CN1953984B - 含有脲基和硅烷基团的碳二亚胺 - Google Patents
含有脲基和硅烷基团的碳二亚胺 Download PDFInfo
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Classifications
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
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- 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
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- C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
- C08G18/025—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing carbodiimide groups
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
本发明涉及含有至少一个通过脲基键合的硅烷基团的碳二亚胺。该碳二亚胺具有下列结构(I),其中n、R1、R2、R3、R4、R5、R6和R7具有下列含义:n为1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19或20;R1为脂族、环脂族、芳脂族或芳族的任选取代的且任选支链的基团;R2为脂族、环脂族、芳脂族或芳族的任选取代的且任选支链的基团;R3为脂族、环脂族、芳脂族或芳族的任选取代的且任选支链的基团;R4为脂族、环脂族、芳脂族或芳族的任选取代的且任选支链的基团;R5为甲基、乙基、-O-CH3、-O-CH2-CH3、-O-CH(CH3)2、-O-C(CH3)3或-O-CH2-CH2-O-CH3;R6为甲基、乙基、-O-CH3、-O-CH2-CH3、-O-CH(CH3)2、-O-C(CH3)3或-O-CH2-CH2-O-CH3;R7为甲基、乙基、-O-CH3、-O-CH2-CH3、-O-CH(CH3)2、-O-C(CH3)3或-O-CH2-CH2-O-CH3。
Description
本发明涉及含有至少一个,优选2-6个,特别优选4个通过脲基键合的硅烷基团的碳二亚胺以及制备这些碳二亚胺的方法。本发明进一步涉及包含本发明碳二亚胺和至少一种选自下组的化合物的混合物:含有酯结构的聚氨酯、聚对苯二甲酸乙二醇酯和/或聚对苯二甲酸丁二醇酯、聚醚酯、聚酰胺酯、聚己内酯、不饱和聚酯树脂、聚酰胺,尤其是包含本发明碳二亚胺且优选含有酯结构的热塑性聚氨酯。本说明书中的术语“硅烷基团”特别是指有机硅基团。
有机碳二亚胺是已知的且例如用作稳定剂以抑制含有酯基的化合物如聚加成和缩聚产物,如聚氨酯的水解降解。碳二亚胺可以通过众所周知的方法,例如经由碱性催化剂在单-或多异氰酸酯上的作用并消除二氧化碳而制备。合适催化剂的实例是含磷杂环化合物、金属羰基化物、phospholine、环磷烯(phospholene)和phospholidine及其氧化物和硫化物。
作为举例,DE-A 4 318 979、DE-A 4 442 724和EP-A 460 481描述了这些碳二亚胺、其制备及其作为稳定剂以抑制聚酯基塑料的水解断裂的用途。
现有技术还公开了碳二亚胺可以用烷氧基硅烷改性。EP-A 969 029、EP-A 785 222、EP-A 507 407、EP-A 1 162 237和US 4 118 536描述了例如具有烷氧基硅烷端基的碳二亚胺的制备。
本发明的目的是开发用做稳定剂以抑制聚酯基塑料的水解断裂的改进碳二亚胺,这些碳二亚胺理想的是易于掺入塑料的起始组分中或塑料本身中,而且不会不利地影响塑料,尤其是聚氨酯弹性体的动态和静态性能。特殊目的在于甚至在经常发生水解的条件下也保留待稳定塑料,尤其是热塑性聚氨酯的性能特征。
