WO2019100357A1 - 一种耐高温的聚氨酯热熔胶的制备方法 - Google Patents

一种耐高温的聚氨酯热熔胶的制备方法 Download PDF

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Publication number
WO2019100357A1
WO2019100357A1 PCT/CN2017/113001 CN2017113001W WO2019100357A1 WO 2019100357 A1 WO2019100357 A1 WO 2019100357A1 CN 2017113001 W CN2017113001 W CN 2017113001W WO 2019100357 A1 WO2019100357 A1 WO 2019100357A1
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Prior art keywords
parts
reaction vessel
hot melt
preparation
melt adhesive
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PCT/CN2017/113001
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English (en)
French (fr)
Inventor
姜贵琳
王建斌
陈田安
解海华
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烟台德邦科技有限公司
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Priority to PCT/CN2017/113001 priority Critical patent/WO2019100357A1/zh
Priority to EP17933109.5A priority patent/EP3696205B1/en
Priority to US16/763,558 priority patent/US10781345B1/en
Priority to JP2020545407A priority patent/JP6917097B2/ja
Publication of WO2019100357A1 publication Critical patent/WO2019100357A1/zh

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Definitions

  • the invention relates to a preparation method of a polyurethane hot melt adhesive, in particular to a preparation method of a high temperature resistant polyurethane hot melt adhesive, belonging to the technical field of chemical adhesives.
  • PUR adhesive has the advantages of fast bonding, non-toxicity, simple process and good bonding strength and flexibility, it is widely used in textile, wood furniture, lamp, home appliance and consumer electronics.
  • the conventional polyurethane hot melt adhesive has a serious drawback, that is, poor high temperature resistance.
  • the traditional PUR is made up of polyester or polyether diol and diisocyanate.
  • the molecular structure is basically linear, and its structure contains many soft segments, which determines that the traditional PUR cannot be applied to 100. Temperature resistance requirements above °C.
  • the invention aims at the shortcoming of the high temperature resistance of the existing polyurethane hot melt adhesive, and provides a preparation method of the high temperature resistant polyurethane hot melt adhesive.
  • a method for preparing a high temperature resistant polyurethane hot melt adhesive, in parts by weight, comprising the following steps:
  • step 2) 1 to 5 parts of the pre-water-removing diluent and 7 to 20 parts of the tackifying resin are added to the reaction vessel after the completion of the step 1), the inert atmosphere is maintained in the reaction vessel, and then the temperature is raised to 100 to 120 ° C. After stirring, the materials are uniformly mixed, and then 25 to 45 parts of the pre-water-removed crystalline polyester polyol and 6 to 20 parts of the polyether polyol are added thereto, and the reaction is kept under stirring for 0.5 to 2 hours;
  • step 3 after adding to the reactor after the end of step 2), 15 to 35 parts of the pre-water-removed polyetheramine, maintaining an inert atmosphere in the reaction vessel, and reacting at 115 to 140 ° C for 1 to 2 hours under stirring;
  • step 3 Adding 0.01 to 0.2 parts of the catalyst to the reaction vessel after the end of step 3), removing the bubbles by vacuuming, discharging, and sealing, and obtaining.
  • the isocyanate we use has a high aromatic ring content and good heat resistance.
  • the functionality of the isocyanate used is greater than 2.5, and the functionality of the NCO group is reduced to about 2.0 with a silane modifier to form a difunctional NCO group, which is then involved in the chain extension reaction of the polyol.
  • the side chain siloxane undergoes hydrolysis and dealcoholization, and the curing reaction progresses to a three-dimensional network structure, thereby forming a high-density cross-linked network structure and improving heat resistance.
  • the crystalline polyester polyol used by us has a special molecular functional structure, and its reactive functional group is polymerized with isocyanate, which effectively improves the crystallinity of the hot melt adhesive and improves the bonding performance of the hot melt adhesive.
  • the polyol used in the present invention is composed of a crystalline polyester polyol mixed with an amorphous polyether polyol, and the amount of the crystalline polyester polyol can be increased to increase the initial strength, but the crystallinity is too large, and the rubber layer is Density will hinder the ingress of water vapor and slow down the curing rate; increasing the amount of non-crystalline polyol can extend the opening time, but the initial strength will decrease. Therefore, it is necessary to balance the amount of various polyols in order to obtain good performance.
  • the present invention can also be improved as follows.
