CN106397729B - 一种可热压定型缓冲材料及其制备方法与应用 - Google Patents

一种可热压定型缓冲材料及其制备方法与应用 Download PDF

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CN106397729B
CN106397729B CN201610797796.7A CN201610797796A CN106397729B CN 106397729 B CN106397729 B CN 106397729B CN 201610797796 A CN201610797796 A CN 201610797796A CN 106397729 B CN106397729 B CN 106397729B
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王博伟
王小刚
陈可儿
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FOSHAN LINZHI POLYMER MATERIALS SCIENCE AND TECHNOLOGY Co Ltd
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Abstract

本发明属于缓冲减震材料的技术领域,公开了一种可热压定型缓冲材料及其制备方法与应用。所述材料由A料和B料制备而成;所述A料由以下按重量份数计的组分组成:聚醚三元醇1型20~50,聚醚三元醇2型20~35,高活性聚合物多元醇15~50,发泡剂0.25~0.35,扩链剂0.5~2.2,交联剂0.15~0.21,催化剂0.18~0.65硅烷表面活性剂0.1~0.3抗氧剂1~3;所述B料为二苯基甲烷二异氰酸酯改性的预聚体,所述B料为A料总重量的35~45%。所述材料性能稳定,缓冲性能优良,可热压定型,具有较高生产效率,较低生产成本;用于制备运动防护产品,产品缓冲性能好,制品表面撕裂强度高,耐磨度好。