该目的由开头所述的碳二亚胺实现。
从纯统计学上讲,聚酯的水解降解将一个分子裂解成两个分子。这伴随有摩尔质量的相应降低。当使用碳二亚胺时,含酸的聚合物基团被拦截,结果是这两个分子相结合。然而,这并未解决分子量降低的问题。本发明碳二亚胺的特别优点在于首先它们作为水解稳定剂具有优异效力,其次它们能够通过碳二亚胺末端处的硅氧烷基团产生交联并因此在聚合物内增加摩尔质量。该特别优点尤其可以用于热塑性材料,在热塑性聚氨酯中特别有利。
本发明的碳二亚胺经由通过脲基将优选4个硅烷基团连接于碳二亚胺上而提供了特别良好的交联能力,这可以导致聚合物分子量显著增加,从而赋予聚合物非常良好的性能。
本发明碳二亚胺的其他优点如下:
■易于制备
■可以无副反应地掺入TPU中
■在加工温度(60℃)下粘度低
■在室温下可泵送
■储存稳定
■作为水解稳定剂有效,尤其当不存在催化剂时,即例如环磷烯氧化物的含量显著降低
■低挥发性
■低成本
■在本体中反应,即无需溶剂
当与常规碳二亚胺进行比较时,使用本发明碳二亚胺制备的TPU具有下列优点:
■在80℃的水中陈化期间具有改进的耐水解性
■在水下陈化期间拉伸强度和断裂拉伸应变改善(增加)
■在水分存在下使用期间硅氧烷基团原位交联,即无需额外的交联操作
■溶胀性能降低
■耐热性增加
■HDT增加
■弹性模量增加
■维卡点增加
优选下列碳二亚胺:
其中n、R1、R2、R3、R4、R5、R6和R7的含义如下:
n:1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19或20,优选2-15,特别优选3-10,
R1:脂族、环脂族、芳脂族(araliphatic)或芳族的,合适的话取代的,合适的话支链的基团,优选具有1-20个,优选2-10个,特别优选2-4个碳原子的亚烷基,
R2:脂族、环脂族、芳脂族或芳族的,合适的话取代的,合适的话支链的基团,优选具有1-20个,优选2-10个,特别优选2-4个碳原子的亚烷基,
R3:脂族、环脂族、芳脂族或芳族的,合适的话取代的,合适的话支链的基团,优选具有1-20个,优选2-10个,特别优选2-4个碳原子的亚烷基,
R4:脂族、环脂族、芳脂族或芳族的,合适的话取代的,合适的话支链的基团,优选具有1-20个,优选2-10个,特别优选2-4个碳原子的亚烷基,
R5:甲基、乙基、-O-CH3、-O-CH2-CH3、-O-CH(CH3)2、-O-C(CH3)3或-O-CH2-CH2-O-CH3,优选-O-CH3或-O-CH2-CH3,特别优选-O-CH3,
R6:甲基、乙基、-O-CH3、-O-CH2-CH3、-O-CH(CH3)2、-O-C(CH3)3或-O-CH2-CH2-O-CH3,优选-O-CH3或-O-CH2-CH3,特别优选-O-CH3,
R7:甲基、乙基、-O-CH3、-O-CH2-CH3、-O-CH(CH3)2、-O-C(CH3)3或-O-CH2-CH2-O-CH3,优选-O-CH3或-O-CH2-CH3,特别优选-O-CH3。特别优选下列碳二亚胺:
其中n的含义如下:1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19或20,优选2-15,特别优选3-10。
实质上,本发明碳二亚胺的制备经由两个反应步骤进行。首先,经由异氰酸酯基团相互之间的众所周知的反应并消除二氧化碳而生产碳二亚胺结构(1),该反应在对该反应是已知的且在开头所述的常规催化剂存在下进行,其次,异氰酸酯基团与具有至少一个,优选2个硅烷基团的仲胺反应(2),得到脲结构。这两个基本步骤(1)和(2)在该方法中的顺序可以根据需要设定,只要对各反应存在游离异氰酸酯基团。
作为举例,在一种得到本发明碳二亚胺的方法中使1,3-二(1-甲基-1-异氰酸酯基乙基)苯在催化剂存在下反应并消除二氧化碳得到碳二亚胺,然后使具有异氰酸酯基团的碳二亚胺与具有至少一个,优选2个硅烷基团,优选三烷氧基硅烷基团的仲胺反应。具有异氰酸酯基团的碳二亚胺的NCO基团与仲胺中对异氰酸酯呈反应性的那些基团,尤其是仲氨基的摩尔比通常为10∶1-0.2∶1,优选5∶1-0.5∶1,特别优选1∶1-0.5∶1,尤其是1∶1。
