氯化聚丙烯和醇酸树脂分级的研究
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摘要
聚合物是由一系列分子量不同的大分子组成的混合物,这使其具有结构组成的非均匀性。分级即是将聚合物样品根据其在溶液中的溶解度对分子量或结构组成的依赖性按照其分子量的大小分离成若干个级分的过程。通过分级制备的窄分子量或结构组成均匀分布的级分,与其它测试技术(GPC,~″C-NMR,DSC,X射线衍射等)联用后,能够得到精确的大分子结构信息。因此聚合物分级作为一种分析和制备技术,在聚合物结构和性能的研究与聚合反应工程等领域有重要的应用。
本文以分级为主要技术,分别选取了转化型涂料和非转化型涂料的两个代表加以研究。
以氯化聚丙烯作为非转化型物质的例子,主要考察了不同氯化度对Mark-Houwink方程式的影响。30%氯化度的氯化聚丙烯用作油墨附着力促进剂已经被较为详细地研究过。本文的重点在于考察用作涂料助剂的氯化度在26%左右氯化聚丙烯的Mark-Houwink方程式以及它与30%氯化度氯化聚丙烯Mark-Houwink的关系,范给出的30%氯化度氯化聚丙烯的Mark-Houwink方程式[η]=0.0174M~(0.6919),事实上可以适用于从26%到35%氯含量的范围的分子量估算。以醇酸树脂为转化型涂料的代表,主要考察了分级产品的酸值、特性粘数和溶度参数以及级分制成的涂膜性质的变化规律。按照文献发表的情况,对长油醇酸树脂分级研究的比较多,而对短油醇酸树脂分级的研究很少看到报道。本文即对国产商品的长油、中油和短油都进行研究,并加以比较;在经典文献中,由于知道具体配方,可以得到Mark-Houwink方程式。然而对于商品而言,并不能知其具体配方,本文中找到了一种代用的方法:即用酸值代替数均分子量来拟合Mark-Houwink方程式,并通过酸值和溶度参数成正比关系来验证酸值这一参数的可靠性,由此得出酸值对于醇酸树脂是一个重要的参数,且较其他参数容易测定,是一种方便的方法。
凝胶色谱仪测定聚合物的分子量及其分布虽然有着其他分级方法有很大的优势,但它得到的级分量少,不能对每个级分进行其它性能方面的研究。本文利用传统的沉淀分级法得到的级分制备了一系列的涂膜,研究它的干燥时间等各种相关指标,证明了对醇酸树脂来说,样品的干燥时间基本上是由分子量较小的组分决定的。因此,醇酸树脂虽属转化型树脂,但和其他树脂一样,分子量分布仍是一个重要的指标。
Polymer is made up of a series of macromolecules,which of molecular weight are different.It leads to the structural heterogeneity of polymer.Namely,fractionation for polymer is that separating it into some fractions according to the molecular weight, and its theory is that the solubility of polymer in Sol.depends on its molecular weight. The molecular weight distributions of fractions become more narrow or homogeneous than before by fractionating,and gain the precise structural information of macromolecules by virtue of other testing techniques,for example,GPC,"C-NMR, DSC and X-ray,and so on.Therefore,as an analytic and preparation technique, polymer fractionation is importance in the study on polymer structure.
In this article,we chose two representatives from convertible coatings and non-convertible coatings in virtue of fractionation as a primary technique.
Viewing chlorinated polypropylene(CPP) as the pattern of non-convertible coatings,mostly studies on the influence of difference of chlorinity on Mark-Houwink equation.It was detailedly studied that 30%chlorinity of CPP was an accelerating agent to printing ink on adhesive power.The emphases of this article is that the Mark-Houwink equation of 26%chlorinity of CPP,and the relation between 26% chlorinity of CPP and 30%chlorinity of CPP on Mark-Houwink equation.Fan's Mark-Houwink equation of 30%chlorinity of CPP is[η]=0.0174M_w~(0.6919).In fact,it is applicable to molecular weight estimation of 26%-35%chlorinity of CPP.
