丙烯酸酯橡胶的分子设计及耐寒性能的研究
摘要
本文以制备耐低温性能更优的耐寒级丙烯酸酯橡胶为目的。首先通过醇酸酯化法制备了二乙二醇单甲醚丙烯酸酯(MOEOEA),然后以MOEOEA为耐油耐低温单体,与丙烯酸乙酯(EA)、丙烯酸丁酯(BA)及硫化点单体氯乙酸乙烯酯(VCA)进行乳液共聚,制得脆性温度可达-30℃以下的丙烯酸酯橡胶。所得主要结论性成果如下：
1.在丙烯酸和二乙二醇单甲醚进行酯化制备MOEOEA的过程中,考察了共沸剂种类及用量、酸醇摩尔比、酯化时间对转化率、产物收率及纯度的影响。当以为苯共沸剂,用量为原料醇质量的120%,酸醇摩尔比1.2：1,酯化时间在7-8h时,酯化率可达到94%以上。用气质联用色谱仪确定产物的准确结构,用气相色谱测定了产物的纯度大于91%,且在此纯度下,收率可保证80%。
2.采用溶液聚合制得了MOEOEA的均聚物及MOEOEA与EA共聚物,对均聚物和共聚物玻璃化温度测定,结果表明均聚物的玻璃化转变温度(Tg)为-86℃,按FOX方程推算的共聚物的玻璃化转变温度(Tg)与实测值相符。
3.采用氧化还原引发体系,研究了MOEOEA/EA/BA/VCA四元乳液共聚行为。当二乙二醇单甲醚丙烯酸酯的用量为总单体用量的20%时,单体转化率为97%,丙烯酸酯共聚物的凝胶含量可控制在2%以下。采用硫／皂化体系,以HAF N300型炭黑作补强剂,采用二段硫化,硫化胶的拉伸强度可达12MPa以上,扯断伸长率为317%,压缩永久变形小于20%,邵氏A硬度为70,脆性温度-32℃以下,达到了预期目的。
The main purpose in this paper is improving in cold tolerance of acrylic rubber gained by emulsion copolymerization of methoxy ethoxy ethoxy acrylate(MOEOEA) with butyl acrylate(BA), ethyl acrylate(EA) and vinyl chloroacetate(VCA).
Firstly, the monomer of MOEOEA was synthesized through esterifying acrylic acid with diethylene glycol monomethyl ether. The effects of the kind and dosage of dehydrating agent, the mole ratio of acid to alcohol, reaction time on conversion, yield and purity were studied. When benzene was used as dehydrating agent the dosage of benzene is 120% to alcohol, the mole ratio of alcohol to acid is 1.2:1, the reaction time is between 7～8h, the conversion of di-ethylene glycol monomethyl ether can reach to 97% and purity is no less than 97%. The objective monomer's structure was characterized by GC-MS and the purity of monomer can reached above 97% determined Gas Chromatogram.
Secondly, the acrylic homopolymers of MOEOEA and copolymers of EA, BA, MOEOEA, VCA were synthesized by emulsion polymerization. The results of DSC showed that the glass-transition temperature (Tg) of homopolymer is-86℃. The glass-transition temperature (Tg) of copolymer is accord with the calculation value through FOX equation.
Thirdly, the behaviors of emulsion polymerization and properties were studied in the presence of redox initiator system and compound emulsifier. When the dosage of MOEOEA is 20wt% to total monomer, the conversion rate was no less than 97% and gel content of ACM(acrylester butadience rubber) can be controlled among 2-15%.
Fourthly, the vulcanizing behaviors and properties were also investigated in detail with sulfur/soap as vulcanizing agent system and with carbon black (HAF N330) as reinforcing agent. After two steps vulcanized, the strength can reach 12MPa above, the elongation at break is 317%, the rate of permanent deformation is less than 20%, the Shore A hardness is from 70 to 75, the brittle temperature which is far lower than that of current ACM is lower than-32℃.