作为替换,在得到本发明碳二亚胺的另一方法中,使1,3-二(1-甲基-1-异氰酸酯基乙基)苯与摩尔比不足1∶1(submolar)的含有至少一个,优选2个硅烷基团,优选三烷氧基硅烷基团的仲胺反应,然后使具有异氰酸酯基团的反应产物在催化剂存在下反应并释放二氧化碳而得到碳二亚胺。
在本方法的该方案中,首先使至多50重量%,优选至多23重量%二异氰酸酯的异氰酸酯基团与仲胺反应,然后使所有或部分游离异氰酸酯基团在催化剂存在下缩合并释放二氧化碳而得到碳二亚胺和/或低聚聚碳二亚胺。
优选首先进行得到碳二亚胺的反应,然后进行具有异氰酸酯基团的碳二亚胺与仲胺的反应。
产物,即本发明碳二亚胺优选具有的NCO含量小于1.0重量%,特别优选0.5-0.01重量%。
经由二异氰酸酯的反应制备本发明碳二亚胺的方法的步骤(I)可以在升高温度,例如50-200℃,优选150-185℃的温度下,有利地在催化剂存在下缩合,同时消除二氧化碳。作为举例,GB-A-1 083 410、DE-B 1 130594(GB-A-851 936)和DE-A-1 156 401(US-A-3 502 722)描述了适于此的方法。已经证明优选合适的催化剂例如为磷化合物,优选选自环磷烯、环磷烯氧化物、phospholidine和phospholine氧化物。聚碳二亚胺的形成通常在反应混合物具有所需NCO基团含量时终止。为此,可以在减压下蒸除催化剂或通过添加钝化剂如三氯化磷使催化剂失活。根据本发明,优选其中用于形成碳二亚胺的催化剂含量小于5.0ppm的碳二亚胺。此外,聚碳二亚胺可以在有或没有在反应条件下呈惰性的溶剂存在下制备。
本领域熟练技术人员可以通过适当选择反应条件如反应温度、催化剂类型和催化剂量以及反应时间而以常规方式调节缩合度。监测反应的最简单方法是测定NCO含量。可以利用其他参数如粘度升高、颜色加深或CO2释放来监测和控制反应。
用于制备本发明碳二亚胺的异氰酸酯可以包括众所周知的异氰酸酯,优选二异氰酸酯。优选使用在下文中也称为TMXDI的1,3-二(1-甲基-1-异氰酸酯基乙基)苯。TMXDI可以与其他众所周知的异氰酸酯混合使用,后者如六亚甲基二异氰酸酯、1-异氰酸酯基-3,3,5-三甲基-5-异氰酸酯基甲基环己烷(异佛尔酮二异氰酸酯)、二(环己基)甲烷二异氰酸酯、三甲基六亚甲基二异氰酸酯、十二烷二异氰酸酯、辛烷二异氰酸酯和/或环己烷-1,4-二异氰酸酯。在这种情况下,优选同时使用至少30%的TMXDI。
本发明碳二亚胺含有至少一个,优选1-20个碳二亚胺结构,平均缩合度(数均),即本发明碳二亚胺中碳二亚胺结构的平均数,特别优选为1-10,尤其优选2-8,尤其是4-6。
对于与异氰酸酯基团的反应以及对于通过脲基引入硅烷基团,可以使用众所周知的具有硅烷基团且优选除了仲氨基外优选不含其他对异氰酸酯呈反应性的基团,尤其羟基和/或伯氨基的仲胺。优选将下列化合物用于与异氰酸酯反应,且这些化合物可以由Osi Specialties得到:
本发明单碳二亚胺和/或低聚聚碳二亚胺作为羧基化合物的受体具有优异的适合性且因此优选用作稳定剂以抑制含有酯基的化合物的水解降解,所述含酯基的化合物例如为含有酯基的聚合物,例如缩聚产物,如热塑性聚酯,例如聚对苯二甲酸乙二醇酯和聚对苯二甲酸丁二醇酯,聚醚酯,聚酰胺,聚酰胺酯,聚己内酯以及不饱和聚酯树脂,还有聚酯酯(polyesterester),例如由聚对苯二甲酸乙二醇酯或聚对苯二甲酸丁二醇酯和聚己内酯组成的嵌段共聚物。还有含有酯基的聚加成产物,如聚氨酯、聚脲和聚氨酯-聚脲弹性体。这些含有酯基的化合物是众所周知的。标准文献对其原料、制备方法、结构和性能具有许多说明。本发明(聚)碳二亚胺在制备聚氨酯的结构组分中的良好溶解性及其与形成的聚氨酯的良好相容性使得它们特别适合作为稳定剂以抑制聚氨酯,优选致密或多孔聚氨酯弹性体,尤其是热塑性聚氨酯以及多孔或致密弹性体的水解降解。
