CN111607061B - 一种无阻燃剂高阻燃低气味全水自结皮聚氨酯泡沫及其制备方法 - Google Patents
一种无阻燃剂高阻燃低气味全水自结皮聚氨酯泡沫及其制备方法 Download PDFInfo
- Publication number
- CN111607061B CN111607061B CN202010331248.1A CN202010331248A CN111607061B CN 111607061 B CN111607061 B CN 111607061B CN 202010331248 A CN202010331248 A CN 202010331248A CN 111607061 B CN111607061 B CN 111607061B
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- polyether polyol
- polyol
- mdi
- polyurethane foam
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5069—Polyethers having heteroatoms other than oxygen having nitrogen prepared from polyepoxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明公开了一种无阻燃剂高阻燃低气味全水自结皮聚氨酯泡沫及其制备方法,原料由A、B两组分组成,按质量份计包括:其中A组分:聚醚多元醇150‑70;聚合物多元醇0‑20;曼尼希聚醚多元醇3‑10;PIPA多元醇10‑30;扩链剂5‑12;反应型催化剂1.5‑3.5;无挥发性催化剂0.01‑0.2;水0.1‑1.0;泡沫稳定剂0.5‑2;其中聚醚多元醇1+聚合物多元醇+曼尼希聚醚多元醇+PIPA多元醇=100;所述组分B是NCO含量为23%‑31wt%的改性全MDI体系异氰酸酯预聚体;所述的聚醚多元醇1为甘油起始、三官能度、分子量为3000‑10000、端伯羟基含量大于70%的高活性聚醚多元醇。A、B组分采用模塑法或自由泡法制得自结皮聚氨酯泡沫,该泡沫在不使用阻燃剂的情况下,仍表现出良好的阻燃性以及较好的环保性,其氧指数≥26%,气味≤3级。
Description
技术领域
本发明属于聚氨酯半硬质泡沫领域,具体属于自结皮聚氨酯泡沫领域。
技术背景
聚氨酯半硬质泡沫塑料(简称半硬泡)是聚氨酯的几大品种之一。它是一种性能介于聚氨醋软泡与硬泡之间的泡沫,特点是具有较高的压缩负荷值和较高的密度,其交联密度远高于软泡而仅次于硬泡。他们手感舒适,外韧内软,在汽车受到撞击时,这种半硬泡能迅速把动能转化为其它形式的能,起到缓冲作用,保护乘员的安全。
聚氨酯自结皮泡沫属于半硬泡的范畴,是根据汽车工业高速发展而开发的聚氨酯泡沫加工的第三代产品。聚氨酯自结皮泡沫又称整皮泡沫,其致密的表皮和泡沫芯体是由同种双组分材料一次制备而成的。致密的表皮可以根据模具的不同形成不同花纹,既美观又起到保护作用;而芯部的泡沫体既降低了制品的密度又使制品具有一定的弹性。由于兼具以上优点,聚氨酯自结皮泡沫被广泛应用于制造汽车方向盘、扶手、头靠等。该产品主要应用于汽车扶手、保险杠等吸能缓冲部件,目前的自结皮泡沫中,作为CFC的替代物,含氢氯氟烃(HCFC)、戊烷、氢氟烃(HFC)、水均可用于制备聚氨酯自结皮泡沫。作为聚氨酯发泡剂的主流产品HCFC-141b也将被禁止使用。相对于以上几种发泡剂来说,水的优点则显而易见,它便宜易得、无毒性、不易燃易爆、ODP值为零。
近年来,水发泡自结皮聚氨酯技术正成为一种发展趋势。美国专利5,166,183、5,216,035、5,234,961、5,236,960、5,236,961、5,266,234、5,284,880、5,338,820、5,514,723和5,658,959中已阐述了相关技术。
近年来,车内的空气环境尤其是车体内的气味和烟雾被列为一项判断舒适与否的新标准。目前,随着国标GB/T 27630-2011《乘用车内空气质量评价指南》出台,对车用方向盘、扶手的环保性能要求也越高越高。汽车方向盘、扶手使用的聚氨酯半硬泡,由于在生产中采用的叔胺类催化剂,在车内小环境内可产生胺臭味,并且在车内温度较高时可产生挥发,部分挥发物凝聚在车窗玻璃上,使玻璃模糊(即雾化)。所以,避免残留催化剂的挥发迁移是降低车内泡沫气味和雾化的最有效途径。
