CN109456458A - 用于鞋材的聚醚酯型tpu及其制备方法 - Google Patents

用于鞋材的聚醚酯型tpu及其制备方法 Download PDF

Info

Publication number
CN109456458A
CN109456458A CN201811140101.3A CN201811140101A CN109456458A CN 109456458 A CN109456458 A CN 109456458A CN 201811140101 A CN201811140101 A CN 201811140101A CN 109456458 A CN109456458 A CN 109456458A
Authority
CN
China
Prior art keywords
ester type
polyether ester
footwear material
type tpu
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201811140101.3A
Other languages
English (en)
Inventor
代金辉
徐艳艳
宋小娜
罗杰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong Inov Polyurethane Co Ltd
Original Assignee
Shandong Inov Polyurethane Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shandong Inov Polyurethane Co Ltd filed Critical Shandong Inov Polyurethane Co Ltd
Priority to CN201811140101.3A priority Critical patent/CN109456458A/zh
Publication of CN109456458A publication Critical patent/CN109456458A/zh
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B1/00—Footwear characterised by the material
    • A43B1/14—Footwear characterised by the material made of plastics
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
    • C08G18/3814—Polyamines
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
    • C08G18/4252—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids derived from polyols containing polyether groups and polycarboxylic acids
    • 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
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/61—Polysiloxanes
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/004—Additives being defined by their length
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/016—Additives defined by their aspect ratio

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

本发明属于高分子材料技术领域，具体涉及一种用于鞋材的聚醚酯型TPU及其制备方法。所述的用于鞋材的聚醚酯型TPU，由下列质量份数的物质组成：二异氰酸酯20‑40份；聚醚酯多元醇50‑70份；羟基硅油3‑8份；碳纳米管0.002‑0.02份；扩链剂5‑10份；催化剂0.5‑1份。制得的聚醚酯型TPU不仅具有优良的耐水解和低温柔顺性，同时还具有力学性能优异和耐热耐油的特性。本发明提供的制备方法，科学合理，简单易行。

