碱溶性苯乙烯—丙烯酸树脂的合成及应用
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摘要
随着环保要求的提高,近年来环保型水性油墨和水性涂料受到普遍的重视,国内迫切需求开发用于水性体系的高性能树脂。低分子量窄分布的碱溶性苯乙烯-丙烯酸树脂因其分子结构具有亲水亲油的特性,适用于水性体系中对颜料颗粒的分散,可以作为在水性油墨、水性涂料中的水溶性分散剂。该类树脂具有高光泽度、快干燥速度的典型特点,分散颜料用时其质均分子量Mw的一般范围在6000~15000,多数在6000~10000之间,分子量分布<2,酸值在200左右,玻璃化温度在100℃左右。
本论文选用了苯乙烯(St)、丙烯酸(AA)作为共聚主单体,然后引入了α-甲基苯乙烯单体(AMS)进行改性。采用常压下半连续溶液聚合的方式,合成了低分子量、窄分布的碱溶性苯丙树脂。探讨了反应单体中丙烯酸含量和α-甲基苯乙烯含量对树脂性能的影响。AMS的引入有效地改善了树脂结构,提高了树脂在水性色浆中的应用性能。实验确定了苯丙树脂合成的最佳配方。
探讨了半连续溶液聚合过程中,主要工艺参数对苯丙树脂分子量大小及分子量分布的影响。选用了二甲基甲酰胺作为反应溶剂,比常用的醇醚类溶剂有更好的效果;同时根据其用量对分子量及其分布的影响,确定了溶剂的最佳用量为体系的40%。升高温度,可以显著降低分子量大小,但分子量分布先变窄后变宽,据此确定了最佳聚合温度;选择近年来得到重要应用的过氧化苯甲酸叔丁酯(TBPB)作为引发剂,提高引发剂用量,可以降低苯丙树脂分子量,使得分子量分布先变窄后变宽,据此确定了引发剂最佳用量;在聚合中使用十二烷基硫醇做分子量调节剂,并确定最佳用量为。最终确定了苯丙树脂合成的最佳工艺条件。
考察了最佳工艺条件下的苯丙树脂和AMS单体改性树脂在水性色浆、颜料色片中的应用,并与进口树脂相应的性能进行了比较。在水性色浆的应用中,探讨了树脂液的粘度、色浆的细度、色浆分散液的分散稳定性和储存稳定性,并筛选出了性能表现最佳的树脂配方;在颜料色片的应用中,进一步探讨了最佳树配方下的苯丙树脂的水溶解性能,包括在常温振荡搅拌和超声波分散条件下的溶解性。实验表明选择的最佳配方下的苯丙树脂可以在水性色浆、颜料色片有较好的应用效果。
As the environmental protection agency ,water-based ink and water-based coatings have been given more focus in recent yeas and the high performance resin is sorely needed to apply to water-based system of them. Water-borne styrene-acrylic resin is just the kind of resin, characterized by low molecular weight , narrow molecular weight distribution and hydrophile-lipophile function, with high acid value, average molecular weight between 6,000 to 15,000 ,especially between 6,000 to 10,000.
In the paper water-borne styrene-acrylic resin was synthesized through semi-batch solution polymerization process, adoptingα-methyl styrene(AMS) as one of the reaction monomers. It was found that the addition of AMS improved the structure of the resin, which improved the properties of resin in application of water-based ink and water-based coatings. The amount of addition had an optimal range which was determined by a series of research.
The average molecular weight and molecular weight distribution index (PDI) are the main factors affecting the dispersion ability of the water-borne styrene-acrylic resin, which are sensitive to the polymerization conditions,such as changes of solvent , molecular regulator, type of initiators, temperature. The N,N-Dimethylformamide(DMF) was chosen as the reaction medium and had an advantage over the regular solvent, such as alcohols and ether. Finally, the optimum technological condition was determined, including the best reaction temperature, the optimum concentration of initiator(TBPB) and molecular regulator.
Under the optimum technological conditions, the styrene-acrylic acrylic resins which is modified or unmodified were applied in water-based colorants and pigment color filters. This paper investigated viscosity of solution, fineness of colorants, the dispersion stability and storage stability of carbon black pigment in the water-based colorants. It also investigated the water solubility of pigment color filters by methods of the oscillating agitation and the ultrasonic dispersed , which were made by different types of styrene-acrylic resin The experimental date shows that some modified styrene-acrylic acrylic resins had better application property, close to the standard sample.