同时,客车新国标GB38262-2019对客车的阻燃性进行了重新定义。其中客车扶手和方向盘要求水平燃烧≤50mm/min,氧指数≥24%。这就要求车用自结皮材料不仅要阻燃,还要环保。
如专利文献CN101597370A中,通过合成一种羟值40-180mgKOH/g的高官能度聚醚,和一种无挥发性或者反应型催化剂配合使用,制得了一种皮层致密,具有较好的耐磨性能和较低的挥发性能的低VOC自结皮泡沫。但这种泡沫的阻燃性达不到要求。
CN103641979A涉及一种矿用聚氨酯自结皮组合物。采用阻燃性聚合物多元醇、阻燃剂和抗静电剂,制得了一种阻燃自结皮泡沫,氧指数可以达到28%。本发明解决了自结皮泡沫的阻燃性能和抗静电性能,制备得到的矿用聚氨酯自结皮组合物具有表皮光滑、高阻燃性和抗静电性,从而为矿用自结皮聚氨酯的安全性提供保障。但该类自结皮由于使用了阻燃剂,泡沫VOC和气味不达标。
专利文献CN105601873A涉及一种汽车方向盘用聚氨酯自结皮组合料及其制备方法,催化剂采用低雾催化剂、延迟性催化剂或反应性催化剂一种或几种,同时对混合异氰酸酯进行改性,制备的汽车方向盘不仅密度低、表面漂亮、物理机械性能好,而且具有气味低、环保、适用温度宽的优点。这种泡沫的阻燃性达不到要求。
专利文献CN108047422A使用反应型催化剂和固体纳米阻燃材料,制得方向盘环保性好具有一定的阻燃作用,但加入的固体阻燃剂容易分层,使用不便。
另有一些泡沫配方中,使用了反应型催化剂和反应型阻燃剂,也可以达到低气味和一定的阻燃性,但这些反应型阻燃剂在组合料中储存稳定性差,影响发泡速度,必须现用现加,使用不便。
综上所述,有必要提供一种综合性能优异、高阻燃、低气味、原液不分层简单易用的自结皮用组合料,满足客车行业不断提高的要求。
发明内容
本发明的第一个目的是提供一种性能优良的高阻燃低气味全水自结皮聚氨酯泡沫,该泡沫在不使用阻燃剂的情况下,仍表现出良好的阻燃性以及较好的环保性,其氧指数≥26%,气味≤3级。
本发明的第二目的是提供高阻燃低气味全水自结皮聚氨酯泡沫的制备方法。
为解决第一个技术问题,本发明提供一种无阻燃剂高阻燃低气味全水自结皮聚氨酯泡沫,原料由A、B两组分组成,按质量份计包括:
A组分:
聚醚多元醇1∶50~70;
聚合物多元醇:0~20;
曼尼希聚醚多元醇:3~10;
PIPA多元醇:10~30;
扩链剂:5~12;
反应型催化剂:1.5~3.5
无挥发性催化剂:0.01~0.2;
水:0.1~1.0;
泡沫稳定剂:0.5~2;
其中聚醚多元醇1+聚合物多元醇+曼尼希聚醚多元醇+PIPA多元醇=100;
组分B是异氰酸根(NCO)含量为23%~31wt%的改性全MDI体系异氰酸酯预聚体。MDI体系异氰酸酯包括二苯基甲烷二异氰酸酯(MDI)单体、氨基甲酸酯改性MDI、碳化二亚胺改性MDI等异氰酸酯的两种及以上的混合物,官能度为2.0~2.7,优选2.1~2.4。
组分A和组分B按100∶40-100的质量比配合使用。
本发明所述的聚醚多元醇1为甘油起始、三官能度、分子量为3000-10000、端伯羟基含量大于70%的高活性聚醚多元醇。
本发明所述的聚合物多元醇为三官能度、固含量25%~45%、苯乙烯、丙烯腈接枝的高活性聚合物多元醇。
本发明所述的曼尼希聚醚多元醇,优选官能度4~5,羟值300-550 mgKOH/g。
本发明所述的PIPA多元醇是由多元醇胺和异氰酸酯在聚醚多元醇1中反应而生成的悬浮分散体,固含量10%~20%,黏度3000~6000mPa.s。具体合成方法如下:在反应器中按质量比100/4~10/5~10加入聚醚多元醇1、多元醇胺和分散剂,混合;加入聚醚多元醇1和异氰酸酯质量比为2/1~1/2的混合物,在30-50℃下反应1~3h,即可得产物。其中多元醇胺优选三乙醇胺,分散剂优选聚乙二醇200或聚乙二醇400等,异氰酸酯优选甲苯二异氰酸酯或者二苯基甲烷二异氰酸酯及其改性物等。异氰酸酯中NCO基与多元醇胺中羟基的物质的量之比成为醇胺指数,一般选择在0.9~1.1。固含量=(多元醇胺质量+多异氰酸酯质量)/总质量。