  • the isocyanate is polymethylene polyphenyl polyisocyanate (PAPI), triphenylmethane triisocyanate (TTI), 2,4-toluene diisocyanate trimer, hexamethylene diisocyanate (HDI) trimer Any one of them is preferably one or more of PM-200 commercially available from Yantai Wanhua Co., Ltd., MR-200 commercially available from Mitsui Chemicals Co., Ltd., and HDI trimer Desmodur N3300 commercially available from Bayer AG, Germany. Kind of mixture.
  • PAPI polymethylene polyphenyl polyisocyanate
  • TTI triphenylmethane triisocyanate
  • HDI trimer Desmodur N3300 commercially available from Bayer AG, Germany.
  • PM-200 commercially available from Yantai Wanhua Co., Ltd.
  • MR-200 commercially available from Mitsui Chemicals Co., Ltd.
  • the silane modifier is mercaptopropyltriethoxysilane (KH-580), mercaptopropyltrimethoxysilane (KH-590), and ethylenediaminopropyltrimethoxysilane (KH-792). , a compound of one or more of N-phenyl- ⁇ -aminopropyltrimethoxysilane (Y-9669).
  • polyetheramine is any one of a polyether diamine containing a terminal amino group, a polyether diamine having a polytetramethylene ether glycol PTMEG as a main chain, and preferably a Hunts, USA.
  • the crystalline polyester polyol is polytetrahydrofuran diol or at least one of adipic acid and 1,4-butanediol, ethylene glycol, diethylene glycol, and 1,6-hexanediol.
  • Alcohol polymerized product In one of the above, the polytetrahydrofuran diol is PTMEG-200, PTMEG-300, and the polyhexamethylene adipate diol is preferably XCP-3000H commercially available from Asahikawa Chemical Co., Ltd., said polycap.
  • the diacid-1,4-butanediol ester diol is preferably POL-356T commercially available from Qingdao Xinyutian Chemical Co., Ltd.
  • polyether polyol is one of polyoxypropylene diol having a molecular weight of 400 to 700 g/mol, and polyoxypropylene-ethylene oxide diol, preferably a commercially available Bluestar Dongda DL-400. , Tianjin Petrochemical PPG204, PPG206, PPG207 one or a mixture of two.
  • the catalyst is dibutyltin dilaurate, stannous octoate, lead octoate, triethylamine, triethylenediamine, cobalt octoate, zinc naphthenate, tetraisobutyl titanate or dimorpholinyldiethyl One of the ethers (DMDEE).
  • the chemical water scavenger is a compound of one or more of p-toluenesulfonyl hydrazide isocyanate (PTSI), triethyl orthoformate, and oxazolidine compound.
  • the diluent is diisopropylnaphthalene, preferably Ruetasolv DI from Lutger, Germany.
  • the tackifying resin is a compound of one or more of a phenolic resin, a terpene resin, a polymerized rosin, an acrylic resin, and a petroleum resin, and preferably an octyl phenolic resin TXN-203 of the Shanxi Research Institute of Chemical Industry, Germany Tegel's petroleum resin Novares LA700P, 2602 xylene resin of Shandong Shengquan Chemical.
  • the polyurethane hot melt adhesive obtained by the method of the invention has the following advantages in addition to excellent high temperature resistance: (1) good toughness and bonding strength, can overcome the influence of the difference of expansion coefficient between different materials, stress Uniform distribution, thus bonding different types of substrates; (2) Excellent resistance to cold and thermal shock: cold shock box at -40 ° C to +100 ° C, no cracking after 24 cycles; (3) low viscosity and easy operation : 100 ° C melt viscosity is lower than 7Pa.S; (4) good thermal stability: 120 ° C heating for 5 hours viscosity increase value is less than 30%; (5) good anti-drop performance: roller drop test, 1000 times without cracking; (6) The final bonding strength is high: the bonding strength between PC and PET is higher than 10.0 MPa.
  • the raw materials in the following examples are all parts by weight; the polyfunctional isocyanate PM-200 is commercially available from Yantai Wanhua; the Desmodur N3300 is commercially available from Bayer, Germany; and the polyfunctional isocyanate MR-200 is commercially available from Mitsui Chemicals, Inc.
  • Polyether polyol PPG204 and polyether polyol PPG207 are commercially available from Tianjin Petrochemical No.3 Factory; polyester polyol POL-356T is commercially available from Qingdao Xinyutian Chemical Co., Ltd.; polyester polyol XCP-3000H is from Jiangsu Xuchuan Chemical Company.
