A PROCESS FOR THE PREPARATION OF HEAT RESISTANT AND TRANSPARENT ACRYLIC RESIN

Abstract: The present invention relates to a process for the preparation of heat resistant and transparent acrylic resin which is characterized by imidizing methacrylic resin in a solution with primary amine or the ammonia compounds generating primary amine in the presence or absence of catalyst and under a suitable temperature condition. The reaction product is the compound of formula (I) comprising more than 10 % by weight of imidized structure unit. Formula (I) wherein R1, R2 and R3 independently represent a hydrogen atom, or unsubstituted and substituted C1 to C20 alkyl, cycloalkyl, aryl, aralkyl, alkaryl, or mixtures thereof.

Description: Title of the invention A process for the preparation of heat resistant and transparent acrylic resin Detailed description of the invention The present invention relates to a process for the preparation of heat resistant and transparent acrylic resin. More particularly, it relates to a process for the preparation of transparent acrylic resin which is improved in heat resistance by introducing imide structure into acrylic polymers in the presence or absence of a catalyst. Up to date, since methylmethacrylate resin has had good transparency, weatherability and mechanical properties, it has been used in highly e- fficient optical materials, decorative materials, automobiles and ele¬ ctric products. However, having low heat deflection temperature of less than 100°C, methylmethacrylate resin has not been used in the field of requiring heat resistance. Therefore, we have required its heat r- esistance improved. As a general the method to improve the heat resistance of acrylic resin is as follows; 1) the method of heating react acrylic acid, methacrylic acid or their ester polymer with a primary amine in the solvent having high boiling point (USP No. 2,146,209), 2) the method of reacting methylmethacrylate polymer with primary amine in the presence of water (USP No. 3,284,425), 3) the method of reacting " acrylic polymer with anhydrous ammonia or an¬ hydrous primary amine in a extruder (USP No. 4,246,374), and 4) the method of reacting methacrylate resin with anhydrous ammonia or anhydrous priiary amine in the presence of a solvent (JP 63-36696). According to the above-mentioned method (1), it is difficult to se¬ parate solvents completely from the imidized polymer product on a com¬ mercial scale, because the boiling point of the solvent is high. Therefore, since the obtained imidized polymer is colored, the transpa¬ rency of final product is deteriorated. Also, as the i idization reaction according to the above-mentioned method (2) is carried out by using a great quantity of water as a di¬ spersion medium, water phase and polymer phase are separated. Accor- dingly, it is difficult to obtain uniform imidized polymer. As the reaction is carried out at higher than the softening temperature of ac¬ rylic polymer, reaction product coagulates around agitator and handling of the reaction product is difficult. Also, according to the above-mentioned method (3) it is difficult to obtain uniform imidized polymers, because polymers having high viscosity a- re reacted with gaseous primary amines. Also, according to the above-mentioned method (4), it is required to remove moisture from acrylic polymers, solvents and amines in order to prevent hydrolysis. Therefore, the present inventors investigated a process assiduously to improve the above-mentioned problems. ¥e could produce acrylic resin having heat resistance and transparency through the following methods. The object of the present invention is to provide a process for the preparation of acrylic resin which has excellent heat resistance and tr- ansparency and maintains all of the good original characteristics of acrylic resin by selecting the suitable solvent dissolving both reactants and products. The other object of the present invention is to provide a process for the preparation of acrylic resin which has excellent heat resistance and transparency by adding some water together with a suitable solvent into a reaction system. The another object of the present invention is to provide a process for the preparation of acrylic resin which has excellent heat resistance and transparency by adding a catalyst and a suitable solvent to reaction system, and using ammonium bicarbonate or their derivatives as a imidzing agent. The another object of the present invention is to provide a process for the preparation of-acrylic resin which has excellent heat resistance and transparency by adding catalyst in the presence of a suitable solvent and pouring some water into the reaction system. The another object of the present invention is to provide a process for the preparation of acrylic resin which has excellent heat resistance and transparency by adding catalyst to the reaction system in the presence of a suitable solvent and under anhydrous condition when methacrylate polymer and ammonia compound are reacted. The detailed description of the present invention is as follows. The present invention