CN113366043A - 可用于制备聚氨酯泡沫的组合物 - Google Patents
可用于制备聚氨酯泡沫的组合物 Download PDFInfo
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- CN113366043A CN113366043A CN202080011485.8A CN202080011485A CN113366043A CN 113366043 A CN113366043 A CN 113366043A CN 202080011485 A CN202080011485 A CN 202080011485A CN 113366043 A CN113366043 A CN 113366043A
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- polyurethane
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- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 54
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- 229920005862 polyol Polymers 0.000 claims abstract description 58
- 150000003077 polyols Chemical class 0.000 claims abstract description 58
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 52
- 229920000570 polyether Polymers 0.000 claims abstract description 52
- 239000012948 isocyanate Substances 0.000 claims description 22
- 150000002513 isocyanates Chemical class 0.000 claims description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 20
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 6
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- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及用某些聚四氢呋喃和任选的聚醚多元醇制备聚氨酯泡沫。该聚氨酯泡沫的特征在于与传统聚氨酯泡沫相比在低温下的硬度增加低并且适合用于可以暴露于低温的产品如雪地靴。
Description
发明领域
本发明涉及一种可用于可能暴露于低温的产品,如运动用品,优选运动鞋或雪地靴,更优选其鞋底中的聚氨酯泡沫。
背景
聚氨酯是一种由氨基甲酸酯(尿烷)键结合的有机单元构成的聚合物并且通常通过具有至少两个异氰酸酯基团的异氰酸酯与具有至少两个羟基的多元醇反应而生产。聚氨酯用于制造高回弹泡沫座椅、鞋类、硬质泡沫保温板、微孔泡沫密封和垫圈、耐用的弹性车轮和轮胎、汽车悬架衬套、电气封装化合物、高性能粘合剂、表面涂料和表面密封剂、合成纤维、地毯衬垫、硬塑料部件、安全套和软管等。
当聚氨酯以泡沫形式用于诸如雪地靴的应用中时,一个重要考量是在低温下的硬度增加程度,这通常与穿戴者的不适感有关。另一考量是随着时间的推移该增加的速率,特别是在例如最初4-6小时内。在该最初阶段之后,预期暴露于低温将随着穿戴者不会在低温下呆甚至更长时间而结束。