  • Polyetheramine D230 is commercially available from Huntsman, USA.
  • Polyetheramine EC301 is commercially available from BASF, Germany, and polyetheramine Versalink.
  • P-250 is commercially available from American Air Chemical Company.
  • step 3 Add 0.2 parts of the catalyst triethylamine to the reaction vessel after the end of step 3), and evacuate the bubbles by vacuuming. Discharge, sealed packaging, and made high temperature resistant polyurethane hot melt adhesive.
  • step 3 Add 25 parts of pre-water-removed polyetheramine D230 to the reaction vessel after the end of step 2), the reactor is filled with nitrogen gas, stirred at 700 rpm, and kept at 130 ° C for 1.5 hours. ;
  • step 4 0.11 part of the catalyst dimorpholinyl diethyl ether DMDEE was added to the reaction vessel after the end of step 3), and the bubbles were removed by vacuum, discharged, and sealed to obtain a high temperature resistant polyurethane hot melt adhesive.
  • step 3 To the reactor after the end of step 3), 0.01 part of dibutyltin dilaurate was added, and the bubbles were removed by vacuum, discharged, and sealed to obtain a high temperature resistant polyurethane hot melt adhesive.
  • step 3 To the reactor after the end of step 3), 0.2 parts of lead octoate was added, and the bubbles were removed by vacuum, discharged, and sealed to obtain a high temperature resistant polyurethane hot melt adhesive.
  • step 3 Add 25 parts of pre-water-removed polyetheramine D230 to the reaction vessel after the end of step 2), the reactor is filled with nitrogen gas, stirred at 700 rpm, and kept at 130 ° C for 1.5 hours. ;
  • step 4 0.11 part of the catalyst tetraisobutyl titanate was added to the reaction vessel after the end of step 3), and the bubbles were removed by vacuum, discharged, and sealed to obtain a high temperature resistant polyurethane hot melt adhesive.
  • the formulation and production process of the traditional moisture-cured PUR adhesive are as follows: 20 parts of polyether polyol PPG210, 45 parts of polyester polyol POL-356T are added to the reaction kettle, and stirred at 500 rpm, at 120 ° C Under vacuum dehydration for 2 hours, the vacuum was maintained at -0.09 MPa. Then, it was cooled to 80 ° C, and 15 parts of 4,4' diphenylmethane diisocyanate MDI was added thereto with stirring, and then the temperature was slowly raised, and the temperature was controlled at 80 ° C while being purged with nitrogen for 2.5 hours.
  • the heating system is first turned on, the temperature is set to 100-130 ° C, the glue is applied with a glue gun, the glue coating process is completed within the open time, and then tested according to the regulations. High temperature resistance, cold shock resistance, drop resistance, bond strength and moisture and heat aging resistance were tested after sizing for 7 days at room temperature. Generally, the highest strength can be achieved by curing at room temperature for 7 days.
  • the ratio of the instantaneous shear strength at 90 °C to the value of the normal temperature shear strength is used to calculate the high temperature strength retention rate, and the high temperature strength retention rate is used to characterize the high temperature resistance of the rubber. This is the core consideration of the present invention. index.
  • the flexibility, bonding strength, cold shock resistance, and drop resistance toughness of the present invention are respectively determined from tensile strength, elongation at break, shear strength at room temperature, drum drop test, and thermal shock resistance of Table 2, respectively. The performance values were characterized; salt spray resistance and wet heat aging resistance were characterized by the values of the test items in Table 3.
  • the performance test analysis of Examples 1 to 3 and Comparative Examples listed in Tables 1 to 3 shows that the polyurethane hot melt adhesive prepared by the present invention not only has good high temperature resistance, but also has excellent resistance. Thermal shock resistance, drop resistance, good bond strength and salt spray resistance to damp heat aging. Therefore, the polyurethane hot melt adhesive provided by the invention can meet the bonding demand of a specific high temperature environment, and has important practical significance for improving the core competitiveness of the domestic polyurethane hot melt adhesive.