is a process for the preparation of a heat resistant and transparent acrylic polymers which is characterized by heating acrylic resin in a suitable solvent with ammonia, primary amine or the ammonia compounds generating ammonia or primary amine under a suitable temperature condition and in the presence or absence of catalyst. Namely, poly(methyl methacrylate) (PMMA) reacts with ammonia compounds generating primary amine such as ammonium bicarbonate or their derivates of the formula (II) in the presence of solvent at 180~350°C in order to int- roduce imide structure into PMMA. Consequently, the obtained methacrylimide group containing polymer of the formula (I ) comprises more than 10% by weight of imideized structure unit, preferably, more than 20% by weight. I R 3 RNH»HC0 8 (D) wherein Ri, R 2 and R β independently represent a hydrogen atom, or unsubstituted and substituted Ci to C 2 o alkyl, cycloalkyl, aryl, aralkyl, alkaryl, or mixtures theirof. Methacrylimide group containing polymer of the present invention is what introduces methacrylimide (dimethylglutarimide) structure into the side chain of acrylic resin. Wherein acrylic polymers introducing imide structre are methylmethacrylate polymer and methylmethacrylate-ethylenic unsaturated monomer copolymer, in which methacrylic acid ester, acylic acid ester, styrene or -methylstyrene or maleic anhydride is used as a ethylenic unsaturated monomer. Methacrylic resin used in produc- ing methacylic copolymer is preferably methylmethacrylate homopolymer, methylmethacylate-methylacylate copolymer, methylmethacylate-styrene copol¬ ymer, and methylmethacyhate-styrene-maleic anhydride copolymer. Though the amount of methylmethacylate structure unit comprised in the above-mentioned copolymer is not fixed, it is preferably at least 50% by weight. Methacrylic acid ester is methylmethacrylate, ethylmethacrylate, pro- pyl ethacrylate, n-butylmethacrylate, isobutylmethacrylate, t-butylmetha- crylate, cyclohexyl methacrylate, benzyl methacrylate, arylmethacrylate and the likes. Acrylic acid ester is ethylacrylate, ethylacrylate, p- ropylacrylate, n-butylacrylate, isobutyl acrylate, t-butylacrylate, cycl- ohexylacrylate, benzylacrylate, arylacrylate and the likes. PMMA among the esters is preferable from a transparent and imidization reactionary p- oint of view. The solvent used in the present invention should not obstruct the imi¬ dization reaction. Moreover, the solvent which can dissolve both acrylic polymers and imidized products is essentially required. Also, if the boiling point of a solvent were pretty high, it would be to difficult removed a solvent after reaction. Oppositely, if the boiling point of a solvent were pretty low, the pressure would rise, therefore, the boiling point of the solvent is preferably 50~160 * O. The solvent dissolving methylmethacrylate polymer is preferably a- romatic hydrocabon compounds such as benzene, toluene and xylene etc., ketones such as methylethyl ketone, ethers such as ethyleneglycol dime- thylether, diglyme, dioxane and tetrahydrofuran, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and butyl alcohol, dim¬ ethylformamide, dimethylsulfoxide and dimethylacetamide etc.. The solvent may be used in single or mixed type. On the one hand the primay amine of the following formula (HI) of imidizing agent to imidize methylmethacrylate polymer is ammonia, met- tyl amine, ethyl amine, n-propyl amine, n-butyl amine, heptyl amine, he- xyl amine, cyclohexyl amine, octyl amine, nonyl amine, decyl amine, dodec- yl amine, hexadecyl amine, octadecyl amine, isobutyl amine, sec-butyl a- mine, t-butyl amine, isopropyl amine, 2-ethylhexyl amine, 2-phenylethyl ami- ine, aryl amine, alanine, benzyla ine, parachlorobenzyla ine, dimetho- xyphenylethyl amine, aniline, bromoaniline, dibromoanilin, tribromoaniline, chloroaniline, dichloroaniline and trichloroaniline, the compound are gaseous or liguid state when the above reaction is carried out. The solid ammonium bicarbonate or their derivatives of the formula (DI) may be used simply and the handling of the compound is easy industrially. RNH 2 ( ) wherein B represents a hydrogen atom, or unsubstituted and substituted Ci to Czo alkyl, cycloalkyl, aryl, aralkyl, alkaryl, or mixtures theirof. The temperature to react methylmethacrylate resin with imidizing agent is preferably 180 ~ 350 β C, more preferably, 200 ~ 300°C. If, the reaction temperature exceeded 350X1, methylmethacrylate polymer decom¬ posed. Oppositely, if the reaction temperature were less than 180 β C, the reaction rate remarkablely decreases so that the imidization process takes a long time. Also, the present invention is a process for the preparation of the methacrylimide group containing polymer that methacrylic resin is reacted with primary amine or the compounds generating primary amine of the f- ormula (HI) in the presence of a suitable solvent at 180 ~ 350"C by adding 5 to 20% by weight of water as an imidization reaction promoter. The amount the imide structure unit among the above polymer is more than 10%, preferably more than 20%. We found that one of