CN109666123B - 一种玻纤增强蜂窝夹芯板用聚氨酯组合物及其使用方法 - Google Patents
一种玻纤增强蜂窝夹芯板用聚氨酯组合物及其使用方法 Download PDFInfo
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Abstract
本发明公开了一种玻纤增强蜂窝夹芯板用聚氨酯组合物及其使用方法,由两种组分组成,A组分:40%~70%聚醚多元醇1,5~10%聚醚多元醇2,5%~10%聚醚多元醇3,0~10%聚酯多元醇1,4%~10%交联剂,5%~15%扩链剂,0.2%~2%泡沫稳定剂,0.2%~1.5%催化剂,5~10%阻燃剂,0.2%~1%水,0.2~2%内脱模剂,0.2~1%其他添加剂;B组分为多亚甲基多苯基多异氰酸酯;聚醚多元醇1为D‑葡糖醇为起始剂,碱金属氢氧化物为催化剂,1,2‑环氧丙烷进行阴离子聚合,再加入环氧乙烷进行封端制备;聚醚多元醇2为双酚A为起始剂,官能度为2的环氧丙烷聚醚多元醇;聚醚多元醇3为丙三醇为起始剂,环氧乙烷封端的聚醚多元醇;聚酯多元醇1为对苯二甲酸与乙二醇通过缩聚反应得到。
Description
技术领域
本发明涉及聚氨酯领域,具体涉及一种玻纤增强蜂窝夹芯板用聚氨酯材料及玻纤增强蜂窝夹芯板的制备方法。
背景技术
随着汽车工业的迅猛发展,汽车内饰材料的轻量化、阻燃性,成为汽车零部件行业关注的重点。玻纤增强蜂窝夹芯板用聚氨酯材料其整体密度可低至0.3-0.5g/cm3,并具有高强度、重量轻、隔音隔热保温等特性,较适合在汽车天窗、备胎盖板、衣帽架等汽车零部件上使用。但由于其密度低,尺寸稳定性差,因此,好的阻燃性及尺寸稳定性成为车用玻纤增强蜂窝夹芯板亟待解决的问题。
阻燃性对于汽车内饰材料来说非常重要,1987年出台了GB8410-1987汽车内饰材料的燃烧特性的强制性标准,但仅参照国家强制性标准GB8410-2006来控制水平燃烧,不足以有效防止、延缓火势的蔓延。各大汽车厂商在此基础上,添加补充了企业的评判标准。如《JT/T1095-2016客车内饰材料的燃烧特性》中对营运客车内饰板材的阻燃特性要求:水平燃烧不低于B、垂直燃烧≤100mm/min、氧指数≥22%和烟密度等级≤70。一般说来,通过添加阻燃剂可同时使水平燃烧、垂直燃烧、氧指数达到更高标准,但与此同时,烟密度等级也将显著提高,不能同时满足上述四个指标要求。
专利文献CN 101641384A公开了一种制备聚氨酯夹层部件的聚氨酯体系,包含A组分和B组分,A组分包括聚醚多元醇、胺类活性增链剂、表面活性剂、内脱模剂、催化剂和发泡剂等,B组分包括异氰酸酯或其预聚体,A、B组分重量比为100∶80~200,该组合料生产时化学触变性好,所制得的复合材料压制后具有极好的边缘。但该材料阻燃性难以达到汽车内饰材料阻燃特性要求。
专利文献CN 105199071A公开了一种聚氨酯组合料,包含A组分和B组分,A组分包括聚醚多元醇、扩链剂、表面活性剂、内脱模剂、催化剂和发泡剂等,B组分包括异氰酸酯或其预聚体,A、B组分重量比为100∶130~180,该组合料所制得的复合材料可具有较高的强度、耐高温性能和较多的脱膜次数,可用于汽车天窗、备胎盖板、建筑装饰和家具。但该材料尤其是制备天窗等具备弧形角度的制品时尺寸稳定性较差,阻燃性难以达到汽车内饰材料阻燃特性要求。
