CN111848903A - 聚氨酯微孔泡沫材料及其制造工艺 - Google Patents

聚氨酯微孔泡沫材料及其制造工艺 Download PDF

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CN111848903A
CN111848903A CN201910980858.1A CN201910980858A CN111848903A CN 111848903 A CN111848903 A CN 111848903A CN 201910980858 A CN201910980858 A CN 201910980858A CN 111848903 A CN111848903 A CN 111848903A
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glycol
butanediol
ethylene glycol
polyol
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蒋树会
叶伟波
李贤成
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Ningbo Turuida Leisure Products Co ltd
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Abstract

一种聚氨酯微孔泡沫材料及其制造工艺,该材料的主要原料包括:A组分、C组分和B组分,所述的A组分、C组分和B组分对应的物料和用量如下:A组分制备原料:聚酯多元醇75‑100重量份,聚醚多元醇0‑25重量份,小分子多元醇5‑9重量份,甘油三醇0‑1重量份,小分子胺0‑5重量份,硅油0.1‑0.6重量份,水0.1‑0.25重量份,发泡剂0‑5重量份,C组分1.0‑1.8重量份,B组分85‑110重量份。该申请能克服目前国内急需要解决的这一技术瓶颈,使得这一类聚氨酯微孔轮胎在运行中易产生高温熔化、力学性能急速降低的安全隐患能到得到彻底解除的聚氨酯微孔泡沫材料。

Description

聚氨酯微孔泡沫材料及其制造工艺
技术领域:
本发明属于聚氨酯微孔弹性体技术领域,具体的它所涉及到的是一种聚氨酯微孔泡沫材料及其制造工艺。
技术背景:
聚氨酯微孔弹性体是介于橡胶、泡沫与塑料之间的一种三位一体的新型聚氨酯材料,兼具有三者的优点,比如有质轻、吸能、抗冲击性能高、回弹性能好,以及力学强度高、压缩应力传递平稳、耐油、抗疲劳、和突出的耐磨性能等很多优点;它的这种综合优点已经被人们广泛地认知和了解,因此该材料最近十几年在世界范围内迅速而广泛地被应用在制鞋、防震、轮胎、缓冲等工业领域。
尽管聚氨酯微孔弹性体有很多上述优点,但是它也不是完美的,也有性能不足的方面,譬如耐热性能并不理想,其主要原因是在这种材料的合成中,形成的聚合物大分子链中含有不耐高温的缩二脲键、脲基甲酸酯键等多方面因素,引起聚氨酯材料的内生热偏大,在某些应用领域如果材料长期在100℃以上的环境中使用,会引起相关的力学性能大幅下降,最终导致材料无法继续使用。这样也就严重影响了它应用范围的进一步拓展,如非道路载重车,某些高速自行车等;一个比较典型的案例是电动自行车或者电动摩托车系列的聚氨酯微孔轮胎,它们的典型特点是轮胎偏小,而且荷载大,速度快(通常是30-40km/h),目前国内使用的情况,通常是轮胎负载75公斤以上跑车测试,速度为40码甚至30码几分钟到半小时左右轮胎就会内部材料熔化,有的好一些的也只能跑到1500-3000公里,但有的耐磨性能达不到要求,测试2000公里轮胎表面左右出现磨损严重,有很多微小胎面颗粒状或粉状物脱落下来,这些都会严重影响轮胎的实际使用寿命;目前从材料合成本身的技术角度看,实际上都没有能很好地解决这个问题,大都是从轮胎外观结构设计方面着手,想了很多办法来减缓和降低聚氨酯微孔弹性体的升温速度,使得材料在高荷载下产生的内生热热量能尽快的散出去,从而有效地降低其内部温度;有的是在轮胎中心温度聚集区填充耐温材料,如金属、塑料空心管,或者塑料(橡胶)实心环型棒。