the reaction promoter used in the present i- nvention is water. If the suitable amount of water was added to the reaction system, it operated as a catalyst and the reation is well carried out. The present invention has advantages that improved heat resistance is obtained by increasing the degree of the imidization in the presence of a suitable amount of water. Moreover, since water increases the so¬ lubility in reaction system, reactivity of imidization reaction is incr¬ eased in the case that ammonia compounds generating primary amine is used. Accordingly, when methylmethacrylimide polymer is procduced, 5 to 20% by weight of water, desirably, 7 to 15% by weight is added to r- eaction system. In the case that the amount of water is less than 5% by weight, heat resistance is decreased by decreasing reactivity. Oppositely, in the case that the amount of water is more than 20% by weight, heterogeneous imi- dized polymer is obtained by separating water phase and polymer phase, and the products are coagulated around reactor axis. Also, the present invention is a process for the preparation of me¬ thacrylimide group containing polymer that acylic resin is reacted in the presence of suitable solvent with aoonium bicarbonate or their derivatives at 100 ~ 350 β C by adding 0.01 to 15% by weight of tetraalkylammonium hydroxide of the formula (IV). The polymer comprise more than 5% by weight of methacylimide group. R^NOH (IV) wherein R represents a hydrogen atom, or unsubstituted and substituted Ci to Czo alkyl, cycloalkyl, aryl, aralkyl, alkaryl, or mixtures theirof. Reactants and reaction temperature are the same as the above-mentioned. The catalyst used in the reaction is desirably tetraalkylammonium hydroxide, such as tetramethylammonium hydroxide pentahydrate, tetraeth- ylammonium hydroxide. Since tetraalkylammonium hydroxide is operated as a basic catalyst in reaction system, the degree of imidization is incre¬ ased. Improved transparent and heat rsistant acrylic resins may be produced because reaction condition (e.g. reaction temperature and pressuare) is miled. Besides, tetraalkylammonium hydroxide is decomposed into trialkyl amine and alcohol by heating, it is easily separated from polymer products. When methylmethacrylimide polymer is produced, the amount of tetraa- lkylammonium hydroxide is preferably 0.01 to 15% by weight, more d- esirably, 0.1 to 7% by weight. If the amount of tetraalkylammonium hydroxide is less than 0.01% by weight, catalytic effect is not signifi¬ cant. Oppositely, if the above-mentioned amount is more than 15% by weight, the material properties of products are deteriorated. Also, the present invention is a process for the preparation of me- thacylimide group containing polymer that acrylic resen is reacted in the presence of a suitable solvent with primary amime or the compounds generating primary amine at 100 ~ 350 β C by adding 0.01 to 15% by weight of tetraalkylammonium hydroxide of the above-mentioned formula (IV) and 5 to 20% by weight of water. The polymer comprises more than 5% by weight of methacrylimide. The present invention is a process for the preparation of methacrylimi¬ de group containing polymer, namely, acrylic resin is reacted in the presence of a suitable solvent with ammonia or primary amine or the ammo- nia compounds generating ammonia or primary amine at 100 ~ 350 * C and under the anhydrous condition by adding tetraalkylammoniunm hydroxide of the above-mentioned formula (IV) as a catalyst. Wherein the amount of methacrylimide group comprised in the polymer is more than 5% by weight. This reaction condition is the same as the above-mentioned except using catalyst under the anhydrous condition. The acrylic resin obtained in the present invention has charateris- tics that heat resistance and transparency are excellently improved and maintains original good optical and mechanical properties, weatherability, molding processibility and productivity. The material properties of the polymer according to the present inv¬ ention were measured in compliance with followings. 1) the confirmation of imidization of the polymer It is measured with potassium bromide (KBr) pellet by using infrared spectrometer (BIORAD, FTIR). 2) the degree of imidization of polymer(%) It is measured by the amount of nitrogen measured by elementary analyis (PERKIN ELMER MODEL: 240B). 