CN108047423A - 环保型聚氨酯足球玩具组合物及其制备方法 - Google Patents
环保型聚氨酯足球玩具组合物及其制备方法 Download PDFInfo
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Abstract
本发明属于聚氨酯技术领域,具体的涉及一种环保型聚氨酯足球玩具组合物及其制备方法。由质量比为100:50~70的A组分和B组分组成;以质量百分数计,原料组成如下:A组分:聚醚多元醇30%~50%;聚合物聚醚多元醇30%~50%;聚酯醚10%~20%;泡沫稳定剂0.5%~1%;交联剂1%~2%;扩链剂1%~2%;发泡剂2%~3%;催化剂0.5%~1%;B组分:聚醚多元醇10%~15%;异氰酸酯75%~80%;开孔剂5%~10%。本发明选用低气味,低挥发性的环保原料制备,所得产品环保无污染,不含易挥发的甲苯二异氰酸酯、一氟二氯乙烷和污染环境的重金属物质;生产工艺简单,减少了加热模具所造成的能源浪费,降低了生产成本,提高了生产效率;制备的环保型聚氨酯足球玩具组合物密度低,制品回弹性高,手感佳,外观漂亮且表面耐撕裂性能强。
Description
技术领域
本发明属于聚氨酯技术领域,具体的涉及一种环保型聚氨酯足球玩具组合物及其制备方法。
背景技术
近几十年来,高回弹软质聚氨酯泡沫玩具球发展迅猛,这类玩具球以手感佳,回弹好,外观漂亮且安全性高的优势,越来越受到大众的喜爱。聚氨酯泡沫玩具球种类繁多,包括聚氨酯泡沫玩具慢回弹指压球,聚氨酯泡沫软式棒球,聚氨酯发泡足球压力球,聚氨酯泡沫玩具熊等。
随着人们环保意识、安全意识及其节约意识的增强,人们对玩具球的安全环保性及其高性能有了越来越严格的要求。目前,市面上的大多数玩具球气味大,挥发性高且现有的玩具球是由蒸汽压高的A料和B料制成,成本高,性能差,生产工艺繁杂。
发明内容
本发明的目的是克服现有技术的不足,提供一种环保型聚氨酯足球玩具组合物。本发明制备的环保型聚氨酯足球玩具组合物具有环保安全、密度低、弹性好、回弹性好和表面耐撕裂性能强的优点;本发明同时提供了其制备方法。
本发明所述的环保型聚氨酯足球玩具组合物,由质量比为100:50~70的A组分和B组分组成;以质量百分数计,原料组成如下:
A组分:
其中交联剂包括交联剂A和四官能度聚醚交联剂NT403,交联剂A和四官能度聚醚交联剂NT403的质量比为1:1-2;
B组分:
聚醚多元醇 10%~15%
异氰酸酯 75%~80%
开孔剂 5%~10%。
其中:
A组分中聚醚多元醇是甘油封端,数均分子量为4500~7000g/mol的聚醚多元醇,优选EP-3600Y(市售,山东蓝星东大化工有限责任公司)。
A组分中聚合物聚醚多元醇是以乙烯基聚醚多元醇为基础,用苯乙烯和丙烯腈接枝共聚且固含量>30%的高活性聚合物聚醚多元醇,优选POPH45(市售,山东隆华新材料有限公司)。
A组分中聚酯醚是2000T或2500T中的一种(市售,山东一诺威新材料有限公司)。
A组分中发泡剂是水、环戊烷或甲酸甲酯中的一种或几种。
A组分中催化剂是反应性催化剂,优选美国气体化工公司生产的A33、CA-25或DC3040中的一种或几种。
A组分中泡沫稳定剂采用聚硅氧烷-氧化烯烃嵌段共聚物,优选DC6070(美国空气化工有限公司)、DC2525(美国空气化工有限公司)或L-580(迈图高新材料集团)中的一种或几种。