US 5234961A公开了一种使用二苯基甲烷二异氰酸酯:聚四氢呋喃预聚物得到的水发整皮聚氨酯泡沫。与不使用该预聚物制备的水发整皮泡沫相比较时,聚氨酯泡沫具有改进的抗磨性和冷挠曲特性。该聚四氢呋喃具有250-2000的分子量。
WO 2018/160945A1公开了一种具有改进机械性能如球回弹性的聚氨酯弹性体泡沫,使用分子量为1900-2100且羟值为53-60的聚四亚甲基醚二醇(聚四氢呋喃)和单乙二醇的组合与4,4'-二苯基甲烷二异氰酸酯的反应产物作为异氰酸酯预聚物制备。
然而,这些申请均未教导如何生产可用于可能暴露于低温的产品,如运动用品,优选运动鞋或雪地靴,更优选其鞋底的在低温下硬度增加或其速率降低的聚氨酯泡沫。
发明概述
本发明的发明人已经发现在聚氨酯泡沫的制备中使用某些聚四氢呋喃作为多元醇可以显著降低聚氨酯泡沫在低温下的硬度增加程度。此外,在聚氨酯泡沫的制备中使用某些额外的聚醚多元醇作为额外的多元醇,在低温下硬度增加程度的降低将减少;然而,随着时间的推移硬度增加的速率将显著降低。基于该类发现,发明人得到了一系列适合用于鞋类应用中的聚氨酯泡沫。
本发明涉及一种由组分A和B构成的双组分聚氨酯形成组合物,其中组分A包含平均羟基官能度不大于3,优选约2且数均分子量对各羟基而言为600-1500,优选750-1250,更优选900-1100的聚四氢呋喃A和聚四氢呋喃以外的平均羟基官能度不大于3,优选约2且数均分子量对各羟基而言为1500-2500,优选1800-2200的任选聚醚多元醇A;并且组分B包含NCO含量基于组分B的总重量为12-25重量%,更优选14-23重量%,最优选15-22重量%的异氰酸酯预聚物,该异氰酸酯预聚物通过使二异氰酸酯和/或多异氰酸酯与平均羟基官能度不大于3,优选约2且数均分子量对各羟基而言为600-1500,优选750-1250,更优选900-1100的聚四氢呋喃B和/或聚四氢呋喃以外的平均羟基官能度不大于3,优选约2且数均分子量对各羟基而言为1500-2500,优选1800-2200的聚醚多元醇B反应而制备。
优选本发明涉及本发明的聚氨酯形成组合物,其中聚四氢呋喃A和聚四氢呋喃B的总和基于整个聚氨酯形成组合物中聚醚多元醇A和B以及聚四氢呋喃A和B的总量为60-100重量%,优选60-80重量%。
优选该聚氨酯形成组合物进一步包含催化剂、发泡剂、表面活性剂、扩链剂和其他任选添加剂作为组分A的成分。
优选聚醚多元醇A和B中的烷氧基重复单元选自乙氧基或丙氧基或其混合物。
本发明还涉及一种由本发明聚氨酯形成组合物制备聚氨酯泡沫的方法,包括:
i)通过混合其成分并使该二异氰酸酯和/或该多异氰酸酯与聚四氢呋喃B和/或聚醚多元醇B反应而制备组分B的步骤,
ii)通过混合其成分而制备组分A的步骤,以及
iii)通过在具有所需形状的模具中混合组分A和B并使组分B中的该异氰酸酯预聚物与组分A中的聚四氢呋喃A和聚四氢呋喃以外的该任选聚醚多元醇A反应而制备该聚氨酯泡沫的步骤。
本发明还涉及一种可以由本发明方法得到的聚氨酯泡沫。
本发明还涉及一种可以暴露于低温的产品,包含本发明的聚氨酯泡沫。
优选该可以暴露于低温的产品是运动用品,优选运动鞋或雪地靴,更优选其鞋底。
详细说明
本发明的聚氨酯泡沫由一种由组分A和组分B构成的双组分聚氨酯形成组合物生产。
组分A包含聚四氢呋喃(下文称为聚四氢呋喃A)和聚四氢呋喃以外的任选聚醚多元醇(下文称为聚醚多元醇A)。组分A可以进一步包含可用于聚氨酯泡沫生产中的传统添加剂,特别是在聚氨酯泡沫的形成中通常加入组分A(即具有多元醇的组分)中的那些。
组分B包含可以通过使二异氰酸酯和/或多异氰酸酯与聚四氢呋喃(下文称为聚四氢呋喃B)和/或聚四氢呋喃以外的聚醚多元醇(下文称为聚醚多元醇B)反应而制备的异氰酸酯预聚物。组分B可以进一步包含可用于聚氨酯泡沫生产中的传统添加剂,特别是在聚氨酯泡沫的形成中通常加入组分B(即具有异氰酸酯的组分)中的那些。
聚四氢呋喃A和B可以相互相同或不同并且可以分别独立地选自常用于制备聚氨酯泡沫的那些。
聚四氢呋喃A和B可以分别具有1200-3000,优选1500-2500,更优选1800-2200的数均分子量和不大于3,优选2-3,更优选约2的平均羟基官能团。
聚醚多元醇A和B可以选自常用于制备聚氨酯泡沫的聚醚多元醇。该聚醚多元醇通常是氧化烯(如氧化乙烯、氧化丙烯或其混合物)在起始多元醇(如甘油、丙二醇或其混合物)上的聚加成反应产物。显然,聚醚多元醇A和B不能是聚四氢呋喃。
对于聚醚多元醇A和B的聚合物分子中的各羟基官能基团而言,聚醚多元醇A和B可以分别具有1500-2500,优选1800-2200的数均分子量。例如,对于具有两个羟基的聚醚多元醇A和B的聚合物分子而言,数均分子量应为3000-5000,优选3600-4400,另一方面,对于具有三个羟基的聚醚多元醇A和B的聚合物分子而言,数均分子量应为4500-7500,优选5400-6600。聚醚多元醇A和B应分别具有不大于3,优选2-3,更优选约2的平均羟基官能度。
该异氰酸酯预聚物可以选自常用于制备聚氨酯泡沫的那些。该异氰酸酯预聚物可以通过使用已知方法使二异氰酸酯和/或多异氰酸酯与聚四氢呋喃B和/或聚醚多元醇B在已知条件下反应而制备。该异氰酸酯预聚物通常在合成后直接使用而不分离未反应二异氰酸酯和/或多异氰酸酯、未反应聚四氢呋喃和/或多元醇以及该合成过程中存在的其他化合物。优选该异氰酸酯预聚物可以在紧临使用前现场制备。
用于制备该双组分聚氨酯形成组合物的异氰酸酯预聚物的二异氰酸酯和/或多异氰酸酯例如是4,4'-亚甲基二苯基异氰酸酯和2,4'-亚甲基二苯基异氰酸酯的混合物。优选4,4'-亚甲基二苯基异氰酸酯的比例大于60重量%,更优选4,4'-亚甲基二苯基异氰酸酯的比例大于80重量%,最优选它基本为纯4,4'-亚甲基二苯基异氰酸酯。
本发明的双组分聚氨酯形成组合物可以包含已知且常用于制备聚氨酯泡沫的其他添加剂,如催化剂、发泡剂、表面活性剂和扩链剂。该添加剂可以加入组分A或组分B或这二者中,除非存在将该添加剂加入组分A或B或这二者中的原因。例如,任何可能由于导致形成不希望副产物的副反应而干扰制备该异氰酸酯预聚物的反应的添加剂不能加入组分B中。通常将大多数添加剂加入组分A中,因为组分A的制备通常是不涉及化学反应的混合操作,而组分B的制备可能涉及异氰酸酯基团和羟基的反应。
作为催化剂,可以使用所有加速异氰酸酯基团和羟基之间反应的化合物。该类化合物是已知的并且例如描述于“Kunststoffhandbuch,第7卷,Polyurethane”,Carl HanserVerlag,1993年第3版,第3.4.1章中。这些化合物包括胺基催化剂和基于有机金属化合物的催化剂。
发泡剂包括化学发泡剂如水和甲酸以及物理发泡剂。物理发泡剂是对起始组分呈惰性,在室温下通常为液体并且在尿烷反应条件下汽化的化合物。物理发泡剂还包括在室温下为气态并且在加压下引入或溶于起始组分中的化合物,例如二氧化碳、低沸点链烷烃、氟代链烷烃和氟代烯烃。
表面活性剂包括包含聚硅氧烷的表面活性剂如硅氧烷-氧化烯共聚物和其他有机聚硅氧烷。也可以使用脂肪醇、羰基合成醇、脂肪胺、烷基酚、二烷基酚、烷基甲酚、烷基间苯二酚、萘酚、烷基萘酚、萘基胺、苯胺、烷基苯胺、甲苯胺、双酚A、烷基化双酚A、聚乙烯醇的烷氧基化产物以及还有甲醛和烷基酚、甲醛和二烷基酚、甲醛和烷基甲酚、甲醛和烷基间苯二酚、甲醛和苯胺、甲醛和甲苯胺、甲醛和萘酚、甲醛和烷基萘酚以及还有甲醛和双酚A的缩合产物的其他烷氧基化产物或者这些泡沫稳定剂中两种或更多种的混合物。