Viewing alkyd resin as the pattern of convertible coatings,mostly studies on the fractions of acid value,inherent viscosity and solubility parameter,and the law of performances on films coating made from fractions.In terms of literature survey,the study on fractionations of long oil alkyd resin is much more than others,but medium and short oil alkyd resins are few.This article aims at three types of domestic product, and compares them.In classic literatures,we can get Mark-Houwink equation because of the knowledge of specific formulation,but to the alkyd resin product,it is lack. This article finds a method to substitute for the former.Namely,Mark-Houwink equation can be fitted by virtue of acid value,instead of number-average molecular weight,and proves the reliability of acid value by direct ratio between solubility parameter and acid value.Therefore,acid value is an important parameter to alkyd resin,and compared with other parameters,it is easy to gain.
Compared with other fractionations,gel permeation chromatography is excellent. But it is difficult to study on other performance because the weight of fractions is lesser.In this article,we use fractional precipitation to get fractions,prepare a series of films coating,and study their drying time,and so on.To alkyd resin,it is proved that drying time is due to the small molecular fractions.Therefore,alkyd resin belongs to convertible coatings,but compared to other resins,molecular weight distribution is still an importance parameter.
本文以分级为主要技术,分别选取了转化型涂料和非转化型涂料的两个代表加以研究。
以氯化聚丙烯作为非转化型物质的例子,主要考察了不同氯化度对Mark-Houwink方程式的影响。30%氯化度的氯化聚丙烯用作油墨附着力促进剂已经被较为详细地研究过。本文的重点在于考察用作涂料助剂的氯化度在26%左右氯化聚丙烯的Mark-Houwink方程式以及它与30%氯化度氯化聚丙烯Mark-Houwink的关系,范给出的30%氯化度氯化聚丙烯的Mark-Houwink方程式[η]=0.0174M~(0.6919),事实上可以适用于从26%到35%氯含量的范围的分子量估算。以醇酸树脂为转化型涂料的代表,主要考察了分级产品的酸值、特性粘数和溶度参数以及级分制成的涂膜性质的变化规律。按照文献发表的情况,对长油醇酸树脂分级研究的比较多,而对短油醇酸树脂分级的研究很少看到报道。本文即对国产商品的长油、中油和短油都进行研究,并加以比较;在经典文献中,由于知道具体配方,可以得到Mark-Houwink方程式。然而对于商品而言,并不能知其具体配方,本文中找到了一种代用的方法:即用酸值代替数均分子量来拟合Mark-Houwink方程式,并通过酸值和溶度参数成正比关系来验证酸值这一参数的可靠性,由此得出酸值对于醇酸树脂是一个重要的参数,且较其他参数容易测定,是一种方便的方法。
凝胶色谱仪测定聚合物的分子量及其分布虽然有着其他分级方法有很大的优势,但它得到的级分量少,不能对每个级分进行其它性能方面的研究。本文利用传统的沉淀分级法得到的级分制备了一系列的涂膜,研究它的干燥时间等各种相关指标,证明了对醇酸树脂来说,样品的干燥时间基本上是由分子量较小的组分决定的。因此,醇酸树脂虽属转化型树脂,但和其他树脂一样,分子量分布仍是一个重要的指标。
Polymer is made up of a series of macromolecules,which of molecular weight are different.It leads to the structural heterogeneity of polymer.Namely,fractionation for polymer is that separating it into some fractions according to the molecular weight, and its theory is that the solubility of polymer in Sol.depends on its molecular weight. The molecular weight distributions of fractions become more narrow or homogeneous than before by fractionating,and gain the precise structural information of macromolecules by virtue of other testing techniques,for example,GPC,"C-NMR, DSC and X-ray,and so on.Therefore,as an analytic and preparation technique, polymer fractionation is importance in the study on polymer structure.
In this article,we chose two representatives from convertible coatings and non-convertible coatings in virtue of fractionation as a primary technique.
Viewing chlorinated polypropylene(CPP) as the pattern of non-convertible coatings,mostly studies on the influence of difference of chlorinity on Mark-Houwink equation.It was detailedly studied that 30%chlorinity of CPP was an accelerating agent to printing ink on adhesive power.The emphases of this article is that the Mark-Houwink equation of 26%chlorinity of CPP,and the relation between 26% chlorinity of CPP and 30%chlorinity of CPP on Mark-Houwink equation.Fan's Mark-Houwink equation of 30%chlorinity of CPP is[η]=0.0174M_w~(0.6919).In fact,it is applicable to molecular weight estimation of 26%-35%chlorinity of CPP.
