CN109666123A - 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 PDF

Info

Publication number
CN109666123A
CN109666123A CN201811462134.XA CN201811462134A CN109666123A CN 109666123 A CN109666123 A CN 109666123A CN 201811462134 A CN201811462134 A CN 201811462134A CN 109666123 A CN109666123 A CN 109666123A
Authority
CN
China
Prior art keywords
polyether polyol
fiberglass reinforced
urethane composition
catalyst
cellular sandwich
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201811462134.XA
Other languages
English (en)
Other versions
CN109666123B (zh
Inventor
孙海欧
杜俊超
温荣政
赵修文
庄远
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Liming Research Institute of Chemical Industry Co Ltd
Original Assignee
Liming Research Institute of Chemical Industry Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Liming Research Institute of Chemical Industry Co Ltd filed Critical Liming Research Institute of Chemical Industry Co Ltd
Priority to CN201811462134.XA priority Critical patent/CN109666123B/zh
Publication of CN109666123A publication Critical patent/CN109666123A/zh
Application granted granted Critical
Publication of CN109666123B publication Critical patent/CN109666123B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6614Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6622Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/32Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203Polyhydroxy compounds
    • C08G18/3206Polyhydroxy compounds aliphatic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/32Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225Polyamines
    • C08G18/3237Polyamines aromatic
    • C08G18/3243Polyamines aromatic containing two or more aromatic rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/32Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271Hydroxyamines
    • C08G18/3278Hydroxyamines containing at least three hydroxy groups
    • C08G18/3281Hydroxyamines containing at least three hydroxy groups containing three hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/4009Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4213Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4804Two or more polyethers of different physical or chemical nature
    • C08G18/4812Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4825Polyethers containing two hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4833Polyethers containing oxyethylene units
    • C08G18/4837Polyethers containing oxyethylene units and other oxyalkylene units
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/487Polyethers containing cyclic groups
    • C08G18/4883Polyethers containing cyclic groups containing cyclic groups having at least one oxygen atom in the ring
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00Foam properties
    • C08G2110/0083Foam properties prepared using water as the sole blowing agent
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

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

一种玻纤增强蜂窝夹芯板用聚氨酯组合物及其使用方法
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2000-3000mPa·s。
2.根据权利要求1所述的玻纤增强蜂窝夹芯用聚氨酯组合物,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。
10.一种制备权利要求1~9之一所述的玻纤增强蜂窝夹芯用聚氨酯组合物的方法: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。
CN201811462134.XA 2018-11-20 2018-11-20 一种玻纤增强蜂窝夹芯板用聚氨酯组合物及其使用方法 Active CN109666123B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811462134.XA CN109666123B (zh) 2018-11-20 2018-11-20 一种玻纤增强蜂窝夹芯板用聚氨酯组合物及其使用方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811462134.XA CN109666123B (zh) 2018-11-20 2018-11-20 一种玻纤增强蜂窝夹芯板用聚氨酯组合物及其使用方法

Publications (2)

Publication Number Publication Date
CN109666123A true CN109666123A (zh) 2019-04-23
CN109666123B CN109666123B (zh) 2021-11-19

Family

ID=66143500

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811462134.XA Active CN109666123B (zh) 2018-11-20 2018-11-20 一种玻纤增强蜂窝夹芯板用聚氨酯组合物及其使用方法

Country Status (1)

