聚乙烯醇缩丁醛的合成与应用研究
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摘要
聚乙烯醇缩丁醛(PVB)是制备夹层安全玻璃的必备材料,随着汽车和建筑行业的发展,夹层安全玻璃的用量越来越大,有广阔的市场前途。PVB在合成的过程中容易结块,影响后处理工序。为解决这一问题,目前各个生产厂家都是在合成的过程中加入各种乳化剂,达到分散的目的,但这又增加了去除乳化剂的工序,增加生产难度和成本。本实验通过研究发现,丁醛在反应体系中的分散不均匀是造成结块的主要原因。通过改变工艺条件,在40-60℃的条件下,将正丁醛加入PVA溶液中,可保证正丁醛分散均匀,降至适当温度后,再滴加盐酸,这样在不加任何乳化剂的条件下也得到了粉末状的PVB产品。研究发现,影响PVB质量因素的还有升温速率、搅拌快慢、后处理温度、水洗等。中试放大实验所得的PVB的缩醛度为77.7%,并制得薄膜及夹层安全玻璃,进行了性能测试。
选用四种增塑剂与自制PVB树脂混合,制得薄膜,利用相容性、拉伸强度、断裂伸长率、玻璃化转变温度、熔体流动速率等数据探讨了不同种类及不同用量的增塑剂对PVB薄膜性能的影响。实验结果表明,极性高的增塑剂与PVB树脂的相容性好,四种增塑剂与PVB的相容性大小依次为:DEHP＞DOP＞DBP＞DOS。在相容范围内,随着增塑剂含量的增加,PVB薄膜的拉伸强度降低,断裂伸长率增加,玻璃化转变温度降低,熔体流动速率增加。而且DEHP对PVB的增塑效果最好,当DEHP的含量为20份时,PVB薄膜的拉伸强度达到30MPa,断裂伸长率达到375%,完全达到国产PVB膜片的物理性能指标。
将自制的PVB增塑后,与玻璃合片,制得夹层安全玻璃,经测试,其雾度≤0.41%,达到夹层玻璃的使用标准。敲击实验结果显示,其敲击值为9～10,落球冲击剥离实验后,夹层玻璃只有裂纹,不断裂,与上海海顿塑胶有限公司生产的PVB相比,自制的PVB与玻璃的粘合力合格,达到安全玻璃的使用要求。
Polyvinyl butyral(PVB) is the essential material for laminated safty glass. With the development of autocar and architecture,PVB is used more and more. But it is easy to agglomerate while PVB being synthesized and it makes it hard for the post-treatment. To solve this problem, almost all the manufacturers use emulsifier to disperse PVB. But this will get another problem that the emulsifier must be removed, wasting plenty of water. Through research, we find that the non-uniform dispersion of butyraldehyde in PVA solution is the main reason of PVB agglomeration. Adding butyraldehyde to the PVA solution at the temperature of 40-60℃can ensure the uniform dispersion of butaraldehyde in PVA solution. HCl is dropped in when the temperature decrease to 15℃.Subsequently, powdered PVB can be got by controlling the rate of heating, the rate of stirring, the temperature of post-treatment and so on. The degree of acetalization of PVB synthesized using 10 times amplified equipment is 77.7%,and we prodece PVB films and laminated safty glasses using this PVB.
PVB films are prepared by choosing four kinds of plasticizers to mix with self-made PVB resin respectively. The effects of the kind and amount of plasticizers on the PVB films are studied by the data of compatibility, tensile strength, breaking elongation, Tg and melt flow rate. The results indicate that polar plasticizers are more compatible with PVB resin. The compatibility of the four plasticizers with PVB resin are: DEHP>DOP>DBP>DOS. Within the compatibility, with the amount of plasticizer increasing, PVB films' tensile strength and Tg decrease, breaking elongation and melt flow rate increase. The plasticization of DEHP on PVB is best, when DEHP:PVB=1:5,PVB film's tensile strength increases to 30MPa,breaking elongation increases to 375.%.