Description

一种可热压定型缓冲材料及其制备方法与应用
技术领域
本发明属于缓冲材料的技术领域,具体涉及一种可热压定型缓冲材料及其制备方法与应用。
背景技术
目前常见的缓冲材料种类繁多,包括一些发泡材料和弹性体,如热塑性橡胶、乳胶、AOSOLITE、EVA、SBR、化学交联聚乙烯发泡材料(XPE)、PU材料等,缓冲性能最好为PU型缓冲材料。
而聚氨酯为一类用途十分广泛的合成材料,其工业化的生产主要是由多元有机异氰酸酯和各种氢给予体化合物(通常如含端羟基的多元醇化合物)反应而制备的。选择不同数目的官能基团和不同类型的官能基团,采用不同的合成工艺,能制备出性能各异,表观形式各种各样的聚氨酯产品。
聚氨酯产品的种类极其丰富,包括从十分柔软到极其坚硬的泡沫塑料,耐磨性能优异的弹性橡胶、高光泽的油漆、涂料,高回弹的合成纤维以及抗绕曲性能优良的合成皮革等,逐渐形成了一个品种多样、性能优异的新型合成材料系列。传统的聚氨酯材料由于其良好的耐磨性能,阻尼性能以及耐疲劳性能和抗震动性能良好,因此聚氨酯在很多领域得到了广泛的应用。
现有的PU型缓冲材料,要取得特殊的实用形状,不能热压定型,只能通过PU模型灌注或裁切+缝纫工艺制作,PU模型灌注生产效率低下,模具成本高;裁切+缝纫工艺材料不美观,易破损。如何在提高缓冲材料性能同时提高生产效率是企业亟需解决的问题。
发明内容
为了克服现有技术的缺点和不足,本发明的首要目的在于提供一种可热压定型缓冲材料。
本发明的另一目的在于提供上述可热压定型缓冲材料的制备方法。
本发明的再一目的在于提供上述可热压定型缓冲材料的应用。所述可热压定型缓冲材料用于运动防护产品中。
本发明的目的通过以下技术方案实现:
一种可热压定型缓冲材料,由A料和B料制备而成;所述A料由以下按重量份数计的组分组成:
所述B料为二苯基甲烷二异氰酸酯改性的预聚体,所述B料为A料总重量的35~45%。
所述A料还包括色料。
所述扩链剂为乙二醇、1,4-丁二醇或1,3-丙二醇中一种以上,优选为乙二醇。
所述交联剂为醇胺类,优选为二乙醇胺。
所述催化剂为N,N-二甲基环己胺、N,N,N′,N′-四甲基亚烷基二胺、三乙胺、N,N-二甲基苄胺,双(2-二甲氨基乙基)醚、三乙烯二胺、有机铋,有机锡中一种以上;优选为双(2-二甲氨基乙基)醚和三乙烯二胺的混合物。
所述双(2-二甲氨基乙基)醚和三乙烯二胺的重量比为(0.03~0.15)∶(0.15~0.5)。
所述抗氧剂优选为抗氧剂1010。
所述聚醚三元醇1型为官能团是3,数均分子量为5000~6000;羟值优选为26~36mgKOH/g;所述聚醚三元醇1型优选为江苏长华聚氨酯科技有限公司的CHE-330N和CHE-828中一种以上。
所述聚醚三元醇2型为官能团是3,数均分子量为400~700;羟值优选为250~320mgKOH/g。
所述高活性聚合物多元醇的固含量为28-45%;所述高活性聚合物多元醇是由聚醚多元醇与苯乙烯、丙烯腈聚合反应得到。所述聚合物多元醇优选为江苏长华聚氨脂科技有限公司生产的CHP-H30或CHP-H45。
所述发泡剂为水。本发明使用水作为发泡剂可以使聚脲的数量上升,使最终成品的支撑力和弹性上升;同时水作为发泡剂,价格低廉、无任何污染。
所述硅烷表面活性剂优选为美国迈图高新技术材料有限公司的Y10366和L3002两者至少一种。
所述二苯基甲烷二异氰酸酯改性的预聚体是将过量的二苯基甲烷二异氰酸酯与聚醚(酯)二元醇反应制备而成的,其中NCO基含量为19~22%。
所述聚醚(酯)二元醇为数均分子量为1000~6000的聚碳酸酯二元醇,聚氧化丙烯二元醇,聚四氢呋喃二元醇,聚己内酯二元醇的至少一种。
所述改性二苯基甲烷二异氰酸酯具体制备方法为:将二苯基甲烷二异氰酸酯与聚醚(酯)二元醇在70-90℃下反应2-3小时至端-NCO基含量为22~24%后,升温至100~110℃,继续反应0.5~1小时,形成端-NCO基含量为19~22%的改性二苯基甲烷二异氰酸酯。
所述可热压定型缓冲材料的制备方法,包括以下步骤:
(1)将聚醚三元醇1型、聚醚三元醇2型、高活性聚合物多元醇、硅烷表面活性剂、扩链剂、交联剂、催化剂、发泡剂和抗氧剂混合均匀,得到A料;所述A料中还包括色料;
(2)将A料与二苯基甲烷二异氰酸酯改性的预聚体即B料搅拌混合,置于模具中,熟化,脱模,静置,得到可热压定型缓冲材料。
所述模具已喷涂脱模剂;所述搅拌混合时间为15~30s,所述搅拌混合的转速为300~700rpm;所述静置时间为12~24h。所述熟化的温度40~60℃,所述熟化时间为20~30min。所述搅拌混合的时间为15~30s。
所述可热压定型缓冲材料应用于运动防护产品领域,包括鞋垫、运动保护片和运动保护垫等。
所述可热压定型缓冲材料通过热压定型制备运动防护产品,所述热压定型的温度为170~200℃,时间为60~120s;具体步骤为:
通过胶粘方式在材料的正面覆上0.05~1.0MM的TPU膜,在材料的背面覆上180~300g/m2的BK布,然后置于加热的模具上(模具温度170~200℃),合上模具,保温60~120秒后打开模具,取出制品。
本发明优选二乙醇胺作为交联剂,二乙醇胺具有交联作用的同时还具有熟化作用;相对于其他交联剂,二乙醇胺的效果较好。
本发明选用三乙烯二胺和双(2-二甲氨基乙基)醚作为催化剂,双(2-二甲氨基乙基)醚是强烈发泡催化剂,它的作用是前期乳化和发泡;三乙烯二胺是凝胶催化剂,属于后期熟化作用。这两者作为催化剂更易于控制发泡的乳白期和脱模时间及泡孔开孔结构。本发明优选三乙烯二胺和双(2-二甲氨基乙基)醚作为催化剂效果较好。
与现有技术相比,本发明具有如下优点及有益效果:
(1)本发明的缓冲材料可以在170~200℃,60~120秒的条件下热压定型,提高了生产效率和降低了生产成本。大批量生产时成本更低,品质更稳定;
(2)将本发明的缓冲材料用于制备运动防护产品,产品缓冲性能好,制品表面撕裂强度高,耐磨度好(表面覆盖了TPU膜,其延伸率可达500%,撕裂强度80Kgf/cm,相对PU材料的100%-150%延伸率,撕裂强度1.0-2.5Kgf/cm,有非常大的提升),制品生产效率高(相对于PU灌注生产工艺7-8分钟的成型周期,热压定型才1-2分钟,效率提升300%)等优点。
具体实施方式
下面结合具体实施例对本发明作进一步地具体详细描述,但本发明的实施方式不限于此,对于未特别注明的工艺参数,可参照常规技术进行。
实施例1~4中所述改性二苯基甲烷二异氰酸酯具体制备方法为:将二苯基甲烷二异氰酸酯与聚醚(酯)二元醇在70-90℃下反应2-3小时至端-NCO基含量为22~24%后,升温至100~110℃,继续反应0.5~1小时,形成端-NCO基含量为19~22%的改性二苯基甲烷二异氰酸酯。所述聚醚(酯)二元醇为数均分子量为2000的聚氧化丙烯二元醇。
实施例1
一种可热压定型缓冲材料的制备方法,包括以下步骤:
(1)将35重量份的5000分子量三官能聚醚多元醇CHE-330N、30重量份的高活性聚合物多元醇CHP-H30(固含量为28%)、35重量份的400分子量三官能聚醚多元醇(聚氧化丙烯三元醇)、0.15重量份硅烷表面活性剂Y10366、2.2重量份乙二醇、0.21重量份二乙醇胺、0.2重量份三乙烯二胺、0.05重量份双(2-二甲氨基乙基)醚、1.0重量份抗氧剂1010和0.35重量份的水混合均匀,得到预混料;所述预混料中还包括色料;
(2)将预混料与按预混料重量的40wt%的二苯基甲烷二异氰酸酯改性的预聚体(NCO基含量为20%)搅拌混合30s(搅拌混合的转速为300r/min),置于已喷好脱模剂的模具中,模具温度为40℃,熟化30min,脱模,静置24h,使用开片机切割得到13MM厚度材料。
以下为所得可热压定型材料的性能测试数据:
项目(测试标准方法) 单位 测试值
密度ASTM D-792 Kg/M3 320
硬度ASTM D2240 Asker C 25
弹性ASTM D2632 6.5
永久变形率ASTM D395-B 6
延伸率ASTM D412 die C 110
撕裂强度ASTM D624 die C KN/m 1.6
拉伸强度ASTM D412 die C Kgf/cm2 6.9
缓冲吸震力ENl621-2@23℃ N 14536
通过胶粘方式在材料的正面覆上0.05MM的TPU膜,在材料的背面覆上180g/m2的BK布,然后置于加热的模具上(模具温度170℃),合上模具,保温120秒后打开模具,取出制品。
以下为所得制品的性能测试数据:
项目(测试标准方法) 单位 测试值
密度ASTM D-792 Kg/M3 320~450
硬度ASTM D2240 Asker C 25-35
弹性ASTM D2632 6.5
永久变形率ASTM D395-B 6
延伸率ASTM D412 die C 180
撕裂强度ASTM D624 die C KN/m 5.8
拉伸强度ASTM D412 die C Kgf/cm2 15
缓冲吸震力EN1621-2@23℃ N 13565
实施例2
一种可热压定型缓冲材料的制备方法,包括以下步骤:
(1)将50重量份的6000分子量三官能聚醚多元醇CHE-828、15重量份的高活性聚合物多元醇CHP-H45(固含量为45%)、35重量份的700分子量三官能聚醚多元醇(聚氧化丙烯三元醇)、0.1重量份硅烷表面活性剂L3002、0.5重量份乙二醇、0.15重量份二乙醇胺、0.5重量份三乙烯二胺、0.15重量份双(2-二甲氨基乙基)醚、1.5重量份抗氧剂1010和0.35重量份的水混合均匀,得到预混料;所述预混料中还包括色料;
(2)将预混料与占预混料重量的45wt%的二苯基甲烷二异氰酸酯改性的预聚体(NCO基含量为20%)搅拌混合15s(搅拌混合的转速为450r/min),置于已喷好脱模剂的模具中,模具温度为60℃,熟化20min,脱模,静置12h,使用开片机切割得到13MM厚度材料。