本发明所述扩链剂优选乙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇或二乙二醇等中的至少一种。
本发明所述的反应性催化剂优选结构上含有活泼羟基或者氨基的化合物,如N’N-二甲基乙醇胺、三甲基羟乙基乙二胺、三甲基羟乙基丙二胺、四甲基二丙基三胺、2-(2-二甲胺基-乙氧基)-乙醇、N,N,N’-三甲基-N’-羟乙基双氨乙基醚或双(二甲氨基)-2-丙醇等中的至少一种。
本发明所述无挥发性催化剂,优选脂肪族羧酸的金属盐、有机碱性化合物或季铵盐类等中的至少一种。
本发明所述的泡沫稳定剂为半硬泡和高回弹泡沫常用的泡沫稳定剂,该类泡沫稳定剂含Si-C键的硅油,用量是聚醚组分总量的0.5%-2%,优选0.5%-1.5%。优选活性较高的品种,合适的泡沫稳定剂包括但不限于德国赢创工业集团的B8715、B8736,美国气体与化学品公司的DC2525、DC6070,美国迈图高新材料集团的L-3629、L-3640等。
改性全MDI体系异氰酸酯预聚体的合成方法如下:将MDI体系异氰酸酯加入反应器中升温到50℃,然后加入脱水后聚醚多元醇2,于60-80℃反应4h,即制得异氰酸根(NCO)含量为23%-31wt%的改性全MDI体系异氰酸。MDI体系异氰酸酯优选碳化二亚胺改性液化MDI与MDI-50的混合物,其中碳化二亚胺改性液化MDI与MDI-50的质量比例为50/50~95/5,优选50/50~80/20。其中碳化二亚胺改性MDI优选BASF公司的MM103C或者科思创公司的CD-C产品;MDI-50为4,4’-二苯基甲烷二异氰酸酯(4,4’-MDI):2,4’-二苯基甲烷二异氰酸酯(2,4’-MDI)为50∶50的纯MDI,如科思创公司的0129产品。聚醚多元醇2为两官能度全环氧丙烷、分子量500-10000的聚醚多元醇。
本发明所述的自结皮聚氨酯泡沫可以采用模塑法或自由泡法制备。将A组分原料按计量混合形成A组分,预聚所得的异氰酸酯为B组分。将A、B组分温度控制在20-40℃(优选30±5℃),使A组分与B组分按比例快速搅拌混合倒入模具或杯子中,进行固化,1.5-3min固化完成后从模具或杯子中取出,即可制得高阻燃低气味自结皮泡沫。这种泡沫可广泛应用于方向盘、扶手、机场椅坐垫、浴缸头靠垫等产品。
本发明所述方法简单实用,所得聚氨酯泡沫模塑材料邵氏A硬度为50-85,整体密度为300-600Kg/m3,氧指数大于等于26%,水平燃烧小于D50mm/min,气味≤3级。产品不仅具有高阻燃性,而且还具有良好的环保性能,克服了现有技术自结皮泡沫不能同时兼顾的缺点,满足新客车标准对车用自结皮的要求。
具体实施方式
下述例子是为了更好地说明本发明的实施效果,但本发明的内容不局限于实施例。
“MDI”是“二苯基甲烷二异氰酸酯”的缩写,比如2,4-MDI是指2,4-二苯基甲烷二异氰酸酯,4,4’-MDI是指4,4’-二苯基甲烷二异氰酸酯;“NCO”是“异氰酸根”的缩写;术语“官能度”是指在聚合反应中,单体分子能够参加缩合聚合反应的官能团数量。本文中所述的“份”,除特别说明外,皆指“质量份”;所述的百分含量,除特别说明外,皆指质量百分含量。
氧指数是指泡沫能维持燃烧所需的最低氧浓度,其大小直接反应了泡沫是否容易燃烧;水平燃烧指水平地夹持材料试样一端,自由端暴露在规定气体的火焰上,通过测定线性燃烧速度来评价燃烧性能的试验方法。
气味测试:将试样裁成5cm×5cm×2cm大小,放入事先准备好的1L容积的干净玻璃瓶中,旋紧瓶盖;在(80±2)℃烘箱中放置2h后打开瓶盖,由5位鉴定人员通过瓶口逸出的气体判断泡沫的气味等级。鉴定标准:气味评判标准分为1~6级,同时也会出现介于两种评判等级之间的情况,泡沫的气味等级取5位鉴定人员测试值的算数平均值。
评分1无气味
评分2有气味,但无干扰性气味
评分3有明显气味,但无干扰性气味
评分4有干扰性气味
评分5有强烈干扰性气味
评分6有不能忍受的气味
实施例配方中使用的原料:
聚醚多元醇1:甘油起始,三官能度,环氧丙烷接枝,环氧乙烷封端多元醇,羟值30-35mgKOH/g,端伯羟基含量大于70%的聚氧化丙烯醚三元醇;
聚合物多元醇:甘油起始,三官能度,羟值18-22mgKOH/g,固含量45%,苯乙烯、丙烯腈接枝的高活性聚合物多元醇;
曼尼希多元醇:四官能度,羟值330mgKOH/g;