用于聚氨酯的扩链剂是具有两个羟基或胺官能基团的低分子量醇或胺化合物。最重要的扩链剂是1,4-丁二醇(BDO)或单乙二醇(MEG)。扩链剂也用作硬化剂。
本发明的聚氨酯形成组合物可以进一步包含一种或多种额外添加剂,如防水解剂、抗静电剂、阻燃剂、抗氧化剂和抗磨剂。
本领域熟练技术人员可以想到相应成分各自可以是混合物。例如,聚醚多元醇A可以是不止一种常用于制备聚氨酯泡沫的聚醚多元醇的混合物,其中它们各自满足上面对聚醚多元醇A所列要求。对于另一实例,聚四氢呋喃B可以是不止一种常用于制备聚氨酯泡沫的聚四氢呋喃的混合物,其中它们各自满足上面对聚四氢呋喃B所列要求。对于再一实例,该异氰酸酯预聚物可以是不止一种常用于制备聚氨酯泡沫的异氰酸酯预聚物的混合物,各自通过使独立选择的二异氰酸酯和/或多异氰酸酯与聚四氢呋喃B和/或聚醚多元醇B反应而制备。
为了确定该双组分聚氨酯形成组合物中相应成分的量,在该双组分聚氨酯形成组合物中使用的该异氰酸酯预聚物的量可以通过如下所定义的指数确定:
指数=(异氰酸酯的实际用量)/(所要求的异氰酸酯理论量)*100
本发明双组分聚氨酯形成组合物的典型指数为85-105,优选约90-100,更优选93-97。
聚四氢呋喃A和B的总量基于整个聚氨酯形成组合物中聚醚多元醇A和B以及聚四氢呋喃A和B的总量大于60重量%,优选60-80重量%。因此,聚醚多元醇A和B的总量基于整个聚氨酯形成组合物中聚醚多元醇A和B以及聚四氢呋喃A和B的总量小于40重量%,优选20-40重量%。
聚四氢呋喃B和聚醚多元醇B的总量与该二异氰酸酯和/或多异氰酸酯的总量之比以使得该异氰酸酯预聚物具有的NCO含量基于组分B的总重量为12-25重量%,更优选14-23重量%,最优选15-22重量%的方式设定。
为了生产该双组分聚氨酯形成组合物的两种组分A和B,组分A可以通过以常规已知的方式混合所有成分而制备。另一方面,组分B可以通过以常规已知的方式混合所有成分而制备,从而发生该二异氰酸酯和/或该多异氰酸酯与聚四氢呋喃B和/或聚醚多元醇B的反应,形成该异氰酸酯预聚物。
本发明的聚氨酯泡沫通过以已知方法在常用于制备聚氨酯泡沫的已知条件下混合该双组分聚氨酯形成组合物的组分A和B而制备。
本发明的聚氨酯泡沫是有利的,因为在低温下其硬度增加小于传统聚氨酯泡沫。在规定的低温下在给定时间t的硬度增加通过将待在环境温度下测量的样品暴露于低温达时段t并以硬度(t)测量样品的硬度而测定。在给定时间t的硬度增加使用下列等式计算:
硬度增加(t)=(硬度(t)-硬度(t0))/(硬度(t0))*100%
其中t0为0。在充分调节之后,硬度(t0)基本与在环境温度下的硬度相同。
在本申请上下文中,“fOH”表示羟基的(平均)官能度。
在本申请上下文中,“低温”是指0℃至-40℃,优选-10℃至-20℃。
实施例
聚四氢呋喃、4,4'-MDI、MEG、BDO由BASF SE,Ludwigshafen,德国得到并且按收到的原样使用。
所用胺催化剂是N,N-二甲基环己基胺。所用聚硅氧烷表面活性剂是来自Momentive Performance Materials Inc.,Waterford,New York,美国的Niax siliconeL1507。额外的添加剂A是乙酰基柠檬酸三丁酯,额外添加剂B是来自BASF SE的1076。所有这些化合物市购得到并且按收到的原样使用。
己二酸和MEG、BDO基聚酯多元醇作为LUPRAPHEN H 951由BASF SE得到并且按收到的原样使用。己二酸和BDO、HDO基聚酯多元醇作为 VP 9066由BASF SE得到并且按收到的原样使用。
将该双组分聚氨酯形成组合物的“指数”设定为95,除非另有明确规定。
