CN111961186A - 一种热塑性聚氨酯弹性体及其制备方法 - Google Patents

一种热塑性聚氨酯弹性体及其制备方法 Download PDF

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CN111961186A
CN111961186A CN202010881305.3A CN202010881305A CN111961186A CN 111961186 A CN111961186 A CN 111961186A CN 202010881305 A CN202010881305 A CN 202010881305A CN 111961186 A CN111961186 A CN 111961186A
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于鹏
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Abstract

本发明提供了一种热塑性聚氨酯弹性体，所述热塑性弹性体由按照重量份数计算，包括以下组分：异氰酸酯10‑40份、多元醇50‑70份、扩链剂5‑15份、偶联剂5‑8份、填料10‑15份，所述异氰酸酯为1,5萘‑二异氰酸酯、异氟尔酮二异氰酸酯、二甲基联苯二异氰酸酯中的一种或几种，所述多元醇为为分子量为1000‑3000。本发明选用分子刚性、规整性和对称性比较高的1,5萘‑二异氰酸酯、异氟尔酮二异氰酸酯、二甲基联苯二异氰酸酯中的一种或几种作为硬段，采用分子量为1000‑3000的聚四氢呋喃醚多元醇、聚己内酯多元醇、聚碳酸酯多元醇中的一种或几种，作为软段，并且添加了经过偶联的填料，提高了有机化合物和无机填料的结合力，提高弹性体的耐热性能，降低内生热。