本发明碳二亚胺在待稳定的且含有酯基的缩聚或聚加成产物中的浓度基于混合物的总重量通常为0.05-10重量%,优选0.1-5重量%。该浓度在个别情况下还可能更高,这取决于塑料所暴露的水解应力水平。
可以使用各种方法将可以根据本发明使用的碳二亚胺引入待稳定的且含有酯基的产物中。例如可以将本发明碳二亚胺与制备聚加成产物的结构组分之一混合,例如与制备聚氨酯的多异氰酸酯和/或多羟基化合物混合,或者可以将碳二亚胺计量加入制备聚氨酯的反应混合物中。在另一程序中,可以将本发明碳二亚胺掺入完全反应的聚加成或缩聚产物熔体中。然而,还可以将聚加成或缩聚产物的颗粒用本发明碳二亚胺涂敷,或与粉碎的、成丸的或造粒的本发明碳二亚胺混合并在随后通过熔体挤出生产模制品的过程中引入塑料组合物中。在制备可倾注聚氨酯弹性体和聚酯基TPU的一个优选实施方案中,首先用本发明碳二亚胺处理含有羧基的聚酯多元醇以降低酸含量,然后使其与多异氰酸酯反应,合适的话加入另外量的碳二亚胺,以及合适的话在额外助剂和添加剂存在下进行反应。还可以通过异氰酸酯组分将本发明碳二亚胺引入聚氨酯中。然而,本发明碳二亚胺在将它们在常规制造方法期间引入含有酯基的聚合物中时特别有用。
本发明碳二亚胺特别优选在制备聚氨酯,例如多孔聚氨酯如微孔聚氨酯,优选聚氨酯弹性体,尤其是热塑性聚氨酯的过程中使用。这些聚氨酯,尤其是聚氨酯弹性体可以通过常规起始组分在本发明碳二亚胺存在下的已知反应而制备,所述组分即异氰酸酯,对异氰酸酯呈反应性的化合物,合适的话发泡剂,优选水,以及合适的话催化剂,还有助剂和/或添加剂。这里优选将本发明碳二亚胺加入包含发泡剂,优选水的组分中。
因此优选的是优选经由异氰酸酯,对异氰酸酯呈反应性的化合物,合适的话发泡剂以及合适的话催化剂,还有助剂和/或添加剂的反应制备聚氨酯,优选热塑性聚氨酯的方法,其中该反应在本发明碳二亚胺存在下进行。
碳二亚胺不仅可以有效用作稳定剂以抑制含有酯基的聚加成或缩聚产物的水解降解,或用于可以用来制备含聚酯的塑料,尤其是聚氨酯橡胶的聚酯醇的脱酸化,而且例如还适于在制备聚酯过程中当达到所需缩聚度时终止酯化反应。
本发明可热塑性加工的聚氨酯弹性体可以用于挤出产品、注塑产品或压延产品以及用于粉末涂覆(powder slush)工艺。
本发明碳二亚胺优选用于热塑性聚氨酯中。本发明因此提供了制备用有机硅基团改性的热塑性聚氨酯(在本说明书中也称为硅烷改性的热塑性聚氨酯,即具有有机硅基团的热塑性聚氨酯)的方法,以及可以如此得到的可交联TPU,尤其是电缆护套、纤维或软管,特别是压缩空气软管,以及通过硅烷基团交联的对应产品。本发明还提供了基于已经通过硅烷基团,尤其是通过硅氧烷基团交联的热塑性聚氨酯的电缆护套、纤维或软管,尤其是压缩空气软管,特别是其中交联的热塑性聚氨酯具有的肖氏A硬度为85-98且根据DIN EN ISO 306(10N/120K/h)的维卡点高于130℃,特别优选高于140℃,尤其高于145℃的电缆护套、纤维或软管。
使用常规方法如注塑或挤出来加工根据本发明制备的通常呈颗粒或粉末形式的TPU,得到注塑产品和挤出产品,例如所需膜、模制品、滚柱、纤维、汽车中的涂层、软管、电缆插头、波纹管、牵引电缆、电缆护套、垫圈、驱动带或缓冲元件。这些注塑和挤出产品还可以由配混材料组成,所述配混材料包含本发明的TPU和至少一种其他热塑性材料,特别是聚乙烯、聚丙烯、聚酯、聚醚、聚苯乙烯、PVC、ABS、ASA、SAN、聚丙烯腈、EVA、PBT、PET、聚甲醛。根据本发明制备的TPU尤其可以用于生产开头所述的产品。
优选的方法使用以众所周知的方法硅烷改性的热塑性聚氨酯来纺丝纤维或挤出软管,尤其是压缩空气软管,然后借助水分通过硅烷基团交联热塑性聚氨酯,合适的话使用加速交联的催化剂。经由硅烷基团的交联反应对本领域熟练技术人员而言是熟知的且是众所周知的。该交联通常经由水分发生且可以通过热或已知用于此的催化剂如路易斯酸、路易斯碱、布朗斯台德酸、布朗斯台德碱加速。待用于优选借助水分交联的催化剂优选为乙酸,有机金属化合物如钛酸酯,铁化合物如乙酰丙酮铁,锡化合物如二乙酸亚锡、二辛酸亚锡、二月桂酸亚锡,或脂族羧酸的二烷基锡盐如二乙酸二丁基锡、二月桂酸二丁基锡等,特别优选二月桂酸亚锡和/或乙酸。