聚氨酯泡沫根据传统程序生产。例如,本发明聚氨酯泡沫可以按如下生产:
i)混合组分B的所有成分以生产组分B;在该步骤过程中二异氰酸酯和/或多异氰酸酯与聚四氢呋喃B和/或聚醚多元醇B反应;
ii)平行于此混合组分A的所有成分以生产组分A;
iii)将两种组分A和B混合并引入具有所需形状的模具中,得到具有所需形状的聚氨酯泡沫产品;在该步骤过程中,组分B中的异氰酸酯预聚物与组分A中的聚四氢呋喃A和聚四氢呋喃以外的任选聚醚多元醇A反应。
聚氨酯泡沫的硬度根据DIN ISO-7619-1中所列程序测定。用于硬度研究的样品尺寸为20cm(长度)×10cm(宽度)×1cm(厚度)。该样品使用具有相同尺寸空腔的模具制备。硬度在厚度方向上测量。
机械性能根据下列标准中所列程序测定。
密度 | DIN 53420 |
硬度 | DIN ISO-7619-1 |
抗磨性 | DIN ISO 4649 |
拉伸强度 | DIN 53504 |
伸长率 | DIN 53504 |
撕裂强度 | DIN ISO 34-1 |
压缩变定 | ASTM D 395 |
对比例1:使用聚酯多元醇制备的聚氨酯泡沫
配方
组分B中NCO基团的重量百分数:18.22%
硬度/时间
时间(小时) | 0 | 1 | 2 | 3 | 4 | 6 | 8 | 12 | 16 | 24 |
在-10℃的硬度 | 47 | 60 | 61 | 61 | 61 | 62 | 62 | 62 | 63 | 63 |
硬度增加% | 28% | 30% | 30% | 30% | 32% | 32% | 32% | 34% | 34% | |
在-20℃下的硬度 | 47 | 63 | 64 | 64 | 64 | 64 | 65 | 65 | 66 | 66 |
硬度增加% | 34% | 36% | 36% | 36% | 36% | 38% | 38% | 40% | 40% |
对比例2:使用聚酯多元醇与1,6-六亚甲基二醇(HDO)制备的聚氨酯泡沫
配方
组分B中NCO基团的重量百分数:18.22%
硬度/时间
时间(小时) | 0 | 1 | 2 | 3 | 4 | 6 | 8 | 12 | 16 | 24 |
在-10℃的硬度 | 44 | 52 | 54 | 54 | 54 | 54 | 55 | 55 | 55 | 55 |
硬度增加% | 18% | 23% | 23% | 23% | 23% | 25% | 25% | 25% | 25% | |
在-20℃下的硬度 | 44 | 55 | 57 | 57 | 57 | 57 | 57 | 58 | 58 | 58 |
硬度增加% | 25% | 30% | 30% | 30% | 30% | 30% | 32% | 32% | 32% |
对比例3:使用聚醚多元醇制备的聚氨酯泡沫
配方
组分B中NCO基团的重量百分数:19.06%
硬度/时间
时间(小时) | 0 | 1 | 2 | 3 | 4 | 6 | 8 | 12 | 16 | 24 |
在-10℃的硬度 | 51 | 60 | 60 | 60 | 60 | 60 | 61 | 61 | 61 | 62 |
硬度增加% | 18% | 18% | 18% | 18% | 18% | 20% | 20% | 20% | 22% | |
在-20℃下的硬度 | 51 | 63 | 63 | 63 | 63 | 63 | 63 | 64 | 64 | 64 |
硬度增加% | 24% | 24% | 24% | 24% | 24% | 24% | 25% | 25% | 25% |
对比例4:使用聚四氢呋喃在低Mn下制备的聚氨酯泡沫
配方
组分B中NCO基团的重量百分数:16.54%
硬度/时间