专利文献CN 107512057A公开了一种聚氨酯层压模塑制品,采用了基于植物油的多元醇或其衍生物和改性物,改善了脱模性,其提供的聚氨酯层压模塑制品具有良好的脱模性和生产率,但阻燃性难以达到汽车内饰材料阻燃特性要求。
发明内容
本发明要解决的第一个技术问题是提供一种玻纤增强蜂窝夹芯板用聚氨酯组合物,制得的玻纤增强蜂窝夹芯板具有较高的冲击强度、耐高温性能、较好的尺寸稳定性和较好的阻燃性。
本发明要解决的第二个技术问题是提供一种制备玻纤增强蜂窝夹芯板的方法。
为解决第一个技术问题,本发明通过以下技术方案来实现:一种玻纤增强蜂窝夹芯用聚氨酯组合物,由A、B两种组分组成,所述A和B组分的重量比为100∶150~190,以重量百分数计包括:
A组分:40%~70%聚醚多元醇1,5~10%聚醚多元醇2,5%~10%聚醚多元醇3,0~10%聚酯多元醇1,4%~10%交联剂,5%~15%扩链剂,0.2%~2%泡沫稳定剂,0.2%~1.5%催化剂,5~10%阻燃剂,0.2%~1%水,0.2~2%内脱模剂,0.2~1%其他添加剂。
B组分:多亚甲基多苯基多异氰酸酯。
本发明所述的聚醚多元醇1为D-葡糖醇为起始剂,采取碱金属氢氧化物为催化剂,1,2-环氧丙烷进行阴离子聚合,再加入环氧乙烷进行封端制备,所得官能度为6.0,数均分子量为300-800。
本发明所述的聚醚多元醇2为双酚A为起始剂,数均分子量在400-800,官能度为2的环氧丙烷聚醚多元醇。
本发明所述的聚醚多元醇3为丙三醇为起始剂,数均分子量在4000-8000,官能度为3的环氧丙烷扩链,环氧乙烷封端的聚醚多元醇。
本发明所述的聚酯多元醇1为对苯二甲酸与乙二醇通过缩聚反应得到,数均分子量在300-500,粘度2000-3000m Pa·s。
本发明所述的扩链剂为1,4-丁二醇、二乙二醇、乙二醇或二丙二醇等及其两种以上混合物;交联剂为丙三醇、4,4’-双仲丁氨基二苯基甲烷、二乙基甲苯二胺、间苯二胺、二乙醇胺或三乙醇胺等及其两种以上混合物。
本发明所述的泡沫稳定剂优选为聚氨酯硬泡硅油,包含但不限于德美世创公司的AK158、AK338、迈图公司的L-6970、赢创公司的B8870。
进一步地,本发明所述的0.2%~1.5%催化剂由重量份0.1%-1%的叔胺类催化剂和0.001%-0.5%的有机金属催化剂组成。叔胺类催化剂包括双(二甲氨基乙基)醚,三亚乙基二胺,N-甲基二环己胺,五甲基二亚丙基三胺,三乙胺、四甲基丙二胺中的一种或两种或多种;有机金属催化剂包括二硫醇二辛基锡、双十二烷硫基二甲基锡、二月桂酸二丁基锡、双十四烷酸二丁基锡、异辛酸铋、异辛酸锌、异辛酸钾等中的一种或两种以上混合物。
本发明所述的阻燃剂优选为膨胀石墨及浙江淳安助剂厂的TCPP、TCEP、FR-V6、三聚氰胺或聚磷酸铵等中的一种或两种以上混合物。
本发明所述的内脱模剂为烷基酰胺、羧酰胺、高级脂肪醇与氧化乙烯加成物、硬脂酸锌等中的一种或两种或多种。
