplished by the process wherein 1 mole of aromatic diol is reacted with at least 2 moles of acrylonitrile in the presence of a basic catalyst with or without solvent similarly with the reaction between aromatic diol and alkyl acrylate at reflux temperature for 15-20 hours or at 130°-140° C. for several hours in an autoclave to obtain an aromatic diol-bimolecular acrylonitrile adduct (b), which is then heated in a mixed solution of 5% aqueous alcohol and acid at reflux temperature for several hours, the respective amount of alcohol and acid being at least 2 times the amount of the adduct (mole basis). 
     The alkyl acrylate to be reacted with the aromatic diol is not particularly limited. Usually a lower alkyl ester of 1-4 carbon atoms is employed. Especially a, methyl ester is practical. 
     The alcohol which is employed for preparation of the aromatic diol-bimolecular alkyl acrylate adduct from the aromatic diol-bimolecular acrylonitrile adduct is not particularly limited, but methanol and ethanol are practical. 
     Suitable examples of basic catalysts which can be used in the reaction system are potassium hydroxide, sodium methoxide and benzyltrimethylammonium hydroxide. The amount of basic catalyst may be about 1-2 percent by weight based on the aromatic diol. The addition reaction is carried out in the presence of a polymerization inhibitor such as hydroquinone. After the addition reaction has been completed, excess acrylic ester and solvent if any are removed from the reaction mixture by distillation. 
     The aromatic diol-bimolecular acrylic ester adduct (a) obtained thusly is further reacted with hydrazine hydrate in the presence of a solvent such as methanol or ethanol at room temperature for several hours, the amount employed of hydrazine hydrate being at least 2 times (mole basis) the amount of the adduct (a). The reaction may be carried out at reflux temperature if necessary. 
     After the completion of the reaction, excess hydrated hydrazine and the solvent are removed from the reaction mixture by distillation, and the precipitated hydrazide is separated and recrystallized from a suitable solvent such as methanol, ethanol or water. The hydrazide of the present invention may be pulverized in fine particles. 
     The hitherto known dibasic acid hydrazides, such as adipic acid hydrazide, sebacic acid hydrazide, isophthalic acid hydrazide and the like, are high melting compound above 180° C., and the epoxy resin compositions incorporating such dibasic acid hydrazides is cured when heated to 150° C. or higher temperatures. Contrary thereto, the hydrazides of the present invention are relatively low melting compounds and provide, when incorporated into an epoxy resin, curable composition which are stable for periods of several weeks at 40° C. and which can thereafter be readily cured at temperatures of as low as about 120°-140° C. to give a colorless, transparent and tough cured product having excellent water resistance. 
     The required amount of curing agent is determined by the number of active hydrogen atoms in the curing agent employed and the number of epoxy groups in the epoxy resins. In general, 0.5-1.5, preferably 0.7-1.2, active hydrogen equivalent weight per epoxy equivalent weight is employed. 
     As epoxy resins which may be applied to the hydrazide curing agents of the present invention, various well-known ones having an average of more than 1 epoxy groups in the molecule may be employed. Representative epoxy resins are those based on glycidyl ethers of polyhydric phenols such as 2,2-bis(4-hydroxyphenyl)-propane (Bisphenol A), resorcinol, hydroquinone, pyrocatechol, saligenin, glycidyl ether of Bisphenol F and glycidyl ether of phenolformaldehyde resin. 
     If necessary, other curing agents, cure accelerators and fillers may be employed in combination with the curing agent of the present invention. 
    
