CN1237986A - 聚醚聚氨酯用于防护服的用途 - Google Patents

聚醚聚氨酯用于防护服的用途 Download PDF

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CN1237986A
CN1237986A CN97199807A CN97199807A CN1237986A CN 1237986 A CN1237986 A CN 1237986A CN 97199807 A CN97199807 A CN 97199807A CN 97199807 A CN97199807 A CN 97199807A CN 1237986 A CN1237986 A CN 1237986A
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polyether
protective clothing
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CN1175019C (zh
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K·布雷赫特
H·-D·阿恩茨
B·约翰
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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
    • C08G18/28—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
    • C08G18/667—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
    • C08G2410/00—Soles

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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)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明涉及由聚醚聚氨酯生产的从蜂窝状到密实的模压塑料用于制造防护服，尤其防护靴的鞋底的用途。

Description

聚醚聚氨酯用于防护服的用途
本发明涉及由聚醚聚氨酯生产的从多孔到密实的模压塑料用于制造防护服，尤其防护鞋底的用途。
模压聚氨酯基塑料是几十年来公知的先有技术。这类模压塑料可以以宽范围的密度和硬度范围生产，用于各种用途，例如作为防护服。
聚氨酯在防护服中的主要用途是作为防护鞋。根据有关防护鞋的结构和性能的现行标准(EN344及以下)，材料的选择直到目前为止一直限制在使用聚酯聚氨酯。排除聚醚聚氨酯的主要原因是这种材料的耐油性和耐汽油性(EN344,4,8,9点，耐燃料性)不够好。
但是，聚酯聚氨酯或通过反应注塑法生产聚酯聚氨酯所需的各成分显示出下列缺点：
·在准备加工时，各成分的高粘度导致不利的成型
·各成分加工所需的高温会缩其适用期
·尤其在农业领域或在湿热气候地区使用时，耐水解性和耐微生物侵蚀性的不足也会导致成品防护鞋的贮存期受限制
·标准聚酯聚氨酯的低温柔曲性差
象聚酯聚氨酯的加工一样，采用反应浇注法或反应注塑法生产聚醚聚氨酯也是先有技术的一部分。根据要求，在单层和双层模压底中及直接制底法中使用不同密度和硬度的聚酯聚氨酯来生产轻便鞋、休闲鞋和运动鞋。
由于聚醚基聚氨酯的新开发，现已令人惊奇地发现，这样的一种聚氨酯用于防护鞋的场合显示出足够的耐燃料性。
本发明提供泡沫模压生产的从多孔到密实的模压聚醚基塑料用于生产防护服的用途。
符合EN 344页标准(在异辛烷中的耐燃料性＜12％体积)的防护服例如是防护鞋、长靴、围裙等。
这种耐燃料性是用例如下面所述的聚酯聚氨酯体系原材料以≥800kg/m3的基底松密度达到的。
从多孔到密实的聚醚聚氨酯基模压塑料是通过将例如从下列成分制备的反应混合物进行泡沫模压生产的。
a)较高分子量聚醚多元醇成分，
b)多异氰酸酯成分，
c)链增长剂，
d)任选的发泡剂，
e)活化剂和任选的，
f)进一步的辅助物质和添加剂。
其中在维持异氰酸酯指数在70～130范围内的同时使这些原料发生反应。
较高分子量的聚醚多元醇成分a)的羟基官能度为2.00，或者基本上包含从下列成分制备的平均羟基官能度为2.02～2.95的混合物：
aa)至少一种羟值为10～115的聚醚二醇，这种二醇是通过下述方法生产的：使一种二官能起始剂丙氧基化，然后使丙氧基化产物乙氧基化，同时使氧化丙烯与氧化乙烯的重量比维持在60∶40～85∶15，和