Country Link
CN (1) CN109666123B (zh)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110964173A (zh) * 2019-12-13 2020-04-07 万华化学(北京)有限公司 用于蜂窝复合材料的聚氨酯组合物及其制备方法、聚氨酯泡沫及其应用
CN111002681A (zh) * 2019-12-12 2020-04-14 惠彩材料科技(苏州)有限公司 一种聚氨酯蜂窝纸板玻毡复合材料及其制备方法
CN111070809A (zh) * 2019-12-23 2020-04-28 江苏吉润住宅科技有限公司 复合板材
CN111499828A (zh) * 2020-04-15 2020-08-07 黎明化工研究设计院有限责任公司 一种低密度高阻燃聚氨酯材料用树脂组合物及其应用
CN112225867A (zh) * 2020-06-02 2021-01-15 南京汇科高分子材料有限公司 用于制备汽车天窗遮阳板和备胎盖板的聚氨酯半硬质泡沫
CN114536928A (zh) * 2021-12-30 2022-05-27 浙江华江科技股份有限公司 一种汽车衣帽架用环保阻燃高承载pu复合材料的制备方法
CN114957586A (zh) * 2022-05-05 2022-08-30 江苏沣鼎新材料有限公司 一种基于玻璃纤维增强复合蜂窝芯材的房车板及加工装置
CN116253853A (zh) * 2023-01-02 2023-06-13 黎明化工研究设计院有限责任公司 一种高粘接快脱模聚氨酯组合物及制备聚氨酯制品的方法和应用
WO2024015544A1 (en) * 2022-07-15 2024-01-18 Basf Se Parcel chute and panel construction therefore, and a process for preparing the same
CN114536928B (zh) * 2021-12-30 2024-05-10 浙江华江科技股份有限公司 一种汽车衣帽架用环保阻燃高承载pu复合材料的制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RO79852A2 (ro) * 1980-07-03 1982-10-11 Combinatul Chimic,Ro Procedeu pentru obtinerea unor spume poliuretanice rigide
CN1426891A (zh) * 2001-12-17 2003-07-02 拜尔公司 用外层和聚氨酯夹芯材料制成的层压零件及其生产方法
CN101641384A (zh) * 2007-03-19 2010-02-03 巴斯夫欧洲公司 制备聚氨酯夹层部件的聚氨酯体系
CN102248727A (zh) * 2011-05-27 2011-11-23 常州市华星新材料科技有限公司 聚氨酯泡沫夹心连续纤维增强复合板材成型工艺
CN105199071A (zh) * 2015-09-16 2015-12-30 万华化学(北京)有限公司 一种聚氨酯组合料、其制备聚氨酯复合材料的方法及制得产品的用途
CN106188485A (zh) * 2016-08-01 2016-12-07 山东诺威新材料有限公司 聚氨酯泡沫塑料发泡材料及其制备方法和应用
CN108503766A (zh) * 2017-02-28 2018-09-07 芜湖美的厨卫电器制造有限公司 组合聚醚、硬质聚氨酯泡沫及其制备方法和热水器

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RO79852A2 (ro) * 1980-07-03 1982-10-11 Combinatul Chimic,Ro Procedeu pentru obtinerea unor spume poliuretanice rigide
CN1426891A (zh) * 2001-12-17 2003-07-02 拜尔公司 用外层和聚氨酯夹芯材料制成的层压零件及其生产方法
CN101641384A (zh) * 2007-03-19 2010-02-03 巴斯夫欧洲公司 制备聚氨酯夹层部件的聚氨酯体系
CN102248727A (zh) * 2011-05-27 2011-11-23 常州市华星新材料科技有限公司 聚氨酯泡沫夹心连续纤维增强复合板材成型工艺
CN105199071A (zh) * 2015-09-16 2015-12-30 万华化学(北京)有限公司 一种聚氨酯组合料、其制备聚氨酯复合材料的方法及制得产品的用途
CN106188485A (zh) * 2016-08-01 2016-12-07 山东诺威新材料有限公司 聚氨酯泡沫塑料发泡材料及其制备方法和应用
CN108503766A (zh) * 2017-02-28 2018-09-07 芜湖美的厨卫电器制造有限公司 组合聚醚、硬质聚氨酯泡沫及其制备方法和热水器