    
     The following examples illustrate the preparation of the hydrazides of the present invention. 
     EXAMPLE 1 ##STR6## 
     25 g (0.227 mole) of catechol, 75 g (1.42 mole) of acrylonitrile, and 0.5 gof sodium methylate were mixed in a 300 ml three-necked flask equipped witha reflux condensor and a stirrer. The mixture was heated under reflux for 20 hours and the reaction mixture was dissolved in benzene. After washing three times with 100 ml of water, benzene and excess acrylonitrile were removed under reduced pressure to obtain the viscous liquid. To this compound, 50 ml of methanol was added, and the mixture was stirred to precipitate the crystals. After filtration, the crystals were washed with methanol and dried in vacuo to obtain 11.2 g of the bimolecular acrylonitrile adduct of catechol (I)-a&#34;. mp 120°˜122° C. ##STR7## 
     A mixture of 1% methanol solution and sulfuric acid (each 30 g) was added to 8 g (0.037 mole) of the adduct thus obtained and was heated under reflux for 7 hours with stirring. To this reaction mixture, 100 ml of water was added to dissolve the produced ammonium sulfate crystals. Then 300 ml of ethyl ether was added to extract the reactor. After washing the extract with 100 ml of 5% sodium hydroxide solution and three times with 100 ml of water, ethyl ether was removed under reduced pressure to obtain 4.6 g of the adduct of catechol and bimolecular methyl acrylate (I-a&#39;). ##STR8## 
     4.5 g (0.028 mole) of the adduct thus obtained and 10 g (0.16 mole) of 80% hydrazine hydrate solution were mixed in a 100 ml three-necked flask equipped with a stirrer. To this mixture, 50 ml of methanol was added and then was allowed to react at 50° C. for 2 hours with stirring. After cooling, the precipitated crystals were filtered, washed with methanol, and dried in vacuo to obtain the target product as white needles. 
     The analytical values are shown below. 
     
         ______________________________________Melting point        145˜146° C.Elemental analysis   C      H      N (%)Found                51.27  6.42   19.71Calculated for C.sub.12 H.sub.18 O.sub.4 N.sub.4                51.06  6.38   19.86Field desorption mass spectrum                [M + H].sup.+  at m/e 283______________________________________ 
    
     EXAMPLE 2 ##STR9## 
     35 g (0.318 mole) of resorcinol, 350 ml (3.89 mole) of methyl acrylate, and0.7 g of potassium hydroxide were mixed in the same flask described in Example 1, and the mixture was heated under reflux for 7 hours with stirring. To the reaction mixture, 4.6 ml of 10% hydrochloric acid solution was added, and excess methyl acrylate was removed under reduced pressure. Then, 1000 ml of ethyl ether was added, and insoluble material (potassium chloride) was filtered out. The residue was washed with 100 ml of 10% sodium hydroxide solution and three times with 100 ml of water, andethyl ether was removed in vacuo to obtain 33.4 g of the adduct of resorcinol and bimolecular methyl acrylate (I-b&#39;, mp 74°˜76° C., white needles). ##STR10## 
     32.3 g (0.115 mole) of the adduct of resorcinol and bimolecular methyl acrylate thus obtained was dissolved in 600 ml of methanol. To this solution, 115 ml (1.84 mole) of 80% hydrazine hydrate solution was added and was allowed to react at 50° C. for 2 hours with stirring. From the reaction mixture, excess hydrazine hydrate and methanol was removed under reduced pressure. The residue was washed with methanol and dried in vacuo to obtain 26.1 g of the target product as white powder. 
     The analytical values are shown below. 
     
         ______________________________________Melting point     143˜144° C.Elemental analysis             C        H      N (%)Found             50.91    6.40   19.82Calculated for C.sub.12 H.sub.18 O.sub.4 N.sub.4             51.06    6.38   19.86Nuclear magnetic resonance spectrumδ(DMSOd.sub.6 /TMS) ##STR11##3.1˜3.6(4H, br, NH.sub.2, (X2))4.08(4H, t, J = 6Hz, OCH.sub.2 CH.sub.2, (X2))6.3˜6.5(3H, m, arom)8.9˜9.1(2H, br, NHNH.sub.2, (X2))Field desorption mass spectrum [M + H].sup.+  at m/e 283______________________________________ 
    
     EXAMPLE 3 ##STR12## 
     According to the procedure described in Example 1, 25 g (0.227 mole) of hydroquinone, 75 g (1.42 mole) of acrylonitrile and 0.6 g of sodium methoxide were mixed and were allowed to react to obtain 35.5 g of the bimolecular acrylonitrile adduct of hydroquinone (I-c&#34;). ##STR13## 
     To 25 g (0.153 mole) of the adduct thus obtained, a mixture of 5% methanol solution and sulfuric acid (each 70 g) was added. Thereafter, the procedure of Example 1 was repeated to obtain 28.0 g of the adduct of hydroquinone and bimolecular methyl acrylate (I-c&#39;). ##STR14## 
     18.0 g (0.063 mole) of the adduct of hydroquinone and methyl acrylate thus obtained were dissolved in 180 ml of methanol, and then 32 g (0.512 mole) of 80% hydrazine hydrate solution were added. The mixture was allowed to react according to the procedure described in Example 1. 16.5 g of the target product were obtained. 
     The analytical values are shown below. 
     