时间(小时) | 0 | 1 | 2 | 3 | 4 | 6 | 8 | 12 | 16 | 24 |
在-10℃的硬度 | 46 | 53 | 54 | 55 | 55 | 55 | 56 | 57 | 58 | 59 |
硬度增加% | 15% | 17% | 20% | 20% | 20% | 22% | 24% | 26% | 28% | |
在-20℃下的硬度 | 46 | 56 | 57 | 57 | 57 | 58 | 58 | 59 | 60 | 62 |
硬度增加% | 22% | 24% | 24% | 24% | 26% | 26% | 28% | 30% | 35% |
对比例5:使用聚四氢呋喃和聚醚多元醇在低Mn下制备的聚氨酯泡沫
配方
在全部聚四氢呋喃和丙二醇起始的聚醚多元醇中全部聚四氢呋喃的重量百分数:62.84%
组分B中NCO基团的重量百分数:18.22%
硬度/时间
时间(小时) | 0 | 1 | 2 | 3 | 4 | 6 | 8 | 12 | 16 | 24 |
在-10℃的硬度 | 46 | 58 | 58 | 58 | 58 | 59 | 59 | 59 | 60 | 60 |
硬度增加% | 26% | 26% | 26% | 26% | 28% | 28% | 28% | 30% | 30% | |
在-20℃下的硬度 | 46 | 60 | 60 | 60 | 60 | 60 | 61 | 61 | 62 | 62 |
硬度增加% | 30% | 30% | 30% | 30% | 30% | 33% | 33% | 35% | 35% |
对比例6:在除了硬化剂外的整个多元醇中的低聚四氢呋喃比下使用聚四氢呋喃
制备的聚氨酯泡沫
配方
在全部聚四氢呋喃和丙二醇起始的聚醚多元醇中全部聚四氢呋喃的重量百分数:51.6%
组分B中NCO基团的重量百分数:19.06
硬度/时间
时间(小时) | 0 | 1 | 2 | 3 | 4 | 6 | 8 | 12 | 16 | 24 |
在-10℃的硬度 | 46 | 52 | 52 | 52 | 53 | 53 | 53 | 53 | 53 | 53 |
硬度增加% | 13% | 13% | 13% | 15% | 15% | 15% | 15% | 15% | 15% | |
在-20℃下的硬度 | 46 | 55 | 55 | 56 | 56 | 56 | 56 | 56 | 56 | 56 |
硬度增加% | 20% | 20% | 22% | 22% | 22% | 22% | 22% | 22% | 22% |
机械性能
发明实施例7
配方
组分B中NCO基团的重量百分数:18.22%
硬度/时间
时间(小时) | 0 | 1 | 2 | 3 | 4 | 6 | 8 | 12 | 16 | 24 |
在-10℃的硬度 | 48 | 49 | 49 | 50 | 51 | 52 | 53 | 54 | 57 | 58 |
硬度增加% | 2% | 2% | 4% | 6% | 8% | 10% | 13% | 19% | 21% | |
在-20℃下的硬度 | 48 | 50 | 51 | 52 | 52 | 54 | 55 | 57 | 59 | 60 |
硬度增加% | 4% | 6% | 8% | 8% | 13% | 15% | 19% | 23% | 25% |
机械性能
密度(g/cm<sup>3</sup>) | 0.40±0.01 |
抗磨性(mm<sup>3</sup>) | 78 |
拉伸强度(N/mm<sup>2</sup>) | 4.35 |
伸长率(%) | 380.1 |
撕裂强度(N/mm) | 19.17 |
压缩变定(%) | 7.4 |
发明实施例8