1.在丙烯酸和二乙二醇单甲醚进行酯化制备MOEOEA的过程中,考察了共沸剂种类及用量、酸醇摩尔比、酯化时间对转化率、产物收率及纯度的影响。当以为苯共沸剂,用量为原料醇质量的120%,酸醇摩尔比1.2：1,酯化时间在7-8h时,酯化率可达到94%以上。用气质联用色谱仪确定产物的准确结构,用气相色谱测定了产物的纯度大于91%,且在此纯度下,收率可保证80%。
2.采用溶液聚合制得了MOEOEA的均聚物及MOEOEA与EA共聚物,对均聚物和共聚物玻璃化温度测定,结果表明均聚物的玻璃化转变温度(Tg)为-86℃,按FOX方程推算的共聚物的玻璃化转变温度(Tg)与实测值相符。
3.采用氧化还原引发体系,研究了MOEOEA/EA/BA/VCA四元乳液共聚行为。当二乙二醇单甲醚丙烯酸酯的用量为总单体用量的20%时,单体转化率为97%,丙烯酸酯共聚物的凝胶含量可控制在2%以下。采用硫／皂化体系,以HAF N300型炭黑作补强剂,采用二段硫化,硫化胶的拉伸强度可达12MPa以上,扯断伸长率为317%,压缩永久变形小于20%,邵氏A硬度为70,脆性温度-32℃以下,达到了预期目的。
The main purpose in this paper is improving in cold tolerance of acrylic rubber gained by emulsion copolymerization of methoxy ethoxy ethoxy acrylate(MOEOEA) with butyl acrylate(BA), ethyl acrylate(EA) and vinyl chloroacetate(VCA).
Firstly, the monomer of MOEOEA was synthesized through esterifying acrylic acid with diethylene glycol monomethyl ether. The effects of the kind and dosage of dehydrating agent, the mole ratio of acid to alcohol, reaction time on conversion, yield and purity were studied. When benzene was used as dehydrating agent the dosage of benzene is 120% to alcohol, the mole ratio of alcohol to acid is 1.2:1, the reaction time is between 7～8h, the conversion of di-ethylene glycol monomethyl ether can reach to 97% and purity is no less than 97%. The objective monomer's structure was characterized by GC-MS and the purity of monomer can reached above 97% determined Gas Chromatogram.
Secondly, the acrylic homopolymers of MOEOEA and copolymers of EA, BA, MOEOEA, VCA were synthesized by emulsion polymerization. The results of DSC showed that the glass-transition temperature (Tg) of homopolymer is-86℃. The glass-transition temperature (Tg) of copolymer is accord with the calculation value through FOX equation.
Thirdly, the behaviors of emulsion polymerization and properties were studied in the presence of redox initiator system and compound emulsifier. When the dosage of MOEOEA is 20wt% to total monomer, the conversion rate was no less than 97% and gel content of ACM(acrylester butadience rubber) can be controlled among 2-15%.
Fourthly, the vulcanizing behaviors and properties were also investigated in detail with sulfur/soap as vulcanizing agent system and with carbon black (HAF N330) as reinforcing agent. After two steps vulcanized, the strength can reach 12MPa above, the elongation at break is 317%, the rate of permanent deformation is less than 20%, the Shore A hardness is from 70 to 75, the brittle temperature which is far lower than that of current ACM is lower than-32℃.
引文
[1]焦书科,夏宇正.丙烯酸酯橡胶的结构-性能及生产技术[J].丙烯酸化工与应用,2008,21(2)：1-14
[2]谢红.丙烯酸酯橡胶生产的应用与市场[J].橡胶科技市场,2007,(9)：9-11.
[3]焦书科,夏宇正.丙烯酸酯橡胶研发进展[J].丙烯酸化工与应用,2007,20(3)：1-14.
[4]焦书科,夏宇正.丙烯酸酯类热塑性弹性体[J].合成橡胶工业,2003,26(3)：129-35.
[5]吴绍吟,马文石.丙烯酸酯橡胶的加工与能行[J].特种橡胶制品,1999,20(3)：1-5.
[6]焦书科,夏宇正.丙烯酸酯类热塑性弹性体研发进展.[J].丙烯酸化工与应用,2002,15(1)；1-9.
[7]焦书科,夏宇正.丙烯酸橡胶生产技术及发展[J]合成橡胶工业,1991 14(5)；313
[8]李用炎.聚丙烯酸橡胶的特性和应用[J].原材料,1992,2)：1-4.
[9]刘大华.合成橡胶工业手册[M].一版.北京；化工工业出版社.1991.1071-1087
[9]Jha A, Bhowmick A K. Thermal degradation and ageing behaviour of novel thermoplastic elastomeric nylon-6/acrylate rubber reactive blends [J]. Polymer Degradation and Stability, 1998,62(3):575-86.
[10]Yoichi Mizuno, Masato Kawase, Toshiro Matsuo. Rubber composition for tire tread including silica and rice husk. [P]US 6378584.2002-4-30
[11]P.Nowak et al Electrically Insulating Compostion [P]US 2105361.1940-7-30
[12]Mast WC, Dietz TJ, Fisher CH. India Rubb World,1945.