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
刘益军: "《聚氨酯原料及助剂手册》", 31 January 2013 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111002681A (zh) * 2019-12-12 2020-04-14 惠彩材料科技(苏州)有限公司 一种聚氨酯蜂窝纸板玻毡复合材料及其制备方法
CN111002681B (zh) * 2019-12-12 2021-11-02 惠彩材料科技(苏州)有限公司 一种聚氨酯蜂窝纸板玻毡复合材料及其制备方法
CN110964173A (zh) * 2019-12-13 2020-04-07 万华化学(北京)有限公司 用于蜂窝复合材料的聚氨酯组合物及其制备方法、聚氨酯泡沫及其应用
CN111070809A (zh) * 2019-12-23 2020-04-28 江苏吉润住宅科技有限公司 复合板材
CN111499828A (zh) * 2020-04-15 2020-08-07 黎明化工研究设计院有限责任公司 一种低密度高阻燃聚氨酯材料用树脂组合物及其应用
CN111499828B (zh) * 2020-04-15 2022-04-12 黎明化工研究设计院有限责任公司 一种低密度高阻燃聚氨酯材料用树脂组合物及其应用
CN112225867A (zh) * 2020-06-02 2021-01-15 南京汇科高分子材料有限公司 用于制备汽车天窗遮阳板和备胎盖板的聚氨酯半硬质泡沫
CN114536928A (zh) * 2021-12-30 2022-05-27 浙江华江科技股份有限公司 一种汽车衣帽架用环保阻燃高承载pu复合材料的制备方法
CN114536928B (zh) * 2021-12-30 2024-05-10 浙江华江科技股份有限公司 一种汽车衣帽架用环保阻燃高承载pu复合材料的制备方法
CN114957586A (zh) * 2022-05-05 2022-08-30 江苏沣鼎新材料有限公司 一种基于玻璃纤维增强复合蜂窝芯材的房车板及加工装置
WO2024015544A1 (en) * 2022-07-15 2024-01-18 Basf Se Parcel chute and panel construction therefore, and a process for preparing the same
CN116253853A (zh) * 2023-01-02 2023-06-13 黎明化工研究设计院有限责任公司 一种高粘接快脱模聚氨酯组合物及制备聚氨酯制品的方法和应用

Also Published As

Publication number Publication date
CN109666123B (zh) 2021-11-19

Similar Documents

Publication Publication Date Title
CN109666123A (zh) 一种玻纤增强蜂窝夹芯板用聚氨酯组合物及其使用方法
EP2726528B1 (en) Flame resistant composition, fiber reinforced polyurethane based composite article comprising the flame resistant composition and its use
CA2603222C (en) Rigid polyurethane-isocyanurate reinforcing foams
CN102504180B (zh) 一种汽车顶棚专用的低密度pu板
CN102825712B (zh) 一种汽车仪表台制作工艺
WO2007112104A2 (en) Polyurethane composite materials
CN103865025A (zh) 一种本质阻燃硬质聚氨酯泡沫塑料
CA2784241A1 (en) Polyurethane composite system having high compressive strength and rigidity
CN108676139A (zh) 一种吸声降噪隔音聚氨酯泡沫材料及其制备方法、应用
CN113248907B (zh) 一种无机填料复合聚氨酯保温板及其制备方法和应用
CN111499828B (zh) 一种低密度高阻燃聚氨酯材料用树脂组合物及其应用
CN114133523B (zh) 轻量化抗动态冲击新能源汽车电池箱用聚氨酯组合物及其制备方法
CN105524245A (zh) 一种高韧性阻燃硬质聚氨酯泡沫板
CN108329458A (zh) 一种玻纤增强聚氨酯复合板及其制备方法
CN109535695A (zh) 高阻燃低挥发压缩残余变量小的座椅聚氨酯发泡材料及其制备方法和应用
CN113549248B (zh) 磁性光稳定剂及制备方法、聚氨酯组合物及聚氨酯复合材料的制备方法
CN106632952B (zh) 一种可热成型聚氨酯泡沫及其制备方法
CN114835874A (zh) 一种高强度低成本复合材料用聚氨酯泡沫芯材及其制备方法、应用
CN114015122A (zh) 一种汽车顶棚基材及其制备方法
CN112266463A (zh) 一种汽车内饰用阻燃型木质素基聚氨酯硬泡及其制备方法
KR100513243B1 (ko) 페놀수지를 적용한 샌드위치형 패널 및 그 제조방법
CN111454557A (zh) 一种阻燃型的不饱和聚酯树脂的制备工艺
CN109988279A (zh) 一种分子链软段阻燃聚氨酯泡沫
CN109880058A (zh) 一种分子链软段阻燃聚氨酯泡沫的制备方法
CN112375198B (zh) 低气味高性能车门内饰板组合料及其制备方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant