WO2020124666A1 - 光响应性粘结胶及其制备方法 - Google Patents

光响应性粘结胶及其制备方法 Download PDF

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WO2020124666A1
WO2020124666A1 PCT/CN2018/124514 CN2018124514W WO2020124666A1 WO 2020124666 A1 WO2020124666 A1 WO 2020124666A1 CN 2018124514 W CN2018124514 W CN 2018124514W WO 2020124666 A1 WO2020124666 A1 WO 2020124666A1
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light
resin
parts
responsive
component
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PCT/CN2018/124514
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English (en)
French (fr)
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宋骏
梁锦宁
陈建军
陈精华
黄恒超
付子恩
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广州市白云化工实业有限公司
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Publication of WO2020124666A1 publication Critical patent/WO2020124666A1/zh

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/34Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/36Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • 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
    • C08G18/62Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6283Polymers of nitrogen containing compounds having carbon-to-carbon double bonds

Definitions

  • the invention relates to the technical field of adhesive glue, in particular to a light-responsive adhesive glue and a preparation method thereof.
  • the recovery process of the power lithium battery can be roughly divided into two steps: disassembly from the battery pack to the battery cell in steps; a single battery cell then recovers the material inside the battery cell by a specific method. Because there is structural glue or potting glue between the cells for protection and adhesion, this layer of glue needs to be destroyed when the battery is disassembled to obtain a single cell.
  • the traditional glue used for bonding the power battery structure will form a glue layer with high cohesive energy between the cells after curing, which is often difficult to be destroyed.
  • the adhesive glue can ensure the strong adhesive effect of the glue in daily use, and at the same time, the short-term irradiation of the ultraviolet lamp can reduce the adhesive strength, and is applied to the packaging of the power battery cell, which is beneficial to the recycling of the power battery.
  • a light-responsive adhesive including component A and component B:
  • the component A is prepared from raw materials including the following components:
  • the light-responsive resin is made by copolymerizing acrylic monomer with azophenyl group and acrylic monomer with hydroxyl group;
  • the component B is prepared from raw materials including the following components:
  • the azophenyl group-bearing acrylic monomer has the structure shown in formula (I):
  • the hydroxyl-bearing acrylic monomer is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate.
  • the method for preparing the light-responsive resin includes the following steps:
  • the weight ratio of the azophenyl acrylic monomer to the hydroxyl-bearing acrylic monomer is 80-120:1.
  • the light-responsive resin has the structure shown in Formula II:
  • the hydroxy resin is one or more of polyether polyol, polyester polyol, modified polyol, and other short-chain polyols, and the viscosity is between 750 and 20000 cps.
  • the solid content is 100%.
  • the hydroxy resin is a polyether polyol, a polyester polyol, and a modified polyol with a weight ratio of 1 to 3:1 to 3:1.
  • the isocyanate resin is one or more of HDI, HDI prepolymer, polymeric MDI, liquefied MDI, and MDI prepolymer, and the viscosity is between 100 and 30000 cps.
  • the flame retardant A and the flame retardant B are independently selected from phosphate, aluminum hydroxide, zinc borate, antimony trioxide, polyphosphate, dimethyl methyl phosphate, FR -109, one or more of TCPP, Weston 430, ExoIit OP550.
  • the flame retardant A is aluminum hydroxide; the flame retardant B is TCPP.
  • the water removing agent A and the water removing agent B are independently selected from one or more of molecular sieve powder, calcium chloride, aluminum sulfate, and oxazolidine.
  • the water removing agent A is molecular sieve powder; the water removing agent B is oxazolidine.
  • the catalyst is one or more of organotin catalysts and tertiary amine catalysts.
  • the organotin catalyst is one or more of stannous octoate and dibutyltin dilaurate; the tertiary amine catalyst is one of triethylenediamine and triethanolamine Or more.
  • the viscosity of the component A is from 8000 to 100,000 cps; the viscosity of the component B is from 100 to 20,000 cps.
  • the volume ratio of the A component and the B component is 1 to 5:1.
  • the auxiliary agent is selected from one or more of diluents, pigments, anti-settling agents, defoamers, dispersants, and leveling agents. Can be routinely selected according to processing needs.
  • the invention also provides a method for preparing the light-responsive adhesive, including the following steps:
  • the isocyanic resin, the water removing agent B and the flame retardant B are mixed, stirred and defoamed.
  • the present invention also provides a light-responsive resin having the structure shown in Formula II:
  • the invention also provides the application of the light-responsive resin in preparing the adhesive.
  • the light-responsive adhesive of the present invention introduces azophenyl groups into the polyurethane adhesive system by adopting specific light-responsive resins under the condition of reasonable compatibility of various components, and utilizes azophenyl groups in ultraviolet light
  • the cis-trans isomerization of the photo changes the physical properties of the glue layer, making the polyurethane adhesive light responsive, and can be easily removed by short light when needed, while also ensuring the adhesive properties of the polyurethane adhesive itself, which can be used in power
  • the bonding of the battery cells in the battery can not only ensure the safety of the power battery but also improve the efficiency of disassembly and recycling after the battery is scrapped in the future, which not only benefits the healthy development of the power battery industry, but also promotes the progress of the power battery recycling industry.
  • the light-responsive adhesive described in the present invention has excellent bonding strength after curing (the curing temperature is between 25°C and 80°C), the adhesive strength of the aluminum plate is greater than 9 MPa, the PC adhesive strength is greater than 7 MPa, and the PET adhesive strength is greater than 9 MPa.
  • the flammability is UL-94V0, the density is 1.05 to 1.45, and the solid content is 90 to 100%.
  • the use of easily dispersed solid flame retardant material aluminum hydroxide (flame retardant A) and low viscosity liquid flame retardant TCPP (flame retardant B) can better adapt to the polyurethane system without causing foaming. And the flame retardant effect is excellent.
  • the molecular sieve powder (water removing agent A) with high water removal efficiency and good dispersibility is supplemented by a small amount of liquid water removing agent oxazolidine (water removing agent B). This choice not only ensures good dispersion of the filler, but also optimizes Flame retardant and water removal performance of the system.
  • This example is the preparation of photoresponsive resin, the steps are as follows:
  • Step 1 Add 50 parts of triethylamine and 50 parts of formic acid to the reaction device placed in an ice water bath, stir for 1 hour and set aside. Add 100 parts of nitrophenol, 100 parts of aniline, 200 parts of lead powder to the reaction kettle, and dissolve in 500 parts of methanol. Nitrogen was introduced and 100 parts of triethylamine formate was added under the greenhouse to react for 3 hours. The insoluble material was removed by filtration, and the filtrate was concentrated under reduced pressure. The concentrated solution was successively used with ether and saturated brine. Wash with distilled water. The organic layer was extracted with ether and dried with a desiccant for 8 hours. After filtration, the filtrate was distilled under reduced pressure. The dark red product obtained was dried in vacuum for another 2 hours. The yield is 85%.
  • Step 2 Take 100 parts of the above synthesized product, 120 parts of 12-bromo-1-dodecanol and 150 parts of potassium bicarbonate dissolved in 500 parts of N,N-dimethylformamide, and react at 90°C 24 hours. The solution is then filtered and dried in vacuo. Recrystallize with ethanol. The yield is 89%.
  • Step 3 Dissolve 100 parts of the product of Step 2 and 34 parts of triethylamine in 100 parts of dichloromethane. A solution of 38 parts of acryloyl chloride in methylene chloride was slowly added to the ice water bath. After the dropwise addition, the reaction was carried out at 25°C for 24 hours. After the reaction is completed, the solution is concentrated under reduced pressure. The concentrated solution is washed with hydrochloric acid solution, saturated sodium bicarbonate solution and common salt solution, and this process is repeated twice. Vacuum drying yielded the product. The product yield was 82%.
  • Step 4 Dissolve 1000 parts of the product obtained in Step 3, 5 parts of chain transfer agent and 1 part of azobisisobutyronitrile in 1200 parts of N,N-dimethylformamide. After the reaction device was sealed, it was subjected to three cycles of freezing-evacuation-thawing-nitrogen ventilation to ensure that the reaction proceeded under anhydrous and anaerobic conditions, and then reacted at 80°C for 28 hours. Then, under the protection of nitrogen, a solution of 10 parts of hydroxyethyl acrylate and 0.01 parts of azobisisobutyronitrile in benzene N,N-dimethylformamide was injected and reacted at 80°C for 8 hours. After terminating the reaction, the reaction solution was concentrated under reduced pressure at 100°C to obtain a light-responsive resin. The product yield was 99%.