实施例
实施例1:
制备本发明稳定剂:异氰酸酯段
在2.0重量份1-甲基-2-环磷烯1-氧化物存在下无溶剂地将1000重量份(4.1mol)NCO含量为34.4重量%的1,3-二(1-甲基-1-异氰酸酯基乙基)苯加热到180℃并在该温度下缩合,温和释放出二氧化碳。一旦反应混合物的NCO含量达到10重量%-为此所需反应时间为约24小时,通过在190℃的温度和0.2毫巴的压力下蒸馏除去加入的催化剂和残留的未反应1,3-二(1-甲基-1-异氰酸酯基乙基)苯。
由此得到730重量份由单-和低聚聚碳二亚胺组成的混合物,该混合物的NCO含量为8重量%,-N=C=N-基团含量为15%,熔点<30℃且根据DIN 6162测定的碘色数为4.0。
使用1H NMR和IR光谱来表征具有异氰酸酯基团且由单-和低聚聚碳二亚胺组成的混合物的结构。
实施例2:
制备本发明稳定剂:脲形成
将来自实施例1的产物加热到100℃。在剧烈搅拌下在约5小时内滴加445g二(三甲氧基甲硅烷基丙基)胺(A-1170硅烷,来自GESilicone Osi Specialties)。然后将反应混合物在120℃下再搅拌2小时。
使用1H NMR和IR光谱来表征含有甲氧基甲硅烷基的聚碳二亚胺的结构。
实施例3:
生产TPU样品
多元醇1)
聚酯多元醇BASF Aktiengesellschaft;(丁二醇/己二醇己二酸酯,分子量2000,OH数=56.1)
多元醇2)
聚酯多元醇BASF Aktiengesellschaft;(丁二醇/乙二醇己二酸酯,分子量2000,OH数=56.1)
将表1所述多元醇在80℃下与1,4-丁二醇混合。然后在搅拌下加入表1所列的各种水解稳定剂。
表1
H01:聚合的碳二亚胺(水解稳定剂),购自Elastogran GmbH
1:单体碳二亚胺(水解稳定剂),购自Rheinchemie GmbH
稳定剂1:在实施例1中制备的稳定剂
在搅拌下将二醇混合物控制到80℃。然后加入425g 4,4’-MDI(亚甲基二苯基二异氰酸酯)并继续搅拌直到反应混合物呈均相。然后将混合物倾入扁平的特氟隆盘中并在125℃下在热板上退火10分钟。将所得TPU膜在100℃下在加热箱中退火24小时。将流延的片材造粒,然后在注塑机中加工而得到2mm注塑片材。测定机械性能并将其列于表2中。
表2
稳定方法 | 肖氏硬度[A] | 拉伸强度[mPas] | 断裂拉伸应变[%] | 抗撕裂传播性[N/mm] | 磨耗[mm<sup>3</sup>] | 密度[g/cm<sup>3</sup>] |
试验1 | 82 | 49 | 580 | 65 | 35 | 1.183 |
试验2 | 82 | 52 | 600 | 68 | 34 | 1.183 |
试验3 | 83 | 47 | 590 | 69 | 35 | 1.182 |
试验4 | 84 | 44 | 630 | 75 | 33 | 1.185 |
稳定方法 | 肖氏硬度[A] | 拉伸强度[mPas] | 断裂拉伸应变[%] | 抗撕裂传播性[N/mm] | 磨耗[mm<sup>3</sup>] | 密度[g/cm<sup>3</sup>] |
试验5 | 84 | 47 | 700 | 67 | 36 | 1.218 |
试验6 | 85 | 50 | 700 | 73 | 41 | 1.218 |
试验7 | 84 | 49 | 680 | 71 | 40 | 1.220 |
稳定方法 | 肖氏硬度[A] | 拉伸强度[mPas] | 断裂拉伸应变[%] | 抗撕裂传播性[N/mm] | 磨耗[mm<sup>3</sup>] | 密度[g/cm<sup>3</sup>] |
试验8 | 85 | 47 | 620 | 70 | 38 | 1.225 |
表3
性能 | 单位 | DIN | ISO |