The haze of the laminated safety glass prepared by self-made PVB film≤0.41%,reaching the standard of industrial use. The results of the pummel and dropping ball impact strip experiments show that, comparing with the PVB manufactured by the SHANGHAI HAIDUN PLASTIC CO.LTD. ,the adhesion of safe-made PVB with glass is eligible.
选用四种增塑剂与自制PVB树脂混合,制得薄膜,利用相容性、拉伸强度、断裂伸长率、玻璃化转变温度、熔体流动速率等数据探讨了不同种类及不同用量的增塑剂对PVB薄膜性能的影响。实验结果表明,极性高的增塑剂与PVB树脂的相容性好,四种增塑剂与PVB的相容性大小依次为:DEHP＞DOP＞DBP＞DOS。在相容范围内,随着增塑剂含量的增加,PVB薄膜的拉伸强度降低,断裂伸长率增加,玻璃化转变温度降低,熔体流动速率增加。而且DEHP对PVB的增塑效果最好,当DEHP的含量为20份时,PVB薄膜的拉伸强度达到30MPa,断裂伸长率达到375%,完全达到国产PVB膜片的物理性能指标。
将自制的PVB增塑后,与玻璃合片,制得夹层安全玻璃,经测试,其雾度≤0.41%,达到夹层玻璃的使用标准。敲击实验结果显示,其敲击值为9～10,落球冲击剥离实验后,夹层玻璃只有裂纹,不断裂,与上海海顿塑胶有限公司生产的PVB相比,自制的PVB与玻璃的粘合力合格,达到安全玻璃的使用要求。
Polyvinyl butyral(PVB) is the essential material for laminated safty glass. With the development of autocar and architecture,PVB is used more and more. But it is easy to agglomerate while PVB being synthesized and it makes it hard for the post-treatment. To solve this problem, almost all the manufacturers use emulsifier to disperse PVB. But this will get another problem that the emulsifier must be removed, wasting plenty of water. Through research, we find that the non-uniform dispersion of butyraldehyde in PVA solution is the main reason of PVB agglomeration. Adding butyraldehyde to the PVA solution at the temperature of 40-60℃can ensure the uniform dispersion of butaraldehyde in PVA solution. HCl is dropped in when the temperature decrease to 15℃.Subsequently, powdered PVB can be got by controlling the rate of heating, the rate of stirring, the temperature of post-treatment and so on. The degree of acetalization of PVB synthesized using 10 times amplified equipment is 77.7%,and we prodece PVB films and laminated safty glasses using this PVB.
PVB films are prepared by choosing four kinds of plasticizers to mix with self-made PVB resin respectively. The effects of the kind and amount of plasticizers on the PVB films are studied by the data of compatibility, tensile strength, breaking elongation, Tg and melt flow rate. The results indicate that polar plasticizers are more compatible with PVB resin. The compatibility of the four plasticizers with PVB resin are: DEHP>DOP>DBP>DOS. Within the compatibility, with the amount of plasticizer increasing, PVB films' tensile strength and Tg decrease, breaking elongation and melt flow rate increase. The plasticization of DEHP on PVB is best, when DEHP:PVB=1:5,PVB film's tensile strength increases to 30MPa,breaking elongation increases to 375.%.
The haze of the laminated safety glass prepared by self-made PVB film≤0.41%,reaching the standard of industrial use. The results of the pummel and dropping ball impact strip experiments show that, comparing with the PVB manufactured by the SHANGHAI HAIDUN PLASTIC CO.LTD. ,the adhesion of safe-made PVB with glass is eligible.