以下为所得可热压定型材料的性能测试数据:
通过胶粘方式在材料的正面覆上0.3MM的TPU膜,在材料的背面覆上200g/m2的BK布,然后置于加热的模具上(模具温度180℃),合上模具,保温100秒后打开模具,取出制品。
以下为所得制品的性能测试数据:
项目(测试标准方法) 单位 测试值
密度ASTM D-792 Kg/M3 320~450
硬度ASTM D2240 Asker C 23-32
弹性ASTM D2632 7
永久变形率ASTM D395-B 5
延伸率ASTM D412 die C 250
撕裂强度ASTM D624 die C KN/m 11
拉伸强度ASTM D412 die C Kgf/cm2 18
缓冲吸震力EN1621-2@23℃ N 15565
实施例3
一种可热压定型缓冲材料的制备方法,包括以下步骤:
(1)将20重量份的5000分子量三官能聚醚多元醇CHE-330N、50重量份的高活性聚合物多元醇CHP-H30(固含量为28%)、30重量份的700分子量三官能聚醚多元醇(聚氧化丙烯三元醇)、0.3重量份硅烷表面活性剂Y10366、1.5重量份乙二醇、0.15重量份二乙醇胺、0.2重量份三乙烯二胺、0.03重量份双(2-二甲氨基乙基)醚、3.0重量份抗氧剂1010和0.25重量份的水混合均匀,得到预混料;所述预混料中还包括色料;
(2)将预混料与其重量的35wt%的二苯基甲烷二异氰酸酯与聚醚多元醇的预聚体(NCO基含量为20%)搅拌混合15s(搅拌混合的转速为700r/min),置于已喷好脱模剂的模具中,模具温度为40℃,熟化25min,脱模,静置12h,使用开片机切割得到13MM厚度材料。
以下为所得可热压定型材料的性能测试数据:
项目(测试标准方法) 单位 测试值
密度ASTM D-792 Kg/M3 350
硬度ASTM D2240 Asker C 28
弹性ASTM D2632 7
永久变形率ASTM D395-B 5.5
延伸率ASTM D412 die C 100
撕裂强度ASTM D624 die C KN/m 1.8
拉伸强度ASTM D412 die C Kgf/cm2 7.5
缓冲吸震力EN1621-2@23℃ N 15536
通过胶粘方式在材料的正面覆上0.5MM的TPU膜,在材料的背面覆上200g/m2的BK布,然后置于加热的模具上(模具温度190℃),合上模具,保温80秒后打开模具,取出制品。
以下为所得制品的性能测试数据:
项目(测试标准方法) 单位 测试值
密度ASTM D-792 Kg/M3 350~480
硬度ASTM D2240 Asker C 28-35
弹性ASTM D2632 7
永久变形率ASTM D395-B 5
延伸率ASTM D412 die C 180
撕裂强度ASTM D624 die C KN/m 18
拉伸强度ASTM D412 die C Kgf/cm2 22
缓冲吸震力EN1621-2@23℃ N 15565
实施例4
一种可热压定型缓冲材料的制备方法,包括以下步骤:
(1)将45重量份的5000分子量三官能聚醚多元醇CHE-330N、35重量份的高活性聚合物多元醇CHP-H30(固含量为28%)、20重量份的700分子量三官能聚醚多元醇(聚氧化丙烯三元醇)、0.2重量份硅烷表面活性剂Y10366、1.8重量份乙二醇、0.15重量份二乙醇胺、0.4重量份三乙烯二胺、0.1重量份双(2-二甲氨基乙基)醚、2.5重量份抗氧剂1010和0.35重量份的水混合均匀,得到预混料;所述预混料中还包括色料;
(2)将预混料与占预混料重量的38wt%的二苯基甲烷二异氰酸酯改性的预聚体(NCO基含量为20%)搅拌混合20s(搅拌混合的转速为500r/min),置于已喷好脱模剂的模具中,模具温度为50℃,熟化25min,脱模,静置12h,使用开片机切割得到13MM厚度材料。
以下为所得可热压定型材料的性能测试数据:
项目(测试标准方法) 单位 测试值
密度ASTM D-792 Kg/M3 320
硬度ASTM D2240 Asker C 28
弹性ASTM D2632 7
永久变形率ASTM D395-B 5.0
延伸率ASTM D412 die C 150
撕裂强度ASTM D624 die C KN/m 1.8
拉伸强度ASTM D412 die C Kgf/cm2 7.2
缓冲吸震力EN1621-2@23℃ N 17536
通过胶粘方式在材料的正面覆上1.0MM的TPU膜,在材料的背面覆上200g/m2的BK布,然后置于加热的模具上(模具温度200℃),合上模具,保温60秒后打开模具,取出制品。
以下为所得制品的性能测试数据:
本发明的上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明权利要求的保护范围之内。