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Abstract

本发明涉及一种耐高温的聚氨酯热熔胶的制备方法，其制备的聚氨酯热熔胶为单组分湿气固化聚氨酯胶粘剂，所制得的热熔胶不仅具有良好的耐高温性能，同时具有优异的抗冷热冲击性、抗跌落韧性以及良好的粘接强度和耐盐雾耐湿热老化性能，对提升国产聚氨酯热熔胶的核心竞争力具有重要的现实意义。

Description

一种耐高温的聚氨酯热熔胶的制备方法 技术领域
本发明涉及一种聚氨酯热熔胶的制备方法，尤其涉及一种耐高温的聚氨酯热熔胶的制备方法，属于化学胶黏剂技术领域。
背景技术
近年来，随着人们对环境保护的愈发重视，环境友好型产品越来越受到普遍的关注。环境友好型胶黏剂因具有无毒无害、无环境污染、使用方便等优势而逐渐成为未来胶黏剂的发展趋势。反应型聚氨酯热熔胶(PUR)作为一种高性能环保型胶黏剂，适应了国内外对环境越来越重视的需要。
由于PUR胶具有粘接快、无毒、工艺简单，又有较好的粘接强度与柔韧性的优点，因此，在纺织、木工家具、车灯、家电及消费电子等方面获得广泛应用。
但是传统的聚氨酯热熔胶存在一个严重的缺陷，即耐高温性能差。我们知道，传统PUR是由聚酯或聚醚二元醇与二异氰酸酯反应而成，分子结构基本是线型的，而且其结构中含有的柔性链段多，因此决定了传统PUR不能适用于100℃以上的耐温粘接要求。
随着经济的发展和科技的进步，市场对耐高温型的PUR的需求日益迫切，因此，研发一种耐高温的PUR粘接材料，成为该领域的迫切需求。
研发耐高温的粘接材料在国外发展迅猛，但在我国起步比较晚，研发机构较少，主要包括烟台德邦科技有限公司等。因此耐高温型PUR的研发，市场潜力巨大。
发明内容
本发明针对现有聚氨酯热熔胶耐高温性能差的缺点，提供一种耐高温的聚氨酯热熔胶的制备方法。
本发明解决上述技术问题的技术方案如下：
一种耐高温的聚氨酯热熔胶的制备方法，按重量份数计，包括如下步骤：
1)将平均官能度大于2.5的异氰酸酯10～20份加入到反应釜中，反应釜内保持惰性氛围，后升温至60～80℃，后向反应釜中加入硅烷改性剂0.3～3.0份，于搅拌条件下保温反应1～3小时，制得平均官能度为1.5～2.0的异氰酸酯衍生物，后向反应釜中加入化学除水剂0.005～0.04份混合均匀；
2)将经预除水处理的稀释剂1～5份、增粘树脂7～20份加入到步骤1)结束后的反应釜中，反应釜内保持惰性氛围，后升温至100～120℃，搅拌使物料混合均匀后向其中加入经预除水处理的结晶性聚酯多元醇25～45份、聚醚多元醇6～20份，于搅拌条件下保温反应0.5～2小时；
3)后向步骤2)结束后的反应釜中加入预除水处理的聚醚胺15～35份，反应釜内保持惰性氛围，搅拌条件下于115～140℃下反应1～2小时；
4)向步骤3)结束后的反应釜中加入催化剂0.01～0.2份，抽真空脱除气泡，出料，密闭包装，即得。
本发明方法所得聚氨酯热熔胶耐高温性能好的原理解释如下：
1)我们采用的异氰酸酯的芳环含量高，耐热性能好。采用的异氰酸酯的官能度大于2.5，用硅烷改性剂将其NCO基团的官能度降至2.0左右,形成双官能结构的NCO基团，后参与多元醇的扩链反应。当粘接固化后，侧链的硅氧烷发生水解脱醇，使固化反应向三维网状结构发展，从而形成高密度的交联网状结构，提高耐热性能。
2)采用聚醚胺与NCO基团扩链反应，生成脲键的耐热性能高于氨酯键，同时也有效地提高了产品的柔韧性、最终粘接强度和抗冲击性。
3)采用特定配比的聚醚多元醇和聚醚胺，在分子链中引入醚键，有效地提高了产品的柔韧性和抗冲击性，避免因分子结构刚性太强而引起开裂、耐冲击性能差等弊端，造成产品脆性太大。