[13]夏宇正,刘文利,石淑先.活性氯型丙烯酸酯橡胶的热可逆共价交联及力学性能[J].合成橡胶工业,2004,27(2)：73-77.
[14]高福年.ACM橡胶的配方设计及加工工艺[J].特种橡胶制品,2002,2(23)：11-14.
[15]赵志正.丙烯酸酯橡胶的耐热性和耐油性[J]世界橡胶工业,2009,36(11)：5-8
[16]Joseph Da Lio,Ravemnna. Vulcanizble compostions based on modified acrylic rubber[P]. EP 5496900 1996-5-5
[17]董汉鹏,李效玉.丙烯酸酯互穿网络聚合物的合成和性能[J]胶体与聚合物,1999,17(1)：1-5.
[18]陈启宏,谢军.环氧充油型丙烯酸酯橡胶的合成及特[J].化工新型材料,2005,33(8)：31-8.
[19]王作龄.丙烯酸酯橡胶及其配方技术[J].世界橡胶工业,1999,26(5)：50-60
[20]吉静,单绍峰.丙烯酸酯橡胶的研究与应用[J].橡胶工业,1999,46(7)：399-403.
[21]王敏.丙烯酸脂橡胶的应用与开发[J].世界橡胶工业,1996,26(5)：50-60.
[22]梁诚.丙烯酸酯橡胶的生产、改性与应用[J].化工新型材料,2004,32(4)：18-20
[23]Wootthikanokkan J, Tunjongnawi P. Investigation of the effect of mixing schemes on cross-link distribution and tensile properties of natural-acrylic rubber blends [J]. Polymer Testing,2003, 22(3):305-12.
[24]Shivakumar E, Dds C K, Segal E, et al. Viscoelastic properties of ternary in situ elastomer composites based on fluorocarbon, acrylic elastomers and thermotropic liquid crystalline polymer blends [J]. Polymer,2005,46(10):3363-71. Kader M A, Bhowmick A K. Thermal ageing, degradation and swelling of acrylate rubber,
[25]fluororubber and their blends containing polyfunctional acrylates [J]. Polymer Degradation and Stability,2003,79(2):283-95.
[26]Logothesis AL. Polym Sci,Polym Chem Ed,1978,(16):2797. JESSADA WONG-ON J W. Dynamic vulcanization of acrylic rubber-blended PVC [J]. Journal
[27]of Applied Polymer Science,2003,88(11):2657-63.
[28]R.S.Tigli, V.Evern. Synthesis and characterization of pure poly(acrylate)latexes[J]. Progress in Organic Coatings,2005,52:144-150.
[29]胡金生,曹同玉,刘庆普.乳液聚合[M].北京；化工工业出版社.1987：7-8.
[30]CAIYUNaiyun Wu C W, Wwihong Guo, CHIFEI WU,. Dynamic mechanical properties of acrylic rubber blended with phenolic resin [J]. Journal of Applied Polymer Science,2008, 109(4):2065-70.
[31]LI Y, IAiwakur Y, Zhao L, et al. Nanostructured Poly(vinylidene fluoride) Materials by Melt Blending with Several Percent of Acrylic Rubber [J]. Macromolecules,2008,41(9):3120-4.
[32]大森英三著,朱传启译.丙烯酸酯共聚物[M].第二版.北京：北京工业出版社.1985：143-152.
[33]刘印文,刘振华.聚丙烯酸酯橡胶的特性及其在制品中的应用[J].弹性体,1996,6(2)：42-51.
[34]Kader MA, Bhowmick AK. Thermal ageing, degradation and swelling of acrylate rubber,fluororubber and their blends containing polyfunctional acrylates[J]. Polymer Degradation and Stability,2003,79:283-295.
[35]Abhijit J, Bhowmick, K A. hermoplastic elastomeric blends of poly(ethylene terephthalate) and acrylate rubber:1. Influence of interaction on thermal, dynamic mechanical and tensile properties[J]. Polymer Degradation and Stability,1997,38(17):4337-4344
[36]董汉鹏,夏宇正.EA／St-AN互穿聚合物网络的加工和力学性能[J]合成橡胶工业,2000,23(5)：307-309.
[37]C, Minet M, Teyssie P. Synthesis and Charateriztion of PMMA-Pn-BA-PMMA by Two-step Radical Polymerization(ATRP)[J]. Macromolecules,1999,32:8277～8282.
[38]Logothesis AL. Polym Sci,Polym Chem Ed,1978,(16):2797.