本论文选用了苯乙烯(St)、丙烯酸(AA)作为共聚主单体,然后引入了α-甲基苯乙烯单体(AMS)进行改性。采用常压下半连续溶液聚合的方式,合成了低分子量、窄分布的碱溶性苯丙树脂。探讨了反应单体中丙烯酸含量和α-甲基苯乙烯含量对树脂性能的影响。AMS的引入有效地改善了树脂结构,提高了树脂在水性色浆中的应用性能。实验确定了苯丙树脂合成的最佳配方。
探讨了半连续溶液聚合过程中,主要工艺参数对苯丙树脂分子量大小及分子量分布的影响。选用了二甲基甲酰胺作为反应溶剂,比常用的醇醚类溶剂有更好的效果;同时根据其用量对分子量及其分布的影响,确定了溶剂的最佳用量为体系的40%。升高温度,可以显著降低分子量大小,但分子量分布先变窄后变宽,据此确定了最佳聚合温度;选择近年来得到重要应用的过氧化苯甲酸叔丁酯(TBPB)作为引发剂,提高引发剂用量,可以降低苯丙树脂分子量,使得分子量分布先变窄后变宽,据此确定了引发剂最佳用量;在聚合中使用十二烷基硫醇做分子量调节剂,并确定最佳用量为。最终确定了苯丙树脂合成的最佳工艺条件。
考察了最佳工艺条件下的苯丙树脂和AMS单体改性树脂在水性色浆、颜料色片中的应用,并与进口树脂相应的性能进行了比较。在水性色浆的应用中,探讨了树脂液的粘度、色浆的细度、色浆分散液的分散稳定性和储存稳定性,并筛选出了性能表现最佳的树脂配方;在颜料色片的应用中,进一步探讨了最佳树配方下的苯丙树脂的水溶解性能,包括在常温振荡搅拌和超声波分散条件下的溶解性。实验表明选择的最佳配方下的苯丙树脂可以在水性色浆、颜料色片有较好的应用效果。
As the environmental protection agency ,water-based ink and water-based coatings have been given more focus in recent yeas and the high performance resin is sorely needed to apply to water-based system of them. Water-borne styrene-acrylic resin is just the kind of resin, characterized by low molecular weight , narrow molecular weight distribution and hydrophile-lipophile function, with high acid value, average molecular weight between 6,000 to 15,000 ,especially between 6,000 to 10,000.
In the paper water-borne styrene-acrylic resin was synthesized through semi-batch solution polymerization process, adoptingα-methyl styrene(AMS) as one of the reaction monomers. It was found that the addition of AMS improved the structure of the resin, which improved the properties of resin in application of water-based ink and water-based coatings. The amount of addition had an optimal range which was determined by a series of research.
The average molecular weight and molecular weight distribution index (PDI) are the main factors affecting the dispersion ability of the water-borne styrene-acrylic resin, which are sensitive to the polymerization conditions,such as changes of solvent , molecular regulator, type of initiators, temperature. The N,N-Dimethylformamide(DMF) was chosen as the reaction medium and had an advantage over the regular solvent, such as alcohols and ether. Finally, the optimum technological condition was determined, including the best reaction temperature, the optimum concentration of initiator(TBPB) and molecular regulator.
Under the optimum technological conditions, the styrene-acrylic acrylic resins which is modified or unmodified were applied in water-based colorants and pigment color filters. This paper investigated viscosity of solution, fineness of colorants, the dispersion stability and storage stability of carbon black pigment in the water-based colorants. It also investigated the water solubility of pigment color filters by methods of the oscillating agitation and the ultrasonic dispersed , which were made by different types of styrene-acrylic resin The experimental date shows that some modified styrene-acrylic acrylic resins had better application property, close to the standard sample.
引文
[1]江巍.颜料的分散[J].上海涂料,2008,46(10):48-49.
[2]徐宗器.高黑度溶剂型黑漆的制备[ J].上海涂料,2008,46(11):24-28.
[3]李琳,许韶华,杨久霞,等.树脂对颜料分散体系的影响[J].现代显示, 2008,(1):71-74.
[4]徐宗器,谢林,马蔚.活性聚合物型颜料分散剂[J],涂料工业,2001,31(4):17-19.
[5]夏必来,林有尚.王永强,等.梳形聚合物分散剂在工业涂料体系中的应用基础研究[J].涂料工业.2008,38(3):17-20.