4)我们采用的结晶性聚酯多元醇，具有特殊的分子官能结构，其活性官能团与异氰酸酯发生聚合反应，有效地改善了热熔胶的结晶性，提高了热熔胶的粘接性能。
5)本发明中采用的多元醇由结晶性聚酯多元醇与非结晶性的聚醚多元醇混合组成，增加结晶性聚酯多元醇的量可以提高初始强度，但是结晶性过大，胶层致密，会妨碍水汽进入，使固化速度减慢；增加非结晶性多元醇的量可以延长开放时间，但初始强度会降低。因此需要平衡各种多元醇的用量，以期获得良好的性能。
在上述技术方案的基础上，本发明还可以做如下改进。
进一步，所述异氰酸酯为多亚甲基多苯基多异氰酸酯(PAPI)、三苯基甲烷三异氰酸酯(TTI)、2,4-甲苯二异氰酸酯三聚体、六甲撑二异氰酸酯(HDI)三聚体中的任意一种，优选为烟台万华股份有限公司市售的PM-200、日本三井化学公司市售的MR-200和德国拜耳公司市售的HDI三聚体Desmodur N3300中的一种或几种的混合物。
进一步，所述硅烷改性剂为巯丙基三乙氧基硅烷(KH-580)、巯丙基三甲氧基硅烷(KH-590)、乙二氨基丙基三甲氧基硅烷(KH-792)、N-苯基-γ-氨丙基三甲氧基硅烷(Y-9669)中的一种或几种的复配。
进一步，所述聚醚胺为含有端氨基的共聚醚二胺、聚四亚甲基醚二醇PTMEG为主链的芳氨端基的聚醚二胺中的任意一种，优选为美国亨斯迈的D230，德国巴斯夫的EC301，美国空气化学的Versalink P-250中的一种。
进一步，所述结晶性聚酯多元醇为聚四氢呋喃二醇或者己二酸与1,4-丁二醇、乙二醇、二甘醇、1,6-己二醇中的至少一种二元醇聚合而成的产物 中的一种，所述的聚四氢呋喃二醇为PTMEG-200，PTMEG-300，所述聚己二酸己二醇酯二醇优选为江苏旭川化学公司市售的XCP-3000H，所述聚己二酸-1，4-丁二醇酯二醇优选为青岛新宇田化工有限公司市售的POL-356T。
进一步，所述聚醚多元醇为分子量介于400～700g/mol的聚氧化丙烯二醇、聚氧化丙烯-氧化乙烯二醇中的一种，优选为市售的蓝星东大的DL-400，天津石化PPG204、PPG206、PPG207中的一种或两种的混合物。
进一步，所述催化剂为二月桂酸二丁基锡、辛酸亚锡、辛酸铅、三乙胺、三亚乙基二胺、辛酸钴、环烷酸锌、钛酸四异丁酯或二吗啉基二乙基醚(DMDEE)中的一种。
进一步，所述化学除水剂为对甲基苯磺酰肼异氰酸酯(PTSI)、原甲酸三乙酯、噁唑烷化合物中的一种或几种的复配。
进一步，所述稀释剂为二异丙基萘，优选德国吕特格公司Ruetasolv DI。
进一步，所述增粘树脂为酚醛树脂、萜烯树脂、聚合松香、丙烯酸树脂、石油树脂中的一种或几种的复配，优选山西省化工研究院辛基酚醛树脂TXN-203,德国吕特格公司的石油树脂Novares LA700P，山东圣泉化工的2602二甲苯树脂。
本发明的方法所得的聚氨酯热熔胶除了具有优异的耐高温性能外，还具有以下几大优势：(1)良好的韧性和粘接强度，可以克服不同材料间的膨胀系数差异的影响，应力分布均匀，从而粘接不同类型的基材；(2)优异的抗冷热冲击性：在-40℃至+100℃冷热冲击箱，24循环后无开裂现象；(3)粘度低易操作：100℃熔融黏度低于7Pa.S；(4)热稳定性好：120℃加热5小时粘度升高值低于30％；(5)抗跌落性能好：滚筒跌落测试，1000次无开裂；(6)最终粘接强度高：PC同PET的材料粘接强度高于10.0MPa。
具体实施方式
以下结合实例对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
