CN107141435A - 聚酯‑醚多元醇、其制法及其制备的聚氨酯高回弹泡沫塑料和聚氨酯高回弹泡沫塑料的制法 - Google Patents

聚酯‑醚多元醇、其制法及其制备的聚氨酯高回弹泡沫塑料和聚氨酯高回弹泡沫塑料的制法 Download PDF

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CN107141435A
CN107141435A CN201710508572.4A CN201710508572A CN107141435A CN 107141435 A CN107141435 A CN 107141435A CN 201710508572 A CN201710508572 A CN 201710508572A CN 107141435 A CN107141435 A CN 107141435A
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polyester
elastic foam
foam plastic
pepa
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李剑锋
孙兆任
王文涛
张士虎
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Shandong Inov New Material Co Ltd
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Abstract

本发明属于高分子合成技术领域，具体涉及一种聚酯‑醚多元醇、其制法及其制备的聚氨酯高回弹泡沫塑料和聚氨酯高回弹泡沫塑料的制法。所述的聚酯‑醚多元醇，是以聚酯多元醇或聚酯多元醇与聚四氢呋喃二醇的混合物为起始剂与环氧烷烃的共聚物，羟值为30‑75mgKOH/g；所述的环氧烷烃为环氧乙烷和环氧丙烷；所述的聚酯多元醇是采用己二酸、新戊二醇、二甘醇和ε‑己内酯制备的。本发明的聚酯‑醚多元醇无色透明，具有残留催化剂含量低、性质稳定的特点；制备的聚氨酯高回弹泡沫塑料，具有配方宽容度好、力学性能优良、耐候性好的特点。

Description

聚酯-醚多元醇、其制法及其制备的聚氨酯高回弹泡沫塑料和 聚氨酯高回弹泡沫塑料的制法
技术领域
本发明属于高分子合成技术领域，具体涉及一种聚酯-醚多元醇、其制法及其制备的聚氨酯高回弹泡沫塑料和聚氨酯高回弹泡沫塑料的制法。
背景技术
聚酯多元醇和聚醚多元醇是聚氨酯中两大主要原料。聚酯多元醇型PU材料耐水解性差，与配方中其他添加剂的相容性差，储存稳定性差，耐温性差，常温下是固体或高粘度液体，不便于操作等；聚醚多元醇型PU材料力学性能较聚酯型差，但由于其良好的耐水解稳定性，常温下为液体，粘度低，发泡范围宽，便于操作，经济性好，原料易得等特性，在聚氨酯材料中发展越来越快。
针对上述两种材料的缺陷，有人采用特殊的聚醚二元醇对聚酯二元醇进行改性，如中国发明专利申请(公开号CN 103265708A)公开了一种改性聚酯多元醇及其制备方法和应用：采用聚碳酸酯和聚醚多元醇对聚己二酸酯二元醇进行改性，该方法在一定程度上还是存在聚酯、聚醚之间单纯的物理混合，材料性质不够稳定；中国发明专利申请(公开号CN103380162A)公开了一种制备聚酯醚醇的方法：采用均苯四甲酸酐和小分子二元醇合成聚酯二元醇，然后采用胺类催化剂，同环氧丙烷催化聚合，该方法合成产品色值较深，且存在胺类物质残留，对于产品使用和储存都有影响；中国发明专利申请(公开号CN 103998488A)公开了一种用于制备混合聚酯-聚醚多元醇的方法，通过使环氧烷烃在羧酸类引发剂的存在下聚合得到目标产物，并且该聚合过程使用双金属氰化络合物和某些镁族、第3族-15族或镧系金属化合物的混合物进行催化，该方法催化剂复杂、不易得、用量大、合成过程存在环氧烷烃活化失效的风险。
发明内容
针对现有技术的不足，本发明的目的是提供一种聚酯-醚多元醇，该聚酯-醚多元醇无色透明，具有残留催化剂含量低、性质稳定的特点，同时提供其制备方法；本发明还提供一种用聚酯-醚多元醇制备的聚氨酯高回弹泡沫塑料，具有配方宽容度好、力学性能优良、耐候性好的特点，同时提供其制备方法。
本发明所述的聚酯-醚多元醇，是以聚酯多元醇或聚酯多元醇与聚四氢呋喃二醇的混合物为起始剂与环氧烷烃的共聚物，羟值为30-75mgKOH/g；
所述的环氧烷烃为环氧乙烷和环氧丙烷；
所述的聚酯多元醇是采用己二酸(AA)、新戊二醇(NPG)、二甘醇(DEG)和ε-己内酯制备的。
ε-己内酯反应活性较高，柔顺性和耐水解性较高；新戊二醇耐水解性、耐候性较好，此外，起到软硬平衡的作用。
聚四氢呋喃二醇可以赋予材料优异的力学性能。
所述的环氧烷烃优选环氧乙烷和环氧丙烷。
所述的聚酯多元醇的制备方法如下：
将己二酸、新戊二醇、二甘醇、ε-己内酯和催化剂钛酸四丁酯投入反应釜中，用氮气置换釜内空气后，开启搅拌，升温至120-130℃反应1h，然后，升温至230℃，保温至酸值＜20mgKOH/g，开始抽真空，当酸值＜1mgKOH/g且羟值在120-130mgKOH/g时，降温，即得所述的聚酯多元醇。
上述制备方法中，也可以保温至理论出水量后，开始抽真空。
所述的己二酸、新戊二醇、二甘醇和ε-己内酯的摩尔百分比如下：
所述的催化剂钛酸四丁酯的用量为己二酸、新戊二醇、二甘醇和ε-己内酯总量的0.005-0.15wt％。
所述的聚酯多元醇与聚四氢呋喃二醇的混合物，其中，所述的聚四氢呋喃二醇的羟值为160-180mgKOH/g，其摩尔量为聚酯多元醇和聚四氢呋喃二醇总摩尔量的0-15％。
本发明所述的聚酯-醚多元醇的制备方法，向耐压反应釜中加入起始剂和双金属氰化络合物催化剂，升温至130-150℃条件下，抽真空至-0.09MPa，鼓氮气2h，脱去小分子单体和水分；然后，滴加部分环氧烷烃至釜内压力为0.10-0.15MPa；釜内压力下降至0以下时(反应激活后)，连续滴加余下的环氧烷烃进行聚合反应，滴加完毕，继续反应1h；抽真空以脱除未反应的残留单体，即得聚酯-醚多元醇。
所述的双金属氰化络合物催化剂的用量占起始剂和环氧烷烃总量的0.0035-0.01wt％。
所述的聚酯-醚多元醇能够用于生产聚氨酯泡沫塑料、聚氨酯合成革树脂、水性聚氨酯胶黏剂、聚氨酯鞋底原液、聚氨酯微孔弹性体、高强度高耐水解聚氨酯弹性体等。
用本发明所述的聚酯-醚多元醇制备的聚氨酯高回弹泡沫塑料，由A组分和B组分制成，其中：
A组分：
B组分：
TDI 24-28.8份；
PM200 16-19.2份；
所述的TDI与PM200的质量比为6：4。
所述的聚醚多元醇是以季戊四醇为起始剂的环氧丙烷与环氧乙烷的共聚物，官能度为4，分子量为7000；所述聚合物多元醇为POP36/28，羟值为25-29mgKOH/g，山东蓝星东大化工有限公司产品。
所述的聚醚多元醇以季戊四醇为起始剂，与环氧丙烷和环氧乙烷聚合而成。优选地，所述的聚醚多元醇是YEP-4700，羟值为32-36mgKOH/g，山东一诺威新材料有限公司产品。
所述的硅油为DC2585、DC2525或DC6070中的一种或两种。
所述的TDI为TDI-80或TDI-65中的一种或两种，是河北沧州大化TDI有限责任公司产品。所述的PM200，是烟台万华集团有限公司产品。
本发明所述的聚氨酯高回弹泡沫塑料的制备方法，步骤如下：
(1)将配方量的聚醚多元醇、聚酯-醚多元醇、聚合物多元醇、二乙醇胺、硅油、A-1、A-33、发泡剂和纯水，在25-30℃条件下充分混合均匀，得到A组分；
(2)将A组分和B组分按100：40的质量比充分混合均匀，注入预热的模具中熟化，得聚氨酯高回弹泡沫塑料。
与现有技术相比，本发明的有益效果如下：
本发明的聚酯-醚多元醇，原料易得，其制备操作简单，物化性质稳定，规模化生产易实现；本发明制备的聚酯-醚多元醇采用完全化学反应的形式将酯键和醚键结合在一个分子链段上，可以赋予材料优异的力学性能和耐候性；用聚酯-醚多元醇制备的聚氨酯高回弹泡沫塑料，具有力学性能优良、配方宽容度好的特点，同时提供其制备方法。
所述的聚氨酯高回弹泡沫塑料各原料分子结构合理搭配赋予材料优异的力学性能和优异的耐水解性、耐候性。同时可以兼有舒适的软硬度和手感。
具体实施方式
下面结合实施例对本发明做进一步说明，但不限定本发明。
实施例中用到的所有原料除特殊说明外，均为市购。
实施例1
(1)聚酯多元醇的制备方法如下：
原料及配比见表1；
将己二酸、新戊二醇、二甘醇、ε-己内酯和催化剂钛酸四丁酯投入反应釜中，用氮气置换釜内空气后，开启搅拌，升温至120℃反应1h，然后，升温至230℃，保温至酸值＜20mgKOH/g，开始抽真空，逐步提高真空度，当酸值＜1mgKOH/g且羟值在122mgKOH/g时，降温，即得所述的聚酯多元醇。
(2)聚酯-醚多元醇的制备方法如下：
向耐压反应釜中加入步骤(1)制备的聚酯多元醇920g(羟值122mgKOH/g)、双金属氰化络合物(DMC催化剂)0.0707g，然后升温至130℃条件下，抽真空至-0.09MPa，鼓氮气，脱去小分子单体和水分，计时2h；然后快速滴加30g环氧丙烷至釜内压力0.10MPa；待反应激活后连续滴加剩余环氧丙烷960g和环氧乙烷110g，在130℃温度下进行聚合反应，加料完毕后继续反应1h；然后抽真空以脱除未反应的残留单体，即得聚酯-醚多元醇。
得到的聚酯-醚多元醇澄清透明。经检测粘度为1345MPa·s(25℃)，OHv＝55.8mgKOH/g。
实施例2
(1)聚酯多元醇的制备方法如下：
原料及配比见表1；
将己二酸、新戊二醇、二甘醇、ε-己内酯和催化剂钛酸四丁酯投入反应釜内，用氮气置换釜内空气后，开启搅拌，升温至125℃反应1h，升温至230℃，保温至酸值＜20mgKOH/g，开始抽真空，逐步提高真空度，当酸值＜1mgKOH/g且羟值在122mgKOH/g时，降温，即得所述的聚酯多元醇。
(2)聚酯-醚多元醇的制备方法如下：
向耐压反应釜中加入步骤(1)制备的聚酯多元醇736g(羟值122mgKOH/g)、聚四氢呋喃二醇132g(羟值170mgKOH/g)、双金属氰化络合物(DMC催化剂)0.0606g，然后升温至140℃条件下，抽真空至-0.09MPa，鼓氮气，脱去小分子单体和水分，计时2h；然后快速滴加47g环氧丙烷至釜内压力0.15MPa；待反应激活后连续滴加剩余环氧丙烷535g和环氧乙烷65g，在140℃温度下进行聚合反应，加料完毕后继续反应1h；然后抽真空以脱除未反应的残留单体，即得聚酯-醚多元醇。
得到的聚酯-醚多元醇澄清透明。经检测，粘度为948MPa·s(25℃)，OHv＝74.2mgKOH/g。
实施例3
(1)聚酯多元醇的制备方法如下：
原料及配比见表1；
将己二酸、新戊二醇、二甘醇、ε-己内酯和催化剂钛酸四丁酯投入反应釜内，用氮气置换釜内空气后，开启搅拌，升温至130℃反应1h，升温至230℃，保温至酸值＜20mgKOH/g，开始抽真空，逐步提高真空度，当酸值＜1mgKOH/g且羟值在125mgKOH/g时，降温，即得所述的聚酯多元醇。
(2)聚酯-醚多元醇的制备方法如下：
向耐压反应釜中加入步骤(1)制备的聚酯多元醇673.2g(羟值125mgKOH/g)、聚四氢呋喃二醇165g(羟值170mgKOH/g)、双金属氰化络合物(DMC催化剂)0.106g，然后升温至150℃条件下，抽真空至-0.09MPa，鼓氮气，脱去小分子单体和水分，计时2h；然后快速滴加32g环氧丙烷至釜内压力0.11MPa；待反应激活后连续滴加剩余环氧丙烷2000g和环氧乙烷160g，在150℃温度下进行聚合反应，加料完毕后继续反应1h；然后抽真空以脱除未反应的残留单体，即得聚酯-醚多元醇。
得到的聚酯-醚多元醇澄清透明。经检测，粘度为1948MPa·s(25℃)，OHv＝37.8mgKOH/g。
表1 实施例1-3制备聚酯多元醇的原料及配比
原料 实施例1 实施例2 实施例3
AA 308g 277g 280g
NPG 201.8g 193.4g 205g
DEG 47.8g 69g 46.4g
ε-己内酯 / 130g 11.4g
钛酸四丁酯 0.008wt％ 0.006wt％ 0.005wt％
实施例4
所述的聚氨酯高回弹泡沫塑料，由A组分和B组分制成，其中：
A组分：
B组分：
TDI/PM200＝6/4 40-48份。
所述的聚酯-醚多元醇采用实施例2制备的聚酯-醚多元醇。
制备方法如下：
(1)将配方量的聚醚多元醇、聚酯-醚多元醇、聚合物多元醇、二乙醇胺、硅油、A-1、A-33、发泡剂和纯水，在25-30℃条件下充分混合均匀，得到A组分；
(2)将A组分和B组分按100：40的质量比充分混合均匀，注入预热的模具中熟化，得聚氨酯高回弹泡沫塑料。
所述的实施例4分为3个试验例，具体如下：
试验例1
原料：见表2。
按照实施例4所述制备方法合成聚氨酯高回弹泡沫塑料，并测试其力学性能。密度采用GB/T6343—1995标准测定；拉伸强度和伸长率按照GB/T528—1998标准测定；撕裂强度按GB/T529—1999标准测定；压缩永久变形按GB/T7759.1—2014标准测定。测试结果见表3。
试验例2
原料：见表2。
按照实施例4所述制备方法合成聚氨酯高回弹泡沫塑料，并测试其力学性能。密度采用GB/T6343—1995标准测定；拉伸强度和伸长率按照GB/T528—1998标准测定；撕裂强度按GB/T529—1999标准测定；压缩永久变形按GB/T7759.1—2014标准测定。测试结果见表3。
试验例3
原料：见表2。
按照实施例4所述制备方法合成聚氨酯高回弹泡沫塑料，并测试其力学性能。密度采用GB/T6343—1995标准测定；拉伸强度和伸长率按照GB/T528—1998标准测定；撕裂强度按GB/T529—1999标准测定；压缩永久变形按GB/T7759.1—2014标准测定。测试结果见表3。
对比例
原料：不使用聚酯-醚多元醇，具体配方见表2。
按照实施例4所述方法合成聚氨酯高回弹泡沫塑料，并测试其力学性能。密度采用GB/T6343—1995标准测定；拉伸强度和伸长率按照GB/T528—1998标准测定；撕裂强度按GB/T529—1999标准测定；压缩永久变形按GB/T7759.1—2014标准测定。测试结果见表3。
表2 实施例4与对比例原料及配方
表3 聚氨酯高回弹泡沫力学性能测试
指标 对比例 试验例1 试验例2 试验例3
密度/kg·m-3 81 81 82 81
拉伸强度/MPa 179.7 209.3 211 248.3
撕裂强度/kN·m-1 8.13 8.80 9.62 11.21
断裂伸长率/％ 61.14 65.29 68.32 81.58
压缩永久变形(75％)，％ 5.5 5.6 6.0 6.3
表3表明制备的聚酯-醚多元醇用于聚氨酯高回弹泡沫，力学性能优良。

Claims (10)

1.一种聚酯-醚多元醇，其特征在于：是以聚酯多元醇或聚酯多元醇与聚四氢呋喃二醇的混合物为起始剂与环氧烷烃的共聚物，羟值为30-75mgKOH/g；
所述的环氧烷烃为环氧乙烷和环氧丙烷；
所述的聚酯多元醇是采用己二酸、新戊二醇、二甘醇和ε-己内酯制备的。
2.根据权利要求1所述的聚酯-醚多元醇，其特征在于：所述的聚酯多元醇的制备方法如下：
将己二酸、新戊二醇、二甘醇、ε-己内酯和催化剂钛酸四丁酯投入反应釜中，用氮气置换釜内空气后，开启搅拌，升温至120-130℃反应1h，然后，升温至230℃，保温至酸值＜20mgKOH/g，开始抽真空，当酸值＜1mgKOH/g且羟值在120-130mgKOH/g时，降温，即得所述的聚酯多元醇。
3.根据权利要求2所述的聚酯-醚多元醇，其特征在于：所述的己二酸、新戊二醇、二甘醇和ε-己内酯的摩尔百分比如下：
所述的催化剂钛酸四丁酯的用量为己二酸、新戊二醇、二甘醇和ε-己内酯总量的0.005-0.15wt％。
4.根据权利要求1所述的聚酯-醚多元醇，其特征在于：所述的聚酯多元醇与聚四氢呋喃二醇的混合物，其中，所述的聚四氢呋喃二醇的羟值为160-180mgKOH/g，其摩尔量为聚酯多元醇和聚四氢呋喃二醇总摩尔量的0-15％。
5.一种权利要求1所述的聚酯-醚多元醇的制备方法，其特征在于：向耐压反应釜中加入起始剂和双金属氰化络合物催化剂，升温至130-150℃条件下，抽真空至-0.09MPa，鼓氮气2h，脱去小分子单体和水分；然后，滴加部分环氧烷烃至釜内压力为0.10-0.15MPa；釜内压力下降至0以下时，连续滴加余下的环氧烷烃进行聚合反应，滴加完毕，继续反应1h；抽真空以脱除未反应的残留单体，即得聚酯-醚多元醇。
6.一种用权利要求1所述的聚酯-醚多元醇制备的聚氨酯高回弹泡沫塑料，其特征在于：由A组分和B组分制成，其中：
A组分：
B组分：
TDI 24-28.8份；
PM200 16-19.2份；
所述的TDI与PM200的质量比为6：4。