硬度 | 肖氏A | 53505 | 868 |
密度 | kg/m<sup>3</sup> | 53479 | 1183 |
拉伸强度 | MPa | 53504 | 37 |
断裂拉伸应变 | % | 53504 | 37 |
抗撕裂传播性 | N/mm | 53515 | 34 |
磨耗 | mm<sup>3</sup> | 53516 | 4649 |
耐水解性的测定
由注塑片材冲压出S2试样并将它们置于含有蒸馏水且放置在处于确定温度(80℃)的温控箱中的玻璃容器(250和500ml)中。在一定间隔(例如每周)取出3个试样。然后将样品在温度和湿度的标准23/50条件下老化不少于30分钟,并测定拉伸强度和断裂拉伸应变。
表4:
测量拉伸强度[MPa]作为时间的函数[天]
经过的时间[天] | 试验1 | 试验2 | 试验3 | 试验4 |
0 | 49 | 52 | 47 | 44 |
7 | 44 | 44 | 44 | 25 |
14 | 45 | 46 | 45 | 7 |
21 | 44 | 44 | 44 | 瓦解 |
28 | 43 | 43 | 44 |
经过的时间[天] | 试验1 | 试验2 | 试验3 | 试验4 |
35 | 42 | 40 | 43 | |
42 | 42 | 38 | 43 | |
49 | 42 | 40 | 43 | |
56 | 42 | 33 | 42 | |
63 | 40 | 17 | 42 | |
70 | 41 | 4.75 | 41 | |
77 | 36 | 2 | 42 | |
84 | 24 | 瓦解 | 40 | |
91 | 6 | 37 | ||
98 | 瓦解 | 33 | ||
105 | 18 | |||
112 | 2 |
表5:
测量断裂拉伸应变[%]作为时间的函数[天]
经过的时间[天] | 试验1 | 试验2 | 试验3 | 试验4 |
0 | 580 | 600 | 590 | 630 |
7 | 520 | 560 | 550 | 770 |
14 | 550 | 570 | 580 | 530 |
21 | 540 | 580 | 590 | 瓦解 |
28 | 550 | 600 | 590 | |
35 | 540 | 580 | 600 | |
42 | 620 | 650 | 590 |
经过的时间[天] | 试验1 | 试验2 | 试验3 | 试验4 |
49 | 590 | 650 | 610 | |
56 | 620 | 730 | 610 | |
63 | 590 | 780 | 620 | |
70 | 610 | 275 | 610 | |
77 | 610 | 40 | 610 | |
84 | 750 | 瓦解 | 600 | |
91 | 450 | 650 | ||
98 | 瓦解 | 800 | ||
105 | 350 | |||
112 | 80 |
表6:
测量拉伸强度[MPa]作为时间的函数[天]
经过的时间[天] | 试验5 | 试验6 | 试验7 | 试验8 |
0 | 47 | 50 | 49 | 47 |
7 | 42 | 41 | 45 | 27 |
14 | - | - | - | 6 |
21 | 39 | 36 | 41 | 瓦解 |
28 | 35 | 32 | 38 | |
35 | 27 | 16 | 33 | |
42 | 7 | 4 | 31 | |
49 | 瓦解 | 瓦解 | 25 | |
56 | 3 |
经过的时间[天] | 试验5 | 试验6 | 试验7 | 试验8 |
63 | 瓦解 | |||
70 |
表7:
测量断裂拉伸应变[%]作为时间的函数[天]
经过的时间[天] | 试验5 | 试验6 | 试验7 | 试验8 |
0 | 700 | 700 | 680 | 620 |
7 | 640 | 660 | 650 | 770 |
14 | - | - | - | 420 |
21 | 690 | 700 | 710 | 瓦解 |