以下实施例中的原料均为重量份数；多官能度异氰酸酯PM-200为烟台万华公司市售；Desmodur N3300为德国拜耳公司市售；多官能度异氰酸酯MR-200为日本三井化学公司市售；聚醚多元醇PPG204、聚醚多元醇PPG207为天津石化三厂市售；聚酯多元醇POL-356T为青岛新宇田化工有限公司市售；聚酯多元醇XCP-3000H为江苏旭川化学公司市售，其羟值为35～39mgKOH/g，酸值为0.1～0.8mgKOH/g；聚醚胺D230为美国亨斯迈公司市售，聚醚胺EC301为德国巴斯夫公司市售，聚醚胺Versalink P-250为美国空气化学公司市售。
实施例1：
1)将多官能度异氰酸酯PM-200计15份加入反应釜中，在氮气保护的条件下升温至80℃，向反应釜中加入硅烷改性剂巯丙基三甲氧基硅烷(KH-590)计3.0份，以700转/分钟的转速搅拌，保温反应1小时，制得平均官能度在1.7的异氰酸酯衍生物。反应结束后，向反应釜中加入原甲酸三乙酯0.04份混合均匀；
2)向反应釜中加入预除水处理的二异丙基萘(DI)1份、2602二甲苯甲醛树脂13份，于氮气保护条件下升温至120℃，搅拌使物料混合均匀，后向其中加入预除水处理的结晶性聚酯多元醇PTMEG-300计25份、聚醚多元醇PPG-204计20份，以400转/分钟的转速搅拌下保温反应1小时20分钟；
3)向步骤2)结束后的反应釜中加入预除水处理的聚醚胺Versalink P-250计35份，反应釜内充氮气保护，以900转/分钟的转速搅拌，保持在115℃下反应1小时；
4)向步骤3)结束后的反应釜中加入催化剂三乙胺0.2份，抽真空脱除气泡， 出料，密闭包装，制得耐高温的聚氨酯热熔胶。
实施例2：
1)将多官能度异氰酸酯Desmodur N3300计10份加入反应釜中，在氮气保护的条件下升温至70℃，向反应釜中加入硅烷改性剂N-苯基-γ-氨丙基三甲氧基硅烷(Y-9669)计1.6份，以550转/分钟的转速搅拌，保温反应3小时，制得平均官能度在1.85的异氰酸酯衍生物。反应结束后，向反应釜中加入除水剂对甲基苯磺酰肼异氰酸酯PTSI0.03份混合均匀；
2)向反应釜中加入预除水处理的二异丙基萘(DI)5份、酚醛树脂TXN-203计7份，于氮气保护条件下升温至110℃，搅拌使物料混合均匀，后向其中加入预除水处理的结晶性聚酯多元醇XCP-3000H计36份、聚醚多元醇DL-400计14份，以600转/分钟的转速搅拌下保温反应2小时；
3)向步骤2)结束后的反应釜中加入预除水处理的聚醚胺D230计25份，反应釜内充氮气保护，以700转/分钟的转速搅拌，保持在130℃下反应1.5小时；
4)向步骤3)结束后的反应釜中加入催化剂二吗啉基二乙基醚DMDEE 0.11份，抽真空脱除气泡，出料，密闭包装，制得耐高温的聚氨酯热熔胶。
实施例3：
1)将多官能度异氰酸酯MR-200计20份加入反应釜中，在氮气保护的条件下升温至60℃，向反应釜中加入硅烷改性剂乙二氨基丙基三甲氧基硅KH-792计0.3份，以400转/分钟的转速搅拌，保温反应2小时，制得平均官能度在2.0的异氰酸酯衍生物。反应结束后，向反应釜中加入噁唑烷类除水剂0.005份混合均匀；
2)向反应釜中加入预除水处理的二异丙基萘(DI)3份、石油树脂LA700P计20份，于氮气保护条件下升温至100℃，搅拌使物料混合均匀，后向其中加入预除水处理的结晶性聚酯多元醇POL-356T计45份、聚醚多元醇PPG-207 计6份，以700转/分钟的转速搅拌下保温反应0.5小时；
3)向步骤2)结束后的反应釜中加入预除水处理的聚醚胺EC-301计15份，反应釜内充氮气保护，以1100转/分钟的转速搅拌，保持在140℃下反应2小时；
4)向步骤3)结束后的反应釜中加入催化剂二月桂酸二丁基锡0.01份，抽真空脱除气泡，出料，密闭包装，制得耐高温的聚氨酯热熔胶。
实施例4：