  • a light-responsive adhesive is prepared by the following steps:
  • the viscosity of the above component A at 25°C is 60,000 cps.
  • MDI prepolymer isocyanate-terminated prepolymer, viscosity of 17000 cps at 25°C
  • oxazolidine 5 parts of oxazolidine
  • TCPP flame retardant 10 parts of TCPP flame retardant
  • the viscosity of the above component B at 25°C is 16500 cps.
  • a light-responsive adhesive is prepared by the following steps:
  • the viscosity of the above component A at 25°C was 56500 cps.
  • the viscosity of the above component B at 25°C is 16000 cps.
  • the preparation of a light-responsive adhesive in this comparative example uses the same raw materials and preparation methods as in Example 3, except that the light-responsive resin is not used, and the correspondingly prepared component A at 25°C
  • the viscosity is 56000cps.
  • the preparation of a light-responsive adhesive in this comparative example uses the same raw materials and preparation methods as in Example 3, with the difference that: the hydrogenated bisphenol A epoxy resin (Stepan EPALLOY 5000) replaces the light-responsiveness Resin.
  • the hardness test method is: GB/T531-1999 Rubber Pocket Hardness Tester Press-in Hardness Test Method;
  • the adhesion test method is: GB/T 13936-1992 vulcanized rubber and metal adhesion tensile shear strength measurement method;
  • the flame retardancy test method is: GB/24267-2009 flame retardant sealant for construction.
  • the light responsiveness test method is as follows:
  • Method 2 Mix the glue of the above Example 3 and Comparative Example 1 and coat it evenly on transparent PVC and PC boards, cure for 168 hours, and determine the tensile shear strength according to GB/T 13936-1992 vulcanized rubber to metal bonding Method: Determine the shear strength before light exposure; place the cured PVC and PC boards in a methylene chloride solvent, irradiate for 8 minutes under ultraviolet light (100w) with a wavelength of 365nm, and stretch according to GB 7124-86 adhesive Test method of shear strength Determination of shear strength after illumination.
  • Table 1 It can be seen from Table 1 that the introduction of light-responsive resins does not cause changes in the hardness and flame retardant properties of polyurethane adhesives.