         ______________________________________Melting point        173˜175° C.Elemental analysis   C      H      N (%)Found                51.33  6.48   19.63Calculated for C.sub.12 H.sub.18 N.sub.4 O.sub.4                51.06  6.38   19.86Field desorption mass spectrum                [M + H].sup.+  at m/e 283______________________________________ 
    
     EXAMPLE 4 ##STR15## 
     40 g (0.175 mole) of bisphenol A, 315 ml (3.5 mole) of methyl acrylate, and6.5 ml of 10% benzyltrimethylammonium hydroxide solution were mixed in the same flask described in Example 1, and the mixture was heated under refluxfor 48 hours with stirring. After cooling to room temperature, 7.3 ml of 10% hydrochloric acid solution was added, and then excess methyl acrylate was removed in vacuo. The residue was dissolved in 1000 ml of ethyl acetate and washed successively with 200 ml of 10% hydrochloric acid solution, pure water, 10% sodium hydroxide solution, and twice with saturated sodium chloride solution. Then ethyl acetate was removed to obtain 27.7 g of the colorless oily substance. The oily substance thus obtained was purified by silica gel column chromatography using a mixture of toluene-acetic acid as an eluent to obtain 10.6 g of the bimolecular methyl acrylate adduct of bisphenol A (I-d&#39;). ##STR16## 
     10.0 g (0.025 mole) of the adduct thus obtained, 100 ml of methanol, and 16ml (0.25 mole) of 80% hydrazine hydrate solution were mixed and allowed to react at room temperature for 5 hours with stirring. From the reaction mixture, excess hydrazine hydrate and methanol were removed under the reduced pressure, and then 50 ml of ethanol was added to the residue to precipitate the crystals. After filtration, the crystals were recrystallized from ethanol and dried in vacuo to obtain 8.26 g of the target product as a white powder. 
     The analytical values are shown below. 
     
         ______________________________________Melting point        136˜140° C.Elemental analysis   C      H      N (%)Found                62.75  6.91   14.11Calculated for C.sub.21 H.sub.28 N.sub.4 O.sub.4                62.98  7.05   13.99Nuclear magnetic resonance spectrumδ(DMSO-d.sub.6 /TMS)1.58(6H, s, CH.sub.3 --C--CH.sub.3)2.52(4H, t, J = 6Hz, --CH.sub.2 C--, (X2))4.17(4H, t, J = 6Hz, --OCH.sub.2 CH.sub.2 --, (X2))3.0 4.5(4H, br, --NHNH.sub.2, (X2))6.82(4H, d, J = 9Hz, arom)7.13(4H, d, J = 9Hz, arom)8.9 9.2(2H, br, --NHNH.sub.2, (X2))Field desorption mass spectrum                [M + H].sup.+  at m/e 401______________________________________ 
    
     EXAMPLE 5 ##STR17## 
     In an autoclave equipped with an electromagnetic stirrer, 40 g (0.2 mole) of bisphenol F, 27.6 g (0.52 mole) of acrylonitrile, and 0.5 g of sodium methylate were mixed. After nitrogen was substituted for air, the mixture was heated at 130°˜140° C. for 5 hours with stirring. After cooling, the reaction mixture was dissolved in 300 ml of benzene andwashed successively with 200 ml of 5% sodium hydroxide solution and 300 ml of water. Then the benzene layer was concentrated, and 100 ml of methanol was added to precipitate the crystals. After filtration, the crystals weredried in vacuo to obtain 6.04 g of the adduct of bisphenol F and bimolecular acrylonitrile (I-e&#34;). mp 100°˜102° C. ##STR18## 
     The mixture of 5% methanol solution (30 g) and sulfuric acid (30 g) was added to 6.0 g (0.0237 mole) of the adduct thus obtained and heated under reflux for 5 hours with stirring, and then 300 ml of toluene was added. After being washed successively with 200 ml of water, 100 ml of 5% sodium hydroxide solution and 300 ml of water, the solution was concentrated and dried to obtain 5.65 g of white solid substance (I-e&#39;). ##STR19## 
     5.65 g (0.015 mole) of the compound thus obtained was dissolved in 56 ml ofmethanol, and then 8.8 g (0.141 mole) of 80% hydrazine hydrate solution wasadded. The mixture was allowed to react at 50° C. for 2 hours with stirring. After filtration, the crystals were washed with methanol and dried in vacuo to obtain 4.16 g of the target product as white powder. 
     The analytical values are shown below. 
     