配方
组分B中NCO基团的重量百分数:18.03%
硬度/时间
时间(小时) | 0 | 1 | 2 | 3 | 4 | 6 | 8 | 12 | 16 | 24 |
在-10℃的硬度 | 47 | 48 | 49 | 50 | 51 | 52 | 53 | 54 | 56 | 57 |
硬度增加% | 2% | 4% | 6% | 9% | 11% | 13% | 15% | 19% | 21% | |
在-20℃下的硬度 | 47 | 49 | 50 | 51 | 52 | 53 | 55 | 57 | 59 | 59 |
硬度增加% | 4% | 6% | 9% | 11% | 13% | 17% | 21% | 26% | 26% |
机械性能
密度(g/cm<sup>3</sup>) | 0.40±0.01 |
抗磨性(mm<sup>3</sup>) | 96 |
拉伸强度(N/mm<sup>2</sup>) | 4.22 |
伸长率(%) | 351.3 |
撕裂强度(N/mm) | 18.78 |
压缩变定(%) | 7.7 |
发明实施例9
配方
在全部聚四氢呋喃和甘油起始的聚醚多元醇中全部聚四氢呋喃的重量百分数:83.06%
组分B中NCO基团的重量百分数:18.22%
硬度/时间
时间(小时) | 0 | 1 | 2 | 3 | 4 | 6 | 8 | 12 | 16 | 24 |
在-10℃的硬度 | 46 | 48 | 49 | 50 | 50 | 51 | 51 | 52 | 53 | 53 |
硬度增加% | 4% | 7% | 9% | 9% | 11% | 11% | 13% | 15% | 15% | |
在-20℃下的硬度 | 47 | 49 | 50 | 51 | 52 | 53 | 55 | 57 | 59 | 59 |
硬度增加% | 4% | 6% | 9% | 11% | 13% | 17% | 21% | 26% | 26% |
机械性能
密度(g/cm<sup>3</sup>) | 0.40±0.01 |
抗磨性(mm<sup>3</sup>) | 187 |
拉伸强度(N/mm<sup>2</sup>) | 3.97 |
伸长率(%) | 369.3 |
撕裂强度(N/mm) | 18.19 |
压缩变定(%) | 7.9 |
发明实施例10
配方
在全部聚四氢呋喃和甘油起始聚醚多元醇中全部聚四氢呋喃的重量百分数:64.14%
组分B中NCO基团的重量百分数:19.06%
硬度/时间
时间(小时) | 0 | 1 | 2 | 3 | 4 | 6 | 8 | 12 | 16 | 24 |
在-10℃的硬度 | 44 | 46 | 47 | 47 | 48 | 48 | 48 | 49 | 49 | 49 |
硬度增加% | 5% | 7% | 7% | 9% | 9% | 9% | 11% | 11% | 11% | |
在-20℃下的硬度 | 47 | 49 | 50 | 51 | 52 | 53 | 55 | 57 | 59 | 59 |
硬度增加% | 4% | 6% | 9% | 11% | 13% | 17% | 21% | 26% | 26% |
机械性能
密度(g/cm<sup>3</sup>) | 0.40±0.01 |
抗磨性(mm<sup>3</sup>) | 246 |
拉伸强度(N/mm<sup>2</sup>) | 3.51 |
伸长率(%) | 323.6 |
撕裂强度(N/mm) | 15.09 |
压缩变定(%) | 8.2 |
由实施例1-10中的试验数据可以得出下列结论。