ab)至少一种羟值为12～56的聚醚三醇，任选地含有基于苯乙烯/丙烯腈共聚物、聚脲或聚亚肼基甲酰胺的填料，相对于成分a)的总重量而言，其量至多为20％(重量)，这种聚醚三醇的制备方法是：使三官能起始剂丙氧基化，然后使氧化丙烯与氧化乙烯的重量比维持在60∶40～85∶15。
多异氰酸酯成分b)是一种含有异氰酸酯基团，且NCO含量为10～25％(重量)的半异聚物，它是由(ⅰ) 4,4′-二异氰酸酯基二苯甲烷与(ⅱ)一种羟值为10～11 5，(平均)羟基官能度为2.0～2.5，由至少一种聚醚二醇或至少一种这样的二醇与至少一种聚醚三醇的混合物构成的聚醚成分和/或羟值为28～115，平均官能度为2.0～2.5的聚酯成分反应制备的，其中所述聚醚二醇是由二官能起始剂进行丙氧基化，然后任选地用相对于该聚醚二醇的重量而言至多40％重量的环氧乙烷将丙氧基化产物进行乙氧基化而制备的，而所述聚醚三醇是由三官能起始剂进行丙氧基化，然后任选地用相对于该聚醚三醇的重量而言至多40％重量的环氧乙烷将丙氧基化产物进行乙氧基化而制备的，其中成分(ⅰ)任选地在反应之前加入，或加入到聚丙二醇分子量为134～700的反应产物中和/或通过使相对于成分(ⅰ)的重量，其量至多为10％重量的液化4,4′-二异氰酸酯基二苯甲烷的部分异氰酸酯基团碳化二亚胺化而得到的反应产物中。
1,2-乙二醇和/或1,4-丁二醇和/或二乙二醇和/或三乙醇胺和/或二乙基甲苯二胺用作成分c)，
而水和/或物理发泡剂，例如R134a(氢氟烷烃混合物)则任选地用作成分d)。
可以考虑的活化剂e)是聚氨酯化学中本身已知的化合物，例如三亚己基二胺、N,N-二甲基苄胺或有机锡化合物，例如二月桂酸二丁基锡或辛酸锡(Ⅱ)。
可以举例提及的进一步使用的辅助物质和添加剂f)是表面活性剂、泡沫稳定剂、泡孔调节剂、内用剥离剂、染料、颜料、水解稳定剂、制霉和抑菌活性剂、光稳定剂、抗氧化剂和抗静电剂(季铵化合物)。
聚氨酯是按照公知的先有技术生产的。通常，这表示将成分a)和c)至f)合并形成“多元醇成分”，然后使其在密闭的模具中，例如在密闭的金属或塑料模具中与多异氰酸酯成分b)以单一步骤进行反应，其中使用传统的两组分混合单元。加入到模具中的反应混合物的量和作为发泡剂而任选使用的水和/或物理发泡剂，例如R134的量在本方法中是以这样的方式计算的，即所得到的模压泡沫的松密度为≥800kg/m3。最重要的应用领域是制鞋，按照本发明是用于生产防护鞋用的从多孔到密实的鞋底。这种鞋的鞋底的松密度较好≥800kg/m3，而且在一个具体实施方案中，与松密度≥400kg/m3的鞋底中间层相连。
实例
下面实例说明用于防护鞋鞋底的配方组成。在所有实例中，均维持异氰酸酯指数为100。用尺寸为20×20×1cm的试片作为试样，用于测定机械性能和耐汽油性(EN344，点4,8,9)。
原材料
多羟基化合物a)
a1聚醚二醇，OH值28,PO/EO重量比70∶30
a2聚醚二醇，OH值28,PO/EO重量比77∶23
多异氰酸酯b)
4,4′-二异氰酸酯基二苯甲烷(MDI)与三丙二醇的反应产物，NCO含量23％。
实例：
实例1-3的配方示于下面表1，而机械性能和耐汽油性则示于表2。
表1(所有数据均为重量份)
    实例1     实例2     实例3
成分a1     90.00     79.27     71.55
成分a2      --     10.00     20.00
 1,4-丁二醇     6.00     7.50      --
 1,2-乙二醇      --     0.50      --
二乙基亚甲苯基二胺      --      -- 6.00
三亚乙基二胺     1.80     0.60     0.20
二月桂酸二丁基锡     0.05     0.03     0.05
三乙醇胺     0.15      --     0.20
水      --     0.10     --
硫酸四烷基铵(Catafor CA 100)     2.00     2.00     2.00
多异氰酸酯b)     33     44     26
表2：机械性能
   实例1    实例2    实例3
    DIN 54320 (kg/m3)     1100     900     1080
硬度DIN 53505 (肖氏A)     60     60     70
抗拉强度DIN 53504 (MPa)     16     8     12
断裂伸长DIN53504 (％)     800     600     610
抗撕裂蔓延强度DIN53516 (kN/m)     18     10     20
耐燃料性EN 344 (％体积变化率)     9.5     10.5     11.5