Description

用于鞋材的聚醚酯型TPU及其制备方法
技术领域
本发明属于高分子材料技术领域，具体涉及一种用于鞋材的聚醚酯型TPU及其制备方法。
背景技术
热塑性聚氨酯弹性体(TPU)是一种性能优良的高分子合成材料，既具有橡胶的弹性又有塑料的硬度，而且还具有良好的机械性能、耐磨性和回弹性能，使其广泛应用于各个工业领域。TPU的软质段可使用多种的聚醇，大致上可分为聚醚系及聚酯系两种。目前许多商品热塑性聚氨酯都是聚酯型的，这种热塑性聚氨酯的耐磨性、抗撕裂性以及拉伸和撕裂强度都优于聚醚型热塑性聚氨酯，聚酯型热塑性聚氨酯在油、脂和水中的溶胀性也比较小。但其在耐水解性、耐微生物降解性和低温性、柔顺性等方面却不具备聚醚型聚氨酯弹性体的优势。TPU鞋材产品具有轻便、弹性好、易加工和可回收等优点，是TPU市场中不可或缺的组成部分，鞋材产品尤其是高端鞋材产品要求产品在拥有良好力学性能的同时必须保持优良的耐水解及耐低温性能。如何克服两者的缺点，实现优势互补成近年来人们关注的热点。
Pxominska等将聚醚与聚酯两种多元醇物理混合后合成弹性体，具有较为优良的综合性能。然而聚酯多元醇粘度较高，物理混合时操作不便，且聚醚、聚酯两种多元醇的相容性差，往往使制得的弹性体性能达不到预期效果。
发明内容
针对现有技术的不足，本发明的目的是提供一种用于鞋材的聚醚酯型TPU，不仅具有优良的耐水解和低温柔顺性，同时还具有力学性能优异和耐热耐油的特性。
同时，本发明还提供其制备方法，科学合理，简单易行。
本发明所述的用于鞋材的聚醚酯型TPU，由下列质量份数的物质组成：
二异氰酸酯为二苯基甲烷二异氰酸酯、氢化苯基甲烷二异氰酸酯或六亚甲基二异氰酸酯中一种或几种。
所述的聚醚酯多元醇的分子量为1000-2000，酯基与醚基的摩尔比为0.8-1.2。
优选的，所述的聚醚酯多元醇的分子量为2000，酯基与醚基的摩尔比为1。
所述的聚醚酯多元醇为聚四氢呋喃二醇/聚己二酸乙二醇酯二醇聚醚酯多元醇、聚氧化丙烯二醇/聚己二酸乙二醇酯二醇聚醚酯多元醇或聚乙二醇/聚己二酸乙二醇酯二醇聚醚酯多元醇中一种或几种。
所述的羟基硅油在25℃下粘度为500-5000cps。
所述的碳纳米管直径为50-200nm，长径比为100-500。
所述的扩链剂为1,4-丁二醇、1,6-己二醇、二羟甲基丙酸或二氯二氨基二苯甲烷中的一种或几种。
所述的催化剂为二月桂酸二丁基锡或辛酸亚锡中的一种或两种。
本发明所述的用于鞋材的聚醚酯型TPU的制备方法，包括以下步骤：
1)将质量比例的二异氰酸酯加入到A储料罐中，将质量比例的聚醚酯多元醇和羟基硅油加入到B储料罐中，将质量比例的扩链剂和催化剂加入到C储料罐中，在搅拌条件下，真空脱水，抽注到双螺杆挤出机中；
2)在双螺杆挤出机加料口加入质量比例的碳纳米管，110℃-190℃下，在双螺杆挤出机中反应，造粒得到TPU颗粒。
所述的步骤1中，真空脱水温度为90-120℃；搅拌速率为400-800r/min。
所述的步骤2中，双螺杆挤出机的喂料段温度为110-120℃，混合段温度为130-150℃，挤出段温度为170-180℃，机头温度为150-160℃。
与现有技术相比，本发明具有如下有益效果：
1.采用聚醚酯多元醇合成TPU提高了TPU的综合性能，其拉伸强度与相同硬度的聚醚型TPU相比提高了29％；经耐水解测试四周后其力学性能保持率可达到50％以上；
2.引入羟基硅油和碳纳米管赋予TPU更好的耐磨和机械强度，制得聚醚酯型TPU的DIN磨耗较之聚醚型TPU也降低了29％。
具体实施方式
下面结合实施例对本发明做进一步的说明。
实施例1
一种用于鞋材的聚醚酯型TPU,由包括以下质量份数的原料组成：
多元醇为聚四氢呋喃二醇/聚己二酸乙二醇酯二醇聚醚酯多元醇(PTMG/PEGA)；羟基硅油在25℃下的粘度为500cp；碳纳米管的直径为100nm，长径比为500；
制备方法包括以下步骤：
1.将二异氰酸酯加入到A储料罐中，将多元醇和羟基硅油加入到B储料罐中，扩链剂和催化剂加入到C储料罐中，在500r/min速率下搅拌，110℃真空脱水，抽注到双螺杆挤出机中；
2.在双螺杆挤出机加料口加入碳纳米管，在120℃下，双螺杆挤出机中反应，造粒得到TPU颗粒；其中双螺杆挤出机的喂料段温度为110℃，混合段温度为130℃，挤出段温度为170℃，机头温度为150℃。
实施例2
一种用于鞋材的聚醚酯型TPU,由以下质量份数的原料组成：
多元醇为聚氧化丙烯二醇/聚己二酸乙二醇酯二醇聚醚酯多元醇；羟基硅油在25℃下的粘度为500cp；碳纳米管的直径为90nm，长径比为400。
制备方法包括以下步骤：
1.将二异氰酸酯加入到A储料罐中，将多元醇和羟基硅油加入到B储料罐中，扩链剂和催化剂加入到C储料罐中，在400r/min速率下搅拌，110℃真空脱水，抽注到双螺杆挤出机中；
2.在双螺杆挤出机加料口加入碳纳米管，在130℃下，双螺杆挤出机中反应，造粒得到TPU颗粒；其中双螺杆挤出机的喂料段温度为120℃，混合段温度为150℃，挤出段温度为180℃，机头温度为160℃。