这方面的专利有很多,如河北的高西恩的专利CN207246763,是在自行车轮胎的侧面打孔来降低胎芯部的升温速度;湖南的杨文君CN 203580518、福建的吴天火CN1651271、广东的叶凯旋CN204383096、山东烟台自行车厂CN2074257等也是类似的轮胎结构设计。
重庆的杰博科技有限公司的发明申请CN103467974介绍了一种增强聚氨酯微孔弹性体复合材料,该方法采用了在聚氨酯微孔泡沫弹性体中添加了无机纳米材料,如纳米二氧化钛、纳米二氧化硅、纳米碳酸钙、有机高岭土、纳米碳纤维、纳米管、分子筛、纳米碳化硅、白炭黑、纳米稀土及其它们的有机改性物。虽然该申请没有提到材料的耐热性,但实际上这些无机材料的加入也能一定程度上改进材料的耐热性;武汉理工大学的王福玲的论文总介绍了用加入玻璃微球来改善微孔弹性体的耐热性;浙江华峰的周巧萍的发明专利CN101486834中介绍了采用OMMT有机纳米蒙脱土改进聚氨酯微孔弹性体的强度和耐热性能等等,但是这些固体物的加入无疑会使组合料的粘度也会明显增加,而且需要增加固体物的分散生产设备,也同时大幅度延长了生产周期,另一方面也明显影响制品发泡生产设备的寿命,大幅度增加生产、材料成本。
浙江的徐明奎专利申请CN107964084A中介绍了一种高速耐热型的轮胎组合料的的技术方案,他是用己二酸,乙二醇,丁二醇和己二醇合成的分子量为2500-3000(羟值为44-37)的聚酯多元醇为主体,再进一步用该聚酯多元醇与MDI反应合成出半预聚体(国内成为B组分),通过浇注发泡而成的轮胎,据介绍能提高耐热性能,该技术与常规的生产方法不同的只是分子量和聚酯多元醇中曾加了少量己二醇有些区别而已,该聚合物大分子链段的结构没有太大的变化,同时分子量的增大会使组分的粘度增加不少,也给生产工艺和设备带来了更高的条件和其性能要求。根据目前国内电动自行车和电动摩托车等非道路用载重型车使用聚氨酯实心微孔轮胎的现状,最主要的耐热性能,基本还不能真正达到实际使用的要求,这也给骑车者或开车者带来不少的麻烦甚至是安全隐患;这一问题是国内多年来聚氨酯合成材料领域,更具体地讲是聚氨酯微孔弹性体工业生产领域急需要解决的技术难题。
发明内容:
本发明针对现有技术的上述不足,提供一种能克服目前国内急需要解决的这一技术瓶颈,使得这一类聚氨酯微孔轮胎在运行中易产生高温熔化、力学性能急速降低的安全隐患能到得到彻底解除的聚氨酯微孔泡沫材料。
为了解决上述技术问题,本发明采用的技术方案为:一种聚氨酯微孔泡沫材料,该材料的主要原料包括:A组分、C组分和B组分,所述的A组分、C组分和B组分对应的物料和用量如下:
A组分制备原料:
Figure BDA0002235131860000021
Figure BDA0002235131860000031
(包括改性小分子胺扩链剂MOCA-BMI)
Figure BDA0002235131860000032
优选的,本发明上述的聚酯多元醇或者聚醚多元醇其分子量为2000-2500,其类型包括如下各种类型中的一种或者多种:
a聚己二酸-乙二醇-丁二醇酯,合成其的原料己二酸-乙二醇-丁二醇的摩尔比:2:1.0-1.05:1.25-1.30;
b聚己二酸-乙二醇-丁二醇-己二醇,合成其的原料己二酸-乙二醇-丁二醇-己二醇的摩尔比为:2:1.0:0.9-1.0:0.4;