[6]周春隆,穆振义.有机颜料化学及工艺学[M].北京:中国石化出版社,2002:247.
[7] Hampton James..Organic pigment and printing ink[J]. American Ink Maker.1985(1):143.
[8]周春隆.超分散6剂及其在颜料中的应用周春隆[J],染料工业.1991,28(3):41.
[9]朱大有译.使水性丙烯酸聚合物可减少有机挥发物(VOC)[J].油墨,2000,(l):5-11.
[10]大森英三[日]著,张育川等译.功能性丙烯酸树脂[M].北京:化学工业出版社,1993:440-460.
[11]于瑞香.水性印刷上光油的剖析与研制[M].天津:天津工业大学,2004:12.
[12]张鹏,王兆华.丙烯酸树脂防腐蚀涂料及应用[M].北京:化学工业出版社,2003:92-106.
[13]汪长春.丙烯酸醋涂料[M].北京:化学工业出版社,2005:293-336.
[14]卢江.高分子化学[M].北京:化学工业出版社,2004:65-80,97-103.
[15] Schmidt,Ronald E.,Schultz. Bulk Polymerization Process for Preparing High Solids and Uniform Copolymers[P].US,4529787,1985.
[16] Hamielec, Archie E, Lawless, etal. Precess for Continuous Bulk Copolymerization of Vinyl Monomers[P] . US,4414370,1983.
[17]魏无际,俞强,崔益华,等.编著,高分子化学与物理基础[M].北京:化学工业出版社,2005:71.
[18]武利民.涂料技术基础[M].北京:化学工业出版社,2002:324-390.
[19]管荣,李建宗,艾照全,等.丙烯酸酯乳液共聚物胶粘剂的合成、性能及应用[J].中国胶粘剂,1994,3(2):43-45.
[20] Bardy ,John W.,Strickland,Franklin D.,Longwith; Chester C.,Aqueous Base-soluble Resin Compositions[P],US,P397952,1976.
[21] ROTH George ,SMITH George ,SINGHAL Shruti . solid acrylic resin using a continuous tube reactor[P],US,04593,1998.
[22]曹贵平,乐慧慧,张明华,等.‘饥饿’反应器中苯乙烯聚合动力学[J],高校化学工程学报,1995,9(l):52一57.
[23]王文俊,李伯耿,于在璋,等.半连续乳液聚合[J],高分子通报,1995,(l):44-49.
[24] Dikaoumakos,Qi Xu,Frank N. Jones,Jamil Baghdachi,etal.Synthisis of Acrylic Resin for High-Solids Coatings by Solution and Separation Polymerization[J].Journal of Coatings Technology,2000,72(908):61-70.
[25]金振华.新型水溶性丙烯酸树脂的应用与发展[J].中国印刷物资商情,2002,(7):20-22.
[26]温绍国,翁志学,黄志明,等.水溶性丙烯酸共聚物的研究进展[J].化工新型材料,1997(2),15-21.
[27] Echte,Adolf,Zizlsperger,etal.Manufacture of Uniform Polymers[P]. US,3954722,1976.
[28] Danjo Keiji,Tsurusaki Takeski,Ko Masaaki,etal.Aqueous colored resin fine particle dispersions for ink-jet inks,printing units,ink cartridges,and ink-jet printing[P].JP,327895,2003.
[29] Sharma Mahendrak,Wang,Richard Hsushien,etal.Waterborne acrylic Polymers containing Polymeric fluorescent compounds[P].US,6162869,2000.
[30] Sawada Michtaka ,Tsutsumi Takehiro, Azuma akishi,etal.Aqueous ink for ink-jet printing[P],US,6031019,2000.
[31] Hidaka Yuki,Tsutsumi Takehiro.Water-based ink[P],EP,1113051,2001.
[32] Nakano Yukihiro.Tsuru Isao, Azuma Kohji, etal..Water-based ink for ink-jet recording[P] ,EP,1059341, 2000.
[33]刘仁,熊万斌.阳离子型丙烯酸树脂的合成及其水溶性研究[J].涂料工业,2005,35(8):37-40.
[34]陈岚,陈义锋,朱传方等..酮醛改性水性丙烯酸酷树脂的合成及性能研究[J].粘接2004,25(2):16-18.
[35]阮丹柯,范宏.水性油墨用苯乙烯一丙烯酸固体树脂合成[J].科技通报,2006,22(l):115-118.
