CN1270606A - 含二价金属磺酸盐基团的可发泡共聚聚酯 - Google Patents
含二价金属磺酸盐基团的可发泡共聚聚酯 Download PDFInfo
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- CN1270606A CN1270606A CN98809150.XA CN98809150A CN1270606A CN 1270606 A CN1270606 A CN 1270606A CN 98809150 A CN98809150 A CN 98809150A CN 1270606 A CN1270606 A CN 1270606A
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- residue
- mole
- acid
- copolyester
- dicarboxylic acid
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- 229920001634 Copolyester Polymers 0.000 title claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 14
- 239000002184 metal Substances 0.000 title claims abstract description 14
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 13
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
Abstract
此处公开的是使其拥有可用宽范围的发泡剂发泡的高熔体粘度和熔体强度的高分子量共聚聚酯组合物。所述共聚聚酯主要包括(A)二酸残基,该二酸残基包括(i)99.9—95%(摩尔)的一种具有8到12个碳原子的芳族二羧酸的残基和(ii)0.1—5.0%(摩尔)的含至少一个连接到一芳环的二价金属磺酸盐基的芳族二羧酸磺酸盐单体的残基,以及(B)二醇残基,该二醇残基包括至少一种具有2到8个碳原子的脂族或环脂族二醇的残基,所述%(摩尔)是以100%(摩尔)二羧酸残基和100%(摩尔)二醇残基为基础计算的。特别优选的是用5-磺基间苯二甲酸镁盐单元改性的聚对苯二甲酸乙二酯。
Description
发明领域
本发明涉及高分子量共聚聚酯组合物,更具体地说,涉及拥有使其可用宽范围发泡剂发泡的高熔体粘度和熔体强度的这种共聚聚酯组合物。
发明背景
热塑性聚合物材料可发泡而用于提供低密度物品诸如膜、杯、食品盘、装饰带和家具构件。例如,含低沸点烃类诸如戊烷的聚苯乙烯珠粒可制成盛热饮诸如咖啡、茶、热巧克力等的轻质发泡杯。聚丙烯可在发泡剂诸如氮气或二氧化碳气体的存在下挤压以提供包装材料的装饰膜和装饰带。同样,聚丙烯可在发泡剂的存在下注模形成轻质家具构件诸如桌腿和形成轻质椅子。
聚酯诸如聚对苯二甲酸乙二酯一般具有比其它聚合物高得多的密度(例如1.3g/cc)。因此,可能有必要将聚酯材料发泡来降低模制件、膜、板、食品盘等的重量。这种发泡制品也具有比未发泡制件更好的绝缘性能。然而,因为一般聚对苯二甲酸乙二酯和相关的聚酯聚合物的低的熔体粘度和低的熔体强度而难以将这种聚酯发泡。该聚酯的低熔体粘度和低熔体强度是一个问题,因为所述聚合物熔体不能足够地保留膨胀气体的气泡。因此需要提供能用常规发泡体系发泡的聚合物。
提供具有高熔体强度和熔体粘度的一条途径涉及将预成形的聚酯用多官能羧酸或多元醇处理来提供分支的聚酯。这种组合物公开于美国专利4132707;4145466;4999388;5000991;5110844;5128383和5134028中。所用的支化剂包括三羧酸和四羧酸以及酸酐诸如1,3,5-苯三酸、1,2,4,5-苯四酸和苯均四酸二酐或多元醇诸如三羟甲基丙烷和季戊四醇。