[39]V.Vijiayabaskar, S.Bhattacharya, V.K.Tikku. Election beam initiated modification of arcylic elastomer in presence of polyfuncitonal monomers[J]. Radation Physics and Chemistry, 2004,71:1045-1058
[40]Brydosn JA. Materials and Their CompoundsChapt 11 London; Elsevier Applied Science Publishers Ltd,1983:231.
[41]粟付平,张洪雁.丙烯酸酯橡胶硫化特性的研究[J].弹性体,1997,7(1)：16-19.
[42]张殿荣,辛振祥.现代橡胶配方设计[M].北京；化学工业出版社.2001：190-195.
[43]延与弘次.低温丙烯酸酯橡胶的加工与性能[J].日本橡胶协会志,1993,66(9)：646-652
[44]谢长熊.丙烯酸酯橡胶的性能和应用[J].合成材料老化与应用,2003,3：28-30.
[45]唐坤明,唐坤珍,唐坤平.国产AR-400型超耐寒级丙烯酸酯橡胶的性能[J].特种橡胶制品,2001,1(22)：25-27.
[46]李超英.日本瑞翁公司合成橡胶的发展[J].现代化工,1991,11(1)：44-8.
[47]Wong-on J W. Dynamic vulcanization of acrylic rubber-blended PVC [J]. Journal of Applied Polymer Science,2003,88(11):2657-63.
[48]TUNCunc Y, Hasirci N, YESILADA A, et al. Comonomer effects on binding performances and morphology of acrylate-based imprinted polymers [J]. Polymer,2006,47(20):6931-40.
[2]谢红.丙烯酸酯橡胶生产的应用与市场[J].橡胶科技市场,2007,(9)：9-11.
[3]焦书科,夏宇正.丙烯酸酯橡胶研发进展[J].丙烯酸化工与应用,2007,20(3)：1-14.
[4]焦书科,夏宇正.丙烯酸酯类热塑性弹性体[J].合成橡胶工业,2003,26(3)：129-35.
[5]吴绍吟,马文石.丙烯酸酯橡胶的加工与能行[J].特种橡胶制品,1999,20(3)：1-5.
[6]焦书科,夏宇正.丙烯酸酯类热塑性弹性体研发进展.[J].丙烯酸化工与应用,2002,15(1)；1-9.
[7]焦书科,夏宇正.丙烯酸橡胶生产技术及发展[J]合成橡胶工业,1991 14(5)；313
[8]李用炎.聚丙烯酸橡胶的特性和应用[J].原材料,1992,2)：1-4.
[9]刘大华.合成橡胶工业手册[M].一版.北京；化工工业出版社.1991.1071-1087
[9]Jha A, Bhowmick A K. Thermal degradation and ageing behaviour of novel thermoplastic elastomeric nylon-6/acrylate rubber reactive blends [J]. Polymer Degradation and Stability, 1998,62(3):575-86.
[10]Yoichi Mizuno, Masato Kawase, Toshiro Matsuo. Rubber composition for tire tread including silica and rice husk. [P]US 6378584.2002-4-30
[11]P.Nowak et al Electrically Insulating Compostion [P]US 2105361.1940-7-30
[12]Mast WC, Dietz TJ, Fisher CH. India Rubb World,1945.
[13]夏宇正,刘文利,石淑先.活性氯型丙烯酸酯橡胶的热可逆共价交联及力学性能[J].合成橡胶工业,2004,27(2)：73-77.
[14]高福年.ACM橡胶的配方设计及加工工艺[J].特种橡胶制品,2002,2(23)：11-14.
[15]赵志正.丙烯酸酯橡胶的耐热性和耐油性[J]世界橡胶工业,2009,36(11)：5-8
[16]Joseph Da Lio,Ravemnna. Vulcanizble compostions based on modified acrylic rubber[P]. EP 5496900 1996-5-5
[17]董汉鹏,李效玉.丙烯酸酯互穿网络聚合物的合成和性能[J]胶体与聚合物,1999,17(1)：1-5.
[18]陈启宏,谢军.环氧充油型丙烯酸酯橡胶的合成及特[J].化工新型材料,2005,33(8)：31-8.
[19]王作龄.丙烯酸酯橡胶及其配方技术[J].世界橡胶工业,1999,26(5)：50-60
[20]吉静,单绍峰.丙烯酸酯橡胶的研究与应用[J].橡胶工业,1999,46(7)：399-403.
[21]王敏.丙烯酸脂橡胶的应用与开发[J].世界橡胶工业,1996,26(5)：50-60.
[22]梁诚.丙烯酸酯橡胶的生产、改性与应用[J].化工新型材料,2004,32(4)：18-20
[23]Wootthikanokkan J, Tunjongnawi P. Investigation of the effect of mixing schemes on cross-link distribution and tensile properties of natural-acrylic rubber blends [J]. Polymer Testing,2003, 22(3):305-12.