引文
[1]高晓明,张念泰.PVB膜片:制造工艺、产品性能与应用前景.塑料加工,2001,30(1):42-43
[2]李国东,张毅.聚乙烯醇缩丁醛树脂的研究与应用.中国胶粘剂.2006,15(6):27-35
[3]罗贵英.聚乙烯醇缩丁醛树脂的生产与应用.贵州化工,2002,27(6):27-29
[4]王学勤,PVB膜片的加工与应用.塑料工程,1993,(4):34-36
[5]徐美君.简介夹层玻璃的配套材料-PVB胶片.中国建材装备,1995(2):34-36
[6]马时渝.Butvar-孟山都生产的PVB树脂.维纶通讯,1998,(2):54-57
[7]M.D.Fernandez,M.J.Fenamdez,P.Hoces.Synthesis of Poly(vinyl butyral)s in Homogeneous Phase and Their Thermal Properties.Journal of Applied Polymer Science,2006,102:5007-5017
[8]李忠森,罗顺贻.聚乙烯醇缩丁醛发展现状.维普资讯.1992,(1):1-15
[9]冯海刚,李粼.聚乙烯醇缩丁醛(PVB)膜片的历史与发前景.国外塑料,2005,23(10):42-48
[10]杨宝武.聚乙烯醇缩丁醛.化工百科全书,第九卷,北京:化学工业出版社,1995:99
[11]陈霞真.夹层玻璃PVB中间膜的国产化.上海建材,1994,(4):23-24
[12]陈美兰.用聚乙烯醇缩丁醛代替玻璃制备的艺术玻璃及其制作方法.CN 1844004A,2006-10-11
[13]张谢源.PVB废水处理新工艺的研究.天津化工,1992,(1):51-55
[14]汤显玉.安全玻璃和中间膜.精细化工,1988,(3):49-56
[15]石万聪,石志博,蒋平平.增塑剂及其应用.北京:化学工业出版社,2002:127-130
[16]张月明.PVB的新型增塑剂-DNHA.增塑剂,2000,(4):18-20
[17]J.J.德埃里科,M.S.克拉奇.紫外线稳定的聚乙烯醇缩丁醛片材.CN 1219184A,1999-6-9
[18]A.P.Marin,L.A.Tatarenko,YU.A.Shlyapnikov.Solubility of antioxidants in polyvinyl butyral.Polymer Degradation and Stability,1998,62:507-511
[19]M·霍斯,B·科尔.由部分缩醛化的聚乙烯醇制成的含增塑剂的薄膜.CN 1284911,2001-2-21
[20]孙宏坚.高速成长中的塑料新材料PVB树脂的性能及应用.塑料制造,2007,11,91-97
[21]苑会林,马沛岚等.聚乙烯醇缩丁醛树脂的性能及应用.工程塑料应用,2004,32(2):43-46
[22]熊劲松.论夹层安全玻璃的特性.广东建材,2001,(1):12-13
[23]吴桂香.夹层玻璃的性能.中国建材,2000,12,81-82
[24]汪秀娟.性能优异的建筑夹层玻璃.广东建材,2000,(06):37-39
[25]冯海刚.使用PVB膜片作为安全玻璃夹层的常见问题与改进方法.塑料工业,2005,33(11):56-58
[26]王崇禾.夹层安全玻璃合片工艺的研究.中国玻璃,2001,(4):26-28
[27]赵劲松.低温低压制造安全玻璃.工程塑料应用,1999,27(11):18-19
[28]Donald B.Baldridge,Wilbraham,Mass.Process of making a polyvinyl butyral composite interlayer for laminated safety glass.US 3982984,1976-9-28
[29]刘志海.夹层玻璃的发展现状及趋势.中国建材,2003,(9):64-69
[30]王永恒.国外安全夹层玻璃的品种及性能的测定.玻璃,1987,(5):27-31
[31]孟继本、陆桂芬等.光致变色纳米复合材料制备及其PVB胶片制备方法.CN 1640929A,2005-7-20
[32]孟继本,陆桂芬等.光致变色纳米复合材料制备聚乙烯醇缩丁醛胶片及其方法.CN 1298783C,2007-2-7
[33]尚贵才,王鸿飞.热反射夹层玻璃.CN 2820861Y,2006-09-27
[34]Degrilh,Robert.Process for the production of polyvinyl butyral having improved proverties.US5349014,1994-09-20