[36]林剑雄,王小妹,麦堪成等.水溶性丙烯酸树脂的合成及表征[J].塑料工业,2003,31(l):l-7.
[37]唐少炎,汤建新.水性油墨的发展及在包装印刷业的应用[J].油墨,2000,(3):10-12.
[38]张霞,朱金丽,房宽峻,等.聚羧酸型分散剂对水性超细颜料分散体系的作用[J].北京服装学院学报,2005,25(1):1-4.
[39] Cartridge D J,Hauxwell F,Pearce R A,A new dispersant for water-based pigments[J].Polym. Paint Coloure J,1994,184:10-12.
[40]刘斐,新型染料分散剂的合成及应用[D] ,上海:东华大学,2007.
[41] J.E. Jaffe,C.D. Campbell,S.B. Hendi,F. Bable, Influence of apparatus geometry and deposition conditions on the structure and topography of thick sputtered coatings[J].Journal of Coatings Teehnology. 1994,66( 832):47-55.
[42] Ginger. G Mayers . Initiators for High-solids Polyacrylates Resins: selection Guidelines andPerformance Review[J].Journal of Coatings Technology,1995,67(841):31-37.
[43] Liu Xin.Synthesis and Structure Control of St/AA/MMA Resin [D],Zhejiang University, 2003.
[44] Pan Zu-ren.Free Radical Polymerization[M],Beijing:Chemical Industry Press,1983.
[45]周震编著.印刷油墨[M].北京:化学工业出版社,2000.
[46] Sun Sun-jie,Zhan Jiang-hong,Zhao Chun-yan.Study and Preparation of Water-borne Resin-Free Colorants [J].Paing & Coating Industry,2011,41(1):32-37.
[47] Fu J M,Li Y.Optical Behavior of Organic Pigments in Aqueous Dispersions and Its Application [J]. J. Colloid Interface Sci.,1998,202:450-455.
[2]徐宗器.高黑度溶剂型黑漆的制备[ J].上海涂料,2008,46(11):24-28.
[3]李琳,许韶华,杨久霞,等.树脂对颜料分散体系的影响[J].现代显示, 2008,(1):71-74.
[4]徐宗器,谢林,马蔚.活性聚合物型颜料分散剂[J],涂料工业,2001,31(4):17-19.
[5]夏必来,林有尚.王永强,等.梳形聚合物分散剂在工业涂料体系中的应用基础研究[J].涂料工业.2008,38(3):17-20.
[6]周春隆,穆振义.有机颜料化学及工艺学[M].北京:中国石化出版社,2002:247.
[7] Hampton James..Organic pigment and printing ink[J]. American Ink Maker.1985(1):143.
[8]周春隆.超分散6剂及其在颜料中的应用周春隆[J],染料工业.1991,28(3):41.
[9]朱大有译.使水性丙烯酸聚合物可减少有机挥发物(VOC)[J].油墨,2000,(l):5-11.
[10]大森英三[日]著,张育川等译.功能性丙烯酸树脂[M].北京:化学工业出版社,1993:440-460.
[11]于瑞香.水性印刷上光油的剖析与研制[M].天津:天津工业大学,2004:12.
[12]张鹏,王兆华.丙烯酸树脂防腐蚀涂料及应用[M].北京:化学工业出版社,2003:92-106.
[13]汪长春.丙烯酸醋涂料[M].北京:化学工业出版社,2005:293-336.
[14]卢江.高分子化学[M].北京:化学工业出版社,2004:65-80,97-103.
[15] Schmidt,Ronald E.,Schultz. Bulk Polymerization Process for Preparing High Solids and Uniform Copolymers[P].US,4529787,1985.
[16] Hamielec, Archie E, Lawless, etal. Precess for Continuous Bulk Copolymerization of Vinyl Monomers[P] . US,4414370,1983.
[17]魏无际,俞强,崔益华,等.编著,高分子化学与物理基础[M].北京:化学工业出版社,2005:71.
[18]武利民.涂料技术基础[M].北京:化学工业出版社,2002:324-390.
[19]管荣,李建宗,艾照全,等.丙烯酸酯乳液共聚物胶粘剂的合成、性能及应用[J].中国胶粘剂,1994,3(2):43-45.
[20] Bardy ,John W.,Strickland,Franklin D.,Longwith; Chester C.,Aqueous Base-soluble Resin Compositions[P],US,P397952,1976.