28 | 680 | 780 | 730 | |
35 | 840 | 900 | 750 | |
42 | 580 | 280 | 810 | |
49 | 瓦解 | 瓦解 | 950 | |
56 | 250 | |||
63 | 瓦解 | |||
70 |
Claims (7)
1.具有下列结构的碳二亚胺:
其中n、R1、R2、R3、R4、R5、R6和R7具有下列含义:
n:1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19或20,
R1:合适的话支链的具有1-20个碳原子的亚烷基,
R2:合适的话支链的具有1-20个碳原子的亚烷基,
R3:合适的话支链的具有1-20个碳原子的亚烷基,
R4:合适的话支链的具有1-20个碳原子的亚烷基,
R5:甲基、乙基、-O-CH3、-O-CH2-CH3、-O-CH(CH3)2、-O-C(CH3)3或-O-CH2-CH2-O-CH3,
R6:甲基、乙基、-O-CH3、-O-CH2-CH3、-O-CH(CH3)2、-O-C(CH3)3或-O-CH2-CH2-O-CH3,
R7:甲基、乙基、-O-CH3、-O-CH2-CH3、-O-CH(CH3)2、-O-C(CH3)3或-O-CH2-CH2-O-CH3。
3.一种包含根据权利要求1或2的碳二亚胺和至少一种选自下组的化合物的混合物:具有酯结构的聚氨酯、聚对苯二甲酸乙二醇酯和/或聚对苯二甲酸丁二醇酯、聚醚酯、聚酰胺酯、聚己内酯、不饱和聚酯树脂、聚酰胺。
4.一种包含根据权利要求1或2的碳二亚胺的热塑性聚氨酯。
5.一种制备根据权利要求1的碳二亚胺的方法,包括使1,3-二(1-甲基-1-异氰酸酯基乙基)苯在催化剂存在下反应并消除二氧化碳而得到碳二亚胺,然后使具有异氰酸酯基团的碳二亚胺与含有至少一个硅烷基团且除了仲氨基外不含其他对异氰酸酯呈反应性的基团的仲胺反应。
6.一种制备根据权利要求1的碳二亚胺的方法,包括使1,3-二(1-甲基-1-异氰酸酯基乙基)苯与摩尔比不足1∶1的含有至少一个硅烷基团且除了仲氨基外不含其他对异氰酸酯呈反应性的基团的仲胺反应,然后使具有异氰酸酯基团的反应产物在催化剂存在下反应并释放二氧化碳而得到碳二亚胺。
7.一种制备聚氨酯的方法,包括在根据权利要求1或2的碳二亚胺存在下进行反应。
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DE102004024196A DE102004024196A1 (de) | 2004-05-13 | 2004-05-13 | Carbodiimide enthaltend Harnstoffgruppen und Silangruppen |
PCT/EP2005/004917 WO2005111048A1 (de) | 2004-05-13 | 2005-05-06 | Carbodiimide enthaltend harnstoffgruppen und silangruppen |
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DE102004024205A1 (de) * | 2004-05-13 | 2005-12-08 | Basf Ag | Polyurethane enthaltend Carbodiimide |
CN101370842B (zh) * | 2006-01-19 | 2011-11-09 | 巴斯夫欧洲公司 | 含有硅烷基团和碳二亚胺基团的聚氨酯粘合剂 |
JP4916007B2 (ja) | 2007-03-01 | 2012-04-11 | 三洋化成工業株式会社 | スラッシュ成形用樹脂粉末組成物及び成形品 |
US8900667B2 (en) * | 2009-12-18 | 2014-12-02 | Ppg Industries Ohio, Inc. | One-component, ambient curable waterborne coating compositions, related methods and coated substrates |