[35]R·狄盖尔.改性聚乙烯醇缩丁醛的制备方法.CN 96107793.X,2002-5-55
[36]李国东、张毅等.一种乳化剂及使用该乳化剂的PVB生产工艺.CN 1769312A,2005-10-28
[37]George E.Cartier,Springfield.Cross-linked polyvinyl butyral.US4874814,1989-10-17
[38]B·帕彭富斯,M·施托伊尔.高分子、交联聚乙烯醇缩丁醛、其生产方法及用途.CN1551890A,2004-12-1
[39]B·帕潘弗斯.高分子量交联聚乙烯醇缩丁醛,它们的生产方法和用途.CN1464884A,2003-12-31
[40]Bernd Papenfuhs,Obertshausen.High-molecular,cross-linked polyvinyl butyrals,method for the production thereof and their use.US 6835784B2,2004-12-28
[41]Misra,Ashok,David,et al.Method of producing ionomeric polyvinyl butyral.US 4968745,1990-11-06
[42]Schafheutle,Markus A,Merten,et al.Aqueous emulsions comprising polyvinyl butyral.US 5525669,1996-06-11
[43]聂文卫.含PET膜的低辐射夹层玻璃.CN 1307969A,2001-8-15
[44]T.R.菲利普斯,具有改良防雾性能的着色聚乙烯醇缩丁醛中间层.CN 1352597A,2002-6-5
[45]庄大明,张弓.一种具有红外反射性能的汽车风挡玻璃及其制备方法.CN 1555989A,2004-01-02
[46]P·袁,J·德里科.具有抗粘连性的聚乙烯醇缩丁醛片材.CN 1777638A,2006-5-24
[47]W·陈.包含双官能表面改性剂的聚乙烯醇缩丁醛片材.CN 1802404A,2006-7-12
[48]W·-C·李,I·-C·W·王.具有增强的表面性能的聚乙烯醇缩丁醛组合物和共混物以及由其制备的制品.CN 1813027A,2006-8-2
[49]R·L·史密斯,D·L·赖默等.具有改善的对玻璃粘合性的聚乙烯醇缩丁醛夹层板及其制备方法.CN 1671787A,2005-9-21
[50]李忠林、罗顺贻,聚乙烯醇缩丁醛发展现状,维普资讯,1992(1):1-15
[51]A.K.Dhalival,J.N.Hay,The characterization of polyvinyl butyral by thermal analysis,Thermochimica Acta,2002,391:245-255
[52]Nabil M.Safy El-Din、Magdy W.Sabaa,Thermal degradation of poly(vinyl butyral)laminated safety glass,Polymer Degradation and Stability,1995,47:283-288
[53]王党生,李涛.微粒状聚乙烯醇缩丁醛制备新工艺.福建化工,1997,(2):5-6
[54]Reejhsinghani.Forming polyvinyl butyral.US5238994,1993-08-23
[55]王玉荣,张春庆.高分子化学与物理实验.大连:大连理工大学出版社,1998
[56]栗方星.缩醛度的准确测定方法.化学工业与工程,1993,11(3):59-60
[57]李锋.聚乙烯醇缩丁醛合成工艺探讨.热固性树脂,2005,20(5):48-50
[58]Sidney C.Overbaugh etc.Preparation of polyvinyl acetal resins.US 2345946A,1944-4-4
[59]卢宝生.二相法制备聚乙烯醇缩丁醛最佳条件的探讨,中国胶粘剂,1993,3(2):25-27
[60]Hans D.Hermnmm,Bad Soden am Taunus et al.Process for the preparation of polyvinyl butyral having improved propertyes.US 4205146,1980-5-27
[61]白国强,李仲谨.PVB树脂有合成与应用.包装工程,2004,(4):19-20