3) heat resistance It is measured by glass transition temperature (Dupont Model: 1090). The more detailed description of the present invention in compliance with examples is as follows. Example 1 To 300cc - autoclave 100 parts by weight of PMMA [Lucky Ltd., IH - 830], 79 parts by weight of ammonium bicarbonate, 268 parts by weight of tetrahyd- rofuran (THF) and 268 parts by weight of methyl alcohol as a mixed solvent were added, and then the reaction mixture was agitated, with refluxing nitrogen for preventing oxidation. Next, the reaction mixture was dissolved by agitating (250 rpm), rea¬ cted at 230°C (inner pressure ; 1470 psi) for 3 hours. After the reation was completed, the solution of methacrylimide group containing polymer was precipitated in n-hexane, filtrated and dried suffic- iently in vacuume oven at 100 β C for 3 hours, to obtain the polymer as a white powder. The obtained polymer was measured with infrared spectrometer, to obtain the data of 1680m" 1 , 1700m ** " 1 and 1720m" 1 which were characteristic band of methacrylimide stucture. The material properties of the above mentioned polymer were repres¬ ented in table 1. Example 2 Following the procedure of Example 1, except using 63 parts by weight of ammonium bicarbonate (NH 4 HC0 s ) as an imidizing agent, 340 parts by weight of tetrahydrofuran and 144 parts by weight of methyl alcohol as a mixed solvent and 810 psi of inner pressure, the polymer was obtained. The material properties were represented in table 1. Example 3 Following the procedure of Example 1, except using 47 parts by weight of ammonium bicarbonate as an imidizing agent, 340 parts by weight of te¬ trahydrofuran and 144 parts by weight of methyl alcohol as a mixed solvent and 780 psi of inner pressure, the polymer was obtained. The material properties ware represented in table 1. Example 4 To 57% by weight of methylmethacrylate (MMA) was added 27% by weight of maleic anhydride (MAH), 16% by weight of styrene(ST), 0.2% by weight of t-dodecylmercaptan as a chain transfer agent, and then the mixture was polymerized in solution (ethylbenzene as a solvent) at 145"C for 2 hours, to obtain the polymer. Following the procedure of the Example 1, 100 parts by weight of MMA-MAH-ST copolymer, 31 parts by weight of ammonium bicarbonate as an imidizing agent, 372 parts by weight of tetrahydrofuran 36 parts by weight of methyl alcohol as a mixed solvent, and 700 psi of inner pressure, to obtain the polymer. The marterial properties of the polymer were represented in table 1. Example 5 Following the procedure of the Example 1, except using 100 parts by weight of ammonium bicarbonate as an imidizing agent, 536 parts by wei- ght of tetrahydrofuran, to obtain the polymer. The meterial properties of the polymer were represented in table 1. Comparative Example 1 To autoclave 100 parts by weight of PMMA and 340 parts by weight of tetrahydrofuran were added, and then gaseous ammonia was added to the reaction mixture in order to make inner pressure 700 psi, to obtain the polymer. The material properties of the polymer were represented in table 1. Tetbl.- * - Examples comparative examples MMA polym 100 100 100 100 100 MMA-MAH-ST copolymer 100 ammonium bicarbonate 79 63 47 31 79 injection of ammonia ammonia (gas) to 700 psi of inner pressure tetrahydrofuran 268 340 340 372 536 340 methyl alcohol 268 144 144 36 the degree of imidi- 76 59 32 30 67 17 zation(%) glass transition 211 187 161 156 197 137 temperature(*C) MMA: methylmethacrylate monomer MAH: maleic anhydride monomer ST: styrene monomer Example 6 To autoclave 100 parts by weight of PMMA [Lucky Ltd., IH - 830], 58 parts by weight of cyclohexyl amine as an imidizing agent, 100 parts by weight of distilled water as a reaction promoter, 456 parts by weight of tetrahydrofuran (THF) and 58 parts by weight of methyl alcohol as a mixed solvent were add, and then the reaction mixture was agitated, with sufficiently refluxing nitrogen for preventing oxidation. Next, the reaction mixture was dissolved by agitating (250rpm), reacted at 200"C for 3 hours. After the reaction was completed, the solution of metha- crylimide group containing polymer was reprecipitated in n-hexane, filtrated and dried sufficiently in vacuume oven at 100'C, to obtain the polymer as a white powder. The obtained polymer was measured with infrared spec¬ trometer, to obtain the data of 1680m" 1 , 1700m" 1 and 1720m" 1 which were characteristic bands of methacrylimide stucture. The material properties of the above polymer were represented in table 2. Example 7 Following the procedure of the Example 6, except using 63 parts by weight of ammonium bicarbonate as an imidizing agent, 60 parts by weight of distilled water as a reaction promoter, 340 parts by weight of tetra- hydrofuran and 146 parts by weight of methyl alcohol as a mixed solvent and 230°C of a reaction temperature, to obtain the polymer. The material properties of the polymer were represented in table 2. Example 8 Following the procedure of the Example 6, except using 47 parts by weight of ammonium bicarbonate as an imidizing agent, 60 parts by weight of distilled water as a reaction promoter, 340 parts by weight of tetra¬ hydrofuran and 146 parts by weight of methyl alcohol as a mixed solvent and 230 β C of a reaction temperature, to obtain the polymer. The material properties of the polymer were represented in table 2. Example 9 Following the procedure of the Example 6, except using 31 parts by weight of ammonium bicarbonate as an imidizing agent, 60 parts by weight of distilled water as a reaction promoter, 340 parts by weight of tetra¬ hydrofuran and 146 parts by weight of methyl alcohol as a mixed solvent, 230 * "C of a reaction temperature, to obtain the polymer. The material properties of the polymer were represented in table 2. Example 10 Following the procedure of the Example 