EP2542601A1 (en) * | 2010-03-02 | 2013-01-09 | PPG Industries Ohio, Inc. | One-component, ambient curable waterborne coating compositions, related methods and coated substrates |
US8623945B2 (en) | 2011-03-18 | 2014-01-07 | Basf Se | Use of oligomeric carbodiimides as stabilizers |
WO2012126797A2 (de) | 2011-03-18 | 2012-09-27 | Basf Se | Verwendung oligomerer carbodiimide als stabilisatoren |
JP2014533752A (ja) | 2011-11-17 | 2014-12-15 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | 重縮合物を加水分解安定化するための添加剤 |
US9376596B2 (en) * | 2012-03-09 | 2016-06-28 | Hitachi Metals, Ltd. | Adhesive film and flat cable using the same |
JP6286433B2 (ja) * | 2012-09-19 | 2018-02-28 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | ポリカルボジイミドの製造方法 |
CN106029730B (zh) * | 2014-02-19 | 2020-07-10 | 巴斯夫欧洲公司 | 由聚酯聚氨酯组成的耐水解聚氨酯模制品 |
EP3517572B1 (en) * | 2017-11-30 | 2021-01-27 | Otis Elevator Company | Load bearing traction members and method |
FR3125423B1 (fr) | 2021-07-23 | 2024-04-26 | Oreal | Composition cosmétique comprenant au moins un composé (poly)carbodiimide et au moins un alcoxysilane aminé |
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EP0628541A1 (de) * | 1993-06-08 | 1994-12-14 | BASF Aktiengesellschaft | Carbodiimide und/oder oligomere Polycarbodiimide auf Basis von 1,3-Bis-(1-methyl-1-isocyanatoethyl)-benzol, ein Verfahren zu ihrer Herstellung und ihre Verwendung als Hydrolysestabilisator |
EP0969029A1 (en) * | 1998-06-05 | 2000-01-05 | Basf Corporation | Novel polycarbodiimide polymers and their use as adhesive intermediate layers in automotive coatings |
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