[62]增子芳弘,河西俊明.聚乙烯醇缩醛树脂及其制造方法.CN 1630670A,2005-6-22
[63]刘立萍,周生贵,肖卓炳.对影响聚乙烯醇缩丁醛产品质量稳定性因素的探讨.精细化工中间体,2003,33(5):49-50
[64]曹慧林,苑会林.高粘度聚乙烯醇缩丁醛树脂及薄膜的制备,化工新型材料,2006,34(4):51-56
[65]D·L·赖默,N·K·里德三世.通过控制聚乙烯醇缩丁醛的立体化学来控制其物理性能的工艺.CN 1675258A,2005-9-28
[66]刘智斌.聚乙烯醇缩丁醛生产装置的技术改造.维纶通讯,1997,17(3):14-17
[67]刘立萍.间接法测定6%PVB甲醇溶液和5%PVB正丁醇溶液的旋转粘度.精细化工中间体,2004.35(3):57-58
[68]孙宏坚,张岩飞等.聚乙烯醇缩丁醛树脂分子量和热性能的测定.河南化工,2003,(8):11-18
[69]H·H·霍菲,A·卡拉吉安尼斯.表面粗糙的聚乙烯醇缩丁醛及其形成方法.CN 1102840A,1995-5-24
[70]George E.Cartier,Springfield et al.Polyvinyl butyral sheet roughness.US 4654179,1987-3-31
[71]孙宏坚,张岩飞等.PVB树脂溶解性质的研究.河南化工,1996,(9):9-11
[72]刘立萍.聚乙烯醇缩丁醛冻胶化温度的测定方法.化学世界,2003,(12):636-638
[73]U·凯勒,H·施藤策尔.含增塑剂的PVB薄膜.US 1518494A,2004-8-4
[74]J·J·德埃里科,B·A·杰姆莫特.增塑聚乙烯醇缩丁醛及片材.CN 1209092A,1999-2-24
[75]Robert H.Fariss,Northampton.Plasticized polyvinyl butyral and interlayer thereof.US 5013780,1991-5-7
[76]James A.Snelgrove,Monson et al.Plasticizer blends for polyvinyl butyral interlayers.US 4144217,1979-5-13
[77]Thomas R.Philips,Belpre,Ohio.Polyvinyl butyral plasticized with tetraethyleneglycol di-2-ethylhexanoate.US 4276351,1981-7-30
[78]Arijit M.Dasgupta,Belchertown et al.Polyvinyl butyral sheet.US 5137954,1992-8-11
[79]Shigeru Numura,tami et al.Interlayer film for laminated glass.US 4452935,1984-6-5
[80]George A.kennar,East Longmeadow,Mass.Interlayer for laminated safety glass.US 4035549A,1977-7-12
[81]Robert H.Fariss,Northampton,Roland J.Tetreault.Plasticezed polyvinyl butyral and interlayer thereof.US 5013779,1991-5-7
[82]冯海刚.安全玻璃夹层用PVB膜片生产工艺配方设计[J].2005,33(7):29-31
[83]曹慧林,苑会林.聚乙烯醇缩丁醛薄膜加工工艺及性能研究.塑料工业,20026,34(6):29-32
[84]B·帕彭富斯,M·施托伊尔.含增塑剂的聚乙烯醇缩丁醛,其制备方法和用途,尤其用于生产夹层安全玻璃和膜的用途.CN 1484671A,2004-3-24
[85]李新法,沈百拴等.PVB的热行为及其热降解过程[J].河南科学,1994,12(2):111-115
[86]Gamal R.Saad,E.EI-Shafee,M.W.Sabaa.Dielectric and mechanical properties in the photo degradation of poly(vinyl butyral)films[J].Polymer degradation and stability,1995,47:209-215
[87]金日光,华幼卿.高分子物理.北京:化学工业出版社,2000
[88]S·J·本尼森,D·L·赖默.具有优异声学性能的聚乙烯醇缩丁醛夹层及其制备方法.CN 1708398A.2005-12-14