实施例3
一种用于鞋材的聚醚酯型TPU,由以下质量份数的原料组成：
多元醇为聚四氢呋喃二醇/聚己二酸乙二醇酯二醇聚醚酯多元醇(PTMG/PEGA)和聚氧化丙烯二醇/聚己二酸乙二醇酯二醇聚醚酯多元醇(PPG/PEGA)；羟基硅油在25℃下的粘度为5000cps；碳纳米管的直径为150nm，长径比为200。
制备方法包括以下步骤：
1.将二异氰酸酯加入到A储料罐中，多元醇、羟基硅油加入到B储料罐中，扩链剂和催化剂加入到C储料罐中，在400-800r/min速率下搅拌，110℃真空脱水，抽注到双螺杆挤出机中；
2.在双螺杆挤出机加料口加入碳纳米管，在110℃-190℃下，双螺杆挤出机中反应，造粒得到TPU颗粒；其中双螺杆挤出机的喂料段温度为110-120℃，混合段温度为130-150℃，挤出段温度为170-180℃，机头温度为150-160℃。
实施例4
一种用于鞋材的聚醚酯型TPU,由以下质量份数的原料组成：
多元醇为聚氧化丙烯二醇/聚己二酸乙二醇酯二醇聚醚酯多元醇(PPG/PEGA)；羟基硅油在25℃下的粘度为800cp；碳纳米管的直径为50nm，长径比为100。
制备方法包括以下步骤：
1.将二异氰酸酯加入到A储料罐中，多元醇、羟基硅油加入到B储料罐中，扩链剂和催化剂加入到C储料罐中，在400-800r/min速率下搅拌，110℃真空脱水，抽注到双螺杆挤出机中；
2.在双螺杆挤出机加料口加入碳纳米管，在110℃-190℃下，双螺杆挤出机中反应，造粒得到TPU颗粒；其中双螺杆挤出机的喂料段温度为110-120℃，混合段温度为130-150℃，挤出段温度为170-180℃，机头温度为150-160℃。
实施例5
一种用于鞋材的聚醚酯型TPU,由以下质量份数的原料组成：
多元醇为聚乙二醇/聚己二酸乙二醇酯二醇聚醚酯多元醇(PEG/PEGA)；羟基硅油在25℃下的粘度为1000cp；碳纳米管的直径为200nm，长径比为500。
用于鞋材的聚醚酯型TPU的制备方法包括以下步骤：
1.将二异氰酸酯加入到A储料罐中，多元醇、羟基硅油加入到B储料罐中，扩链剂和催化剂加入到C储料罐中，在400-800r/min速率下搅拌，110℃真空脱水，抽注到双螺杆挤出机中；2.在双螺杆挤出机加料口加入碳纳米管，在110℃-190℃下，双螺杆挤出机中反应，造粒得到TPU颗粒。其中双螺杆挤出机的喂料段温度为110-120℃，混合段温度为130-150℃，挤出段温度为170-180℃，机头温度为150-160℃。
对比例1
一种用于鞋材的聚醚酯型TPU,由包括以下质量份数的原料组成：
其中多元醇为聚己二酸乙二醇酯二醇多元醇(PEGA)；羟基硅油在25℃下的粘度为500cp；碳纳米管的直径为100nm，长径比为500。
制备方法与实施例1相同。
对比例2
一种用于鞋材的聚醚酯型TPU,由包括以下质量份数的原料组成：
其中多元醇为聚四氢呋喃二醇多元醇(PTMG)；羟基硅油在25℃下的粘度为500cp；碳纳米管的直径为100nm，长径比为500。
制备方法与实施例1相同。
对比例3
一种用于鞋材的聚醚酯型TPU,由包括以下质量份数的原料组成：
其中多元醇为聚四氢呋喃二醇/聚己二酸乙二醇酯二醇聚醚酯多元醇(PTMG/PEGA)；羟基硅油在25℃下的粘度为500cp。
制备方法与实施例1相同。
上述实施例与对比例所得的弹性体颗粒通过注塑转化成测试样品，测定其力学性能、耐水解性能、磨耗。拉伸强度、撕裂强度、断裂伸长率、邵氏硬度以及磨耗分别按照GB/T529—2009、GB/T 529—2009、GB/T529—1991、GB/T 531—1992以及DIN53516GB9867进行测试，测试结果见表1。耐水解性能测试标准按照GB/T 12000-2003，测试结果见表2。
表1实施例1-5和对比例1-3产品力学性能测试结果
表2实施例1-5和对比例1-3产品耐水解性能测试结果
项目 7d保持率/％ 14d保持率/％ 21d保持率/％ 28d保持率/％
实施例1 77 69 64 57
实施例2 78 67 66 58
实施例3 77 69 63 53
实施例4 75 68 61 54
实施例5 78 68 63 56
对比例1 70 35 20 —
对比例2 75 70 64 57
对比例3 77 70 62 55
由表1和表2的结果可知，本发明通过选用聚醚酯多元醇制备TPU，并配合羟基硅油、碳纳米管以及其他原料作用，在保持了较高的拉伸强度和断裂伸长率的同时赋予材料良好的耐水解性能和耐磨性满足鞋材产品要求。
申请人声明，以上所述仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，所属技术领域的技术人员应该明了，任何属于本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，均落在本发明的保护范围和公开范围之内。

