公开(公告)号：US4176224A

公开(公告)日：1979-11-27

申请号：US889584

申请日：1978-03-23

申请人： Peter Bier ,  Rudolf Binsack ,  Hugo Vernaleken

发明人： Peter Bier ,  Rudolf Binsack ,  Hugo Vernaleken

IPC分类号： C08G63/00 ,  C08G63/18 ,  C08G63/181

CPC分类号： C08G63/18

摘要： The present invention is concerned with thermoplastic terephthalic acid copolyesters which crystallize more rapidly than homopolyethylene terephthalate and are based on a diol component which is about 98 to 99.9 mol % of ethylene glycol and the balance 2-ethylhexane-1,3-diol. The acid component may be up to about 10.0 mol % of other than terephthalic acid or its dimethyl ester.This invention is also concerned with a process of synthesizing such copolyesters by esterifying or transesterifying the acid and diol components between about 150.degree. and 250.degree. C. in the presence of appropriate catalysts. The condensation product may be subject to polycondensation at about 200.degree. to 300.degree. C. under reduced pressure in the presence of esterification catalysts. In a preferred embodiment the 2-ethylhexane-1,3-diol is added after the initial reaction between the acid component and the ethylene glycol and preferably after the degree of polycondensation is greater than 4.

摘要翻译： 本发明涉及热塑性对苯二甲酸共聚酯，其比对苯二甲酸聚对苯二甲酸丙二醇酯更快地结晶，并且基于约98-99.9摩尔％的乙二醇和余量的2-乙基己烷-1,3-二醇的二醇组分。 除了对苯二甲酸或其二甲酯之外，酸组分可以高达约10.0mol％。 本发明还涉及通过在合适的催化剂存在下在约150℃和250℃之间酯化酯化或酯交换合成这种共聚酯的方法。 在酯化催化剂存在下，缩合产物可在减压下在约200℃至300℃下进行缩聚反应。 在优选的实施方案中，在酸组分和乙二醇的最初反应之后，优选在缩聚度大于4之后加入2-乙基己烷-1,3-二醇。

公开(公告)号：US4223125A

公开(公告)日：1980-09-16

申请号：US40386

申请日：1979-05-18

申请人： Peter Bier ,  Rudolf Binsack

发明人： Peter Bier ,  Rudolf Binsack

IPC分类号： C08K5/12 ,  C08L67/02 ,  C08G63/18

CPC分类号： C08K5/12 ,  C08L67/02 ,  C08L67/025

摘要： This invention relates to polyalkylene terephthalates which crystallize rapidly, and process of making such compositions and a process of using such compositions in injection molding. The compositions comprise polyalkylene terephthalates with intrinsic viscosities in excess of about 0.4 dl/g in 1:1 phenol/tetrachloroethane at 25.degree. C. and at least about 0.5 wt. %, based on the weight of resin and additive, of an aromatic carboxylic acid ester. These compositions may be prepared by intimately mixing the ingredients, for example by extrusion. These compositions, particularly those wherein the polyester consists essentially of polyethylene terephthalate, may be injection molded with mold temperatures less than about 120.degree. C. and still retain a significant degree of crystallinity even with short mold residence times.

摘要翻译： 本发明涉及快速结晶的聚对苯二甲酸亚烷基酯，以及制备这种组合物的方法和在注射成型中使用这些组合物的方法。 该组合物包含在25℃下在1:1苯酚/四氯乙烷中的特性粘度超过约0.4dl / g的聚对苯二甲酸亚烷基酯和至少约0.5wt。 ％，基于树脂和添加剂的重量，芳族羧酸酯。 这些组合物可以通过例如通过挤出紧密混合成分来制备。 这些组合物，特别是其中聚酯基本上由聚对苯二甲酸乙二醇酯组成的组合物可以在模具温度低于约120℃的情况下进行注模，并且即使在较短的模具停留时间内仍保持显着程度的结晶度。

公开(公告)号：US4136089A

公开(公告)日：1979-01-23

申请号：US825121

申请日：1977-08-16

申请人： Peter Bier ,  Rudolf Binsack ,  Hugo Vernaleken

发明人： Peter Bier ,  Rudolf Binsack ,  Hugo Vernaleken

IPC分类号： C08G63/183 ,  C08G63/78 ,  C08G63/18

CPC分类号： C08G63/183 ,  C08G63/78

摘要： Terephthalic copolyesters, the diol component of which consists of ethylene glycol and 2.2-diethyl propane-1.3-diol crystallize more rapidly than pure polyethylene terephthalate and can be molded in a way comparable to butylene terephthalate.

公开(公告)号：US4223106A

公开(公告)日：1980-09-16

申请号：US730208

申请日：1976-10-06

申请人： Peter Bier ,  Rudolf Binsack ,  Dieter Rempel

发明人： Peter Bier ,  Rudolf Binsack ,  Dieter Rempel

IPC分类号： C08G63/00 ,  C08G63/181 ,  C08G63/46 ,  C08G63/66 ,  C08F8/00

CPC分类号： C08G63/00 ,  C08G63/66

摘要： Polyethylene terephthalate copolymers comprising (I) blocksegments having a glass transition temperature below 0.degree. C. and (II) polyethylene terephthalate segments modified with certain diols having 3 to 10 carbon atoms, have an excellent rate of crystallization and necessitate mould temperatures of below 100.degree. C.

摘要翻译： 包含（I）玻璃化转变温度低于0℃的块状物的聚对苯二甲酸乙二醇酯共聚物和（II）用某些具有3-10个碳原子的二醇改性的聚对苯二甲酸乙二醇酯链段具有优异的结晶速率，并且模具温度低于100℃ C。

公开(公告)号：US4115371A

公开(公告)日：1978-09-19

申请号：US802858

申请日：1977-06-02

申请人： Peter Bier ,  Rudolf Binsack

发明人： Peter Bier ,  Rudolf Binsack

IPC分类号： C08L67/00 ,  C08G63/00 ,  C08G63/78 ,  C08G63/82 ,  C08K3/32 ,  D01F6/92 ,  C08G63/34 ,  C08G63/32

CPC分类号： C08K3/32

摘要： A process for the production of high molecular weight low color polyethylene terephthalates using a particulaarly effective polycondensation catalyst is disclosed. Titanium tetrabutylate is added to the reaction mixture after the initial esterification or transesterification reaction is about 95% complete and the polycondensation is completed at temperatures between about 200 and 270.degree. C under reduced pressure. Metaphosphoric acid or its alkali or alkaline earth metal salts are added with the titanium tertrabutylate to control the color. Commonly accepted catalysts may be employed for the initial esterification or transesterification. Polymers with intrinsic viscosities in excess of 0.7 dl/g and yellowness numbers less than 6 can be produced.

摘要翻译： 公开了一种使用特别有效的缩聚催化剂生产高分子量低颜色聚对苯二甲酸乙二醇酯的方法。 在初始酯化反应或酯交换反应完成约95％之后，向反应混合物中加入四丁基钛，缩聚反应在约200-270℃的温度下在减压下完成。 将偏磷酸或其碱金属或碱土金属盐与叔丁醇钛一起加入以控制颜色。 常用的催化剂可用于初始酯化或酯交换。 特性粘度超过0.7dl / g，黄度数小于6的聚合物。

公开(公告)号：US4435546A

公开(公告)日：1984-03-06

申请号：US40385

申请日：1979-05-18

申请人： Peter Bier ,  Rudolf Binsack

发明人： Peter Bier ,  Rudolf Binsack

IPC分类号： C08K5/12 ,  C08L67/02 ,  C08F283/00 ,  C08G63/76 ,  C08L67/00

CPC分类号： C08K5/12 ,  C08L67/02 ,  C08L67/025

摘要： Polyalkylene terephthalates containing 0.5-30% by weight of monomeric aliphatic carboxylic acid esters have a higher crystallization speed and thus allow lower mold temperatures and shorter injection cycles. The polyalkylene terephthalates generally have intrinsic viscosities in excess of about 0.4 dl/g in 1:1 phenol tetrachloroethane at 25.degree. C. and are at least about 90 mol % terephthalic acid based. The ester additive is based on aliphatic cycloaliphatic or araliphatic carboxylic acids, with sebacic and adipic being preferred, and aliphatic, cycloaliphatic or araliphatic alcohols.Faster crystallization rates can be imparted to polyalkylene terephthalates by mixing them with the ester additive and melt homogenizing the mixture.

摘要翻译： 含有0.5-30重量％单体脂肪族羧酸酯的聚对苯二甲酸亚烷基酯具有较高的结晶速度，从而允许较低的模具温度和较短的注射循环。 聚对苯二甲酸亚烷基酯通常在25℃在1：1苯酚四氯乙烷中具有超过约0.4dl / g的特性粘度，并且是至少约90mol％对苯二甲酸。 酯添加剂基于脂族环脂族或芳脂族羧酸，优选癸二酸和己二酸，脂肪族，脂环族或芳脂族醇。 聚对苯二甲酸亚烷基酯通过与​​酯添加剂混合并使混合物熔融均匀化，可以提高结晶速度。

公开(公告)号：US4314928A

公开(公告)日：1982-02-09

申请号：US164458

申请日：1980-06-30

申请人： Peter Bier ,  Rudolf Binsack

发明人： Peter Bier ,  Rudolf Binsack

IPC分类号： C08G63/78 ,  C08G63/00 ,  C08G63/181 ,  C08G63/183 ,  C08G63/80 ,  C08L67/00

CPC分类号： C08G63/80 ,  C08G63/183

摘要： The present invention relates to a polyethylene terephthalate copolyester which crystallizes rapidly and a process to synthesize such a polymer. The polymer is produced by melt homogenizing pure polyethylene terephthalate segments (with minimum intrinsic viscosities above about 0.2 dl/g) with certain specified C.sub.4-10 diols, allowing the mixture to solidify and subjecting the solid product to a solid phase post-condensation reaction. The copolyester has a minimum intrinsic viscosity of 0.4 dl/g and crystallizes more rapidly than either pure polyethylene terephthalate of equivalent molecular weight or copolyester from the same acid and diol units wherein the pure polyethylene terephthalate segments are not significantly prepolymerized before reaction with the co-diols. In a preferred embodiment about 0.23 to 9.1 parts of co-diol per 100 parts of polyethylene terephthalate segment are melt homogenized in an extruder and the extrudate is subject to solid state condensation by the application of elevated temperatures and reduced pressure.

摘要翻译： 本发明涉及一种快速结晶的聚对苯二甲酸乙二醇酯共聚酯和一种合成这种聚合物的方法。 通过将纯聚对苯二甲酸乙二醇酯片段（具有最高特性粘度高于约0.2dl / g）与某些特定的C 4-10二醇熔融均匀来制备聚合物，使混合物固化并使固体产物进行固相缩合反应。 共聚多酯具有0.4dl / g的最小特性粘度并且比来自相同的酸和二醇单元的当量分子量的纯聚对苯二甲酸乙二醇酯或共聚多酯结晶得更快，其中纯聚对苯二甲酸乙二醇酯链段在与共聚酯反应之前没有显着预聚， 二醇。 在优选的实施方案中，每100份聚对苯二甲酸乙二醇酯链段约0.23至9.1份共二醇在挤出机中熔融均化，并通过施加升高的温度和减压使挤出物进行固态冷凝。

公开(公告)号：US4207230A

公开(公告)日：1980-06-10

申请号：US875047

申请日：1978-02-03

申请人： Peter Bier ,  Rudolf Binsack

发明人： Peter Bier ,  Rudolf Binsack

IPC分类号： C08G63/00 ,  C08G63/18 ,  C08G63/181 ,  C08G63/183 ,  C08G63/66 ,  C08G63/672 ,  C08G63/78 ,  C08G63/91 ,  C08L67/02 ,  C08L71/02

CPC分类号： C08G63/672 ,  C08G63/183 ,  Y10S260/35

摘要： The current invention is concerned with block copolyesters of low glass transition temperature segments and ethylene glycol based polyester segments linked together by carboxylic acid ester groups and special diols, and a process for preparing these copolyesters. These copolyesters display molded resin properties similar to polyethylene terephthalate but crystallization behavior similar to polybutylene terephthalate, i.e. they have high strength and superior solvent resistance, but they also crystallize rapidly. They are made by subjecting low glass transition temperature (less than 0.degree. C.) polymers with carboxyl, hydroxyl or reactive ester end groups to esterification or transesterification conditions with ethylene glycol based polyester segments having a minimum intrinsic viscosity of 0.2 dl/g and special diols having four to ten carbon atoms with 3 or 4 carbon atoms between the hydroxyl groups in the presence of appropriate catalysts. In a preferred embodiment, the three components are subject to melt homogenization in an extruder and the solidified extrudate is subject to a solid state polycondensation reaction.

摘要翻译： 本发明涉及低羧酸酯基和特殊二醇连接在一起的低玻璃化转变温度段和基于乙二醇的聚酯链段的嵌段共聚酯，以及这些共聚酯的制备方法。 这些共聚酯显示与聚对苯二甲酸乙二醇酯类似的模塑树脂性能，但结晶行为类似于聚对苯二甲酸丁二醇酯，即它们具有高强度和优异的耐溶剂性，但它们也快速结晶。 它们是通过将具有羧基，羟基或活性酯端基的低玻璃化转变温度（低于0℃）的聚合物与具有0.2dl / g的最小特性粘度的乙二醇基聚酯链段进行酯化或酯交换反应而制成的，并且特殊 在合适的催化剂存在下，羟基之间具有4至10个碳原子数为3或4个碳原子的二元醇。 在优选的实施方案中，三种组分在挤出机中进行熔融均匀化，固化的挤出物进行固态缩聚反应。

公开(公告)号：US4086212A

公开(公告)日：1978-04-25

申请号：US658816

申请日：1976-02-17

申请人： Peter Bier ,  Rudolf Binsack ,  Hugo Vernaleken

发明人： Peter Bier ,  Rudolf Binsack ,  Hugo Vernaleken

IPC分类号： C08L67/00 ,  C08G63/00 ,  C08G63/18 ,  C08G63/181 ,  C08G63/183 ,  C08G63/78 ,  C08K3/40 ,  C08L67/02 ,  C08G63/12

CPC分类号： C08G63/183 ,  C08G63/78

摘要： Terephthalic copolyesters, the diol component of which mainly consists of ethylene glycol units, crystallize more rapidly than pure polyethylene terephthalate and can be moulded in a way comparable to polybutylene terephthalate.

摘要翻译： 对苯二甲酸共聚酯，其二醇组分主要由乙二醇单元组成，比纯聚对苯二甲酸乙二醇酯更快地结晶，并且可以以与聚对苯二甲酸丁二醇酯相当的方式成型。

公开(公告)号：US4223113A

公开(公告)日：1980-09-16

申请号：US40387

申请日：1979-05-18

申请人： Peter Bier ,  Rudolf Binsack

发明人： Peter Bier ,  Rudolf Binsack

IPC分类号： C08K5/12 ,  C08L67/02 ,  C08G63/76

CPC分类号： C08K5/12 ,  C08L67/02 ,  C08L67/025

摘要： Polyalkylene terephthalates containing 0.5-30% by weight of oligomeric carboxylic acid polyesters have a higher crystallization speed and thus allow lower mold temperatures and shorter injection cycles. The polyalkylene terephthalates generally have intrinsic viscosities in excess of about 0.4 dl/g in 1:1 phenol tetrachloroethane at 25.degree. C. and are at least about 90 mol % terephthalic acid based. The oligomer additive is based on carboxylic acids, with sebacic and adipic being preferred, and aliphatic, cycloaliphatic or araliphatic dihydric alcohols. This additive has a minimum polymerization degree of 2 and a maximum number-average molecular weight of about 6000.Faster crystallization rates can be imparted to polyalkylene terephthalates by mixing them with the ester additive and melt homogenizing the mixture.

摘要翻译： 含有0.5-30％（重量）低聚羧酸聚酯的聚对苯二甲酸亚烷基酯具有较高的结晶速度，从而允许较低的模具温度和较短的注射循环。 聚对苯二甲酸亚烷基酯通常在25℃在1：1苯酚四氯乙烷中具有超过约0.4dl / g的特性粘度，并且是至少约90mol％对苯二甲酸。 低聚物添加剂基于羧酸，优选癸二酸和己二酸，脂肪族，脂环族或芳脂族二元醇。 该添加剂的最小聚合度为2，最大数均分子量为约6000.通过将它们与酯添加剂混合并将混合物熔融均化，可以将聚对苯二甲酸亚烷基酯提供更快的结晶速率。