[2]李国东,张毅.聚乙烯醇缩丁醛树脂的研究与应用.中国胶粘剂.2006,15(6):27-35
[3]罗贵英.聚乙烯醇缩丁醛树脂的生产与应用.贵州化工,2002,27(6):27-29
[4]王学勤,PVB膜片的加工与应用.塑料工程,1993,(4):34-36
[5]徐美君.简介夹层玻璃的配套材料-PVB胶片.中国建材装备,1995(2):34-36
[6]马时渝.Butvar-孟山都生产的PVB树脂.维纶通讯,1998,(2):54-57
[7]M.D.Fernandez,M.J.Fenamdez,P.Hoces.Synthesis of Poly(vinyl butyral)s in Homogeneous Phase and Their Thermal Properties.Journal of Applied Polymer Science,2006,102:5007-5017
[8]李忠森,罗顺贻.聚乙烯醇缩丁醛发展现状.维普资讯.1992,(1):1-15
[9]冯海刚,李粼.聚乙烯醇缩丁醛(PVB)膜片的历史与发前景.国外塑料,2005,23(10):42-48
[10]杨宝武.聚乙烯醇缩丁醛.化工百科全书,第九卷,北京:化学工业出版社,1995:99
[11]陈霞真.夹层玻璃PVB中间膜的国产化.上海建材,1994,(4):23-24
[12]陈美兰.用聚乙烯醇缩丁醛代替玻璃制备的艺术玻璃及其制作方法.CN 1844004A,2006-10-11
[13]张谢源.PVB废水处理新工艺的研究.天津化工,1992,(1):51-55
[14]汤显玉.安全玻璃和中间膜.精细化工,1988,(3):49-56
[15]石万聪,石志博,蒋平平.增塑剂及其应用.北京:化学工业出版社,2002:127-130
[16]张月明.PVB的新型增塑剂-DNHA.增塑剂,2000,(4):18-20
[17]J.J.德埃里科,M.S.克拉奇.紫外线稳定的聚乙烯醇缩丁醛片材.CN 1219184A,1999-6-9
[18]A.P.Marin,L.A.Tatarenko,YU.A.Shlyapnikov.Solubility of antioxidants in polyvinyl butyral.Polymer Degradation and Stability,1998,62:507-511
[19]M·霍斯,B·科尔.由部分缩醛化的聚乙烯醇制成的含增塑剂的薄膜.CN 1284911,2001-2-21
[20]孙宏坚.高速成长中的塑料新材料PVB树脂的性能及应用.塑料制造,2007,11,91-97
[21]苑会林,马沛岚等.聚乙烯醇缩丁醛树脂的性能及应用.工程塑料应用,2004,32(2):43-46
[22]熊劲松.论夹层安全玻璃的特性.广东建材,2001,(1):12-13
[23]吴桂香.夹层玻璃的性能.中国建材,2000,12,81-82
[24]汪秀娟.性能优异的建筑夹层玻璃.广东建材,2000,(06):37-39
[25]冯海刚.使用PVB膜片作为安全玻璃夹层的常见问题与改进方法.塑料工业,2005,33(11):56-58
[26]王崇禾.夹层安全玻璃合片工艺的研究.中国玻璃,2001,(4):26-28
[27]赵劲松.低温低压制造安全玻璃.工程塑料应用,1999,27(11):18-19
[28]Donald B.Baldridge,Wilbraham,Mass.Process of making a polyvinyl butyral composite interlayer for laminated safety glass.US 3982984,1976-9-28
[29]刘志海.夹层玻璃的发展现状及趋势.中国建材,2003,(9):64-69
[30]王永恒.国外安全夹层玻璃的品种及性能的测定.玻璃,1987,(5):27-31
[31]孟继本、陆桂芬等.光致变色纳米复合材料制备及其PVB胶片制备方法.CN 1640929A,2005-7-20
[32]孟继本,陆桂芬等.光致变色纳米复合材料制备聚乙烯醇缩丁醛胶片及其方法.CN 1298783C,2007-2-7
[33]尚贵才,王鸿飞.热反射夹层玻璃.CN 2820861Y,2006-09-27
[34]Degrilh,Robert.Process for the production of polyvinyl butyral having improved proverties.US5349014,1994-09-20