6, except using 15 parts by weight of ammonium bicarbonate as an imidizing agent, 60 parts by weight of distilled water as a reaction promoter, 340 parts by weight of tetra¬ hydrofuran and 146 parts by weight of methyl alcohol as a mixed solvent and 230 β C of a reaction temperature, to obtain the polymer. The material properties of the polymer were represented in table 2. Comparative Example 2 Following the procedure of the Example 6, except using 100 parts by weight of PMMA, 58 parts by weight of cyclohexyl amine as an imidizing agent, 456 parts by weight of tetrahydrofuran and 58 parts by weight of methyl alcohol, to obtain the polymer. The material properties of the polymer were represented in table 2. Comparative Example 3 Following the procedure of the Example 7, except using 100 parts by weight of PMMA, 63 parts y weight of ammonium bicarbonate as an imidizing agent, 340 parts by weight of tetrahydrofuran and 146 parts by weight of methyl alcohol, to obtain the polymer. The material properties of the polyme were represented in table 2. Comparative Example 4 Following the procedure of the Example 8, except using 100 parts by weight of PMMA, 47 parts by weight of ammonium bicarbonate as an imidizing agent, 340 parts by weight of tetrahydrofuran and 146 parts by weight of methyl alcohol, to obtain the polymer. The material properties of the polymer were represented in table 2. Comparative xam le 5 Following the procedure of the Example 9, except using 100 parts by weight of PMMA, 31 parts by weight of ammonium bicarbonate as an imidizing agent, 340 parts by weight of tetrahydrofuran and 146 parts by weight of methyl alcohol, to obtain the polymer. The material properties of the polymer were represented in table 2. Comparative Example 6 Following the procedure of the Example 10, except using 100 parts by weight of PMMA, 15 parts by weight of ammonium hicarbonate as an imi¬ dizing agent, 340 parts by weight of tetrahydrofuran and 146 parts by weight of methyl alcohol, to obtain the polymer. The material properties of the polymer were represented in table 2. Comparative Example 7 Following the procedure of the Example 7, except using 100 parts by weight of PMMA, 63 parts by weight of ammonium bicarbonate as an imi¬ dizing agent, 25 parts by weight of distlled water 340 parts by weight of tetrahydrofuran and 146 parts by weight of methyl alcohol, to obtain the polymer. The material properties of the polymer were represented in table 2. Comparative Example 8 Following the procedure of the Example 7, except using 100 parts by weigh of PMMA, 63 parts by weight of ammonium bicarbonate as an imid- ing agent, 250 parts by weight of distlled water 340 parts by weight of tetrahydrofuran and 146 parts by weight of methyl alcohol, to obtain the polymer. The material properties of the polymer were represented in table 2. Comparative Example 9 Following the procedure of the Example 7, except using 100 parts by weight of PMMA, 63 parts by weight of ammonium bicarbonate as an imidiz- ing agent and 380 parts by weight of water, to obtain the polymer. The material properties of the polymer were represented in table 2. Tab l e *** : The polymer coagulated around agitated axis, glass transition te¬ mperature of the polymer could not be measured. Example 11 To 1.8/-autoclave methylmethacrylate polymer [Lucky Ltd., IH-830], 39 parts by weight of ammonium bicarbonate as an imidizing agent, 9 parts by weight of tetramethyl aoonium hydroxide pentahydrate, 455 parts by weight of tetrahydrofuran and 55 parts by weight of methyl alcohol as a mixed solvent were added, and then the reaction mixture was dissolved by agitating (250rpm), reacted at 210°C of reaction temperature for 3 hours (inner pressure; 550 psi). After the reaction was completed, the solution of methyl ethacrylimide group containing polymer was reprecipi- tated in n-hexane, filtrated and dried sufficiently in vacuume oven at 100°C, to obtain the polymer as a white powder. The obtained polymer was measured with infrared spectrometer, to obtain the data of 1680cm" 1 , 1700cm" 1 and 1720cm" 1 which were character¬ istic bands of methacrylimide stucture. The material properties of the polymer were represented in table 3. Example 12 Following the procedure of the Example 11, except using 39 parts by weight of aoonium bicarbonate as an imidizing agent, 18.3 parts by weight of tetraethylaoonium hydroxide (40% solution) as an imidization reaction catalyst, 455 parts by weight of tetrahydrofuran and 55 parts by weight of methyl alcohol as a mixed solvent and 210 * C of reaction tempera¬ ture, to obtain the polymer. The material properties of the polymer were represented in table 3. Example 13 27% by weight of maleic anhydride (MAH), 16% by weighyt of styrene (ST), 0.2% by weight of t-docecylmercaptan as a chain transfer agent were added to 57% by weight of methylmetlacrylate (MMA), and then the reaction mixture was polymerized in solution (ethylbenzene as a solvent) at 145°C for 2 hours, to obtain the polymer. Following the procedure of the Example 11, except using 100 parts by weight of the obtained