本发明所述的其他添加剂,包括炭黑、抗氧剂、光稳定剂等;其中炭黑为中性乙炔炭黑、抗氧剂为受阻酚类抗氧剂,如BASF公司的Irganox 245、台湾双键化工的Chinox 1010中的一种,光稳定剂为受阻胺光稳定剂,如BASF公司的Tinuvin 292、Tinuvin 622SF、Tinuvin 770DF中的一种或两种或多种。
为解决第二个技术问题,本发明提供一种制备玻纤增强蜂窝夹芯板的方法:准备一个核心层和至少一个纤维增强层,将纤维增强层施用于核心层的一面或两面,用机械手将纤维和核心层固定好,将A、B组分混合物均匀施用于纤维增强层,放入100-130℃的模具中,合模,10秒后开模放气,再合模,10秒后开模放气,再合模,60s-120s开模即可得到制品。
本发明所述的核心层的材料可为蜂窝状纸、蜂窝状金属或蜂窝状塑料中的一种或两种或多种。所用纤维增强层可为面密度≤600g/m2的无碱玻璃纤维短切毡、玻璃布或天然纤维织物中的一种或两种或多种。
本发明所述聚氨酯A组分黏度为1000~2000m Pa·s,B组分黏度为200~250mPa·s,混合后10秒内黏度急剧上升,混合物喷涂时无明显流淌和滴落。
本发明所述的聚氨酯组合物在25℃于混合后起发时间为80~100s。
本发明采取双酚A为起始剂的聚醚,通过三聚反应和阻燃剂配合,在提高氧指数的同时,降低了烟密度等级。
本发明所述的聚氨酯组合物固化初始强度较高,防止了开模时夹层部件气压过高引起胀裂,制备的玻纤增强蜂窝夹芯板弧形角度尺寸稳定性较好。
本发明所述的聚氨酯组合物能够用于制备玻纤增强蜂窝夹芯板,制得的夹芯板具有较高的冲击强度、耐高温性能、较好的尺寸稳定性和较好的阻燃性。玻纤增强蜂窝夹芯板性能如下:冲击强度3~6KJ/m2,氧指数≥24%,烟密度等级≤70,尺寸稳定性<1%,可用于汽车天窗、汽车备胎盖板、衣帽架等,但不限于此。本发明的聚氨酯组合物在制备聚氨酯夹层部件过程中不滴落不流淌,降低了对设备的污损。
具体实施方式
下面结合实施例对本发明作详细说明,但本发明的内容不局限于实施例。实施例配方所用的原料:
PPG1:以D-葡糖醇为起始剂,环氧丙烷接枝,环氧乙烷封端多元醇,封端率60%,官能度为6,羟值450。
PPG2:以双酚A为起始剂,环氧丙烷接枝多元醇,官能度为2,羟值200。
PPG3:以丙三醇为起始剂,环氧丙烷接枝,环氧乙烷封端多元醇,官能度为3,羟值35。
聚酯多元醇1:对苯二甲酸乙二醇酯,官能度为2,羟值300。
泡沫稳定剂:迈图公司的L-6970。
催化剂1:江苏省江都市大江化工实业有限公司的A1。
炭黑:洛阳黑金龙公司的BR-288。
异氰酸酯:BASF公司的Lupranate M20S。
实施例1-4
复合材料的制备:准备一个核心层和至少一个纤维增强层,将纤维增强层施用于核心层的一面或两面,用机械手将纤维和核心层固定好,将一种聚氨酯A、B组分分别保持在25℃,并将反应混合物均匀施用于纤维增强层,放入130℃的模具中,合模,10秒后开模放气,再合模,10秒后开模放气,再合模,60s开模即可得到制品。原料重量份及玻纤增强蜂窝夹芯板材料性能见表1。
表1实施例1-4原料重量份及玻纤增强蜂窝夹芯板材料性能
Claims (10)