[24]Shivakumar E, Dds C K, Segal E, et al. Viscoelastic properties of ternary in situ elastomer composites based on fluorocarbon, acrylic elastomers and thermotropic liquid crystalline polymer blends [J]. Polymer,2005,46(10):3363-71. Kader M A, Bhowmick A K. Thermal ageing, degradation and swelling of acrylate rubber,
[25]fluororubber and their blends containing polyfunctional acrylates [J]. Polymer Degradation and Stability,2003,79(2):283-95.
[26]Logothesis AL. Polym Sci,Polym Chem Ed,1978,(16):2797. JESSADA WONG-ON J W. Dynamic vulcanization of acrylic rubber-blended PVC [J]. Journal
[27]of Applied Polymer Science,2003,88(11):2657-63.
[28]R.S.Tigli, V.Evern. Synthesis and characterization of pure poly(acrylate)latexes[J]. Progress in Organic Coatings,2005,52:144-150.
[29]胡金生,曹同玉,刘庆普.乳液聚合[M].北京；化工工业出版社.1987：7-8.
[30]CAIYUNaiyun Wu C W, Wwihong Guo, CHIFEI WU,. Dynamic mechanical properties of acrylic rubber blended with phenolic resin [J]. Journal of Applied Polymer Science,2008, 109(4):2065-70.
[31]LI Y, IAiwakur Y, Zhao L, et al. Nanostructured Poly(vinylidene fluoride) Materials by Melt Blending with Several Percent of Acrylic Rubber [J]. Macromolecules,2008,41(9):3120-4.
[32]大森英三著,朱传启译.丙烯酸酯共聚物[M].第二版.北京：北京工业出版社.1985：143-152.
[33]刘印文,刘振华.聚丙烯酸酯橡胶的特性及其在制品中的应用[J].弹性体,1996,6(2)：42-51.
[34]Kader MA, Bhowmick AK. Thermal ageing, degradation and swelling of acrylate rubber,fluororubber and their blends containing polyfunctional acrylates[J]. Polymer Degradation and Stability,2003,79:283-295.
[35]Abhijit J, Bhowmick, K A. hermoplastic elastomeric blends of poly(ethylene terephthalate) and acrylate rubber:1. Influence of interaction on thermal, dynamic mechanical and tensile properties[J]. Polymer Degradation and Stability,1997,38(17):4337-4344
[36]董汉鹏,夏宇正.EA／St-AN互穿聚合物网络的加工和力学性能[J]合成橡胶工业,2000,23(5)：307-309.
[37]C, Minet M, Teyssie P. Synthesis and Charateriztion of PMMA-Pn-BA-PMMA by Two-step Radical Polymerization(ATRP)[J]. Macromolecules,1999,32:8277～8282.
[38]Logothesis AL. Polym Sci,Polym Chem Ed,1978,(16):2797.
[39]V.Vijiayabaskar, S.Bhattacharya, V.K.Tikku. Election beam initiated modification of arcylic elastomer in presence of polyfuncitonal monomers[J]. Radation Physics and Chemistry, 2004,71:1045-1058
[40]Brydosn JA. Materials and Their CompoundsChapt 11 London; Elsevier Applied Science Publishers Ltd,1983:231.
[41]粟付平,张洪雁.丙烯酸酯橡胶硫化特性的研究[J].弹性体,1997,7(1)：16-19.
[42]张殿荣,辛振祥.现代橡胶配方设计[M].北京；化学工业出版社.2001：190-195.
[43]延与弘次.低温丙烯酸酯橡胶的加工与性能[J].日本橡胶协会志,1993,66(9)：646-652
[44]谢长熊.丙烯酸酯橡胶的性能和应用[J].合成材料老化与应用,2003,3：28-30.
[45]唐坤明,唐坤珍,唐坤平.国产AR-400型超耐寒级丙烯酸酯橡胶的性能[J].特种橡胶制品,2001,1(22)：25-27.
[46]李超英.日本瑞翁公司合成橡胶的发展[J].现代化工,1991,11(1)：44-8.
[47]Wong-on J W. Dynamic vulcanization of acrylic rubber-blended PVC [J]. Journal of Applied Polymer Science,2003,88(11):2657-63.
[48]TUNCunc Y, Hasirci N, YESILADA A, et al. Comonomer effects on binding performances and morphology of acrylate-based imprinted polymers [J]. Polymer,2006,47(20):6931-40.