c聚己二酸-乙二醇-丁二醇-新戊二醇酯,合成其的原料己二酸-乙二醇-丁二醇-新戊二醇的摩尔比为:2:1.2-1.3:0.9:0.2;
d聚己二酸-乙二醇-丁二醇-丙二醇酯,合成其的原料己二酸-乙二醇-丁二醇-丙二醇的摩尔比为:2:1.1-1.2:1.0:0.2;
e聚癸二酸-乙二醇-丁二醇-二乙二醇酯,合成其的原料癸二酸-乙二醇-丁二醇-二乙二醇的摩尔比为:2:1.1:1.0:0.2-0.25;
f聚己内酯多元醇,分子量2000-2500;
g聚四氢呋喃醚二醇,分子量2000-2500;
h DMC聚丙二醇多元醇(用双金属催化剂合成的聚丙二醇多元醇)分子量为2000-8000,如商品牌号SD-30,DDL-4000等;。
i DMC聚丙三元醇(用双金属催化剂合成的聚丙三醇多元醇)分子量6000,如商品牌号accailm-6220,TRIOL-6000等(可选)。
进一步优选的,所述的DMC聚丙二醇多元醇的分子量为4000。
进一步优选的,所述的小分子多元醇可以是如下中的一种或者多种:乙二醇,丙二醇,二乙二醇,丁二醇,二丙二醇,1,6-己二醇,三甘醇,甲基丙二醇,新戊二醇,环己二醇,甘油,三羟基丙烷,三羟甲基乙烷;HQEE(对苯二酚二羟乙基醚),HER(间苯二酚双(羟乙基)醚,间苯二酚-双(b羟乙基)醚,1,3-双(2-羟乙氧基)苯)。
进一步优选的,所述的小分子胺可以是如下中的一种或者多种:二乙醇胺,三乙醇胺,三异丙醇胺,摩卡,二甲硫基甲苯二胺,二乙基甲苯二胺,改性小分子胺(氨基封端聚氨基-双马来酰亚胺低聚物)或称为改性小分子胺扩链剂。
优选的,本发明上述的C组分催化剂包括如下的一种或者多种:有机锡类,如:T-12(二丁基锡二月桂酸酯),T-120,2,4-EMI(2-乙基-4甲基咪唑);胺类的:A-1(70%双(二甲氨基乙基)醚的二丙二醇溶液或70%双(二甲氨基乙基)醚溶液),A-33(33%的三乙烯二胺溶液),A-33EG(33%的三乙烯二胺的乙二醇溶液);四异丙基钛酸酯。
优选的,本发明上述硅油可以是DC-193(DC-193道康宁水溶性硅油),B-8681(自结皮硅油B8681),Y-10366(聚氨酯高回弹模塑硅油)等中的一种或者多种。
优选的,本发明的发泡剂可以是物理发泡剂M.C,141b(聚氨酯发泡剂141B)中的一种或者多种。
优选的,本发明B组分为主要通过熔化的MDI、液化MDI、可选加入的均苯四酸酐与聚酯多元醇或者聚醚多元醇反应获得。
本发明还提供一种上述聚氨酯微孔泡沫材料的制备方法,具体步骤包括:
(1)聚酯多元醇的合成:
首先将全部的合成聚酯多元醇所用的己二酸或者癸二酸与二元醇投入反应釜中,经过通氮气置换空气后逐步升温,在125-145℃缩聚反应开始进行脱水完成后,再逐步升温,氮气保护下加入催化剂;并在230-240℃保温2-4小时,并逐级抽真空进一步脱水,当羟值、水分分析合格后降温到80℃以下出料密闭包装;通过本合成方法合成出聚酯多元醇型号从a到e;
(2)异氰酸酯组分(B组分)的合成:
将熔化的MDI(二苯甲烷二异氰酸酯)和液化MDI真空吸入反应釜中,在50-80℃之间逐步加入聚酯多元醇或者聚醚多元醇充分反应,然后可选加入均苯四酸酐(可选加入,根据需要也可以不加入)继续反应,并保持温度在70-80℃之间,测试NCO%达到要求后、真空处理脱除气泡后降温出料,充氮并密闭包装;
(3)改性扩链剂的合成工艺
将双马来酰亚胺投入反应釜中,再投入MOCA(3,3'-二氯-4,4'-二氨基二苯基甲烷),然后加热到135-140℃,熔化后即开始搅拌并保持温度30-50分钟,形成以MOCA的氨基封端的聚氨基-双马来酰亚胺低聚物,反应完成后降温到85-95℃放出,常温固化成棕色透明块状固体;