PIPA多元醇:将500g TEP-551c(天津三石化产品)、35g三乙醇胺、50gPEG-400混合加入三口烧瓶中,搅拌10min。将醇胺指数1.0的TEP-551c与TDI混合物124g缓慢加入三口烧瓶中,在30-50℃下反应1~3h,即得固含量为13.7%的PIPA多元醇。
扩链剂:乙二醇、二乙二醇;
发泡剂:水;
反应型催化剂:反应型催化剂如美国气体公司的PC-17、DABCO T产品,亨斯曼公司的DPA、ZR-70产品。
无挥发性催化剂:(2-羟基丙基)三甲基甲酸铵(TMR-2);
泡沫稳定剂:美国气体公司的DC2525产品;
阻燃剂:磷酸三(2-氯丙基)酯(TCPP);
碳化二亚胺改性液化MDI:BASF公司的MM103C产品或者科思创公司的CD-C产品;
聚醚多元醇2:DL-4000(二官能度,羟值28mgKOH/g,全环氧丙烷接枝的聚醚多元醇)。
B组分1:NCO含量28.0%的异氰酸酯预聚体,制作方法如下:将液化MDI600g、400gMDI-50依次加入反应器升温到50℃,然后将100g聚醚多元醇DL-4000加入反应器中,于60-80℃反应4h,即制得异氰酸根(NCO)含量为28%的改性全MDI体系异氰酸。
B组分2:NCO含量26.5%的异氰酸酯预聚体,制作方法如下:将液化MDI600g、400gMDI-50依次加入三口烧瓶升温到50℃,然后将157g聚醚多元醇DL-4000加入反应器中,于60-80℃反应4h,即制得异氰酸根(NCO)含量为26.5%的改性全MDI体系异氰酸。
表1为实施例与对比例配方。
高阻燃低气味自结皮聚氨酯泡沫材料的制备:按表1所示质量将聚醚、发泡剂、硅油、催化剂等各原料按比例配制成A组分,按比例称取B组分,A、B组分温度控制在25℃左右,将异氰酸酯倒入聚醚组分中,用机械搅拌高速搅拌6-8s,快速将物料倒入尺寸200mm×200mm×10mm的铝模中,在模具内熟化2min后脱模,获得自结皮泡沫制品。泡沫制品放置72小时后,测试物性。按下述标准或方法进行测试:
表1实施例E1-E6和对比例C1-C2原料配方和泡沫性能
从表1看出,本发明在环保和阻燃方面可以满足营运客车行业的新要求。
本发明的高阻燃水发泡自结皮聚氨酯可以推广至其他相近领域的应用,比如用于制造家具的扶手、机场座椅、浴缸靠垫等,这对于本领域的技术人员来说是显而易见的。因此,在不违背本发明的思想下,本领域技术人员可以在此基础上对本发明做出的各种改动或者修改,同样应属于本发明的范围。
Claims (9)
1.一种无阻燃剂高阻燃低气味全水自结皮聚氨酯泡沫,原料由A、B两组分组成,按质量份计包括:
A组分:
聚醚多元醇1:50~70;
聚合物多元醇:0~20;
曼尼希聚醚多元醇:3~10;
PIPA多元醇:10~30;
扩链剂:5~12;
反应型催化剂:1.5~3.5
无挥发性催化剂:0.01~0.2;
水:0.1~1.0;
泡沫稳定剂:0.5~2;
其中聚醚多元醇1+聚合物多元醇+曼尼希聚醚多元醇+PIPA多元醇=100;
组分B是异氰酸根(NCO)含量为23%~31wt%的改性全MDI体系异氰酸酯预聚体;
所述的聚醚多元醇1为甘油起始、三官能度、分子量为3000~10000、端伯羟基含量大于70%的高活性聚醚多元醇;
所述无挥发性催化剂选自脂肪族羧酸的金属盐、有机碱性化合物或季铵盐类及其混合物;
组分A和组分B按100∶40~100的质量比配合使用。
2.根据权利要求1所述的无阻燃剂高阻燃低气味全水自结皮聚氨酯泡沫,其特征是所述的聚合物多元醇为三官能度、固含量25%~45%、苯乙烯、丙烯腈接枝的高活性聚合物多元醇;所述的曼尼希聚醚多元醇官能度为4~5,羟值为300~550mgKOH/g;所述的PIPA多元醇是由多元醇胺和异氰酸酯在聚醚多元醇1中反应生成的悬浮分散体,固含量10%~20%,黏度3000~6000mPa.s。
3.根据权利要求2所述的无阻燃剂高阻燃低气味全水自结皮聚氨酯泡沫,其特征是所述的PIPA多元醇是由如下方法制备:在反应器中按质量比100/4~10/5~10加入聚醚多元醇1、多元醇胺和分散剂,混合;加入聚醚多元醇1和异氰酸酯质量比为2/1~1/2的混合物,在30-50℃下反应1~3h,即可得产物。