MMA-MAH-ST copoalymer, 44 parts by weight of amm- onium bicarbonate as an imidizing agent, 10 parts by weight of tetrame- thylammonium hydroxide pentahydrate as an imidization reaction catalyst, 388 parts by weight of tetrahydrofuran and 46 parts by weight of methyl alc¬ ohol as a mixed solvent and 540 psi of inner pressure, to obtain the poly¬ mer. The material properties of the polymer were represented in table 3. Example 14 Following the procedure of the Example 11, except using 100 parts by weight of MMA-MAH-ST obtained in Example 13, 44 parts by weight of aoo¬ nium bicarbonate as an imidizing agent, 19 parts by weight of tetraeth- ylammonium hydroxide (40% solution) as an imidization reaction catalyst, 388 parts by weight of tetrahydrofuran and 46 parts by weight of methyl alc¬ ohol as a mixed solvent and 560 psi of inner pressure, to obtain the po¬ lymer. The material properties of the polymer were represented in table 3. Comparative Example 10 Following the procedure of the Example 11, except using 100 parts by weight of methylmethacrylate, 39 parts by weight of aoonium bicarbonate as an imidizing agent, 455 parts by weight of tetrahydrofuran and 55 parts by weight of methyl alcohol as a mixed solvent, 210°C of reaction temper- ature and 500 psi of inner pressure, to obtain the polymer. The material properties of the polymer were represented in table 3. Comparative Example 11 Following the procedure of the Example 11, 100 parts by weight of MMA-MAH-ST copolymer obtained in Example 13, 44 parts by weight of aoo¬ nium bicarbonate as an imidizing agent, 382 parts by weight of tetrahydrof¬ uran and 46 parts by weight of methyl alcohol as a mixed solvent, 500 psi of inner pressure, to obtain the poeymer. The material properties of the polymer were represented in table 3. Table Example 15 To 1.81-autoclave 100 parts by weight of methylmethacrylate polymer [Lucky Ltd., IH-830], 14 parts by weight of methyla ine as an imidizing agent, 7 parts by weight of tetramethylaoonium hydroxide pentahydrate as a catalyst, 19 parts by weight of distilled water, 455 parts by weight of tetrahydrofuran and 55 parts by weight of methyl alcohol as a mixed solvent were added, and then the reaction mixture was dissolved by agita¬ ting (250 rpm), reacted at 170 β C for 3 hours (inner pressure; 550 pis). After the reaction was completed, the solution of methylmethacrylimide group containing polymer was reprecipitated in n-hexane, filtrated and dried sufficiently in vacuume oven at 100'C, to obtain the polymer as a white powder. The obtained polymer was measured with infrared spectrometer, to obtain the data of 1680cm -1 1700cm" 1 and 1720cm" 1 which were characteristic bands of methymethacrylimide stucture. The material properties of the above polymer were represented in table 4. Example 16 Following the procedure of the Example 15, except 190"C of reaction temperature, to obtain the polymer. The material properties of the poly¬ mer were represented in table 4. Example 17 Following the procedure of the Example 15, except 210'C of reaction terperature, to obtain the polymer. The material properties of the poly¬ mer were represented in table 4. Comparative Example 12 Following the procedure of the Example 15, except not using catalyst and 170°C of reaction temperature, to obtain the polymer. The material properties of the polymer were represented in table 4. Comparative Example 13 Following the procedure of the Example 15, except not using catalyst and 190 β C of reaction temperature, to obtain the polymer. The material properties of the polymer were represented in table 4. Comparative Example 14 Following the procedure of the Example 15, except not using catalyst and 210°C of reaction temperature, to obtain the polymer. The material properties of the polymer were represented in table 4. Table 4 Example 18 To 1.8 -autoclave 100 parts by weight of sufficiently dried meth¬ ylmethacrylate polymer [Lucky Ltd., IH-830], 57 parts by weight of anhydrous cyclohexyl amine as an imidizing agent, 8.2 parts by weight of tetramethyla- mmonium hydroxide pentahydrate (25% in methanol) as a catlyst, 455 parts by weight of anhydrous tetrahydrofuran and 55 parts by weight of anhydrous methyl alcohol were added, and then the reaction mixture was dissolved by agitating (250 rpm) for preventing oxidation, reacted at 190 for 3 hours (inner pressure ; 250 pis). After the reaction was completed, the solution of methylmethacrylimide group containing polymer was reprecipitated in n-hexane, filtrated and dried sufficiently in vacuume oven at 100°C, to obtain the polymer as a white powder. The obtained polymer was measured with infrared spectrometer, to obtain the data of 1680cm * " 1 , 1700cm * " 1 and 1720cm" 1 which were characteristic bands of methylmethac¬ rylimide structure. The material properties of the polymer were represe- nted in table 2. Example 19 Following the procedure of the Example 18, except using 100 parts by weight of sufficiently dried methylmethacrylate polymer [Lucky Ltd., IH- 830], 37 parts by weight of anhydrous propylamine as an imidizing agent, tetramethyl ammonium