1)将多官能度异氰酸酯PM-200计15份加入反应釜中，在氮气保护的条件下升温至80℃，向反应釜中加入硅烷改性剂巯丙基三甲氧基硅烷(KH-590)计3.0份，以700转/分钟的转速搅拌，保温反应1小时，制得平均官能度在1.7的异氰酸酯衍生物。反应结束后，向反应釜中加入原甲酸三乙酯0.04份混合均匀；
2)向反应釜中加入预除水处理的二异丙基萘(DI)1份、聚合松香13份，于氮气保护条件下升温至120℃，搅拌使物料混合均匀，后向其中加入预除水处理的结晶性聚酯多元醇PTMEG-300计25份、聚醚多元醇PPG-204计20份，以400转/分钟的转速搅拌下保温反应1小时20分钟；
3)向步骤2)结束后的反应釜中加入预除水处理的聚醚胺Versalink P-250计35份，反应釜内充氮气保护，以900转/分钟的转速搅拌，保持在115℃下反应1小时；
4)向步骤3)结束后的反应釜中加入催化剂辛酸铅0.2份，抽真空脱除气泡，出料，密闭包装，制得耐高温的聚氨酯热熔胶。
实施例5：
1)将多官能度异氰酸酯Desmodur N3300计10份加入反应釜中，在氮气保护的条件下升温至70℃，向反应釜中加入硅烷改性剂N-苯基-γ-氨丙基三甲氧基硅烷(Y-9669)计1.6份，以550转/分钟的转速搅拌，保温反应3 小时，制得平均官能度在1.85的异氰酸酯衍生物。反应结束后，向反应釜中加入除水剂对甲基苯磺酰肼异氰酸酯PTSI0.03份混合均匀；
2)向反应釜中加入预除水处理的二异丙基萘(DI)5份、丙烯酸树脂计7份，于氮气保护条件下升温至110℃，搅拌使物料混合均匀，后向其中加入预除水处理的结晶性聚酯多元醇XCP-3000H计36份、聚醚多元醇DL-400计14份，以600转/分钟的转速搅拌下保温反应2小时；
3)向步骤2)结束后的反应釜中加入预除水处理的聚醚胺D230计25份，反应釜内充氮气保护，以700转/分钟的转速搅拌，保持在130℃下反应1.5小时；
4)向步骤3)结束后的反应釜中加入催化剂钛酸四异丁酯0.11份，抽真空脱除气泡，出料，密闭包装，制得耐高温的聚氨酯热熔胶。
对比实施例：
传统湿气固化PUR胶的配方及生产工艺如下：将聚醚多元醇PPG210计20份，聚酯多元醇POL-356T计45份加入反应釜中，以500转/分钟的转速搅拌，于120℃下真空脱水2小时，真空度保持在-0.09MPa。然后冷却到80℃，边搅拌遍加入4,4'二苯基甲烷二异氰酸酯MDI计15份，然后缓慢升温，控制温度在80℃，同时充氮气保护，反应2.5小时。待取样分析NCO％含量达到设计值后，再加入萜烯增粘树脂15份，催化剂二月桂酸二丁基锡0.1份和三乙烯二胺0.4份。在温度为110℃的条件下抽真空至无气泡，然后出料，密闭包装，放置待用。此胶在工艺使用时，先开启加热系统，温度设置为100～130℃，用胶枪涂胶，涂胶过程确保在开放时间内完成，再按规定进行测试。耐高温性能、抗冷热冲击性能、抗跌落韧性、粘接强度及耐湿热老化性能，均由施胶后室温放置7天后测试。一般室温固化7天可以达到最高强度。
为了验证本发明的方法所得聚氨酯热熔胶的技术效果，我们将实施例1～3所得的聚氨酯热熔胶与对比实施例制备的聚氨酯热熔胶按胶粘剂试验 标准进行常温剪切强度、90℃即时剪切强度、拉伸强度、断裂伸长率、抗冷热冲击性能、滚筒跌落测试、盐雾测试和双85老化测试，数据结果如表1、表2、表3所示。
其中用90℃即时剪切强度的数值与常温剪切强度的数值之比，计算出高温强度保持率，根据高温强度保持率的数值大小来表征胶的耐高温性能，这是本发明的核心考量指标。另外，本发明所述的柔韧性、粘接强度、抗冷热冲击性能、抗跌落韧性分别由表2的拉伸强度、断裂伸长率、常温剪切强度、滚筒跌落测试、抗冷热冲击性能的数值进行表征；耐盐雾和耐湿热老化性能由表3检测项目的数值进行表征。
表1 实施例1～3与对比实施例所得产品的耐高温性能测试对比