Claims (9)

1.一种可热压定型缓冲材料,其特征在于:由A料和B料制备而成;所述A料由以下按重量份数计的组分组成:
所述B料为二苯基甲烷二异氰酸酯改性的预聚体,所述B料为A料总重量的35~45%;
所述聚醚三元醇1型为官能团是3,数均分子量为5000~6000;所述聚醚三元醇2型为官能团是3,数均分子量为400~700;
所述二苯基甲烷二异氰酸酯改性的预聚体是将过量的二苯基甲烷二异氰酸酯与聚醚(酯)二元醇反应制备而成的,其中NCO基含量为19~22%;
所述聚醚(酯)二元醇为数均分子量为1000~6000的聚碳酸酯二元醇,聚氧化丙烯二元醇,聚四氢呋喃二元醇,聚己内酯二元醇的至少一种。
2.根据权利要求1所述可热压定型缓冲材料,其特征在于:所述聚醚三元醇1型的羟值为26~36mgKOH/g;所述聚醚三元醇2型的羟值为250~320mgKOH/g;
所述高活性聚合物多元醇的固含量为28~45%;所述高活性聚合物多元醇是由聚醚多元醇与苯乙烯、丙烯腈聚合反应得到;
所述扩链剂为乙二醇、1,4-丁二醇或1,3-丙二醇中一种以上;
所述交联剂为醇胺类;
所述催化剂为N,N-二甲基环己胺、N,N,N',N'-四甲基亚烷基二胺、三乙胺、N,N-二甲基苄胺,双(2-二甲氨基乙基)醚、三乙烯二胺、有机铋、有机锡中一种以上。
3.根据权利要求2所述可热压定型缓冲材料,其特征在于:所述聚醚三元醇1型为CHE-330N和CHE-828中一种以上;所述聚合物多元醇为CHP-H30或CHP-H45中一种以上;
所述扩链剂为乙二醇;所述交联剂为二乙醇胺;所述催化剂为双(2-二甲氨基乙基)醚和三乙烯二胺的混合物。
4.根据权利要求1所述可热压定型缓冲材料,其特征在于:所述A料还包括色料;所述抗氧剂为抗氧剂1010;所述发泡剂为水;
所述硅烷表面活性剂为Y10366和L3002两者至少一种。
5.根据权利要求1所述可热压定型缓冲材料,其特征在于:所述改性二苯基甲烷二异氰酸酯具体制备方法为:将二苯基甲烷二异氰酸酯与聚醚(酯)二元醇在70~90℃下反应2~3小时至端-NCO基含量为22~24%后,升温至100~110℃,继续反应0.5~1小时,形成端-NCO基含量为19~22%的改性二苯基甲烷二异氰酸酯。
6.根据权利要求1~5任一项所述可热压定型缓冲材料的制备方法,其特征在于:包括以下步骤:
(1)将聚醚三元醇1型、聚醚三元醇2型、高活性聚合物多元醇、硅烷表面活性剂、扩链剂、交联剂、催化剂、发泡剂和抗氧剂混合均匀,得到A料;所述A料中还包括色料;
(2)将A料与二苯基甲烷二异氰酸酯改性的预聚体即B料搅拌混合,置于模具中,熟化,脱模,静置,得到可热压定型缓冲材料。
7.根据权利要求6所述可热压定型缓冲材料的制备方法,其特征在于:所述搅拌混合时间为15~30s,所述搅拌混合的转速为300~700rpm;所述静置时间为12~24h;所述熟化的温度40~60℃,所述熟化时间为20~30min;所述搅拌混合的时间为15~30s。
8.根据权利要求1~5任一项所述可热压定型缓冲材料的应用,其特征在于:所述可热压定型缓冲材料应用于运动防护产品领域。
9.根据权利要求8所述的应用,其特征在于:所述可热压定型缓冲材料通过热压定型制备运动防护产品,所述热压定型的温度为170~200℃,时间为60~120s。
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Application publication date: 20170215

Assignee: GUANGDONG HUDIAN CUSHION MATERIAL TECHNOLOGY Co.,Ltd.

Assignor: Foshan Linzhi Polymer Materials Science And Technology Co.,Ltd.

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Denomination of invention: A kind of cushion material which can be shaped by hot pressing and its preparation method and Application

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