CN108047423B - 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 PDF

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CN108047423B
CN108047423B CN201711338877.1A CN201711338877A CN108047423B CN 108047423 B CN108047423 B CN 108047423B CN 201711338877 A CN201711338877 A CN 201711338877A CN 108047423 B CN108047423 B CN 108047423B
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郭勇生
辛兰霞
崔玉志
吴淑廷
张倩
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Shandong Yinuowei Sports Industry Co ltd
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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

环保型聚氨酯足球玩具组合物及其制备方法
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：
Figure BDA0001507938930000011
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：
Figure BDA0001507938930000041
B组分为：
Figure BDA0001507938930000042
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：
Figure BDA0001507938930000051
B组分为：
Figure BDA0001507938930000052
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：
Figure BDA0001507938930000061
B组分为：
Figure BDA0001507938930000062
Figure BDA0001507938930000071
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
Figure BDA0001507938930000072

Claims (4)

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100：51～70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：
Figure FDA0002765050140000011
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；交联剂A是二乙醇胺、三乙醇胺或甘油中的一种或几种；
B组分:
聚醚多元醇 10％～15％
异氰酸酯 75％～80％
开孔剂 5％～10％；
其中：A组分中聚酯醚是2000T或2500T中的一种；
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；
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；
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；
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。
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：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。
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。
4.一种权利要求1-3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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