(4)羟基组分(A组分)的配制:
将聚酯多元醇或者聚醚多元醇,保持在40-60℃的温度下泵入反应釜中,搅拌开始并加入小分子多元醇和/或小分子胺、甘油,硅油、水、发泡剂,搅拌均匀60-90分钟后即可放料密闭包装;
(5)微孔弹性体的制造
将上述步骤分别做成的A、B和C组分(催化剂)按照计量比例,通过浇注机与聚氨酯轮胎成型装置做成耐热性良好的轮胎。
本发明的优点和有益效果:
1.普通聚酯型聚氨酯轮胎上机跑车测试,一般速度以30km/h和负载75Kg,通常运行几十公里,几百公里后就会因升温太高而出现轮胎中心溶化、破裂。很难达到3000公里的要求;而使用本发明材料制成的轮胎(14*2.5)在40km/h和负载75Kg的条件下,连续跑车测试9000公里后停止了测试,轮胎外部温度稳定在36-38℃之间,轮胎没有变化,测试结束后,轮胎胎面中间的合模线飞边仍然存在,没有发现有磨损粉末掉落现象。
2.本发明通过原材料、工艺及其配方的调整与改进,在组分的合成过程中加入均苯四酸酐,使得原来的聚氨酯大分子链段中***了刚性、耐高温的聚酰亚胺链段(形成酰亚胺异氰酸酯预聚体),通过进一步改进扩链剂,将双马来酰亚胺(BMI)与MOCA(3,3'-二氯-4,4'-二氨基二苯基甲烷或二邻氯二苯胺甲烷)进行Micheal加成反应,形成具有刚性、耐高温、双马来酰亚胺分子链的端氨基大分子扩链剂,有效增加了聚氨酯大分子中的刚性并且耐高温的链段,提高了聚氨酯材料的耐热、耐磨性能、拉伸、撕裂强度和耐水解性,采用这种方法提高聚氨酯微孔弹性体的耐热性能是明显的;到目前为止,在微孔聚氨酯弹性体的研究和工业化生产领域,国内外尚未见到有这方面的专利和报道。
具体实施方式
以下结合实施例对本发明专利加以详细说明。但是本发明不仅仅局限于以下实施例。
实施例1
首先是脂肪二元酸系聚酯多元醇的合成(这里包括上述聚酯多元醇型号从a到e):
首先将己二酸671.6公斤,乙二醇144.9公斤,1,4-丁二醇264.5公斤投入反应釜中,密闭反应釜盖,然后抽真空大约10-15分钟后慢慢打开氮气阀门用氮气导入解除真空至常压为止,反应釜开始加热升温,当温度升到100℃以后,开始搅拌并且泠凝器开始通冷却水,当温度达到130℃左右,有水流出,缩聚反应开始,保持温度1-1.5小时,控制出水速度不宜过快,整个反应过程中回流塔塔顶溜出液体的温度不应超过100-105℃,当出水明显降低后,开始采升温,通常从150-190℃升温阶段控制在2.5-3.0小时,温度在200℃左右在氮气保护下加入催化剂四异丙基钛酸酯218克,从200-225℃升温阶段控制在1.5-2.0小时,当温度达到225℃时,开始恒温,在225℃恒温一小时,取样分析羟值并调整到要求值后可以开始降低釜内压力;即进行阶段抽真空,最后在高真空下保持不低于60分钟,合计抽真空3小时左右;最后充入氮气解除真空并降温低于100℃,取样分析酸值、羟值、水分含量。羟值为:44-56左右,酸酯为:0.2,水分小于0.1为合格。出料密闭包装。分子量控制在2000-2500左右为宜。
该聚酯多元醇被标记为聚酯多元醇-a其它同类的聚酯多元醇按照上述给定的摩尔比例并根据本合成工艺条件可以得到同样分子量的聚酯多元醇。分别标记为聚酯多元醇聚酯多元醇-b,聚酯多元醇-c,聚酯多元醇-d,聚酯多元醇-e;聚醚多元醇外购商品。
实施例2