使用本发明所定义的聚四氢呋喃,所制备的聚氨酯泡沫与传统聚氨酯泡沫相比在低温下具有低硬度增加。这尤其由实施例1+2+3和7+8的对比显而易见。这表明该聚氨酯泡沫适合用于可以暴露于低温的产品,如运动用品,优选运动鞋或雪地靴,更优选其鞋底,其中希望在低温下的硬度增加低。
使用本发明所定义的聚四氢呋喃和聚醚多元醇的组合,所制备的聚氨酯泡沫与传统聚氨酯泡沫相比在低温下在长时间内具有甚至更低的硬度增加,但是在最初几个小时内的硬度增加比单独使用聚四氢呋喃要高。这尤其由实施例7+8和9+10的对比显而易见。这表明该聚氨酯泡沫适合用于可以暴露于低温的产品,如运动用品,优选运动鞋或雪地靴,更优选其鞋底,其中希望在长时间内在低温下的硬度增加低。
单独使用聚四氢呋喃以及使用聚四氢呋喃和聚醚多元醇的组合制备的聚氨酯都是有用的。对于雪地靴应用而言,在许多情况下该雪地靴并不以延长的时段,如超过4小时至6小时暴露于低温。单独使用聚四氢呋喃制备的聚氨酯对该应用提供低硬度增加。然而,硬度增加在该延长的时段之后稍高。这通常不是问题,因为预计雪地靴通常不会如此长时间暴露于低温。另一方面,对于其中预计雪地靴以延长的时段,如超过4小时至6小时暴露于低温的那些情形,尽管使用聚四氢呋喃和聚醚多元醇的组合制备的聚氨酯在最初几个小时内在低温下不能提供非常好的硬度增加(然而仍可接受),但硬度增加甚至在该延长的时段之后将保持在低位,使得该聚氨酯尤其可用于该类应用。然而,聚醚多元醇的含量不能非常高,否则机械性能,特别是抗磨性差。
熟练技术人员可以想到本发明聚氨酯泡沫可用于该类性能是希望的任何其他应用中。
Claims (8)
1.一种由组分A和B构成的双组分聚氨酯形成组合物,其中组分A包含平均羟基官能度不大于3,优选约2且数均分子量对各羟基而言为600-1500,优选750-1250,更优选900-1100的聚四氢呋喃A和聚四氢呋喃以外的平均羟基官能度不大于3,优选约2且数均分子量对各羟基而言为1500-2500,优选1800-2200的任选聚醚多元醇A;并且
组分B包含NCO含量基于组分B的总重量为12-25重量%,更优选14-23重量%,最优选15-22重量%的异氰酸酯预聚物,所述异氰酸酯预聚物通过使二异氰酸酯和/或多异氰酸酯与平均羟基官能度不大于3,优选约2且数均分子量对各羟基而言为600-1500,优选750-1250,更优选900-1100的聚四氢呋喃B和/或聚四氢呋喃以外的平均羟基官能度不大于3,优选约2且数均分子量对各羟基而言为1500-2500,优选1800-2200的聚醚多元醇B反应而制备。
2.权利要求1的聚氨酯形成组合物,其中聚四氢呋喃A和聚四氢呋喃B的总和基于整个聚氨酯形成组合物中聚醚多元醇A和B以及聚四氢呋喃A和B的总量为60-100重量%,优选60-80重量%。
3.权利要求1或2的聚氨酯形成组合物,进一步包含催化剂、发泡剂、表面活性剂、扩链剂和其他任选添加剂作为组分A的成分。
4.权利要求1-3中任一项的聚氨酯形成组合物,其中所述聚醚多元醇A和B中的所述烷氧基重复单元选自乙氧基或丙氧基或其混合物。
5.一种由权利要求1-4中任一项的聚氨酯形成组合物制备聚氨酯泡沫的方法,包括:
i)通过混合其成分并使所述二异氰酸酯和/或所述多异氰酸酯与所述聚四氢呋喃B和/或所述聚醚多元醇B反应而制备组分B的步骤,
ii)通过混合其成分而制备组分A的步骤,以及
iii)通过在具有所需形状的模具中混合组分A和B并使组分B中的所述异氰酸酯预聚物与组分A中的所述聚四氢呋喃A和聚四氢呋喃以外的所述任选聚醚多元醇A反应而制备所述聚氨酯泡沫的步骤。
6.可以由权利要求5的方法得到的聚氨酯泡沫。
7.一种可以暴露于低温的产品,包含权利要求6的聚氨酯泡沫。
8.权利要求7的产品,为运动用品,优选运动鞋或雪地靴,更优选其鞋底。
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