4.根据权利要求3所述的无阻燃剂高阻燃低气味全水自结皮聚氨酯泡沫,其特征是多元醇胺为三乙醇胺;分散剂为聚乙二醇200或聚乙二醇400;异氰酸酯为甲苯二异氰酸酯或者二苯基甲烷二异氰酸酯及其改性物。
5.根据权利要求1所述的无阻燃剂高阻燃低气味全水自结皮聚氨酯泡沫,其特征是MDI体系异氰酸酯是指二苯基甲烷二异氰酸酯(MDI)单体、氨基甲酸酯改性MDI、碳化二亚胺改性MDI两种及以上的混合物,官能度为2.0-2.7。
6.根据权利要求1所述的无阻燃剂高阻燃低气味全水自结皮聚氨酯泡沫,其特征是改性全MDI体系异氰酸酯预聚体由以下方法制备:将MDI体系异氰酸酯加入反应器中升温到50℃,然后加入脱水后聚醚多元醇2,于60-80℃反应4h,即制得异氰酸根(NCO)含量为23%-31wt%的改性全MDI体系异氰酸;聚醚多元醇2为两官能度全环氧丙烷,分子量500-10000的聚醚多元醇。
7.根据权利要求6所述的无阻燃剂高阻燃低气味全水自结皮聚氨酯泡沫,其特征是MDI体系异氰酸酯是指碳化二亚胺改性液化MDI与MDI-50的混合物,其中碳化二亚胺改性液化MDI与MDI-50的质量比例为50/50~95/5。
8.根据权利要求1~7之一所述的无阻燃剂高阻燃低气味全水自结皮聚氨酯泡沫,其特征是所述扩链剂选自乙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇或二乙二醇及其混合物;反应性催化剂选自N’N-二甲基乙醇胺、三甲基羟乙基乙二胺、三甲基羟乙基丙二胺、四甲基二丙基三胺、2-(2-二甲胺基-乙氧基)-乙醇、N,N,N’-三甲基-N’-羟乙基双氨乙基醚或双(二甲氨基)-2-丙醇及其混合物;所述泡沫稳定剂是指含Si-C键的硅油。
9.一种制备权利要求1~8之一所述的无阻燃剂高阻燃低气味全水自结皮聚氨酯泡沫的方法:将A组分原料按计量混合形成A组分,预聚所得的异氰酸酯为B组分;A、B组分温度控制在20-40℃,将A、B组分按比例快速搅拌混合倒入模具或杯子中固化,1.5-3min后从模具或杯子中取出,即得。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010331248.1A CN111607061B (zh) | 2020-04-15 | 2020-04-15 | 一种无阻燃剂高阻燃低气味全水自结皮聚氨酯泡沫及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010331248.1A CN111607061B (zh) | 2020-04-15 | 2020-04-15 | 一种无阻燃剂高阻燃低气味全水自结皮聚氨酯泡沫及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111607061A CN111607061A (zh) | 2020-09-01 |
CN111607061B true CN111607061B (zh) | 2022-04-15 |
Family
ID=72194815
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010331248.1A Active CN111607061B (zh) | 2020-04-15 | 2020-04-15 | 一种无阻燃剂高阻燃低气味全水自结皮聚氨酯泡沫及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111607061B (zh) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113388084B (zh) * | 2021-07-05 | 2022-10-14 | 黎明化工研究设计院有限责任公司 | 一种pip灌泡头枕用环保组合物及其制备方法和应用 |
CN114716638B (zh) * | 2022-04-14 | 2023-12-01 | 佳化化学科技发展(上海)有限公司 | 一种聚氨酯自结皮泡沫及其制备方法和应用 |
CN115141350A (zh) * | 2022-08-23 | 2022-10-04 | 安徽大学 | 一种环保阻燃的汽车发动机罩盖用半硬质聚氨酯泡沫塑料及其制备方法 |