[35]R·狄盖尔.改性聚乙烯醇缩丁醛的制备方法.CN 96107793.X,2002-5-55
[36]李国东、张毅等.一种乳化剂及使用该乳化剂的PVB生产工艺.CN 1769312A,2005-10-28
[37]George E.Cartier,Springfield.Cross-linked polyvinyl butyral.US4874814,1989-10-17
[38]B·帕彭富斯,M·施托伊尔.高分子、交联聚乙烯醇缩丁醛、其生产方法及用途.CN1551890A,2004-12-1
[39]B·帕潘弗斯.高分子量交联聚乙烯醇缩丁醛,它们的生产方法和用途.CN1464884A,2003-12-31
[40]Bernd Papenfuhs,Obertshausen.High-molecular,cross-linked polyvinyl butyrals,method for the production thereof and their use.US 6835784B2,2004-12-28
[41]Misra,Ashok,David,et al.Method of producing ionomeric polyvinyl butyral.US 4968745,1990-11-06
[42]Schafheutle,Markus A,Merten,et al.Aqueous emulsions comprising polyvinyl butyral.US 5525669,1996-06-11
[43]聂文卫.含PET膜的低辐射夹层玻璃.CN 1307969A,2001-8-15
[44]T.R.菲利普斯,具有改良防雾性能的着色聚乙烯醇缩丁醛中间层.CN 1352597A,2002-6-5
[45]庄大明,张弓.一种具有红外反射性能的汽车风挡玻璃及其制备方法.CN 1555989A,2004-01-02
[46]P·袁,J·德里科.具有抗粘连性的聚乙烯醇缩丁醛片材.CN 1777638A,2006-5-24
[47]W·陈.包含双官能表面改性剂的聚乙烯醇缩丁醛片材.CN 1802404A,2006-7-12
[48]W·-C·李,I·-C·W·王.具有增强的表面性能的聚乙烯醇缩丁醛组合物和共混物以及由其制备的制品.CN 1813027A,2006-8-2
[49]R·L·史密斯,D·L·赖默等.具有改善的对玻璃粘合性的聚乙烯醇缩丁醛夹层板及其制备方法.CN 1671787A,2005-9-21
[50]李忠林、罗顺贻,聚乙烯醇缩丁醛发展现状,维普资讯,1992(1):1-15
[51]A.K.Dhalival,J.N.Hay,The characterization of polyvinyl butyral by thermal analysis,Thermochimica Acta,2002,391:245-255
[52]Nabil M.Safy El-Din、Magdy W.Sabaa,Thermal degradation of poly(vinyl butyral)laminated safety glass,Polymer Degradation and Stability,1995,47:283-288
[53]王党生,李涛.微粒状聚乙烯醇缩丁醛制备新工艺.福建化工,1997,(2):5-6
[54]Reejhsinghani.Forming polyvinyl butyral.US5238994,1993-08-23
[55]王玉荣,张春庆.高分子化学与物理实验.大连:大连理工大学出版社,1998
[56]栗方星.缩醛度的准确测定方法.化学工业与工程,1993,11(3):59-60
[57]李锋.聚乙烯醇缩丁醛合成工艺探讨.热固性树脂,2005,20(5):48-50
[58]Sidney C.Overbaugh etc.Preparation of polyvinyl acetal resins.US 2345946A,1944-4-4
[59]卢宝生.二相法制备聚乙烯醇缩丁醛最佳条件的探讨,中国胶粘剂,1993,3(2):25-27
[60]Hans D.Hermnmm,Bad Soden am Taunus et al.Process for the preparation of polyvinyl butyral having improved propertyes.US 4205146,1980-5-27
[61]白国强,李仲谨.PVB树脂有合成与应用.包装工程,2004,(4):19-20
[62]增子芳弘,河西俊明.聚乙烯醇缩醛树脂及其制造方法.CN 1630670A,2005-6-22