含二羧酸磺化单体的聚酯公开于美国专利3734874、3779993、4335220、4233196、3853820和5053482中。美国专利3734874和4233196涉及包含至少8%(摩尔)磺化单体和大量双官能乙二醇醚组分的可水分散的无定形聚酯。美国专利3853820描述了具有至少20%(摩尔)身为乙二醇缩聚物的聚乙二醇的可水分散的无定形聚酯。此外,美国专利5053482描述了用于一次性产品诸如一次性尿布的基于含20-40%(摩尔)二乙二醇的聚对苯二甲酸乙二酯聚酯的成纤维和成膜聚酯。美国专利4499262和4579936描述了用于制造瓶子的聚酯组合物。
美国专利5399595公开了包含少量含一价金属离子诸如碱金属的二羧酸磺酸盐单体的残基的聚酯和由其制备的发泡制品。按照该专利,在所述聚酯中碱金属磺酸盐单体如5-钠代磺基间苯二甲酸的残基的存在提供了提高了熔体粘度的共聚聚酯组合物。
本发明简述
因此,本发明的一个目标是提供拥有赋予所述聚酯特别可用于挤压、模塑或发泡制成有用的物品的改善的熔体强度和熔体粘度的结晶疏水聚酯。
本发明的另一目标是提供源于一种或多种芳族二羧酸、一种包含二价金属离子的二羧酸磺酸盐单体和至少一种脂族或环脂族二醇的新的共聚聚酯组合物,这种共聚聚酯组合物可制成展现出良好物理性能和外观的物品。
这些目标和其它目标可通过本发明来达到,本发明提供了具有0.70-1.20dL/g的固有粘度和高至足可在挤压或模塑操作时发泡的熔体强度和熔体粘度的共聚聚酯,其中所述共聚聚酯主要包括(A)二羧酸残基,该二羧酸残基包括(i)99.9-95%(摩尔)的一种具有8到12个碳原子的芳族二羧酸的残基和(ii)0.1-5.0%(摩尔)的含至少一个连接到芳环的二价金属磺酸盐基的芳族二羧酸磺酸盐单体的残基,和(B)二元醇残基,它包括至少一种具有2到8个碳原子的脂族或环脂族二醇的残基,所述%(摩尔)是以100%(摩尔)二羧酸残基和100%(摩尔)二醇残基为基础计算的。
按照本发明,还提供了增加在制备发泡物品中所用共聚聚酯的熔体粘度和熔体强度的方法,所述共聚聚酯主要由来自100%(摩尔)二羧酸组分的残基和来自二元醇组分的残基组成,所述方法包括使0.1-5.0%(摩尔)包含至少一个连接到芳环的二价金属磺酸盐基团的二羧酸磺酸盐单体共聚成共聚聚酯。
本发明的详细说明
宽范围的聚酯组合物都可用少量二羧酸磺基单体改性而提供具有良好发泡特性的提高的熔体粘度和熔体强度的共聚聚酯组合物。适合发泡的聚合物必须具有足以在模塑或挤压操作中保留膨胀气体气泡的熔体粘度和熔体强度。良好的熔体粘度和熔体强度对具有均匀壁厚的硬质泡沫塑料和发泡容器的制造也是重要的。
基于100%(摩尔)二酸残基和100%(摩尔)二醇残基,本发明的聚酯主要由包括对苯二甲酸残基、萘二甲酸残基和二羧酸磺酸盐单体残基的二羧酸残基以及包括脂族醇或环脂族醇的二醇残基组成。术语“主要由…组成”是指除了对苯二甲酸或萘二甲酸残基、二羧酸磺酸盐单体残基和二元醇组分残基外,只要所述聚酯的基本特征和主要特征没有受实质性的影响,那么所述共聚聚酯中也可存在其它二羧酸和二元醇。例如,本发明的共聚聚酯可任选用多至25%(摩尔)的基于100%(摩尔)二酸残基的一种或多种源于非对苯二甲酸的二羧酸的残基或适用的合成等价物和二羧酸磺酸盐单体来改性。这种另外的二羧酸包括优选具有8到14个碳原子的芳族二羧酸、优选具有4到12个碳原子的脂族二羧酸或优选具有8到12个碳原子的环脂族二羧酸。与对苯二甲酸和二羧酸磺酸盐单体一起包括于其中的二羧酸的例子有:邻苯二甲酸、间苯二甲酸、1,4-环己烷二甲酸、1,4-萘二甲酸、2,5-萘二甲酸、2,6-萘二甲酸、2,7-萘二甲酸、环己烷二乙酸、联苯基(diphenyl)-4,4’-二甲酸、琥珀酸、癸二酸、辛二酸、己二酸、戊二酸、壬二酸、富马酸、马来酸、衣康酸等。所述聚酯可从两种或多种上述二羧酸制备。所述二酸残基可源于所述二羧酸或酯或酰氯或在某些情况下来自于二羧酸的酸酐。