         ______________________________________Melting point        182˜183° C.Elemental analysis   C      H      N (%)Found                61.48  6.53   14.87Calculated for C.sub.19 H.sub.24 N.sub.4 O.sub.4                61.29  6.45   15.05Field desorption mass spectrum                [M + H].sup.+  at m/e 373______________________________________ 
    
     EXAMPLE 6 
     Reactivity, water resistance, and storage stability of the formulated epoxyresin were evaluated. 
     1. Preparation of the sample 
     The formulation of each sample is shown in Table 1. Each sample was stirredfor 1 hour with defoaming under reduced pressure by using a mixing and grinding machine. 
     2. Evaluation of the reactivity 
     (1) The sample was put into a gear oven for 60 minutes and cured temperature was measured. 
     (2) The sample was heated at 150° C. for 60 minutes and then at 60° C. for 180 minutes. The resulting cured resin was observed withthe naked eye. 
     3. Water resistance 
     1 g of the sample was put into a frame of 25 mm diameter and heated at 150° C. for 60 minutes and then at 160° C. for 180 minutes. The cured resin thus obtained was soaked in 50 cc of 40° C. hot water, and the weight change was measured. 
     4. Storage stability 
     The sample was put into a gear oven set to 40° C., and the day required for the sample becoming non-fluidity was measured. 
     
                       TABLE 1______________________________________  Formulation No.  1    2      3      4    5    6    7    8______________________________________Epon 828*.sup.1    100    100    100  100  100  100  100  100Sample (I)-a     37Sample (I)-b     37Sample (I)-c            37Sample (I)-d                 52Sample (I)-e                      49Adipic                                 23dihydrideIsophtalic                                  26dihydrideDicyan-                                          28diamide______________________________________*.sup.1 A product of Shell Chemical Co. bisphenol A type epoxy resin havinepoxy equivalent of 175˜210. 
    
     
                       TABLE 2______________________________________Cured temperatureFormulation No.          Cured Temperature______________________________________No. 1          120° C.No. 2          120No. 3          140No. 4          120No. 5          140No. 6          160No. 7          160No. 8          180______________________________________ 
    
     
                       TABLE 3______________________________________Appearance of the cured resinFormulation No.         Appearance______________________________________No. 1         Stiff and transparent materialNo. 2         Stiff and transparent materialNo. 3         Stiff and transparent materialNo. 4         Stiff and transparent materialNo. 5         Stiff and transparent materialNo. 6         Opaque white colored materialNo. 7         Opaque white colored gelNo. 8         Less transparent material______________________________________ 
    
     
                       TABLE 4______________________________________Water resistanceFormulation No.          Water absorption______________________________________No. 1          + 1.8 wt %No. 2          1.7No. 3          1.5No. 4          1.6No. 5          1.8No. 6          2.9No. 7          1.8No. 8          --*.sup.1______________________________________*.sup.1 cannot be measured because the sample was not fullcured 
    
     
                       TABLE 5______________________________________Storage stabilityFormulation No. Storage stability______________________________________No. 1           &gt;4 weeksNo. 2           &#34;No. 3           &#34;No. 4           &#34;No. 5           &#34;No. 6           &#34;No. 7           &#34;No. 8           &#34;______________________________________ 
    
     The results of Table 2˜5 shows that the curing agent for epoxy resin in this invention has excellent storage stability, reactivity, and water resistance. 
     Especially, the reactivity of this agent is superior and the resulting cured resin is stiff and transparent compared with that of the control agent.