A组分中扩链剂是乙二醇(EG)、一缩二乙二醇(DEG)、1,4-丁二醇(1,4-BG)或一缩二丙二醇(DPG)中的一种或几种。
A组分中交联剂A是二乙醇胺(DEOA)、三乙醇胺(TEA)或甘油中的一种或几种。
B组分中聚醚多元醇是甘油封端,数均分子量为4500~7000g/mol的聚醚多元醇,优选EP-3600Y(市售,山东蓝星东大化工有限责任公司);开孔剂是Yukol 8331、GK350D或KY1206(山东一诺威聚氨酯股份有限公司)中的一种或几种。
B组分中异氰酸酯是纯MDI、碳化二亚胺改性的MDI、MDI-50或聚合MDI(俗称粗MDI)中的一种或多种。
本发明所述的环保型聚氨酯足球玩具组合物的制备方法,具体包括以下步骤:
A组分的制备
先将聚醚多元醇、聚酯醚、聚合物聚醚多元醇投入反应釜中搅拌,然后加入扩链剂、催化剂、发泡剂、泡沫稳定剂和交联剂,在室温条件下,搅拌1-2小时,即得A组分;
B组分的制备
将聚醚多元醇和开孔剂加入反应釜,搅拌升温至90-100℃,真空条件下脱水脱气1-2小时,将温度降至室温,加入纯MDI和MDI-50,升温到75-80℃,反应0.5~2小时,加入聚合MDI,搅拌均匀即得B组分;
环保型聚氨酯足球玩具组合物的制备
将A组分与B组分按100:50~70的质量比混合均匀,注入玩具模具中,密封,7-8分钟后开模,即得环保型聚氨酯足球玩具组合物。
作为一个优选的技术方案,本发明所述的环保型聚氨酯足球玩具组合物的制备方法,具体包括以下步骤:
A组分的制备
先将基于配方量的聚醚多元醇、高活性聚酯醚、聚合物聚醚多元醇投入反应釜中搅拌,然后依次加入称量好的扩链剂、催化剂、发泡剂、泡沫稳定剂和普通小分子的交联剂,聚醚交联剂NT403粘度大,室温条件下不易分散,为更好的分散NT403,将基于配方量的NT403均匀分散在发泡剂水中,然后加入反应釜中搅拌。投完所有料后,在室温条件下,转速为60-100转/分钟,搅拌1-2小时,取样进行检验,满足工艺参数,发出满意泡沫,即得A组分合格产品;
B组分的制备
将基于配方量的聚醚多元醇和开孔剂投入反应釜,搅拌升温至90-100℃,真空条件下脱水脱气1-2小时,将温度降至室温,加入纯MDI和MDI-50,升温到75-80℃,反应1小时,加入聚合MDI,搅拌均匀即得B组分;
环保型聚氨酯足球玩具组合物的制备
使用时,将A组分和B组分按100:50~70的质量比混合均匀,机械注入玩具模具中,密封,7-8分钟后开模,即可得到聚氨酯泡沫玩具。
本发明具有以下有益效果:
(1)本发明的原料选用气味低挥发性小的反应性催化剂组成无毒A料,B料采用蒸汽压很低(1.5*104Pa,20℃)的纯MDI(二苯基甲烷二异氰酸酯)、碳化二亚胺改性的MDI、MDI-50或聚合MDI组成,所得产品环保无污染,不含易挥发的甲苯二异氰酸酯、一氟二氯乙烷和污染环境的重金属物质;
(2)本发明的产品引入了新型的四官能度聚醚交联剂NT403,NT403和普通的交联剂协同使用,不仅降低了足球玩具的密度,而且使得制得的制品弹性好,回弹性高,表面耐撕裂性能强;
(3)本发明的产品原料中使用新型的高活性聚酯醚,更使得制品密度低,弹性好,手感佳,且操作简单,外观漂亮且表面耐撕裂性能强,满足市场多种要求;
(4)本发明A组分和B组分按比例混合后常温下即可反应,生产工艺简单,减少了加热模具所造成的能源浪费,降低了生产成本,提高了生产效率。
具体实施方式
以下结合实施例对本发明作进一步描述。