hydroxide (25% in methanol) as a catalyst, 455 parts by weight of anhydrous tetrahydrofuran and 55 parts by weight of anhydrous methyl alcohol as a solvent, 190"C (inner pressure;300 psi) of a reaction temperature, to obtain the polymer. The material properties of the polymer were represented in table 5. ExaiPle 20 27% by weight of maleic anhydride (MAH), 16% by weight of styrene, 0.2% by weight of t-dodecylmercaptan were added to 57% by weight of methlmethacrylate (MMA), and then the reaction mixture was polymerized in solution (ethylbenzene as a solvent), to obtain the copolymer. Following the procedure of the Example 18, except using 100 parts by weight of completely dried MMA-MAH-ST copolymer, 68 parts by weight of anhydrous cyclohexyl amine as an imidizing agent, 6.9 parts by weight of tetramethyl aoonium hydroxide, 46 parts by weight of anhydrous methyl alcohol and lOO - (inner pressure ; 260 psi) of a reaction temperature, to obtain the polymer. The material properties of the polymer were represented in table 5. Example 21 Following the procedure of the Example 18, except using 100 parts by weight of completely dried MMA-MAH-ST obtained in Example 20, 41 parts by weight of anhydrous propyl amine as an imidizing agent, 6.9 parts by weight of as a catalyst, 382 parts by weight of anhydrous tetrahydrofuran and 46 parts by weight of anhydrous methyl alcohol as a solvent, and 190°C (inner pressure;300 psi) of a reaction temperature, to obtain the polymer. The material properties of the polymer were represented in table 5. Example 22 Following the procedure of the Example 18, except 210"C (inner pres- sure ; 400 psi) of to obtain the polymer. The material properties of the polymer were represented in table 5. Example 23 Following the procedure of the Example 19, 210°C (inner pressure;450 psi) of a reaction temperature, to obtain the polymer. The material pr- operties of the polymer were represented in table 5. Example 24 Following the procedure of the Example 20, except 210"C (inner pres¬ sure ; 450 psi) a reaction temperature, to obtain the polymer. The mat¬ erial properties of the polymer were represented in table 5. Example 25 Following the procedure of the Example 21, except 210°C (inner pres¬ sure ; 450 psi) of a reaction temperature, to obtain the polymer. The material properties of the polymer were represented in table 5. Comparative Examples 15~22 Following the procedure of the Example 18~25, except not using ca¬ talyst, to obtain the polymer. The material properties of the polymer were represented in table 5. Table Examples 18 19 20 21 22 23 24 25 MMA polymer 100 100 - - 100 100 MMA-MAH-ST copolymer - 100 100 - - 100 100 propyl amine 37 - 41 - 37 - 41 cyclohexyl amine 57 - 68 - 57 - 68 tetramethyl amonium hydr¬ 8.2 8.2 6.9 6.9 8.2 8.2 6.9 6.9 oxide (in 25% methanol) tetrahydrofuran 455 455 382 382 455 455 382 382 methyl alcohol 55 55 46 46 55 55 46 46 reaction temperature (%) 190 190 190 190 210 210 210 210 reaction time(h) 3 3 3 3 3 3 3 3 N content (%) 1.133.152.802.693.553.504.053.96 the degree of imidization(%) 9 2833.235.3 38 3247.336.9 glass transition temperatur- 137 133 169 141 168 138 184 142 eCC) Table 5 (QPrrtined) Comparative Examples 15 16 17 18 19 20 21 22 MMA polymer 100 100 - - 100 100 MMA-MAH-ST copolymer - 100 100 - - 100 100 propyl amine 37 - 41 - 37 - 41 cyclohexyl amine 57 68 57 68 tetramethyl amonium hydroxide (in 25% metharol) tetrahydrofuran 455 455 382 382 455 455 382 382 methyl alcohol 55 55 46 46 55 55 46 46 reaction temperature (%) 190 190 190 190 210 210 210 210 reaction time(h) 3 3 3 3 3 3 3 3 N content (%) 1.122.282.622.553.153.323.493.40 the degree of imidization(%) 8 1931.232.5 32 3044.532.7 glass transition temperatur- 134 128 166 139 163 134 181 140 eCC)

Claims: C »s 1. A process for the preparation of heat resistant and transparent ac¬ rylic resin which is characterized by imidizing acrylic resin in a solution with ammonia, primary amine or the aoonia conpounds generating aoonia or primary amine in the presence or absence of catalyst and under a suitable temperature condition. 2. The process according to claim 1, wherein the acrylic resin is m- ethylmethacrylate polymer or methylmethacrylate-ethylenic unsaturated monon- er copolymer. 3. The process according to claim 1, wherein the methylmethacrylate- ethylenic unsaturated monomer copolymer comprises more than 50% by wei¬ ght of methylmethacrylate structure unit. 4. The process according to claim 1, wherein the primary amine is the compound of the following formula (HI). RNHz (IE) wherein R represents a hydrogen atom, or unsubstituted and substituted Ci to Czo alkyl, cycloalkyl, aryl, aralkyl, alkaryl, or mixtures theirof. 5. The process according to claim 1, wherein the compounds generating primary amine is urea, 1,3-dimethyl urea, 1,3-diethyl urea, ammonium acet- ate, the compound of the following formula (II) or their derivatives. wherein R represents a hydrogen atom, or unsubstituted and substituted Ci to Czo alkyl, cycloalkyl, aryl, aralkyl, alkaryl, or mixtures theirof. 