Viewing alkyd resin as the pattern of convertible coatings,mostly studies on the fractions of acid value,inherent viscosity and solubility parameter,and the law of performances on films coating made from fractions.In terms of literature survey,the study on fractionations of long oil alkyd resin is much more than others,but medium and short oil alkyd resins are few.This article aims at three types of domestic product, and compares them.In classic literatures,we can get Mark-Houwink equation because of the knowledge of specific formulation,but to the alkyd resin product,it is lack. This article finds a method to substitute for the former.Namely,Mark-Houwink equation can be fitted by virtue of acid value,instead of number-average molecular weight,and proves the reliability of acid value by direct ratio between solubility parameter and acid value.Therefore,acid value is an important parameter to alkyd resin,and compared with other parameters,it is easy to gain.
Compared with other fractionations,gel permeation chromatography is excellent. But it is difficult to study on other performance because the weight of fractions is lesser.In this article,we use fractional precipitation to get fractions,prepare a series of films coating,and study their drying time,and so on.To alkyd resin,it is proved that drying time is due to the small molecular fractions.Therefore,alkyd resin belongs to convertible coatings,but compared to other resins,molecular weight distribution is still an importance parameter.
引文
[1]郑昌仁,高聚物分子量及其分布[M],化学工业出版社,1986
[2]赵亚光,李丽,醇酸涂料生产实用技术问答[M],化学工业出版社,2003
[3]陈士杰等,涂料工艺[M],1997
[4]潘祖仁,高分子化学[M],1986
[5]葛发祥,氯化等规聚丙烯[J],安徽化工1993,(2):5-12
[6]Siye Tang,Dazhuang Liu.Determination of three-dimension solubility parameters of chlorinated polypropylene by ultrasonic degradation[J].Physics Chemistry of Liquids.2006,44(5):490-498.
[7]Robert J.Clemens,Progr.Org.Coat[J],1994,24(1-4):43-54
[8]李军.氯化聚丙烯及其应用前景[J].现代化工.1996,(6):20-23
[9]邓舜杨.塑料用涂料[M].上海:上海科学技术文献出版社,1984
[10]S.L.Kangas and F.N.Jones,J.coat.Technol[M],1987,59(744),99
[11]J.Kumanotani,H.hironori,and H.masuda,Adv,org.coat.Sci[J],Tech.ser,1984
[12]贺英,涂料树脂化学[M],化学工业出版社,2007
[13]耿耀宗,涂料树脂化学[M],中国轻工业出版社,1993
[15]叶家波,胡乔生,涂料用醇酸树脂的改性研究[J],江西化工,2006.1
[14]向斌,杨永峰,高固体份涂料的应用及发展趋势[J],现代涂料与涂装,2007.10
[16]Erich,S.J.F.;Laven,J.;Pel,L.;Huinink,H.P.;Kopinga,K.Influence of catalyst type on the curing process and netuork structure of alkyd coatings.Polymer[J](2006),47(4),1141-1149.
[17]Klaasen,R.P.;van der Leeuw,R.P.C.Fast drying cobalt-free high solids alkyd paints.Progress in Organic Coatings[J](2006),55(2),149-153.
[18]van Gorkum,Remy;Bouwman,Elisabeth.The oxidative drying of alkyd paint catalysted by metal complexes.Coordination Chemistry Reviews[C](2005),249(17-18),1709-1728.
[19]Micciche,Fabrizio;Oostveen,Eef;van Haveren,Jacco;van der Linde,Robert.The combination of reducing agents/iron as environ friendlier alternatives for Co-based driers in the drying of alkyd paints. Progress in Organic Coatings[J] (2005), 53(2), 99-105
[20] van Haveren, Jacco; Oostveen, Eef A.; Micciche, Fabrizio; Weijnen, John G. J. Towards sustainability alkyd resins and alkyd drying agents based on renewable resources. European Coatings Journal [J] (2005), (1-2), 16-19.
[21] Steinert, Andreas. Siccatives effective drying without cobalt. New highly reactive manganese-based driers for high-solid alkyd paints .European Coatings Journal[J] (2005), (3), 84-86, 88.