CN116284654A (zh) * | 2023-01-02 | 2023-06-23 | 黎明化工研究设计院有限责任公司 | 一种低气味、快速脱模自结皮聚氨酯泡沫组合物及其制备方法 |
CN116789925A (zh) * | 2023-07-07 | 2023-09-22 | 江苏米尔化工科技有限公司 | 一种无甲醛低气味聚氨酯泡沫材料及其制备方法 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4371629A (en) * | 1980-09-29 | 1983-02-01 | Texaco Inc. | Preparation of a semiflexible energy management polyether polyurethane foam using as a crosslinker-surfactant an ethylene oxide adduct of a Mannich condensate prepared from the reaction of nonyl phenol, diethanolamine and formaldehyde |
EP0970134B1 (en) * | 1997-03-25 | 2001-09-05 | Huntsman International Llc | Process for preparing flexible polyurethane foam |
US6825238B2 (en) * | 2003-01-29 | 2004-11-30 | Air Products And Chemicals, Inc. | Low acid organometallic catalyst for the production of flexible, semi-flexible and rigid polyurethane foams |
CN101597370B (zh) * | 2008-06-06 | 2011-04-13 | 上海合达聚合物科技有限公司 | 一种水发泡自结皮聚氨酯组合物、其制备方法及应用 |
CN102875771B (zh) * | 2012-09-30 | 2014-06-11 | 滕州市华海新型保温材料有限公司 | 阻燃型连续玻璃纤维增强聚氨酯枕木材料用组合聚醚及其制备方法 |
CN103073986B (zh) * | 2012-12-19 | 2015-03-11 | 万华化学(宁波)容威聚氨酯有限公司 | 一种高级阻燃聚氨酯喷涂泡沫材料及其制备方法 |
CN103694434B (zh) * | 2013-12-16 | 2016-02-10 | 中国林业科学研究院林产化学工业研究所 | 用于聚氨酯泡沫的无卤反应型阻燃剂及其制备方法和应用 |
CN103965247A (zh) * | 2014-05-23 | 2014-08-06 | 厦门大学 | 一种含磷含氮结构型阻燃多元醇及其制备方法与应用 |
CN104119498B (zh) * | 2014-07-21 | 2017-05-10 | 万华节能科技集团股份有限公司 | 一种阻燃聚氨酯喷涂硬质泡沫塑料 |
WO2016061068A1 (en) * | 2014-10-13 | 2016-04-21 | Air Products And Chemicals, Inc. | Polyurethane catalysts from sulfur based salts |
CN107922579B (zh) * | 2015-06-01 | 2021-06-08 | 赢创运营有限公司 | 用于聚氨酯应用的反应性胺催化剂 |
CN107857865B (zh) * | 2017-11-20 | 2021-07-16 | 郑州精益达汽车零部件有限公司 | 一种汽车座椅用全水环保阻燃型胀气记忆聚氨酯泡沫及其制备方法 |
-
2020
- 2020-04-15 CN CN202010331248.1A patent/CN111607061B/zh active Active
Also Published As
Publication number | Publication date |
---|---|