此外,本发明的聚酯可任选用多至25%(摩尔)基于100%(摩尔)二醇的一种或多种乙二醇以外的二醇改性。这种另外的二醇包括优选具有3到8个碳原子的环脂族二醇。这种与乙二醇一起包括其中的二醇的例子有:1,4-环己烷二甲醇、二乙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,3-己二醇、3-甲基-2,4-戊二醇、2-甲基-1,4-戊二醇、2,2,4-三甲基-1,3-戊二醇、2,2-二甲基-1,3-丙二醇、2,2-二乙基-1,3-丙二醇、2-乙基-2-丁基-1,3-丙二醇、2-乙基-2-异丁基-1,3-丙二醇、1,6-己二醇、2,2,4-三甲基-1,6-己二醇、硫代二乙醇、2-乙基-1,3-己二醇、1,4-二(羟乙氧基)苯、2,2-二(4-羟基环己基)丙烷、2,2-二-(3-羟基乙氧基苯基)丙烷、2,2-二-(4-羟基丙氧基苯基)丙烷等。聚酯可从两种或多种上述二醇制备。
所述聚酯的二羧酸磺基单体组分源于包含二价磺酸盐基团的二羧酸或其酯。所述磺酸盐的金属离子可以是Mg++、Zn++、Ca++、Ba++、Co++等。所述磺酸盐基团与芳族酸环诸如苯、萘、联苯、氧基联苯、磺酰基联苯或亚甲基联苯环相连。优选所述磺酸盐单体是磺酸盐取代的邻苯二甲酸、对苯二甲酸、间苯二甲酸、萘-2,7-二羧酸的残基。最优选,所述磺酸盐单体残基为间苯二甲酸-5-磺酸镁残基。
所述二羧酸磺酸盐单体残基以基于总二酸含量的0.1-5%(摩尔)的所需量存在。在本发明中含二价金属离子的二羧酸磺酸盐单体的使用提供了具增加了的熔体粘度和熔体强度的可发泡共聚聚酯组合物。所述二价金属离子用作在这些共聚聚酯中在相邻或毗连聚合物链的侧磺酸根离子的离子连接剂,并因此提供了由于强离子键形成的“假分支”或“假交联”效应。这导致了所得到共聚聚酯高度增强的熔体强度和熔体粘度。
除了存在所述二羧酸磺酸盐单体外,本发明的聚酯也必须具有高的分子量以便获得足以发泡的熔体强度和熔体粘度。对于本发明来说,高分子量聚酯被定义为固有粘度(I.V.)大于0.70dL/g的聚酯。重要的是要注意聚酯的固有粘度与提供具有足够用于发泡的熔体强度和熔体粘度的聚酯所需的二羧酸磺酸盐单体量之间存在的关系。例如,具有0.75dL/g固有粘度的聚酯需要0.25-0.5%(摩尔)的磺酸盐单体。具有1.0-1.1dL/g固有粘度的聚酯只需0.1-0.2%(摩尔)可用于发泡的磺化单体。因此,加入的二羧酸磺化单体的量一般与聚酯的固有粘度成反比。
为了获得本发明所需的高分子量聚酯,需要使用熔体相聚合和固态聚合的组合。使用这种组合是因为产生高分子量的熔体相聚合引起聚合物的热降解。在熔体聚合中,将二羧酸或其成酯衍生物和一种或多种二醇在150-300℃的温度和0.0266kPa(0.2mmHg)的压力下、在酯化和/或聚酯化催化剂的存在下加热。一般来说,所述二羧酸或其衍生物在大气压和指定范围低端的温度下与所述二醇酯化或酯交换。然后通过提高温度和降低压力来进行缩聚,同时从混合物除去过量二醇。所述缩聚反应持续到聚合物熔体的固有粘度达到0.35dL/g或更大。这时,将熔体冷却形成固体物并切粒、切屑、制粒或粉碎。
然后将得到的粒料或其它固体形式在215℃固态聚合,其中二醇通过将惰性气体诸如氮气循环或吹过所制粒料来除去。缩聚反应就此在固态下进行。所述固态缩聚反应持续到所述聚合物达到0.70dl/g或更大的固有粘度。
优选的本发明的共聚聚酯具有0.7-1.2dL/g的固有粘度并主要由(A)99.75-97.0%(摩尔)对苯二甲酸残基和0.25-0.3%(摩尔)含选自Mg++、Zn++、Ca++、Ba++和Co++的二价金属的间苯二甲酸5-磺酸盐残基以及(B)乙二醇残基组成,其中所述摩尔百分比是以100%(摩尔)二酸残基和100%(摩尔)乙二醇残基为基础计算的。特别优选所述间苯二甲酸5-磺酸盐残基源于间苯二甲酸5-磺酸镁的共聚聚酯。
本发明的聚合物组合物易于通过各种方法来发泡。所述方法包括将惰性气体诸如氮气或二氧化碳在挤压或模塑操作时注入到熔体中。或者,也可使用惰性烃类气体诸如甲烷、乙烷、丙烷、丁烷和戊烷、或氯氟烃、氢氯氟烃、氢氟烃等。另一种方法包括将化学发泡剂与聚酯干混并然后将组合物挤压或模塑成发泡制品。在挤压或模塑操作中,惰性气体诸如氮气从发泡剂释出并提供发泡作用。典型的发泡剂包括偶氮二碳酰胺、1,2-亚肼基碳酰胺、二亚硝基五亚甲基四胺、对甲苯磺酰基-1,2-亚肼基羧酸盐、5-苯基-3,6-二氢-1,3,4-氧杂-二嗪-2-酮;硼氢化钠;碳酸氢钠、5-苯基四唑、p,p’-氧基二(苯磺酰肼)等。还一种方法包括将碳酸钠或碳酸氢钠与一部分聚酯粒料共混、将一种有机酸诸如柠檬酸与另一部分聚酯粒料共混并然后将两种类型粒料的共混物在高温下挤压或模塑。碳酸钠和柠檬酸相互作用释放出的二氧化碳气体在所述熔体中提供了发泡作用。