1.一种玻纤增强蜂窝夹芯板用聚氨酯组合物,由A、B两种组分组成,A和B组分的重量比为100∶150~190,以重量百分数计包括:
A组分:40%~70%聚醚多元醇1,5~10%聚醚多元醇2,5%~10%聚醚多元醇3,0~10%聚酯多元醇1,4%~10%交联剂,5%~15%扩链剂,0.2%~2%泡沫稳定剂,0.2%~1.5%催化剂,5~10%阻燃剂,0.2%~1%水,0.2~2%内脱模剂,0.2~1%其他添加剂;
B组分:多亚甲基多苯基多异氰酸酯;
所述的聚醚多元醇1为D-葡糖醇为起始剂,采取碱金属氢氧化物为催化剂,1,2-环氧丙烷进行阴离子聚合,再加入环氧乙烷进行封端制备,所得官能度为6.0,数均分子量为300-800;
所述的聚醚多元醇2为双酚A为起始剂,数均分子量在400-800,官能度为2的环氧丙烷聚醚多元醇;
所述的聚醚多元醇3为丙三醇为起始剂,数均分子量在4000-8000,官能度为3的环氧丙烷扩链,环氧乙烷封端的聚醚多元醇;
所述的聚酯多元醇1为对苯二甲酸与乙二醇通过缩聚反应得到,数均分子量在300-500,粘度2000-3000m Pa·s。
2.根据权利要求1所述的玻纤增强蜂窝夹芯板用聚氨酯组合物,所述的扩链剂为1,4-丁二醇、二乙二醇、乙二醇或二丙二醇及其两种以上混合物。
3.根据权利要求1所述的玻纤增强蜂窝夹芯板用聚氨酯组合物,所述的交联剂为丙三醇、4,4’-双仲丁氨基二苯基甲烷、二乙基甲苯二胺、间苯二胺、二乙醇胺或三乙醇胺及其两种以上混合物。
4.根据权利要求1所述的玻纤增强蜂窝夹芯板用聚氨酯组合物,所述的泡沫稳定剂为聚氨酯硬泡硅油。
5.根据权利要求1所述的玻纤增强蜂窝夹芯板用聚氨酯组合物,所述的催化剂由重量份0.1%-1%的叔胺类催化剂和0.001%-0.5%的有机金属催化剂组成。
6.根据权利要求5所述的玻纤增强蜂窝夹芯板用聚氨酯组合物,叔胺类催化剂是指双(二甲氨基乙基)醚,三亚乙基二胺,N-甲基二环己胺,五甲基二亚丙基三胺,三乙胺、四甲基丙二胺中的一种或两种或多种;有机金属催化剂是指二硫醇二辛基锡、双十二烷硫基二甲基锡、二月桂酸二丁基锡、双十四烷酸二丁基锡、异辛酸铋、异辛酸锌或异辛酸钾中的一种或两种以上混合物。
7.根据权利要求1所述的玻纤增强蜂窝夹芯板用聚氨酯组合物,所述的阻燃剂为膨胀石墨及浙江淳安助剂厂的TCPP、TCEP、FR-V6或三聚氰胺或聚磷酸铵及其混合物。
8.根据权利要求1所述的玻纤增强蜂窝夹芯板用聚氨酯组合物,所述的内脱模剂为烷基酰胺、羧酰胺、高级脂肪醇与氧化乙烯加成物、硬脂酸锌中的一种及其混合物。
9.根据权利要求1所述的玻纤增强蜂窝夹芯板用聚氨酯组合物,所述的其他添加剂,包括炭黑、抗氧剂或光稳定剂。
10.一种采用权利要求1~9之一所述的聚氨酯组合物制备玻纤增强蜂窝夹芯板的方法:准备一个核心层和至少一个纤维增强层,将纤维增强层施用于核心层的一面或两面,用机械手将纤维和核心层固定好,将A、B组分混合物均匀施用于纤维增强层,放入100-130℃的模具中,合模10秒开模放气,再合模10秒开模放气,再合模60s-120s开模即可得到制品。
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