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WO2018094611A1 - 一种柔软聚氨酯发泡材料 - Google Patents

一种柔软聚氨酯发泡材料 Download PDF

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Publication number
WO2018094611A1
WO2018094611A1 PCT/CN2016/106928 CN2016106928W WO2018094611A1 WO 2018094611 A1 WO2018094611 A1 WO 2018094611A1 CN 2016106928 W CN2016106928 W CN 2016106928W WO 2018094611 A1 WO2018094611 A1 WO 2018094611A1
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polyol
polytetrahydrofuran polyol
polytetrahydrofuran
weight
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PCT/CN2016/106928
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English (en)
French (fr)
Inventor
李红领
苏志锋
谭鹏展
郑发山
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广州艾科新材料股份有限公司
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Priority to PCT/CN2016/106928 priority Critical patent/WO2018094611A1/zh
Publication of WO2018094611A1 publication Critical patent/WO2018094611A1/zh

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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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen

Definitions

  • the present invention relates to a foamed material, especially a soft polyurethane foamed material.
  • Polyether polyurethane soft foams are generally used in the production of insole materials, usually prepared by reacting one or more polyether polyols, chain extenders, water and other auxiliaries with prepolymerized MDI, usually at a density of 0.2- 0.5g/cm3, its products are soft and have good hydrolysis resistance.
  • Polyester polyurethane soft foam is used in the preparation of sole material, usually by using one or more polyester polyols, combined with chain extender, foaming agent, catalyst and other additives to react with prepolymerized MDI.
  • Ether polyols have higher mechanical properties and tear properties.
  • polyester polyurethane has improved mechanical properties, it has high density, high hardness, and easy hydrolysis, and it is difficult to meet the needs of customers due to wet heat compression deformation.
  • the present invention provides a polyurethane foam material having excellent mechanical properties and resistance to moisture and heat compression deformation, and is particularly suitable for preparing a high-grade polyurethane insole.
  • a soft polyurethane foaming material comprising: a polytetrahydrofuran polyol A in a weight fraction of 60-90, a weight fraction of 10-30 polytetrahydrofuran polyol B, and a weight fraction of 0- 5 chain extender, other auxiliary components of 1-30 parts by weight, pre-polymerized MDI of 75-80 parts by weight, polytetrahydrofuran polyol A having a molecular weight of 1000-4000, a minimum functionality of 2, and an OH value of 14 -56 mg KOH / g, polytetrahydrofuran polyol B has a molecular weight of 500-1500 and a functionality of at least 2.
  • the prepolymerized MDI is a prepolymerized 4-4-MDI having an NCO content of 12% to 32%.
  • the invention has the beneficial effects that the present invention adopts two polyether polyols to replace the traditional polyether polyols to improve the mechanical properties thereof, and the effect thereof is equivalent to that of the conventional polyester polyols, and the mechanical properties are improved while ensuring the wet heat compression deformation.
  • the stability of the customer meets the needs of the customer, while using a specific pre-polymerized MDI as a polyurethane B component, greatly improving its yellowing resistance.
  • NCO refers to the isocyanate group in chemical materials, and its value refers to the isocyanate contained in 100g sample.
  • 4-4-MDI is 4,4'-diphenylmethane diisocyanate.
  • the hydroxyl value (OH value) means that the amount of hydroxyl groups per gram of material corresponds to the amount of hydroxide of potassium hydroxide.
  • the present invention provides a soft polyurethane foaming material comprising a polytetrahydrofuran polyol A in an amount of 60-90 parts by weight, a 10-30 polytetrahydrofuran polyol B in parts by weight, a chain extender in an amount of 0-5 parts by weight, and parts by weight. 1-30 other auxiliary, 75-80 parts by weight of prepolymerized MDI, polytetrahydrofuran polyol A has a molecular weight of 1000-4000, a minimum functionality of 2, an OH value of 14-56 mg KOH / g, polytetrahydrofuran The alcohol B has a molecular weight of 500 to 1,500 and a functionality of at least 2.
  • the prepolymerized MDI is a prepolymerized 4-4-MDI having an NCO content of 12% to 32%.
  • the ingredients are stirred uniformly to form a slurry
  • Example 2 Density / g / cm3 0.35 0.35 0.35 Hardness / C 35 28 25
  • Tensile force / Kg / cm 9.8 18.6 16.8 Elongation/% 150 250
  • 300 DIE C tear / Kg / cm2 4.5 8.5 7.9
  • Wet heat compression deformation /% 40 twenty two 20 Yellowing resistance 2.5 4.5 4
  • Examples 1 and 2 have a higher improvement in tensile strength, elongation and DIE C tear performance relative to the comparative examples, and the wet heat compression deformation performance is effective. Reduced, the yellowing resistance has a greater improvement.
  • the invention adopts two polyether polyols to replace the traditional polyether polyols to improve the mechanical properties thereof, and the effect thereof is equivalent to the traditional polyester polyols, and the mechanical properties are improved while ensuring the stability of the wet heat compression deformation to meet the customer's needs.
  • the specific pre-polymerized MDI is used as the polyurethane B component, and the yellowing resistance is greatly improved;
  • the polyurethane soft foam prepared by the invention has excellent mechanical properties and resistance to moist heat compression deformation, and is particularly suitable for preparing a high-grade polyurethane insole.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