  • Tables 2 and 3 show that the urethane adhesive introduced with photo-initiated resin has undergone tremendous changes in the physical properties of the adhesive under ultraviolet light. Specifically, under ultraviolet light irradiation, the hardness and shear strength of the polyurethane adhesive are significantly reduced, which can be easily removed, and compared with the comparative example 1 which does not introduce a light-responsive resin, the polyurethane adhesive is combined with ultraviolet light in a short time. There is no obvious physical property change, which is difficult to remove.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

本发明涉及一种光响应性粘结胶及其制备方法。所述光响应性粘结胶包括A组分和B组分:所述A组分由包括如下组分的原料制备而成:羟基树脂100份、光响应性树脂50~90份、阻燃剂A10~150份、催化剂0.01~5份、除水剂A1~5份、助剂1~10份;其中,所述光响应性树脂由带有偶氮苯基的丙烯酸单体与带有羟基的丙烯酸单体共聚制成;所述B组分由包括如下组分的原料制备而成:异氰酸树脂100份、除水剂B1~8份、阻燃剂B10~15份。该粘结胶能够在日常使用中保证胶水强的粘结作用,同时通过紫外灯的短暂照射可以降低粘接强度,应用于动力电池电芯的封装,有利于动力电池的回收再利用。

Description

光响应性粘结胶及其制备方法 技术领域
本发明涉及粘结胶技术领域,特别是涉及一种光响应性粘结胶及其制备方法。
背景技术
近些年,全球动力锂电池产业由于新能源汽车的爆发迎来高速发展。但是在动力锂电池市场快速扩张的同时,报废动力电池的回收问题也逐渐突显。有关数据显示:在2018年,仅中国地区,累计废旧动力锂电池就超过12GWH、报废量超过17万吨。随着时间的推移,动力锂电池回收的压力将会越来越大。
现阶段,动力锂电池的回收过程大致可以分为两个步骤:从电池包分步拆解到电芯;单个电芯再通过特定的方法回收电芯里面的材料。由于电芯之间存在起保护和粘接作用的结构胶或灌封胶,拆解电池时需要破坏这层胶水才能获取单个电芯。而传统的用于动力电池结构粘接的胶水在固化完全后会在电芯之间形成内聚能很高的胶水层,往往很难被破坏。
发明内容
基于此,有必要提供一种光响应性粘结胶。该粘结胶能够在日常使用中保证胶水强的粘结作用,同时通过紫外灯的短暂照射可以降低粘接强度,应用于动力电池电芯的封装,有利于动力电池的回收再利用。
一种光响应性粘结胶,包括A组分和B组分:
以重量份数计,所述A组分由包括如下组分的原料制备而成:
Figure PCTCN2018124514-appb-000001
Figure PCTCN2018124514-appb-000002
其中,所述光响应性树脂由带有偶氮苯基的丙烯酸单体与带有羟基的丙烯酸单体共聚制成;
以重量份数计,所述B组分由包括如下组分的原料制备而成:
异氰酸树脂         100份
除水剂B            1~8份
阻燃剂B            10~15份。
在其中一个实施例中,所述带有偶氮苯基的丙烯酸单体具有如式(I)所示结构:
Figure PCTCN2018124514-appb-000003
所述带有羟基的丙烯酸单体为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯中的一种或多种。
在其中一个实施例中,所述光响应性树脂的制备方法,包括如下步骤:
将所述带有偶氮苯基的丙烯酸单体与链转移剂、引发剂混合,以溶剂溶解;惰性气体保护下,于75~85℃反应25~30小时;然后再在惰性气体保护下,加入所述带有羟基的丙烯酸单体和引发剂,于75~85℃反应5~10小时;终止反应后将反应液减压浓缩,即得所述光响应性树脂;其中所述带有偶氮苯基的丙烯酸 单体与带有羟基的丙烯酸单体的重量比为80~120:1。
在其中一个实施例中,所述光响应性树脂具有式II所示结构:
Figure PCTCN2018124514-appb-000004
其中,n=10~50,m=10~30。
在其中一个实施例中,所述的羟基树脂为聚醚多元醇、聚酯多元醇、改性多元醇、其他短链多元醇中的一种或者多种混合,粘度在750~20000cps之间,固含量为100%。