异氰酸酯部分(B组分)的合成(称为B-1对比例)将已经溶化的MDI:60公斤,液化MDI-100L:6公斤,真空吸入反应釜中并保持温度在50-75℃之间,并用氮气解除真空,开动反应釜搅拌,加入磷酸量按照30-50PPM比例,然后将温度为40-50℃的聚酯多元醇-a 35公斤用齿轮泵打入反应釜中,因为异氰酸酯与羟基的反应是放热的,打入聚酯多元醇的速度要根据反应温度的高低来控制,通常控制温度不高于75-80℃,如果温度过高也可以通过夹套通冷却水来降低釜内温度,通常在40-90分钟内完成,聚酯多元醇加完后,控制温度在80℃反应80-120分钟,测定NCO%含量达到预定的要求(20.0-20.2%)后即可降温到60℃以下放料,充氮气后密闭保存。通常需要保存在15-40℃的环境中。温度过低可能会出现糊状甚至变成固体。
实施例3
异氰酸酯部分(B组分)的合成(标记为B-2),将已经溶化的MDI:60公斤,液化MDI-100L:6公斤,真空吸入反应釜中并保持温度在50-75℃之间,并用氮气解除真空,开动反应釜搅拌,然后将温度保持为40-50℃的聚酯多元醇-a 35公斤用齿轮泵打入反应釜中,因为异氰酸酯与羟基的反应是放热的,打入聚酯多元醇的速度要根据反应温度的高低来控制,通常控制温度不高于75-80℃,如果温度过高也可以通过夹套通冷却水来降低釜内温度,通常在40-90分钟内完成,聚酯多元醇加完后,再将均苯四甲酸二酐0.5公斤分4-6次投入反应釜,加入的时间间隔,根据反应产生的气泡情况来定,保持反应液面有较少气泡;加料完成后控制温度在80℃反应80-120分钟,测定NCO%含量达到预定的要求(20.0-20.4%)后即可降温到60℃以下放料,充氮气后密闭保存。通常需要保存在15-40℃的环境中。温度过低可能会出现糊状甚至变成固体。
实施例4
异氰酸酯部分(B组分)的合成(标记为B-3),将已经溶化的MDI:61公斤,液化MDI-100L:5公斤,真空吸入反应釜中并保持温度在50-75℃之间,开动反应釜搅拌,然后将分子量为4000的DMC聚丙二醇醚多元醇-h 20公斤,分子量为6000、用环氧乙烷(EO)封端、双金属催化(DMC)、聚丙三醇醚多元醇-i 15公斤分别用齿轮泵打入反应釜中,因为异氰酸酯与羟基的反应是放热的,打入聚酯多元醇的速度要根据反应温度的高低来控制,通常控制温度不高于75-80℃,如果温度过高也可以通过夹套通冷却水来降低釜内温度,通常在40-90分钟内完成,根据反应产生的气泡的多少再将均苯四甲酸二酐1.0公斤分4-6次投入反应釜,加入的时间间隔根据反应液面的气泡多少来控制,加料完成后控制温度在80℃反应80-120分钟,测定NCO%含量达到预定的要求后(20.1-20.4%)即可降温到60℃以下放料,充氮气后密闭保存。
实施例5
改性小分子胺扩链剂的合成
将15公斤的双马来酰亚胺投入50升反应釜中,然后再投入22.5公斤的MOCA,然后加热到135-140℃,搅拌并保持温度40分钟,形成以MOCA的氨基封端聚氨基-双马来酰亚胺低聚物,反应完成后降温到95℃放出,采用小包装。常温固化成棕色透明块状固体。
实施例6
羟基部分(A组分)的配制(标记为A-1对比)
将45-50℃分子量为2000的聚酯多元-a 89公斤加入到反应釜中,开动搅拌,然后加入乙二醇7.5公斤,甘油0.35公斤,硅油0.35公斤,水0.2公斤,开动物料循环齿轮泵打循环,充分混合均匀后(大约60-90分钟),测定并确认粘度,水分含量后,即可放料装桶,密闭包装。
实施例7
羟基部分(A组分)的配制(标记为A-2)
将分子量为6000的聚醚三元醇(Triol-6000)86公斤加入到反应釜中,开动搅拌,然后加入乙二醇7.5公斤,甘油0.5公斤,改性小分子胺扩链剂MOCA-BMI(双马来酰亚胺)低聚物2.5公斤,硅油0.35公斤,水0.2公斤,DBU(,8-二氮杂二环十一碳-7-烯)0.2公斤,开动物料循环齿轮泵打循环,充分混合均匀后(大约60-90分钟),测定并确认粘度,水分含量后,即可放料装桶,密闭包装。
实施例8
羟基部分(A组分)的配制(标记为A-3)