在许多情况下,对于可发泡聚酯组合物来说,成核剂诸如滑石粉、TiO2、或少量聚烯烃物质诸如聚乙烯、聚丙烯、乙烯或丙烯共聚物等也是有益的添加剂。某些成核剂对于产生发泡点和影响发泡片或发泡物体的腔体大小十分重要。
公开了各种发泡方法和设备的专利包括美国专利5116881、5134028、4626183、5128383、4746478、5110844、5000991和4761256。其它有关发泡技术的背景资料可参见纽约州纽约市John Wiley andSons,Inc 1980年出版的Kirk-Othmer Encyclopedia of ChemicalTechnology,第三版,11卷,82到145页和纽约州纽约市JohnWileyand Sons,Inc 1985年出版的the Encyclopedia of Polymer Science andEngineering,第二版,2卷,434到446页。
许多其它组分也可加入到本发明的组合物中以增强共混物的性能特性。例如,此中可包括例如缓冲剂、抗氧化剂、金属钝化剂、着色剂、磷稳定剂、冲击性改善剂、成核剂、紫外光和热稳定剂等。所有这些添加剂和其用途均为本领域技术人员所熟悉,并不需要展开讨论。因此,只有有限的几个会被涉及,应该理解只要这些化合物不妨碍完成本发明的目标,其任何一种均可使用。
所需的添加剂包括冲击性改善剂和抗氧化剂。为本领域技术人员所熟悉并可用于本发明的典型的商品化冲击性改善剂的例子包括乙烯/丙烯三元共聚物、基于苯乙烯的嵌段共聚物和各种丙烯酸芯/壳型冲击性改善剂。所述冲击性改善剂可以占总组合物0.1-25%(重量)的常规量使用,并优选以占组合物0.1-10%(重量)的量使用。可用于本发明的典型的商品化抗氧化剂的例子包括但不限于受阻酚、亚磷酸盐、焦亚磷酸盐、聚亚磷酸盐和其混合物。也可使用芳族和脂族亚磷酸盐化合物的混合物。
此中所示结果所用的材料和试验方法如下:
固有粘度(I.V.)使用每100毫升溶剂(包括60%(重量)苯酚和40%(重量)四氯乙烷)含有0.50克聚合物在25℃下测定。
熔体强度和离模膨胀按照ASTM D3836测定:使用一台Instron流变仪将熔融聚酯在20秒-1的剪切速率下向下通过0.1英寸直径和0.25英寸长的模并让挤出物自由落下。离模膨胀通过测定刚从模孔出来的挤出物的直径并除以孔径来测定。离模膨胀以百分离模膨胀率来报告。测量(从模孔测定)挤出物六英寸长度末端的直径。从下式得到百分熔体强度: 其中D为保持有六英寸挤出物长度的挤出物英寸为单位的直径。如果D小于0.1英寸,那么熔体强度为负数,因为在挤出物的直径上没有增加。如果D大于0.1英寸,那么熔体强度为正数。
伸长:ASTM-D 638
挠曲模量:ASTM-D790
挠曲强度:ASTM-D790
热挠曲温度:ASTM-D785
伊佐德冲击强度:ASTM-D256
洛克威尔硬度:ASTM-D648
拉伸强度:ASTM-D638
所述聚酯的5-镁磺基间苯二甲酸残基的摩尔百分数通过采用X-射线荧光技术测量硫的百分含量来测定。所述二醇和酸基的摩尔百分数通过气相色谱或核磁共振来测定。
本发明提供的共聚聚酯和其制备方法进一步通过下面的实施例来说明,其中除非另加说明,所有份数和百分数均以重量计。
实施例1