7.根据权利要求6所述的聚氨酯高回弹泡沫塑料，其特征在于：所述的聚醚多元醇是以季戊四醇为起始剂的环氧丙烷与环氧乙烷的共聚物，官能度为4，分子量为7000；所述聚合物多元醇为POP36/28，羟值为25-29mgKOH/g。
8.根据权利要求6所述的聚氨酯高回弹泡沫塑料，其特征在于：所述的硅油为DC2585、DC2525或DC6070中的一种或两种。
9.根据权利要求6所述的聚氨酯高回弹泡沫塑料，其特征在于：所述的TDI为TDI-80或TDI-65中的一种或两种。
10.一种权利要求6-9任一所述的聚氨酯高回弹泡沫塑料的制备方法，其特征在于：步骤如下：
(1)将配方量的聚醚多元醇、聚酯-醚多元醇、聚合物多元醇、二乙醇胺、硅油、A-1、A-33、发泡剂和纯水，在25-30℃条件下充分混合均匀，得到A组分；
(2)将A组分和B组分按100：40的质量比充分混合均匀，注入预热的模具中熟化，得聚氨酯高回弹泡沫塑料。
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CN111100251A (zh) * 2018-10-25 2020-05-05 山东蓝星东大有限公司 聚合物聚酯多元醇的合成工艺
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CN110003440A (zh) * 2019-04-24 2019-07-12 东莞市腾崴塑胶制品有限公司 一种聚酯醚海绵及制备方法
CN110218293B (zh) * 2019-06-26 2021-07-23 山东宏鑫源钢板有限公司 铝镁锰聚氨酯屋面板及其制备工艺
CN110218293A (zh) * 2019-06-26 2019-09-10 山东宏鑫源钢板有限公司 铝镁锰聚氨酯屋面板及其制备工艺
CN114127147A (zh) * 2019-07-22 2022-03-01 陶氏环球技术有限责任公司 聚氨酯组合物、用所述聚氨酯组合物制备的产品和所述产品的制备方法
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WO2021012140A1 (en) * 2019-07-22 2021-01-28 Dow Global Technologies Llc Polyurethane compositions, products prepared with same and preparation methods thereof
CN114127147B (zh) * 2019-07-22 2024-05-03 陶氏环球技术有限责任公司 聚氨酯组合物、用所述聚氨酯组合物制备的产品和所述产品的制备方法
CN112831019A (zh) * 2020-12-31 2021-05-25 山东一诺威聚氨酯股份有限公司 镜面型超高弹聚氨酯鞋底树脂及其制备方法
CN113817434A (zh) * 2021-08-30 2021-12-21 山东一诺威新材料有限公司 含卤阻燃聚氨酯热熔胶及其制备方法
CN113956784A (zh) * 2021-10-18 2022-01-21 丽水学院 一种生态合成革用水性可见光驱动成膜涂饰剂
CN116265506A (zh) * 2021-12-16 2023-06-20 长华化学科技股份有限公司 聚醚酯多元醇的制备方法
CN114989404A (zh) * 2022-07-04 2022-09-02 梦百合家居科技股份有限公司 一种含酯基改善慢回弹海绵抗压性能的聚醚多元醇及其制备方法
CN115677964A (zh) * 2022-10-10 2023-02-03 山东一诺威新材料有限公司 聚脲a组分及制备方法和包含该a组分的聚脲及制备方法
CN116396443A (zh) * 2023-06-07 2023-07-07 山东蓝星东大有限公司 聚四氢呋喃醚二醇改性聚合物多元醇的合成方法
CN116396443B (zh) * 2023-06-07 2023-09-08 山东蓝星东大有限公司 聚四氢呋喃醚二醇改性聚合物多元醇的合成方法

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