[22] Pilemand, C.; Wallstroem, E.; Poulsen, P. Brunn. Pitture e Vernici, Substitution of Co driers and methyl ethyl ketoxine in oxidative drying systems. European Coatings[J],(2005), 81(2), 7-20.
[23] Pilemand, Charlotte; Wallstrom, Eva; Poulsen, Pia Brunn. Substitution of cobalt driers and methyl ethyl ketoxine in oxidative drying systems. FATIPEC Congress[C] (2004), 27th(Vol. 2), 649-666.
[24] van Haveren, J.; Oostveen, E. A.; Micciche, F.; Weijnen, J. G. J. How biobased products contribute to establishment of sustainable, pathalate free, plasticizers and coatings. ACS Symposium Series [J] (2006), 921 (Feedstocks for the Future), 99-115.
[25] Erich, S. J. F.; Van der Ven, L. G. J.; Huinink, H. P.; Pel, L.; Kopinga, K. Curing processes in solvent-borne alkyd coatings with different combinations. Journal of Physical Chemistry B[J] (2006), 110(15), 8166-8170.
[26] Stava, Vit; Vesely, David; Kalenda, Petr; Erben, Milan. Study of properties of metallocence complexs as driers for air drying coatings.[P]Czech Republic, CODEN: 69ILOM AN 2006:976352,May 22-24, 2006 (2006),
[27] Van Haveren, J.; Oostveen, E. A.; van der Walle, R.; Micciche, F.; Weijnen, J. G. J. How biobased products can contribute to establishment of sustainable coatings. FATIPEC Congress[C] (2004), 27th(Vol. 3), 907-920.
[28]Taylor,Philip Louis.Autoxidizable architectural coating compositions.[P]U.K,CODEN:PIXXD2 WO 2007017032 A1 20070215
[29]Oyman,Z.Okan;Ming,W.;Van der Linde,R.Drying of alkyd emulsions in the presence of a cobalt-free drier.FATIPEC Congress[C](2004),27th 2
[30]Van Gorkum,Remy;Bouwman,Elisabeth;Reedijk,Driers for alkyd-based coatings[P].Jan.Eur.Pat.Appl.(2004),14 pp.
[31]何平笙,高分子物理实验[M],中国科学技术出版社,2002
[32]虞志光,高聚物分子量及其分布的测定[M],上海科学技术出版社,1984
[33]谢小莉,曾舫,童真,聚(N—异丙基丙烯酞胺)的分级和表征[J],华南理工大学学报(自然科学版)1998,26(3)
[34]L.Wild,Branehingdistributionsinlinearlow-densitypolyethylenes[J],Polym PrePr 1982,23(2)
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[51]GB/T1727-92
[52]GB/T1728-79(89)
[53]GB/T6739-86
[54]GB/T1732-93
[55]GB/T9286-88
[2]赵亚光,李丽,醇酸涂料生产实用技术问答[M],化学工业出版社,2003
[3]陈士杰等,涂料工艺[M],1997
[4]潘祖仁,高分子化学[M],1986
[5]葛发祥,氯化等规聚丙烯[J],安徽化工1993,(2):5-12
[6]Siye Tang,Dazhuang Liu.Determination of three-dimension solubility parameters of chlorinated polypropylene by ultrasonic degradation[J].Physics Chemistry of Liquids.2006,44(5):490-498.
[7]Robert J.Clemens,Progr.Org.Coat[J],1994,24(1-4):43-54
[8]李军.氯化聚丙烯及其应用前景[J].现代化工.1996,(6):20-23
[9]邓舜杨.塑料用涂料[M].上海:上海科学技术文献出版社,1984
[10]S.L.Kangas and F.N.Jones,J.coat.Technol[M],1987,59(744),99
[11]J.Kumanotani,H.hironori,and H.masuda,Adv,org.coat.Sci[J],Tech.ser,1984
[12]贺英,涂料树脂化学[M],化学工业出版社,2007
[13]耿耀宗,涂料树脂化学[M],中国轻工业出版社,1993
[15]叶家波,胡乔生,涂料用醇酸树脂的改性研究[J],江西化工,2006.1
[14]向斌,杨永峰,高固体份涂料的应用及发展趋势[J],现代涂料与涂装,2007.10
[16]Erich,S.J.F.;Laven,J.;Pel,L.;Huinink,H.P.;Kopinga,K.Influence of catalyst type on the curing process and netuork structure of alkyd coatings.Polymer[J](2006),47(4),1141-1149.