6. The process according to claim 5, the compounds generating primary amine is the aoonium bicarbonate of the above-mentioned formular (II) or their derivatives. 7. The process according to claim 1 or 6, the imidization reaction c- arried out at the temperature of 180 to 350 β C. 8. The process according to claim 7, the reaction product is the com¬ pound of the following formula (I) comprising more than 10% by we¬ ight of imidized structure unit. i R 3 wherein Ri, R 2 and R 3 independently represent a hydrogen atom, or unsubstituted and substituted Ci to Czo alkyl, cycloalkyl, aryl, aralkyl, alkaryl, or mixtures theirof. 9. The process according to claim 1 or 6, wherein the imidization react¬ ion is carried out in the presence of 0.01 to 15% by weight of catalyst ofthe following formula (IV) and at the temperature of 100 to 350°C. IUN0H (IV) wherein R represents a hydrogen atom, or unsubstituted and substituted Ci to Czo alkyl, cycloalkyl, aryl, aralkyl, alkaryl, or mixtures theirof. 10. The process according to claim 9, wherein the reaction product is the compound of the following formula ( I ) comprising more than 10% by weight of imidized structure unit. . I R 8 wherein Ri, R z and R 3 independently represent a hydrogen atom, or unsubstituted and substituted Ci to C zo alkyl, cycloalkyl, aryl, aralkyl, alkaryl, or mixtures theirof. 11. The process according to claim 7 or 8, wherein the solvent is one or more than two selected from the group consisting of benzene, toluene, xy- lene, methylethylketone, ethylenglycoldimethylether, diglyme, dioxane, tet¬ rahydrofuran, dimethylformamide, dimethyl sulfoxide, dimethylacetamide, methyl alcohol, ethyl alcohol, isopropyl alcohol and butyl alcohol, and the boiling points of the solvents are the range of 50 to 160°C. 12. The process according to claim 1~5, the imidization reaction is carried in the presence of 5 to 20% by weight of water and at the temperature of 180 to 350°C. 13. The process according to claim 12, the solvent is one or more than two selected from the group consisting of benzene, toluene, xylene, methylethylketone, ethylenglycoldimethylether, diglyme, dioxane, tetrahy- ofuran, dimethylformamide, dimethyl sulfoxide, dimethylacetamide, methyl alcohol, ethyl alcohol, isopropyl alcohol and butyl alcohol, and the boiling points of the solvents are the range of 50 to 160°C. 14. The process according to claim 12, the reaction product is the compound of the following formula ( I ) conrprising 10% by weight of imidized structure unit. 0 = C C = 0 \ / N I R 3 wherein Ri, Rz and R 3 independently represent a hydrogen atom, or unsubstituted and substituted Ci to C zo alkyl, cycloalkyl, aryl, aralkyl, alkaryl, or mixtures theirof. 15. The process according to claim 1~5, the imidization reaction is carried out in the presence of 0.01 to 15% by weight of the catalyst of the following formula (IV) and 5 to 20% by weight of water at the temperature of 100 to 350 β C. »N0H (IV) wherein R represents a hydrogen atom, or unsubstituted and substituted Ci to Czo alkyl, cycloalkyl, aryl, aralkyl, alkaryl, or mixtures theirof. 16. The process according to claim 15, the solvent is one or more t- han two selected from the group consisting of benzene, toluene, xylene, methylethylketone, ethylenglycoldimethylether, diglyme, dioxane, tetrahydr¬ ofuran, dimethylformamide, dimethyl sulfoxide, dimethylacetamide, methyl alcohol, ethyl alcohol, isopropyl alcohol and butyl alcohol, and the boil¬ ing points of the solvents are the range of 50 to 160 β C. 17. The process according to claim 15, the reaction product is the compound of the following formula (I ) comprising more than 5% by weight of imidized structure unit. \ / N f R 3 wherein Ri, R 2 and R 3 independently represent a hydrogen atom, or unsubstituted and substituted Ci to C ϊo alkyl, cycloalkyl, aryl, aralkyl, alkaryl, or mixtures theirof. 18. The process according to claim 1~5, the imidization reaction is carried out in the presence of 0.01 to 15% by weight of catalyst of the following formula (IV) and at the temperature of 100 to 350°C. R. NOH (IV) wherein R represents a hydrogen atom, or unsubstituted and substituted Ci to Czo alkyl, cycloalkyl, aryl, aralkyl, alkaryl, or mixtures theirof. 19. The process according to 18, the solvent is one or more than two selected from the group consisting of benzene, toluene, xylene, methyle- thylketone, ethylenglycoldimethylether, diglyme, dioxane, tetrahydrofuran, dimethylfromamide, dimethyl sulfoxide, dimethylacetamide, methyl alcohol, ethyl alcohol, isopropyl alcohol and butyl alcohol, and the boiling points of the solvents are the range of 50 to 160°C. 20. The process according to 18, the reaction product is the compound of the following formula ( I ) comprising more than 5% by weight of imidized structure unit. I R 3 wherein Ri, Rz and S 3 independently represent a hydrogen atom, or unsubstituted and substituted Ci to Czo alkyl, cycloalkyl, aryl, aralkyl, alkaryl, or mixtures theirof.

Inventors: HUR YOUNG SAM, KIM JIN BAEK, HUR, YOUNG, SAM, KIM, JIN, BAEK
Applicants: LUCKY LTD, LUCKY, LTD.
Application year: 1990
Main classification: C08F8
IPC codes: C08F8, C08L33