[63]刘立萍,周生贵,肖卓炳.对影响聚乙烯醇缩丁醛产品质量稳定性因素的探讨.精细化工中间体,2003,33(5):49-50
[64]曹慧林,苑会林.高粘度聚乙烯醇缩丁醛树脂及薄膜的制备,化工新型材料,2006,34(4):51-56
[65]D·L·赖默,N·K·里德三世.通过控制聚乙烯醇缩丁醛的立体化学来控制其物理性能的工艺.CN 1675258A,2005-9-28
[66]刘智斌.聚乙烯醇缩丁醛生产装置的技术改造.维纶通讯,1997,17(3):14-17
[67]刘立萍.间接法测定6%PVB甲醇溶液和5%PVB正丁醇溶液的旋转粘度.精细化工中间体,2004.35(3):57-58
[68]孙宏坚,张岩飞等.聚乙烯醇缩丁醛树脂分子量和热性能的测定.河南化工,2003,(8):11-18
[69]H·H·霍菲,A·卡拉吉安尼斯.表面粗糙的聚乙烯醇缩丁醛及其形成方法.CN 1102840A,1995-5-24
[70]George E.Cartier,Springfield et al.Polyvinyl butyral sheet roughness.US 4654179,1987-3-31
[71]孙宏坚,张岩飞等.PVB树脂溶解性质的研究.河南化工,1996,(9):9-11
[72]刘立萍.聚乙烯醇缩丁醛冻胶化温度的测定方法.化学世界,2003,(12):636-638
[73]U·凯勒,H·施藤策尔.含增塑剂的PVB薄膜.US 1518494A,2004-8-4
[74]J·J·德埃里科,B·A·杰姆莫特.增塑聚乙烯醇缩丁醛及片材.CN 1209092A,1999-2-24
[75]Robert H.Fariss,Northampton.Plasticized polyvinyl butyral and interlayer thereof.US 5013780,1991-5-7
[76]James A.Snelgrove,Monson et al.Plasticizer blends for polyvinyl butyral interlayers.US 4144217,1979-5-13
[77]Thomas R.Philips,Belpre,Ohio.Polyvinyl butyral plasticized with tetraethyleneglycol di-2-ethylhexanoate.US 4276351,1981-7-30
[78]Arijit M.Dasgupta,Belchertown et al.Polyvinyl butyral sheet.US 5137954,1992-8-11
[79]Shigeru Numura,tami et al.Interlayer film for laminated glass.US 4452935,1984-6-5
[80]George A.kennar,East Longmeadow,Mass.Interlayer for laminated safety glass.US 4035549A,1977-7-12
[81]Robert H.Fariss,Northampton,Roland J.Tetreault.Plasticezed polyvinyl butyral and interlayer thereof.US 5013779,1991-5-7
[82]冯海刚.安全玻璃夹层用PVB膜片生产工艺配方设计[J].2005,33(7):29-31
[83]曹慧林,苑会林.聚乙烯醇缩丁醛薄膜加工工艺及性能研究.塑料工业,20026,34(6):29-32
[84]B·帕彭富斯,M·施托伊尔.含增塑剂的聚乙烯醇缩丁醛,其制备方法和用途,尤其用于生产夹层安全玻璃和膜的用途.CN 1484671A,2004-3-24
[85]李新法,沈百拴等.PVB的热行为及其热降解过程[J].河南科学,1994,12(2):111-115
[86]Gamal R.Saad,E.EI-Shafee,M.W.Sabaa.Dielectric and mechanical properties in the photo degradation of poly(vinyl butyral)films[J].Polymer degradation and stability,1995,47:209-215
[87]金日光,华幼卿.高分子物理.北京:化学工业出版社,2000
[88]S·J·本尼森,D·L·赖默.具有优异声学性能的聚乙烯醇缩丁醛夹层及其制备方法.CN 1708398A.2005-12-14