Claims (4)

1．从多孔到密实的模压聚醚基塑料用于模压发泡制造防护服的用途。
2．按照权利要求1的用途，用于制造防护鞋鞋底。
3．按照权利要求2的用途，其特征在于该鞋底的松密度为≥800kg/m3。
4．按照权利要求2的用途，其特征在于该鞋底与松密度≥400kg/m3的鞋底中间层相连。
CNB971998078A 1996-11-22 1997-11-10 聚醚聚氨酯用于防护服的用途 Expired - Fee Related CN1175019C (zh)

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DE19648509A DE19648509A1 (de) 1996-11-22 1996-11-22 Verwendung von Polyether-PUR für Sicherheitskleidung
DE19648509.6 1996-11-22

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JP (1) JP2001506676A (zh)
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AU (1) AU5551398A (zh)
DE (2) DE19648509A1 (zh)
ES (1) ES2172824T3 (zh)
IL (1) IL129858A (zh)
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CN1315901C (zh) * 2002-10-14 2007-05-16 拜尔材料科学股份公司 微孔聚氨酯弹性体、其制备方法及其应用
CN104757722A (zh) * 2015-04-01 2015-07-08 大连华工创新科技股份有限公司 E-tpu发泡防护服装
CN104945594A (zh) * 2015-05-29 2015-09-30 德州市鑫华润聚氨酯鞋材股份有限公司 一种耐水解、耐低温聚氨酯及其制备方法

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DE102004009939A1 (de) * 2004-02-26 2005-09-15 Basf Ag Quellbeständige Polyurethanintegralschaumstoffe
ITMI20101084A1 (it) * 2010-06-16 2011-12-16 Dow Global Technologies Inc Suole poliuretaniche di scarpe preparate usando polioli a base di ossido di propilene

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1315901C (zh) * 2002-10-14 2007-05-16 拜尔材料科学股份公司 微孔聚氨酯弹性体、其制备方法及其应用
CN104757722A (zh) * 2015-04-01 2015-07-08 大连华工创新科技股份有限公司 E-tpu发泡防护服装
CN104945594A (zh) * 2015-05-29 2015-09-30 德州市鑫华润聚氨酯鞋材股份有限公司 一种耐水解、耐低温聚氨酯及其制备方法

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AU5551398A (en) 1998-06-22
US20020013377A1 (en) 2002-01-31
DE19648509A1 (de) 1998-05-28
CN1175019C (zh) 2004-11-10
EP0939780B1 (de) 2002-02-13
TR199901098T2 (xx) 1999-07-21
KR20000057180A (ko) 2000-09-15
WO1998023659A1 (de) 1998-06-04
ES2172824T3 (es) 2002-10-01
EP0939780A1 (de) 1999-09-08
DE59706407D1 (de) 2002-03-21
KR100522989B1 (ko) 2005-10-21
PT939780E (pt) 2002-07-31
TW460497B (en) 2001-10-21
IL129858A0 (en) 2000-02-29
US6521676B2 (en) 2003-02-18
IL129858A (en) 2003-05-29

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