Claims (10)

1.一种用于鞋材的聚醚酯型TPU，其特征在于：由下列质量份数的物质组成：
二异氰酸酯为二苯基甲烷二异氰酸酯、氢化苯基甲烷二异氰酸酯或六亚甲基二异氰酸酯中一种或几种。
2.根据权利要求1所述的用于鞋材的聚醚酯型TPU，其特征在于：聚醚酯多元醇的分子量为1000-2000，酯基与醚基的摩尔比为0.8-1.2。
3.根据权利要求2所述的用于鞋材的聚醚酯型TPU，其特征在于：聚醚酯多元醇为聚四氢呋喃二醇/聚己二酸乙二醇酯二醇聚醚酯多元醇、聚氧化丙烯二醇/聚己二酸乙二醇酯二醇聚醚酯多元醇或聚乙二醇/聚己二酸乙二醇酯二醇聚醚酯多元醇中一种或几种。
4.根据权利要求1所述的用于鞋材的聚醚酯型TPU，其特征在于：羟基硅油在25℃下粘度为500-5000cps。
5.根据权利要求1所述的用于鞋材的聚醚酯型TPU，其特征在于：碳纳米管直径为50-200nm，长径比为100-500。
6.根据权利要求1所述的用于鞋材的聚醚酯型TPU，其特征在于：扩链剂为1,4-丁二醇、1,6-己二醇、二羟甲基丙酸或二氯二氨基二苯甲烷中的一种或几种。
7.根据权利要求1所述的用于鞋材的聚醚酯型TPU，其特征在于：催化剂为二月桂酸二丁基锡或辛酸亚锡中的一种或两种。
8.一种权利要求1所述的用于鞋材的聚醚酯型TPU的制备方法，其特征在于：包括以下步骤：
1)将质量比例的二异氰酸酯加入到A储料罐中，将质量比例的聚醚酯多元醇和羟基硅油加入到B储料罐中，将质量比例的扩链剂和催化剂加入到C储料罐中，在搅拌条件下，真空脱水，抽注到双螺杆挤出机中；
2)在双螺杆挤出机加料口加入质量比例的碳纳米管，110℃-190℃下，在双螺杆挤出机中反应，造粒得到TPU颗粒。
9.根据权利要求8所述的用于鞋材的聚醚酯型TPU的制备方法，其特征在于：步骤1中，真空脱水温度为90-120℃；搅拌速率为400-800r/min。
10.根据权利要求8所述的用于鞋材的聚醚酯型TPU的制备方法，其特征在于：步骤2中，双螺杆挤出机的喂料段温度为110-120℃，混合段温度为130-150℃，挤出段温度为170-180℃，机头温度为150-160℃。
CN201811140101.3A 2018-09-28 2018-09-28 用于鞋材的聚醚酯型tpu及其制备方法 Pending CN109456458A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811140101.3A CN109456458A (zh) 2018-09-28 2018-09-28 用于鞋材的聚醚酯型tpu及其制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811140101.3A CN109456458A (zh) 2018-09-28 2018-09-28 用于鞋材的聚醚酯型tpu及其制备方法

Publications (1)

Publication Number Publication Date
CN109456458A true CN109456458A (zh) 2019-03-12

Family

ID=65607117

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811140101.3A Pending CN109456458A (zh) 2018-09-28 2018-09-28 用于鞋材的聚醚酯型tpu及其制备方法

Country Status (1)

Country Link
CN (1) CN109456458A (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110616032A (zh) * 2019-10-28 2019-12-27 姚国江 一种有机-无机硅改性聚氨酯超疏水涂料及其制法
CN116284679A (zh) * 2023-05-18 2023-06-23 山东一诺威聚氨酯股份有限公司 超亲水防雾热塑性聚氨酯弹性体材料及其制备方法和应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1705693A (zh) * 2002-10-21 2005-12-07 拜尔材料科学股份公司 聚氨酯弹性体,其制备方法和其应用
CN104066759A (zh) * 2012-01-23 2014-09-24 巴斯夫欧洲公司 聚醚酯多元醇及其制备方法
CN108047424A (zh) * 2017-12-14 2018-05-18 山东诺威聚氨酯股份有限公司 坐垫用改性mdi及制备方法
CN108164980A (zh) * 2017-12-28 2018-06-15 山东诺威聚氨酯股份有限公司 用于3d打印的碳纳米管改性tpu材料及其制备方法
CN108467480A (zh) * 2018-03-22 2018-08-31 上海联景高分子材料有限公司 聚醚改性聚酯多元醇及其聚合而成的热塑性聚氨酯弹性体