[21] ROTH George ,SMITH George ,SINGHAL Shruti . solid acrylic resin using a continuous tube reactor[P],US,04593,1998.
[22]曹贵平,乐慧慧,张明华,等.‘饥饿’反应器中苯乙烯聚合动力学[J],高校化学工程学报,1995,9(l):52一57.
[23]王文俊,李伯耿,于在璋,等.半连续乳液聚合[J],高分子通报,1995,(l):44-49.
[24] Dikaoumakos,Qi Xu,Frank N. Jones,Jamil Baghdachi,etal.Synthisis of Acrylic Resin for High-Solids Coatings by Solution and Separation Polymerization[J].Journal of Coatings Technology,2000,72(908):61-70.
[25]金振华.新型水溶性丙烯酸树脂的应用与发展[J].中国印刷物资商情,2002,(7):20-22.
[26]温绍国,翁志学,黄志明,等.水溶性丙烯酸共聚物的研究进展[J].化工新型材料,1997(2),15-21.
[27] Echte,Adolf,Zizlsperger,etal.Manufacture of Uniform Polymers[P]. US,3954722,1976.
[28] Danjo Keiji,Tsurusaki Takeski,Ko Masaaki,etal.Aqueous colored resin fine particle dispersions for ink-jet inks,printing units,ink cartridges,and ink-jet printing[P].JP,327895,2003.
[29] Sharma Mahendrak,Wang,Richard Hsushien,etal.Waterborne acrylic Polymers containing Polymeric fluorescent compounds[P].US,6162869,2000.
[30] Sawada Michtaka ,Tsutsumi Takehiro, Azuma akishi,etal.Aqueous ink for ink-jet printing[P],US,6031019,2000.
[31] Hidaka Yuki,Tsutsumi Takehiro.Water-based ink[P],EP,1113051,2001.
[32] Nakano Yukihiro.Tsuru Isao, Azuma Kohji, etal..Water-based ink for ink-jet recording[P] ,EP,1059341, 2000.
[33]刘仁,熊万斌.阳离子型丙烯酸树脂的合成及其水溶性研究[J].涂料工业,2005,35(8):37-40.
[34]陈岚,陈义锋,朱传方等..酮醛改性水性丙烯酸酷树脂的合成及性能研究[J].粘接2004,25(2):16-18.
[35]阮丹柯,范宏.水性油墨用苯乙烯一丙烯酸固体树脂合成[J].科技通报,2006,22(l):115-118.
[36]林剑雄,王小妹,麦堪成等.水溶性丙烯酸树脂的合成及表征[J].塑料工业,2003,31(l):l-7.
[37]唐少炎,汤建新.水性油墨的发展及在包装印刷业的应用[J].油墨,2000,(3):10-12.
[38]张霞,朱金丽,房宽峻,等.聚羧酸型分散剂对水性超细颜料分散体系的作用[J].北京服装学院学报,2005,25(1):1-4.
[39] Cartridge D J,Hauxwell F,Pearce R A,A new dispersant for water-based pigments[J].Polym. Paint Coloure J,1994,184:10-12.
[40]刘斐,新型染料分散剂的合成及应用[D] ,上海:东华大学,2007.
[41] J.E. Jaffe,C.D. Campbell,S.B. Hendi,F. Bable, Influence of apparatus geometry and deposition conditions on the structure and topography of thick sputtered coatings[J].Journal of Coatings Teehnology. 1994,66( 832):47-55.
[42] Ginger. G Mayers . Initiators for High-solids Polyacrylates Resins: selection Guidelines andPerformance Review[J].Journal of Coatings Technology,1995,67(841):31-37.
[43] Liu Xin.Synthesis and Structure Control of St/AA/MMA Resin [D],Zhejiang University, 2003.
[44] Pan Zu-ren.Free Radical Polymerization[M],Beijing:Chemical Industry Press,1983.
[45]周震编著.印刷油墨[M].北京:化学工业出版社,2000.
[46] Sun Sun-jie,Zhan Jiang-hong,Zhao Chun-yan.Study and Preparation of Water-borne Resin-Free Colorants [J].Paing & Coating Industry,2011,41(1):32-37.
[47] Fu J M,Li Y.Optical Behavior of Organic Pigments in Aqueous Dispersions and Its Application [J]. J. Colloid Interface Sci.,1998,202:450-455.