实施例1
实施例1的环保型聚氨酯足球玩具组合物以质量分数计,原料组成如下:
A组分为:
B组分为:
实施例1的环保型聚氨酯足球玩具组合物的制备方法如下:
A组分的制备
将称量好的聚醚多元醇EP-3600Y、聚酯醚2000T和聚合物聚醚多元醇POPH45投入反应釜中搅拌,然后依次加入称量好的泡沫稳定剂DC6070和DC2525、交联剂DEOA和TEA、四官能度聚醚交联剂NT403、催化剂A33、催化剂CA-25、扩链剂EG和发泡剂H2O,为将NT403更好的分散,将事先称量好的NT403完全均匀溶入水中,加入反应釜,在室温的条件下搅拌混合1小时后,取样检测,满足生产工艺,得到需要的泡沫,即得A组分合格产品。
B组分的制备
室温的条件下将聚醚多元醇EP3600Y和开孔剂Yukol8331在室温的条件下加入反应釜中,搅拌升温至90℃,真空条件下(-0.09MPa)脱水脱气1小时,将温度降至室温,加入纯MDI和MDI-50,升温到75℃条件下,反应1小时,检测-NCO含量达到预设值后,加入粗MDI,搅拌均匀取样检测-NCO含量达到预设值(-NCO的含量为26.1%),即得到所需B组分。
环保型聚氨酯足球玩具组合物的制备
使用时,将A组分和B组分按照100:60的质量配比混合均匀后筑入模具,密封,7分钟后开模,即可得到聚氨酯泡沫玩具。
实施例2
实施例2的环保型聚氨酯足球玩具组合物以质量分数计,原料组成如下:
A组分为:
B组分为:
实施例2的环保型聚氨酯足球玩具组合物的制备方法如下:
A组分的制备
将称量好的聚醚多元醇EP-3600Y、聚酯醚2500T与聚合物聚醚多元醇POPH45投入反应釜中搅拌,然后依次加入称量好的泡沫稳定剂DC6070、泡沫稳定剂DC2525、交联剂DEOA、交联剂TEA、四官能度聚醚交联剂NT403、催化剂A33、催化剂CA-25、发泡剂H2O和扩链剂EG,为将NT403更好的分散,将事先称量好的NT403完全均匀溶入水中,加入反应釜,在室温的条件下搅拌混合1小时后,取样检测,满足生产工艺,得到需要的泡沫,即得A组分合格产品。
B组分的制备
室温的条件下将聚醚多元醇EP-3600Y和开孔剂GK350D在室温的条件下加入反应釜中,搅拌升温至100℃,真空条件下(-0.09MPa)脱水脱气2小时,将温度降至室温,加入纯MDI和液化,升温到80℃条件下,反应1.5小时,检测-NCO含量达到预设值(-NCO的质量百分数为25.91%)后,加入粗MDI,搅拌均匀取样检测,合格后,即得到所需B组分。
环保型聚氨酯足球玩具组合物的制备
使用时,将A组分和B组分按照100:51的质量比混合均匀后筑入模具,密封,8分钟后开模,即可得到聚氨酯泡沫玩具。
实施例3
实施例3的环保型聚氨酯足球玩具组合物以质量分数计,原料组成如下:
A组分为:
B组分为:
实施例3的环保型聚氨酯足球玩具组合物的制备方法如下:
A组分的制备
将称量好的聚醚多元醇EP-3600Y、聚酯醚2000T和聚合物聚醚多元醇POPH45投入反应釜中搅拌,然后依次加入称量好的泡沫稳定剂DC6070、泡沫稳定剂DC2525、交联剂DEOA、交联剂TEA、四官能度聚醚交联剂NT403、催化剂A33、催化剂CA-25、发泡剂环戊烷和扩链剂EG,为将NT403更好的分散,将事先称量好的NT403完全均匀溶入水中,加入反应釜,在室温的条件下搅拌混合1小时后,取样检测,满足生产工艺,得到需要的泡沫,即得A组分合格产品。