本发明提供一种柔软聚氨酯发泡材料，其特征在于：包含重量份为60-90的聚四氢呋喃多元醇A、重量份为10-30聚四氢呋喃多元醇B、重量份为0-5的扩链剂、重量份为1-30的其他助剂、重量份为75-80的预聚MDI，聚四氢呋喃多元醇A的分子量为1000-4000，官能度最少为2，OH值为14-56mgKOH/g，聚四氢呋喃多元醇B的分子量为500-1500，官能度最少为2。本发明的有益效果为：本发明采用两种聚醚多元醇替代传统聚醚多元醇以改善其力学性能，其效果与传统聚酯多元醇相当，改善力学性能的同时又能保证其湿热压缩形变的稳定性以满足客户需求，同时采用特定预聚MDI作为聚氨酯B组分，大大改善其耐黄变性能。

Description

一种柔软聚氨酯发泡材料 技术领域
本发明涉及一种发泡材料，尤其是一种柔软聚氨酯发泡材料。
背景技术
聚醚型聚氨酯软泡一般应用于鞋垫材料的生产，通常采用一种或多种聚醚多元醇，扩链剂，水以及其他助剂与预聚MDI进行反应制备而得，通常密度为0.2-0.5g/cm3，其制品柔软，耐水解性能好。聚酯型聚氨酯软泡被用于鞋底材料的制备，通常采用一种或多种聚酯多元醇，结合扩链剂，发泡剂，催化剂等助剂与预聚MDI进行反应而得，相对聚醚多元醇而言具有较高的力学性能以及撕裂性能。
聚醚型聚氨酯最大的不足为力学性能偏低，抗撕裂能力差，且易发黄，无法满足高端客户需求。聚酯型聚氨酯虽然具有改进的力学性能，但密度较大，硬度较高，且易水解，湿热压缩形变很难满足客户需求。
发明内容
针对现有技术的不足，本发明提供一种具有优异的力学性能以及耐湿热压缩形变性能的聚氨酯发泡材料，特别适用于制备高档聚氨酯鞋垫。
本发明的技术方案为：一种柔软聚氨酯发泡材料，其特征在于：包含重量份为60-90的聚四氢呋喃多元醇A、重量份为10-30聚四氢呋喃多元醇B、重量份为0-5的扩链剂、重量份为1-30的其他助剂、重量份为75-80的预聚MDI，聚四氢呋喃多元醇A的分子量为1000-4000，官能度最少为2，OH值为14-56mgKOH/g，聚四氢呋喃多元醇B的分子量为500-1500，官能度最少为2。
预聚MDI为预聚4-4-MDI，其NCO含量为12％-32％。
本发明的有益效果为：本发明采用两种聚醚多元醇替代传统聚醚多元醇以改善其力学性能，其效果与传统聚酯多元醇相当，改善力学性能的同时又能保证其湿热压缩形变的稳定性以满足客户需求，同时采用特定预聚MDI作为聚氨酯B组分，大大改善其耐黄变性能。
具体实施方式
下面结合附图对本发明的具体实施方式作进一步说明：
名词解释：NCO是指化学材料中异氰酸酯基，其值是指100g试样所含的异氰酸酯 (-NCO)基团的质量。4-4-MDI为4，4`-二苯基甲烷二异氰酸酯。羟值(OH值)，是指每克材料含羟基的数量相当于氢氧化钾的氢氧根的量。
本方案提供一种柔软聚氨酯发泡材料，包含重量份为60-90的聚四氢呋喃多元醇A、重量份为10-30聚四氢呋喃多元醇B、重量份为0-5的扩链剂、重量份为1-30的其他助剂、重量份为75-80的预聚MDI，聚四氢呋喃多元醇A的分子量为1000-4000，官能度最少为2，OH值为14-56mgKOH/g，聚四氢呋喃多元醇B的分子量为500-1500，官能度最少为2。
预聚MDI为预聚4-4-MDI，其NCO含量为12％-32％。
(一)以下为本方案的一个对比例和两个实施例的组分配比：
Figure PCTCN2016106928-appb-000001
(二)本材料的制备流程：
1)按照组分配比进行配料，搅拌均匀，形成浆料；
2)模具启动预热；
3)在模具内部喷涂水性脱模剂；
4)灌注浆料；
5)合模熟化，注意保温；
6)出模；
7)修边；
8)入库。
(三)针对对比例和两个实施例进行测试项目：
测试项目 对比例 实施例1 实施例2
密度/g/cm3 0.35 0.35 0.35
硬度/C 35 28 25
拉伸力/Kg/cm 9.8 18.6 16.8
伸长率/％ 150 250 300
DIE C撕裂/Kg/cm2 4.5 8.5 7.9
压缩形变/％ 12 10 12
湿热压缩形变/％ 40 22 20
耐黄变性 2.5 4.5 4
由上表可知，实施本发明方案后了，实施例1和实施例2相对于对比例在拉伸力、伸长率和DIE C撕裂的性能方面具有较高的提升，湿热压缩形变性能有效降低，耐黄变性方面具有较大的改善。
本发明采用两种聚醚多元醇替代传统聚醚多元醇以改善其力学性能，其效果与传统聚酯多元醇相当，改善力学性能的同时又能保证其湿热压缩形变的稳定性以满足客户需求，同时采用特定预聚MDI作为聚氨酯B组分，大大改善其耐黄变性能；本发明制备的聚氨酯软泡具有优异的力学性能以及耐湿热压缩形变性能，特别适用于制备高档聚氨酯鞋垫。
上述实施例和说明书中描述的只是说明本发明的原理和最佳实施例，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。