将45-50℃分子量为2000的聚酯多元-b 84公斤加入到反应釜中,开动搅拌,然后加入乙二醇7.0公斤,三异丙醇胺0.5公斤,改性小分子胺扩链剂MOCA-BMI低聚物5.0公斤,硅油0.35公斤,水0.2公斤,DBU 0.2公斤,开动物料循环齿轮泵打循环,充分混合均匀后(大约60-90分钟),测定并确认粘度,水分含量后,即可放料装桶,密闭包装。
实施例9
羟基部分(A组分)的配制(标记为A-4)
将45-50℃分子量为2000的聚酯多元-d 81.5公斤加入到反应釜中,开动搅拌,然后加入乙二醇6.5公斤,甘油0.35公斤,改性小分子胺扩链剂MOCA-BMI低聚物8.0公斤,硅油0.35公斤,水0.25公斤,DBU 0.25公斤,开动物料循环齿轮泵打循环,充分混合均匀后(大约60-90分钟),测定并确认粘度,水分含量后,即可放料装桶,密闭包装。
实施例10
微孔弹性体的制造
首先将上述配制而成的A、B、催化剂(C组分)在烘箱内加热到40℃,然后将A、B组分分别倒入到低压罐内,然后将催化剂按照计量比例加入到A料罐内开动搅混合,并保持恒温在35-40℃左右,按照计量的比例,采用低压聚氨酯浇注机和轮胎成型机的组合成型方法制造出聚氨酯微孔轮胎,将脱模出来的轮胎放入120℃的烘箱中6小时高温硫化,然后取出室温后硫化7天。同时可以采用规定尺寸的模具制造出同样密度的测试样片进行测试。
耐热性能测试的方法是:将测试样品片材放在110℃的烘箱内20天后取出样品在23℃放置24小时后再进行拉伸强度、伸长率测试。
表1为本发明的微孔弹性体配方
Figure BDA0002235131860000091
表2自由发泡成型的耐热微孔弹性体的物理性能
Figure BDA0002235131860000092
Figure BDA0002235131860000101
表3耐热性能变化对比(110℃20天热空气处理)
Figure BDA0002235131860000102
从热处理前后的测试数据对比可以明显看处,没有改进的对比配方样品拉伸强度下降了41.26%,而属于本发明的两个配方-3、配方-4样品分别下降了16.67%和12.33%;可以说本发明的微孔聚氨酯弹性体耐热性能的提高是明显的,轮胎也实际分别经过了8000和9000公里的两次跑车测试,轮胎外部温度一直维持在36-38℃之间,这些测试数据都证明,利用本发明的技术而生产的轮胎,其耐热性能是优良的。
尽管上述公布了本发明的具体实施配方,但是并不仅仅限于本发明说明书和实施例中的几种配方,它完全可以被适用于的各种适合本发明的领域,对于熟悉本领域的技术人员而言,可以很容易的进行另外的修改,因此在不背离权利要求及等同范围所限定的一般概念下,本发明并不限于特定的细节和这里已经公布的实施例。

Claims (10)

1.一种聚氨酯微孔泡沫材料,其特征在于:该材料的主要原料包括:A组分、C组分和B组分,所述的A组分、C组分和B组分对应的物料和用量如下:
A组分制备原料:
聚酯多元醇 75-100重量份,
聚醚多元醇 0-25重量份,
小分子多元醇 5-9重量份,
甘油三醇 0-1重量份,
小分子胺 0-5重量份,
硅油 0.1-0.6重量份,
水 0.1-0.25重量份,
发泡剂 0-5重量份,
C组分 1.0-1.8重量份,
B组分 85-110重量份(指数为:1.0-1.05)。
2.根据权利要求1所述的聚氨酯微孔泡沫材料,其特征在于:所述的聚酯多元醇或者聚醚多元醇其分子量为2000-2500,其类型包括如下各种类型中的一种或者多种:
a 聚己二酸-乙二醇-丁二醇酯,合成其的原料己二酸-乙二醇-丁二醇的摩尔比:2:1.0-1.05:1.25-1.30;