Figure PCTCN2017113001-appb-000001
表2 实施例1～3与对比实施例所得产品的机械性能测试对照
Figure PCTCN2017113001-appb-000002
表3 实施例1～3与对比实施例所得产品的耐水耐老化性能测试对比
Figure PCTCN2017113001-appb-000003
总之，由表1～表3中列出的实施例1～3与对比实施例的性能测试分析表明，本发明制备的聚氨酯热熔胶不仅具有良好的耐高温性能，同时该胶具有优异的抗冷热冲击性、抗跌落韧性以及良好的粘接强度和耐盐雾耐湿热老化性能。所以，本发明所提供的聚氨酯热熔胶，能够满足特定高温环境的粘接需求，对提升国产聚氨酯热熔胶的核心竞争力具有重要的现实意义。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种耐高温的聚氨酯热熔胶的制备方法，其特征在于，按重量份数计，包括如下步骤：
    1)将平均官能度大于2.5的异氰酸酯10～20份加入到反应釜中，反应釜内保持惰性氛围，升温至60～80℃，后向反应釜中加入硅烷改性剂0.3～3.0份，于搅拌条件下保温反应1～3小时，制得平均官能度为1.5～2.0的异氰酸酯衍生物，后向反应釜中加入化学除水剂0.005～0.04份混合均匀；
    2)将经预除水处理的稀释剂1～5份、增粘树脂7～20份加入到步骤1)结束后的反应釜中，反应釜内保持惰性氛围，后升温至100～120℃，搅拌使物料混合均匀后向其中加入经预除水处理的结晶性聚酯多元醇25～45份、聚醚多元醇6～20份，于搅拌条件下保温反应0.5～2小时；
    3)后向步骤2)结束后的反应釜中加入预除水处理的聚醚胺15～35份，反应釜内保持惰性氛围，搅拌条件下于115～140℃下反应1～2小时；
    4)向步骤3)结束后的反应釜中加入催化剂0.01～0.2份，抽真空脱除气泡，出料，密闭包装，即得。
  2. 根据权利要求1所述的制备方法，其特征在于，所述异氰酸酯为多亚甲基多苯基多异氰酸酯、三苯基甲烷三异氰酸酯、2,4-甲苯二异氰酸酯三聚体、六甲撑二异氰酸酯三聚体中的任意一种。
  3. 根据权利要求1所述的制备方法，其特征在于，所述硅烷改性剂为巯丙基三乙氧基硅烷、巯丙基三甲氧基硅烷、乙二氨基丙基三甲氧基硅烷、N-苯基-γ-氨丙基三甲氧基硅烷中的一种或几种的复配。
  4. 根据权利要求1所述的制备方法，其特征在于，所述聚醚胺为含有端氨基的共聚醚二胺、聚四亚甲基醚二醇PTMEG为主链的芳氨端基的聚醚二胺中的任意一种。
  5. 根据权利要求1所述的制备方法，其特征在于，所述结晶性聚酯多元醇为聚四氢呋喃二醇或者己二酸与1,4-丁二醇、乙二醇、二甘醇、1,6-己二醇中的至少一种二元醇聚合而成的产物中的一种。
  6. 根据权利要求1所述的制备方法，其特征在于，所述聚醚多元醇为分子量介于400～700g/mo l的聚氧化丙烯二醇、聚氧化丙烯-氧化乙烯二醇中的一种。
  7. 根据权利要求1所述的制备方法，其特征在于，所述催化剂为二月桂酸二丁基锡、辛酸亚锡、辛酸铅、三乙胺、三亚乙基二胺、辛酸钴、环烷酸锌、钛酸四异丁酯或二吗啉基二乙基醚中的一种。
  8. 根据权利要求1-7中任一项所述的制备方法，其特征在于，所述化学除水剂为对甲基苯磺酰肼异氰酸酯、原甲酸三乙酯、噁唑烷化合物中的一种或几种的复配。
  9. 根据权利要求1-7中任一项所述的制备方法，其特征在于，所述稀释剂为二异丙基萘。
  10. 根据权利要求1-7中任一项所述的制备方法，其特征在于，所述增粘树脂为酚醛树脂、萜烯树脂、聚合松香、丙烯酸树脂、石油树脂中的一种或几种的复配。
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