B组分的制备
室温的条件下将聚醚多元醇EP3600Y和开孔剂Yukol8331在室温的条件下加入反应釜中,搅拌升温至95℃,真空条件下(-0.09MPa)脱水脱气1.5小时,将温度降至室温,加入纯MDI和MDI-50,升温到78℃条件下,反应1小时,检测-NCO含量达到预设值后(-NCO的质量百分数为26.1%),加入粗MDI,搅拌均匀取样检测,合格后,即得到所需组分。
环保型聚氨酯足球玩具组合物的制备
使用时,将A组分和B组分按照100:70的质量比混合均匀后筑入模具,密封,7分钟后开模,即可得到聚氨酯泡沫玩具。
表1实施例1-3环保型聚氨酯足球玩具组合物性能测试表
Claims (9)
1.一种环保型聚氨酯足球玩具组合物,其特征在于:由质量比为100:50~70的A组分和B组分组成;以质量百分数计,原料组成如下:
A组分:
其中交联剂包括交联剂A和四官能度聚醚交联剂NT403,交联剂A和四官能度聚醚交联剂NT403的质量比为1:1-2;
B组分:
聚醚多元醇 10%~15%
异氰酸酯 75%~80%
开孔剂 5%~10%。
2.根据权利要求1所述的环保型聚氨酯足球玩具组合物,其特征在于:A组分中聚醚多元醇是甘油封端,数均分子量为4500~7000g/mol的聚醚多元醇。
3.根据权利要求1所述的环保型聚氨酯足球玩具组合物,其特征在于:A组分中聚合物聚醚多元醇是以乙烯基聚醚多元醇为基础,用苯乙烯和丙烯腈接枝共聚且固含量>30%的高活性聚合物聚醚多元醇。
4.根据权利要求1所述的环保型聚氨酯足球玩具组合物,其特征在于:A组分中聚酯醚是2000T或2500T中的一种;发泡剂是水、环戊烷或甲酸甲酯中的一种或几种;催化剂是反应性催化剂;泡沫稳定剂采用聚硅氧烷-氧化烯烃嵌段共聚物。
5.根据权利要求1所述的环保型聚氨酯足球玩具组合物,其特征在于:A组分中扩链剂是乙二醇、一缩二乙二醇、1,4-丁二醇或一缩二丙二醇中的一种或几种。
6.根据权利要求1所述的环保型聚氨酯足球玩具组合物,其特征在于:交联剂A是二乙醇胺、三乙醇胺或甘油中的一种或几种。
7.根据权利要求1所述的环保型聚氨酯足球玩具组合物,其特征在于:B组分中聚醚多元醇是甘油封端,数均分子量为4500~7000g/mol的聚醚多元醇;开孔剂是Yukol 8331、GK350D或KY1206中的一种或几种。
8.根据权利要求1所述的环保型聚氨酯足球玩具组合物,其特征在于:B组分中异氰酸酯是纯MDI、碳化二亚胺改性的MDI、MDI-50或聚合MDI中的一种或几种。
9.一种权利要求1-8任一所述的环保型聚氨酯足球玩具组合物的制备方法,其特征在于:具体包括以下步骤:
A组分的制备:
先将聚醚多元醇、聚酯醚、聚合物聚醚多元醇投入反应釜中搅拌,然后加入扩链剂、催化剂、发泡剂、泡沫稳定剂和交联剂,在室温条件下,搅拌1-2小时,即得A组分;
B组分的制备:
将聚醚多元醇和开孔剂加入反应釜,搅拌升温至90-100℃,真空条件下脱水脱气1-2小时,将温度降至室温,加入纯MDI和MDI-50,升温到75-80℃,反应0.5~2小时,加入聚合MDI,搅拌均匀即得B组分;
环保型聚氨酯足球玩具组合物的制备:
将A组分与B组分按100:50~70的质量比混合均匀,注入玩具模具中,密封,7-8分钟后开模,即得环保型聚氨酯足球玩具组合物。
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