b 聚己二酸-乙二醇-丁二醇-己二醇,合成其的原料己二酸-乙二醇-丁二醇-己二醇的摩尔比为:2:1.0:0.9-1.0:0.4;
c 聚己二酸-乙二醇-丁二醇-新戊二醇酯,合成其的原料己二酸-乙二醇-丁二醇-新戊二醇的摩尔比为:2:1.2-1.3:0.9:0.2;
d 聚己二酸-乙二醇-丁二醇-丙二醇酯,合成其的原料己二酸-乙二醇-丁二醇-丙二醇的摩尔比为:2:1.1-1.2:1.0:0.2;
e 聚癸二酸-乙二醇-丁二醇-二乙二醇酯,合成其的原料癸二酸-乙二醇-丁二醇-二乙二醇的摩尔比为:2:1.1:1.0:0.2-0.25;
f 聚己内酯多元醇,分子量2000-2500;
g 聚四氢呋喃醚二醇,分子量2000-2500;
h DMC聚丙二醇多元醇,分子量为2000-8000;
i DMC聚丙三元醇,分子量6000。
3.根据权利要求2所述的聚氨酯微孔泡沫材料,其特征在于:所述的DMC聚丙二醇多元醇的分子量为4000。
4.根据权利要求2所述的聚氨酯微孔泡沫材料,其特征在于:所述的小分子多元醇为如下中的一种或者多种:乙二醇,丙二醇,二乙二醇,丁二醇,二丙二醇,1,6-己二醇,三甘醇,甲基丙二醇,新戊二醇,环己二醇,甘油,三羟基丙烷,三羟甲基乙烷;HQEE,HER。
5.根据权利要求2所述的聚氨酯微孔泡沫材料,其特征在于:所述的小分子胺为如下中的一种或者多种:二乙醇胺,三乙醇胺,三异丙醇胺,摩卡,二甲硫基甲苯二胺,二乙基甲苯二胺,改性小分子胺。
6.根据权利要求1所述的聚氨酯微孔泡沫材料,其特征在于:所述的C组分催化剂包括如下的一种或者多种:有机锡类,胺类,四异丙基钛酸酯。
7.根据权利要求1所述的聚氨酯微孔泡沫材料,其特征在于:所述的硅油是DC-193,B-8681, Y-10366中的一种或者多种。
8.根据权利要求1所述的聚氨酯微孔泡沫材料,其特征在于:所述的发泡剂是物理发泡剂M.C, 141b中的一种或者多种。
9.根据权利要求1所述的聚氨酯微孔泡沫材料,其特征在于:所述的B组分为主要通过熔化的MDI、液化MDI、可选加入的均苯四酸酐与聚酯多元醇或者聚醚多元醇反应获得。
10.一种聚氨酯微孔泡沫材料的制备方法,其特征在于:具体步骤包括:
(1)聚酯多元醇的合成:
首先将全部的合成聚酯多元醇所用的己二酸或者癸二酸与二元醇投入反应釜中,经过通氮气置换空气后逐步升温,在125-145℃缩聚反应开始进行脱水基本完成后,再逐步升温,氮气保护下加入催化剂;并在230-240℃保温2-4小时,并逐级抽真空进一步脱水,当羟值、水分分析合格后降温到80℃以下出料密闭包装;通过本合成方法合成出聚酯多元醇型号从a到e;
(2)异氰酸酯组分即B组分的合成:
将熔化的MDI(二苯甲烷二异氰酸酯)和液化MDI真空吸入反应釜中,在50-80℃之间逐步加入聚酯多元醇或者聚醚多元醇充分反应,然后可选加入均苯四酸酐继续反应,并保持温度在70-80℃之间,测试NCO%达到要求后、真空处理脱除气泡后降温出料,充氮并密闭包装;
(3)改性扩链剂的合成工艺
将双马来酰亚胺投入反应釜中,再投入MOCA,然后加热到135-140℃,熔化后即开始搅拌并保持温度30-50分钟,形成以MOCA的氨基封端的聚氨基-双马来酰亚胺低聚物,反应完成后降温到85-95℃放出,常温固化成棕色透明块状固体;
(4)羟基组分即A组分的配制:
将聚酯多元醇或者聚醚多元醇,保持在40-60℃的温度下泵入反应釜中,搅拌开始并加入小分子多元醇或小分子胺、甘油,硅油、水、发泡剂,搅拌均匀60-90分钟后即可放料密闭包装;
(5)微孔弹性体的制造
将上述步骤分别做成的A、B和催化剂按照计量比例,通过浇注机与聚氨酯轮胎成型装置做成轮胎。
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