Description

一种热塑性聚氨酯弹性体及其制备方法
技术领域
本发明聚氨酯技术领域，特别涉及一种热塑性聚氨酯弹性体及其制备方法。
背景技术
聚氨酯一般是由含有异氰酸酯基的多异氰酸酯，含活泼氢的聚醚多元醇或者聚酯多元醇，小分子二元醇作扩链剂所合成的线型高分子材料，聚氨酯弹性体具有耐磨、耐油、耐撕裂、耐化学腐蚀等优良性能，在许多工业领域得到广泛的应用，而普通聚氨酯如甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)等由于其内生热高，在长时间受到高强度的动态负载下极易提前老化分解。
发明内容
为克服现有技术的缺点和不足，本发明提供了一种热塑性聚氨酯弹性体，可以在动态负载下降低聚氨酯弹性体的内生热。
为了实现上述目的，本发明提供了一种热塑性聚氨酯弹性体，由按照重量份数计算，包括以下组分：异氰酸酯10-40份、多元醇50-70份、扩链剂5-15份、偶联剂5-8份、填料10-15份，所述异氰酸酯为1,5萘-二异氰酸酯(NDI)、异氟尔酮二异氰酸酯(IPDI)、二甲基联苯二异氰酸酯(TODI)中的一种或几种，所述多元醇分子量为1000-3000。
优选的，所述多元醇为聚四氢呋喃醚多元醇(PTMEG)、聚己内酯多元醇(PCL)、聚碳酸酯多元醇(PCDL)中的一种或几种。
优选的，所述扩链剂为1,4-丁二醇(BDO)、1,3-丙二醇、丙三醇中一种或几种。
优选的，所述偶联剂为γ-氨丙基三乙氧基硅烷、N-(β-氨乙基)-γ-氨丙基甲基二甲氧基、乙烯基三甲氧基硅烷、三异硬脂酸钛酸异丙酯、二(二辛基焦磷酰氧基)氧代酯钛酸中的一种或几种。
优选的，所述填料为白炭黑、轻钙、硅藻土、玻璃纤维其中的一种。
另外，本发明还提供了一种用塑性聚氨酯弹性体的制备方法，包括以下步骤：
S1:偶联填料的制备：
S1-1:将偶联剂用乙醇和水进行水解；
S1-2:将填料和水解后的偶联剂放入球磨机中高速混合4h，室温静置24h后，进行干燥、冷却得到偶联后的填料；
S2:预聚体组分的制备：
S2-1:将多元醇加入反应釜中，温度控制在100-120℃，真空脱水0.5h后，加入偶联填料，继续搅拌抽真空2-2.5h；
S2-2将温度降至40-60℃，加入异氰酸酯，保持温度在80℃，反应2-2.5h得到预聚体。
S3:聚氨酯弹性体的制备：
将制得的预聚体的温度升至100-120℃，加入扩链剂进行搅拌，搅拌均匀后倒入已预热的模具中，1-2h后进行脱模，于100-120的环境中固化12-16h。
优选的，所述偶联剂、乙醇、水的质量比为1：(6-8)：2。
优选的，制得的所述预聚体的NCO含量为6-10％。
本发明的聚氨酯弹性体体系的异氰酸酯选用分子刚性、规整性和对称性比较高的1,5萘-二异氰酸酯、异氟尔酮二异氰酸酯、二甲基联苯二异氰酸酯中的一种或几种作为硬段，采用分子量为1000-3000的聚四氢呋喃醚多元醇、聚己内酯多元醇、聚碳酸酯多元醇中的一种或几种，作为软段，并且添加了经过偶联的填料，提高了有机化合物和无机填料的结合力，提高弹性体的耐热性能，降低内生热。
具体实施方式
下面结合具体实施例对本发明进行进一步描述，但是本发明不局限于这些实施例。
实施例和对比例中涉及到简称代表的物质如下：
PTMG-1000：分子量为1000的聚四氢呋喃醚多元醇，德国BASF公司；
PTMG-2000：分子量为2000的聚四氢呋喃醚多元醇，德国BASF公司；
T4692:分子量为2000的聚碳酸酯多元醇,旭化成化学株式会社；
T4671:分子量为1000的聚碳酸酯多元醇,旭化成化学株式会社；
T5650J:分子量为800的聚碳酸酯多元醇,旭化成化学株式会社；
PCL210N:分子量为1000的聚碳酸酯多元醇,日本大赛璐化学工业株式会社；
PCL220N:分子量为2000的聚己内酯多元醇,日本大赛璐化学工业株式会社；
NDI：1,5-萘二异氰酸酯，科思创聚合物有限公司；
IPDI:异氟尔酮二异氰酸酯,科思创聚合物有限公司；
TODI:二甲基联苯二异氰酸酯,郑州阿尔法化工有限公司；
BDO:1,4-丁二醇:上海麦克林生化科技有限公司；
1,3-丙二醇:上海麦克林生化科技有限公司；
丙三醇:上海麦克林生化科技有限公司；
KH550:γ-氨丙基三乙氧基硅烷,郑州阿尔法化工有限公司；
KH602:N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷,郑州阿尔法化工有限公司；
KH171:乙烯基三甲氧基硅烷,郑州阿尔法化工有限公司；
AC-100:三异硬脂酸钛酸异丙酯：南京奥诚化工有限公司；
AC-311:二(二辛基焦磷酰氧基)氧代酯钛酸：南京奥诚化工有限公司；
白炭黑：R974，赢创德固赛；
轻钙：YR-1323,灵寿县怡然矿产品加工厂；
硅藻土：A0103,灵寿县怡然矿产品加工厂；
玻璃纤维:A0103,灵寿县怡然矿产品加工厂.
实施例1
本实施例提供的一种热塑性聚氨酯弹性体，所述热塑性弹性体由按照重量份数计算，包括以下组分：NDI 21份、TODI 2份、T4692 35份、T5650J 15份、PTMG-1000 5份、BDO 5份、丙三醇2份、KH171 5份、白炭黑10份。