[17]Klaasen,R.P.;van der Leeuw,R.P.C.Fast drying cobalt-free high solids alkyd paints.Progress in Organic Coatings[J](2006),55(2),149-153.
[18]van Gorkum,Remy;Bouwman,Elisabeth.The oxidative drying of alkyd paint catalysted by metal complexes.Coordination Chemistry Reviews[C](2005),249(17-18),1709-1728.
[19]Micciche,Fabrizio;Oostveen,Eef;van Haveren,Jacco;van der Linde,Robert.The combination of reducing agents/iron as environ friendlier alternatives for Co-based driers in the drying of alkyd paints. Progress in Organic Coatings[J] (2005), 53(2), 99-105
[20] van Haveren, Jacco; Oostveen, Eef A.; Micciche, Fabrizio; Weijnen, John G. J. Towards sustainability alkyd resins and alkyd drying agents based on renewable resources. European Coatings Journal [J] (2005), (1-2), 16-19.
[21] Steinert, Andreas. Siccatives effective drying without cobalt. New highly reactive manganese-based driers for high-solid alkyd paints .European Coatings Journal[J] (2005), (3), 84-86, 88.
[22] Pilemand, C.; Wallstroem, E.; Poulsen, P. Brunn. Pitture e Vernici, Substitution of Co driers and methyl ethyl ketoxine in oxidative drying systems. European Coatings[J],(2005), 81(2), 7-20.
[23] Pilemand, Charlotte; Wallstrom, Eva; Poulsen, Pia Brunn. Substitution of cobalt driers and methyl ethyl ketoxine in oxidative drying systems. FATIPEC Congress[C] (2004), 27th(Vol. 2), 649-666.
[24] van Haveren, J.; Oostveen, E. A.; Micciche, F.; Weijnen, J. G. J. How biobased products contribute to establishment of sustainable, pathalate free, plasticizers and coatings. ACS Symposium Series [J] (2006), 921 (Feedstocks for the Future), 99-115.
[25] Erich, S. J. F.; Van der Ven, L. G. J.; Huinink, H. P.; Pel, L.; Kopinga, K. Curing processes in solvent-borne alkyd coatings with different combinations. Journal of Physical Chemistry B[J] (2006), 110(15), 8166-8170.
[26] Stava, Vit; Vesely, David; Kalenda, Petr; Erben, Milan. Study of properties of metallocence complexs as driers for air drying coatings.[P]Czech Republic, CODEN: 69ILOM AN 2006:976352,May 22-24, 2006 (2006),
[27] Van Haveren, J.; Oostveen, E. A.; van der Walle, R.; Micciche, F.; Weijnen, J. G. J. How biobased products can contribute to establishment of sustainable coatings. FATIPEC Congress[C] (2004), 27th(Vol. 3), 907-920.
[28]Taylor,Philip Louis.Autoxidizable architectural coating compositions.[P]U.K,CODEN:PIXXD2 WO 2007017032 A1 20070215
[29]Oyman,Z.Okan;Ming,W.;Van der Linde,R.Drying of alkyd emulsions in the presence of a cobalt-free drier.FATIPEC Congress[C](2004),27th 2
[30]Van Gorkum,Remy;Bouwman,Elisabeth;Reedijk,Driers for alkyd-based coatings[P].Jan.Eur.Pat.Appl.(2004),14 pp.
[31]何平笙,高分子物理实验[M],中国科学技术出版社,2002
[32]虞志光,高聚物分子量及其分布的测定[M],上海科学技术出版社,1984
[33]谢小莉,曾舫,童真,聚(N—异丙基丙烯酞胺)的分级和表征[J],华南理工大学学报(自然科学版)1998,26(3)
[34]L.Wild,Branehingdistributionsinlinearlow-densitypolyethylenes[J],Polym PrePr 1982,23(2)
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[51]GB/T1727-92
[52]GB/T1728-79(89)
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[54]GB/T1732-93
[55]GB/T9286-88