CN111607061A (zh) | 2020-09-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111607061B (zh) | 一种无阻燃剂高阻燃低气味全水自结皮聚氨酯泡沫及其制备方法 | |
EP1770117B1 (en) | Silanol-Functionalized compounds for the preparation of polyurethane foams | |
CA2567850C (en) | Process for preparing polyurethane foams having reduced voc emissions | |
CN107857865B (zh) | 一种汽车座椅用全水环保阻燃型胀气记忆聚氨酯泡沫及其制备方法 | |
US4980388A (en) | Use of carbon dioxide adducts as blowing agents in cellular and microcellular polyureas | |
JP2001151841A (ja) | 開放セルポリウレタン軟質フォームを製造するためのシリコーン界面活性剤 | |
CN111718462B (zh) | 一种汽车方向盘用自结皮聚氨酯泡沫快速脱模组合物及其制备方法 | |
CA2302191A1 (en) | Low density flexible polyurethane foams | |
US5106884A (en) | Flexible polyurea foams having controlled load bearing qualities | |
CN107266656B (zh) | 用于制造聚氨酯泡沫及其模塑制品的组合物 | |
US5084486A (en) | Reactive feed stream to replace inert blowing agent feed stream in a polyurethane foam process | |
WO2019030071A1 (en) | POLYMERIC COMPONENTS WITH ISOCYANATE FUNCTION AND POLYURETHANE ARTICLES FORMED FROM RECYCLED POLYURETHANE ARTICLES AND ASSOCIATED METHODS OF FORMING THESE POLYURETHANE ARTICLES | |
AU704491B2 (en) | Polyol formulation for producing latex-like flexible polyurethane foam | |
JP2613441B2 (ja) | 発泡ポリウレタンの製法 | |
TW512152B (en) | Flame-resistant HR cold-cure moulded foam with reduced smoke intensity and toxicity | |
JP4104537B2 (ja) | ポリウレタンフォームの製造法 | |
CN111454419B (zh) | 一种全水发泡半硬质pu泡沫 | |
WO2021030055A1 (en) | Polyurethane foam | |
JP4178390B2 (ja) | 硬質ポリウレタンフォーム成形用組成物、及び該組成物を用いた硬質ポリウレタンフォームの製造方法 | |
US6822013B1 (en) | Polyol combination | |
CN116284654A (zh) | 一种低气味、快速脱模自结皮聚氨酯泡沫组合物及其制备方法 | |
JPH06507935A (ja) | 改良された物理持性を有するポリウレタン | |
JPH01225611A (ja) | 発泡合成樹脂の製造方法 | |
JPH01225612A (ja) | 発泡合成樹脂の製造方法 | |
CN114409870A (zh) | 基于改性异氰酸酯制得的高阻燃交通工具座椅用聚氨酯泡沫材料 |
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 |