将乙酸镁[Mg(OAc)2.4H2O;Aldrich;383.88g;3.58当量]溶解于在一个三升烧杯中的800毫升蒸馏水中。同时在另外的一升烧杯中制备4份5-钠代磺基间苯二甲酸二甲酯(各50克,0.169当量)的热蒸馏水(各200毫升)溶液。将含乙酸镁溶液的烧杯置于电热板上并使用磁搅棒剧烈搅拌。将四份5-钠代磺基间苯二甲酸二甲酯溶液一次一份缓慢加入到上面搅拌的溶液中。将得到的含白色沉淀物的混合物加热并继续搅拌直到获得透明溶液。停止搅拌和加热并让溶液冷却到室温。在大瓷漏斗中收集白色沉淀物并用少量冷蒸馏水(约100毫升)洗涤。将沉淀物转移到一个干净的三升烧杯中并剧烈搅拌加入1000毫升蒸馏水并使用大瓷漏斗过滤。将沉淀物再用冷蒸馏水(约100毫升)洗涤一次。接着,将沉淀物与1400毫升蒸馏水一起置于另一个干净的三升烧杯中,并在搅拌下在电热板上加热直到溶解得到透明溶液。将含这种溶液的烧杯用铝箔盖上并用48小时让其冷却和结晶。通过在瓷漏斗上过滤收集形成的白色晶体并在室温和中度真空下干燥2小时;然后在环境压力和温度下干燥24小时。然后在60℃和18英寸Hg真空下于烘箱中干燥24小时。干燥的产物为5-镁磺基间苯二甲酸二甲酯,其重量为190克(94.8%收率)。将产物通过分析技术诸如傅立叶红外、1H-核磁共振、卡尔费休滴定、DSC、TGA、重量法定硫、ICP等全面定性。
实施例2
在一个聚合物合成器中装入49.75%(摩尔)对苯二甲酸二甲酯、100%(摩尔)乙二醇、0.50%(摩尔)5-镁磺基间苯二甲酸二甲酯和1%(摩尔)乙酸钠。往该混合物加入20ppm Ti(以四异丙氧化钛的形式)、55ppm Mn(以乙酸锰四水合物的形式)、80ppm Co(以乙酸钴的形式)和230ppm Sb(以氧化锑的形式)。将混合物在剧烈搅拌下用氮气吹洗并开始加热到200℃。一小时后,温度上升到210℃。两小时后,加入108ppm P(以Zonyl A的形式)并将温度升到280℃。这时停止氮气冲洗并抽真空而使反应器中的压力降低到0.2mmHg。维持在280℃下搅拌并减压40分钟。接近该阶段结束时,由于树脂熔体的高熔体强度和熔体粘度,搅拌变得非常困难。如此制备熔体相制备的共聚物并且这种共聚物具有0.61dL/g的固有粘度、-68%的熔体强度和2%的离模膨胀。然后通过常规的固态化方法将聚合物固态化(在215℃8小时)而使其具有0.90dL/g的固有粘度。固态化的共聚聚酯具有约-21%的熔体强度和10%的离模膨胀。
参照具体的实施方案已经对本发明进行了详细说明,但是应当理解在本发明的精神和范围内可实施各种变化和修改。
Claims (7)
1.一种具有0.70-1.20dL/g的固有粘度和高至足可在挤压或模塑操作时发泡的熔体强度和熔体粘度的共聚聚酯,其中所述共聚聚酯主要包括(A)二酸残基,所述二酸残基包括(i)99.9-95%(摩尔)的一种具有8到12个碳原子的芳族二羧酸的残基和(ii)0.1-5.0%(摩尔)的含至少一个连接到一芳族环的二价金属磺酸盐基的芳族二羧酸磺酸盐单体的残基,以及(B)二醇残基,该残基包括至少一种具有2到8个碳原子的脂族或环脂族二醇的残基,所述%(摩尔)是以100%(摩尔)二羧酸残基和100%(摩尔)二醇残基为基础计算的。
2.按照权利要求1的共聚聚酯,其中所述二酸残基(A)包括99.9-95%(摩尔)对苯二甲酸残基、萘二甲酸残基或其混合物和(ii)0.1-5.0%(摩尔)间苯二甲酸5-金属磺酸盐的残基,其中所述金属为Mg++、Zn++、Ca++、Ba++或Co++。
3.一种具有0.7-1.2dL/g的固有粘度的共聚聚酯,其主要包括(A)99.75-97.0%(摩尔)对苯二甲酸残基和0.25-0.3%(摩尔)含一个选自Mg++、Zn++、Ca++、Ba++和Co++的二价金属的间苯二甲酸5-磺酸盐残基以及(B)乙二醇残基,其中所述%(摩尔)是以100%(摩尔)二酸残基和100%(摩尔)乙二醇残基为基础计算的。
4.按照权利要求3的共聚聚酯,其中所述间苯二甲酸5-磺酸盐残基源于间苯二甲酸5-磺酸镁。
5.一种包括一种共聚聚酯的发泡物品,所述共聚聚酯具有0.70-1.20dL/g的固有粘度和高至足可在挤压或模塑操作时发泡的熔体强度和熔体粘度,其中所述共聚聚酯主要包括(A)二酸残基,该二酸残基包括(i)99.9-95%(摩尔)的一种具有8到12个碳原子的芳族二羧酸的残基和(ii)0.1-5.0%(摩尔)的含至少一个连接到一芳环的二价金属磺酸盐基的芳族二羧酸磺酸盐单体的残基,以及(B)二醇残基,该二醇残基包括至少一种具有2到8个碳原子的脂族或环脂族二醇的残基,所述%(摩尔)是以100%(摩尔)二羧酸残基和100%(摩尔)二醇残基为基础计算的。