Claims (2)

  1. 一种柔软聚氨酯发泡材料，其特征在于：包含重量份为60-90的聚四氢呋喃多元醇A、重量份为10-30聚四氢呋喃多元醇B、重量份为0-5的扩链剂、重量份为1-30的其他助剂、重量份为75-80的预聚MDI，聚四氢呋喃多元醇A的分子量为1000-4000，官能度最少为2，OH值为14-56mgKOH/g，聚四氢呋喃多元醇B的分子量为500-1500，官能度最少为2。
  2. 根据权利要求1所述的柔软聚氨酯发泡材料，其特征在于：预聚MDI为预聚4-4-MDI，其NCO含量为12％-32％。
PCT/CN2016/106928 2016-11-23 2016-11-23 一种柔软聚氨酯发泡材料 WO2018094611A1 (zh)

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Publication number Priority date Publication date Assignee Title
CN115073706A (zh) * 2021-10-22 2022-09-20 上海联景高分子材料有限公司 一种增强型etpu及其制备方法和应用
WO2024041007A1 (zh) * 2022-08-25 2024-02-29 足力健老龄产业发展有限公司北京分公司 一种石墨烯鞋垫及其制备方法

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CN106560481A (zh) * 2015-11-18 2017-04-12 广州艾科新材料股份有限公司 一种柔软聚氨酯发泡材料

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US20090131606A1 (en) * 2007-11-20 2009-05-21 Bayer Materialscience Ag Polyurethane/polyurea elastomers based on 2,4'-diphenylmethane diisocyanate prepolymers and the production thereof
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115073706A (zh) * 2021-10-22 2022-09-20 上海联景高分子材料有限公司 一种增强型etpu及其制备方法和应用
CN115073706B (zh) * 2021-10-22 2023-12-22 上海联景高分子材料有限公司 一种增强型etpu及其制备方法和应用
WO2024041007A1 (zh) * 2022-08-25 2024-02-29 足力健老龄产业发展有限公司北京分公司 一种石墨烯鞋垫及其制备方法

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