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1705693A (zh) * 2002-10-21 2005-12-07 拜尔材料科学股份公司 聚氨酯弹性体,其制备方法和其应用
CN104066759A (zh) * 2012-01-23 2014-09-24 巴斯夫欧洲公司 聚醚酯多元醇及其制备方法
CN108047424A (zh) * 2017-12-14 2018-05-18 山东诺威聚氨酯股份有限公司 坐垫用改性mdi及制备方法
CN108164980A (zh) * 2017-12-28 2018-06-15 山东诺威聚氨酯股份有限公司 用于3d打印的碳纳米管改性tpu材料及其制备方法
CN108467480A (zh) * 2018-03-22 2018-08-31 上海联景高分子材料有限公司 聚醚改性聚酯多元醇及其聚合而成的热塑性聚氨酯弹性体

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
崔洪犁等: ""聚脲弹性体材料耐磨性能的探讨"", 《聚氨酯工业》 *
殷景华等: "《功能材料概论》", 31 August 2017, 哈尔滨工业大学出版社 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110616032A (zh) * 2019-10-28 2019-12-27 姚国江 一种有机-无机硅改性聚氨酯超疏水涂料及其制法
CN116284679A (zh) * 2023-05-18 2023-06-23 山东一诺威聚氨酯股份有限公司 超亲水防雾热塑性聚氨酯弹性体材料及其制备方法和应用
CN116284679B (zh) * 2023-05-18 2023-09-01 山东一诺威聚氨酯股份有限公司 超亲水防雾热塑性聚氨酯弹性体材料及其制备方法和应用

Similar Documents

Publication Publication Date Title
CN105542114B (zh) 一种软段中含有氰基的热塑性聚氨酯弹性体及其制备方法
US2912408A (en) Storage stable mixture of a diisocyanate and the reaction product of a polyester, a glycol and a diisocyanate, and method of making same
EP3581603A1 (en) Thermoplastic organosilicone-polyurethane elastomer and preparation method therefor
CN110156952B (zh) 一种可双重固化聚氨酯增韧树脂及其制备方法与应用
CN1044284A (zh) 热塑性聚氨酯
CN110885550B (zh) 一种有机硅改性热塑性聚氨酯弹性体及其制备方法
CN1708527A (zh) 聚氨酯化合物及由其制备的制品
CN107793989B (zh) 一种塑胶跑道用单组份聚氨酯胶粘剂及其制备方法
CN101165095A (zh) 浇注型聚氨酯弹性体组合物
US4010146A (en) Polyol blends and polyurethane prepared therefrom
CN106977682A (zh) 一种u型枕用超柔软tpu薄膜及其制备方法
CN104140520A (zh) 一种超软质高弹性耐水解高剥离的湿式聚氨酯树脂及其制备方法
CN109456458A (zh) 用于鞋材的聚醚酯型tpu及其制备方法
CN109851746A (zh) 纤维素改性tpu薄膜材料及其制备方法
CN113045730B (zh) 一种基于生物基的混炼型聚氨酯橡胶及制备方法与应用
CN108070069A (zh) 低硬度高回弹低熔点热塑性聚氨酯弹性体及制法和应用
CN110072902A (zh) 具有高的抗撕裂蔓延强度的热塑性聚氨酯
KR20070094501A (ko) 압출 성형용 투습 방수성 열가소성 폴리우레탄
KR101313713B1 (ko) 내수성이 우수한 폴리우레탄 수분산 수지 조성물, 이를 이용한 폴리우레탄 수분산 수지의 제조방법 및 이 제조방법에 의해 제조된 폴리우레탄 수분산 수지를 포함하는 폴리우레탄 수분산 접착제
CN106957404A (zh) 一种耐黄变tpu薄膜及其制造方法
CN111117549B (zh) 一种使用papi制备的单组份聚氨酯密封胶
CN106957523A (zh) 一种用于轮胎胎面的热塑性聚氨酯及其制备方法
CN109337355B (zh) 一种高耐刮热塑性聚氨酯弹性体及其制备方法
CN111040422A (zh) 一种肤感tpu薄膜及其制备方法
CN106008898A (zh) 一种高防潮且耐寒热的热塑性聚氨酯弹性体及其制备方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20190312