6.一种包括一种共聚聚酯的发泡物品,所述共聚聚酯具有0.7-1.2dL/g的固有粘度并主要包括(A)99.75-97.0%(摩尔)的对苯二甲酸残基和0.25-0.3%(摩尔)的含一个选自Mg++、Zn++、Ca++、Ba++和Co++的二价金属的间苯二甲酸5-磺酸盐残基以及(B)乙二醇残基,其中所述%(摩尔)是以100%(摩尔)二酸残基和100%(摩尔)乙二醇残基为基础计算的。
7.按照权利要求6的发泡制品,其中所述间苯二甲酸5-磺酸盐残基源于间苯二甲酸5-磺酸镁。
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US5363497P | 1997-07-23 | 1997-07-23 | |
US09/118,165 | 1998-07-16 | ||
US09/118,165 US5922782A (en) | 1997-07-23 | 1998-07-16 | Foamable copolyesters prepared from divalent metal containing co-ionomers |
US60/053,634 | 1998-07-16 |
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BR (1) | BR9811285A (zh) |
DE (1) | DE69827133T2 (zh) |
DK (1) | DK0998513T3 (zh) |
WO (1) | WO1999005198A1 (zh) |
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CN110952161A (zh) * | 2019-12-16 | 2020-04-03 | 扬州富威尔复合材料有限公司 | 一种低熔点弹性聚酯纤维及其制备方法 |
CN113290975A (zh) * | 2021-03-09 | 2021-08-24 | 浙江泰普森实业集团有限公司 | 一种可平封边的铝蜂窝夹芯复合桌面板及其制作方法 |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN110952161A (zh) * | 2019-12-16 | 2020-04-03 | 扬州富威尔复合材料有限公司 | 一种低熔点弹性聚酯纤维及其制备方法 |
CN110952161B (zh) * | 2019-12-16 | 2021-06-29 | 扬州富威尔复合材料有限公司 | 一种低熔点弹性聚酯纤维及其制备方法 |
CN113290975A (zh) * | 2021-03-09 | 2021-08-24 | 浙江泰普森实业集团有限公司 | 一种可平封边的铝蜂窝夹芯复合桌面板及其制作方法 |
CN113290975B (zh) * | 2021-03-09 | 2024-03-29 | 浙江泰普森实业集团有限公司 | 一种可平封边的铝蜂窝夹芯复合桌面板及其制作方法 |
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DE69827133D1 (de) | 2004-11-25 |
US5922782A (en) | 1999-07-13 |
WO1999005198A1 (en) | 1999-02-04 |
EP0998513B1 (en) | 2004-10-20 |
JP2002505343A (ja) | 2002-02-19 |
DK0998513T3 (da) | 2005-02-14 |
US5922829A (en) | 1999-07-13 |
EP0998513A1 (en) | 2000-05-10 |
BR9811285A (pt) | 2000-08-29 |
DE69827133T2 (de) | 2005-03-03 |
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