本实施例按照以下方法制备
S1:偶联填料的制备：
S1-1:将KH171用乙醇和水进行水解，KH171、乙醇、水的质量比为1：7：2；
S1-2:将白炭黑和水解后的偶联剂放入球磨机中高速混合4个小时，室温静置24h后，进行干燥、冷却得到偶联后的白炭黑；
S2:预聚体组分的制备：
S2-1:将T4692、T5650J、PTMG-1000加入反应釜中，温度控制在100-120℃，真空脱水0.5h后，加入偶联白炭黑，继续搅拌抽真空2-2.5h；
S2-2将温度降至40-60℃，加入NDI、TODI，保持温度在80℃，反应2-2.5h得到预聚体，制得预聚体的NCO含量为6.9％。
S3:聚氨酯弹性体的制备：
将制得的预聚体的温度升至100-120℃，加入BDO、丙三醇进行搅拌，搅拌均匀后倒入已预热的模具中，1-2h后进行脱模，于100-120的环境中固化14h。
实施例2
本实施例提供的一种热塑性聚氨酯弹性体，所述热塑性弹性体由按照重量份数计算，包括以下组分：NDI 23.8份、T4692 28份、T5650J 15份、PCL210N 8份、BDO 6份、KH602 4份、AC-100 2份、白炭黑10份、玻璃纤维5份。
本实施例按照以下方法制备
S1:偶联填料的制备：
S1-1:将KH602、AC-100用乙醇和水进行水解，偶联剂(KH602和AC-100)、乙醇、水的质量比为1：6：2；
S1-2:将白炭黑、玻璃纤维和水解后的偶联剂放入球磨机中高速混合4个小时，室温静置24h后，进行干燥、冷却得到偶联后的白炭黑和玻璃纤维；
S2:预聚体组分的制备：
S2-1:将T4692、T5650J、PCL210N加入反应釜中，温度控制在100-120℃，真空脱水0.5h后，加入偶联处理后白炭黑和玻璃纤维，继续搅拌抽真空2-2.5h；
S2-2将温度降至40-60℃，加入NDI，保持温度在80℃，反应2-2.5h得到预聚体，制得预聚体的NCO含量为8.1％。
S3:聚氨酯弹性体的制备：
将制得的预聚体的温度升至100-120℃，加入BDO进行搅拌，搅拌均匀后倒入已预热的模具中，1-2h后进行脱模，于100-120的环境中固化16h。
实施例3
本实施例提供的一种热塑性聚氨酯弹性体，所述热塑性弹性体由按照重量份数计算，包括以下组分：NDI 7.2份、IPDI 24份、T4671 7份、T5650J 30份、PCL220N 8份、1,3-丙二醇5份、丙三醇3份、KH550 5份、AC-311 2份、轻钙8份、硅藻土4份。
本实施例按照以下方法制备
S1:偶联填料的制备：
S1-1:将KH550、AC-311用乙醇和水进行水解，偶联剂(KH550和AC-311)、乙醇、水的质量比为1：8：2；
S1-2:将白炭黑和水解后的偶联剂放入球磨机中高速混合4个小时，室温静置24h后，进行干燥、冷却得到偶联后的白炭黑；
S2:预聚体组分的制备：
S2-1:将T4671、T5650J、PCL220N加入反应釜中，温度控制在100-120℃，真空脱水0.5h后，加入偶联白炭黑，继续搅拌抽真空2-2.5h；
S2-2将温度降至40-60℃，加入NDI、TODI，保持温度在80℃，反应2-2.5h得到预聚体，制得预聚体的NCO含量为9.8％。
S3:聚氨酯弹性体的制备：
将制得的预聚体的温度升至100-120℃，加入1,3-丙二醇、丙三醇进行搅拌，搅拌均匀后倒入已预热的模具中，1-2h后进行脱模，于100-120的环境中固化16h。
对比例1
将PTMG-1000加入反应釜中，温度控制在100-120℃，真空脱水2-2.5后，加入4,4-二苯基甲烷二异氰酸酯制得预聚体，预聚体的NCO含量为7％，将制得的预聚体的温度升至100-120℃，加入BDO、丙三醇进行搅拌，搅拌均匀后倒入已预热的模具中，1-2h后进行脱模，于100-120的环境中固化14h。
对比例2
将PTMG-1000加入反应釜中，温度控制在100-120℃，真空脱水2-2.5后，加入4,4-二苯基甲烷二异氰酸酯制得预聚体，预聚体的NCO含量为8％，将制得的预聚体的温度升至100-120℃，加入BDO进行搅拌，搅拌均匀后倒入已预热的模具中，1-2h后进行脱模，于100-120的环境中固化16h。
对比例3
将PTMG-1000加入反应釜中，温度控制在100-120℃，真空脱水2-2.5后，加入4,4-二苯基甲烷二异氰酸酯制得预聚体，预聚体的NCO含量为10％，将制得的预聚体的温度升至100-120℃，加入1,3-丙二醇、丙三醇进行搅拌，搅拌均匀后倒入已预热的模具中，1-2h后进行脱模，于100-120的环境中固化16h。
实验方法：采用GB/T1687-2016标准对实施例1-3和对比例1-3进行压缩疲劳测试。
上述实施例1-3和对比例1-3的性能测试结果如表1所述。
表1实施例1-3和对比例1-3的性能测试结果
Figure BDA0002654205060000081
从上述试验表明本发明制备的热塑性聚氨酯弹性体具有优异的动态疲劳性能，内生热低，耐热性能好。
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。

Claims (8)

1.一种热塑性聚氨酯弹性体，其特征在于，按照重量份数计算，包括以下组分：异氰酸酯10-40份、多元醇50-70份、扩链剂5-15份、偶联剂5-8份、填料10-15份，所述异氰酸酯为1,5萘-二异氰酸酯、异氟尔酮二异氰酸酯、二甲基联苯二异氰酸酯中的一种或几种，所述多元醇的分子量为1000-3000。
2.根据权利要求1所述的一种热塑性聚氨酯弹性体，其特征在于，所述多元醇为聚四氢呋喃醚多元醇、聚己内酯多元醇、聚碳酸酯多元醇中的一种或几种。
3.根据权利要求2所述的一种热塑性聚氨酯弹性体，其特征在于，所述扩链剂为1,4-丁二醇、1,3-丙二醇、丙三醇中一种或几种。
4.根据权利要求1所述的一种热塑性聚氨酯弹性体，其特征在于，所述偶联剂为γ-氨丙基三乙氧基硅烷、N-(β-氨乙基)-γ-氨丙基甲基二甲氧基、乙烯基三甲氧基硅烷、三异硬脂酸钛酸异丙酯、二(二辛基焦磷酰氧基)氧代酯钛酸中的一种或几种。
5.根据权利要求4所述的一种热塑性聚氨酯弹性体，其特征在于，所述填料为白炭黑、轻钙、硅藻土、玻璃纤维其中的一种。
6.一种权利要求1-5任意一项所述的热塑性聚氨酯弹性体的制备方法，其特征在于，包括如下步骤：
S1:偶联填料的制备：
S1-1:将偶联剂用乙醇和水进行水解；
S1-2:将填料和水解后的偶联剂放入球磨机中高速混合4h，室温静置24h后，进行干燥、冷却得到偶联后的填料；
S2:预聚体组分的制备：
S2-1:将多元醇加入反应釜中，温度控制在100-120℃，真空脱水0.5h后，加入偶联填料，继续搅拌抽真空2-2.5h；
S2-2将温度降至40-60℃，加入异氰酸酯，保持温度在80℃，反应2-2.5h得到预聚体。
S3:聚氨酯弹性体的制备：
将制得的预聚体的温度升至100-120℃，加入扩链剂进行搅拌，搅拌均匀后倒入已预热的模具中，1-2h后进行脱模，于100-120℃的环境中固化12-16h。
7.根据权利要求6所述的一种热塑性聚氨酯弹性体的制备方法，其特征在于，所述偶联剂、乙醇、水的质量比为1：(6-8)：2。
8.根据权利要求7所述的所述的一种热塑性聚氨酯弹性体的制备方法，其特征在于，制得的所述预聚体的NCO含量为6-10％。
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