在其中一个实施例中,所述羟基树脂为重量比为1~3:1~3:1的聚醚多元醇、聚酯多元醇和改性多元醇。
在其中一个实施例中,所述的异氰酸树脂为HDI、HDI预聚体、聚合MDI、液化MDI、MDI预聚体中的一种或者多种混合,粘度在100~30000cps。
在其中一个实施例中,所述阻燃剂A、阻燃剂B分别独立的选自磷酸酯、氢氧化铝、硼酸锌、三氧化二锑、聚磷酸酯、甲基磷酸二甲酯、FR-109、TCPP、Weston 430、ExoIit OP550中的一种或几种。
在其中一个实施例中,所述阻燃剂A为氢氧化铝;所述阻燃剂B为TCPP。
在其中一个实施例中,所述除水剂A、除水剂B分别独立的选自分子筛粉末、氯化钙、硫酸铝、噁唑烷中的一种或几种。
在其中一个实施例中,所述除水剂A为分子筛粉末;所述除水剂B为噁唑 烷。
在其中一个实施例中,所述催化剂为有机锡类催化剂、叔胺类催化剂中的一种或多种。
在其中一个实施例中,所述有机锡类催化剂为辛酸亚锡、二月桂酸二丁基锡中的一种或多种;所述叔胺类催化剂为三亚乙基二按、三乙醇胺中的一种或多种。
在其中一个实施例中,所述A组分粘度在8000~100000cps;所述B组分粘度在100~20000cps。
在其中一个实施例中,所述A组分和B组分的体积比为1~5:1。
在其中一个实施例中,所述助剂选自稀释剂、颜料、防沉剂、消泡剂、分散剂、流平剂中的一种或多种。可根据加工需要进行常规选用。
本发明还提供所述的光响应性粘结胶的制备方法,包括如下步骤:
A组份的制备:
将所述羟基树脂、阻燃剂A、除水剂A混合,搅拌;
所得混合物中加入所述光响应性树脂和催化剂,搅拌,脱泡,即可;
B组份的制备:
将所述异氰酸树脂、除水剂B和阻燃剂B混合,搅拌、脱泡,即可。
本发明还提供一种具有如式II所示结构的光响应性树脂:
Figure PCTCN2018124514-appb-000005
其中,n=10~50,m=10~30。
本发明还提供所述的光响应性树脂在制备粘结胶中的应用。
本发明原理及优点如下:
传统的聚氨酯胶在固化之后很难改变其物理性质,因此难以兼顾日常使用中的粘结性与拆除时的便利性。本发明的光响应性粘结胶,在合理配伍各组分的情况下,通过采用特定的光响应性树脂,将偶氮苯基团引入到聚氨酯胶体系,利用偶氮苯基团在紫外灯光照下的顺反异构转换改变胶水层的物性,使聚氨酯胶具有光响应性,在需要时通过短暂的光照即可便利的拆除,同时还能够保证聚氨酯胶本身粘接性能,可运用于动力电池中电芯的粘接,既可以保证动力电池的安全性又能提高未来电池报废后的拆解回收效率,不但有利于动力电池产业的健康发展,更能促进动力电池回收行业的进步。
本发明所述的光响应性粘结胶固化(固化温度在25℃到80℃)后粘结强度优异,铝板粘接力大于9MPa,PC粘接力大于7MPa,PET粘接力大于9MPa,阻燃性为UL-94V0,密度为1.05~1.45,固含量90~100%。
进一步地,采用易分散的固体阻燃材料氢氧化铝(阻燃剂A)与低粘度液体阻燃剂TCPP(阻燃剂B)相配合,能够更好的适应聚氨酯体系,不引起发泡,且阻燃效果优异。另外,采用除水效率高且分散性好的分子筛粉末(除水剂A)辅以少量液体除水剂噁唑烷(除水剂B),这样选择既保证填料的分散性好,又优化了体系的阻燃和除水性能。
具体实施方式
以下结合具体实施例对本发明的光响应性粘结胶及其制备方法作进一步详细的说明。
以下实施例中所涉及的份数均指重量份数。
以下实施例中所用试剂均可从市场常规购得。
实施例1
本实施例为光响应性树脂的制备,步骤如下:
Figure PCTCN2018124514-appb-000006
其中,n=10~50,m=10~30。
步骤1:将50份的三乙胺和50份的甲酸加入到置于冰水浴的反应装置中,搅拌1小时后备用。往反应釜中加入100份硝基苯酚、100份苯胺、200份铅粉,溶于500份甲醇中。通入氮气,温室下加入制备好的100份三乙胺甲酸盐反应3小时。过滤除去不溶物,滤液减压浓缩。再将浓缩液依次用乙醚、饱和盐水。蒸馏水洗涤。有机层用乙醚萃取,加入干燥剂干燥8小时。过滤后将滤液减压蒸馏。获得的暗红色产物再真空干燥2小时。产率85%。
步骤2:取100份上述合成的产物,120份的12-溴-1-十二醇和150份的碳酸氢钾溶于500份的N,N-二甲基甲酰胺之中,90℃下反应24小时。之后将溶液 过滤,真空干燥。再用乙醇重结晶。产率89%。
步骤3:取100份步骤2的产物和34份的三乙胺溶于100份二氯甲烷中。在冰水浴中缓慢加入溶有38份丙烯酰氯的二氯甲烷溶液。滴加完毕后,25℃下反应24小时。反应完毕后减压浓缩,浓缩液分别经过盐酸溶液、饱和碳酸氢钠溶液和食盐溶液洗涤,循环此过程两次。真空干燥得到产物。产物收率82%。
步骤4:将1000份步骤3获得的产物,5份的链转移剂和1份的偶氮二异丁腈溶解于1200份的N,N-二甲基甲酰胺中。反应装置密封好后经过三次冷冻-抽真空-解冻-通氮气的循环操作,以保证反应在无水无氧条件下进行,之后在80℃下反应28小时。之后在氮气保护下注入溶解10份丙烯酸羟乙酯和0.01份偶氮二异丁腈的苯N,N-二甲基甲酰胺溶液,再在80℃下反应8小时。终止反应后将反应液在100℃下减压浓缩获得光响应性树脂。产物收率99%。
实施例2
本实施例一种光响应性粘结胶的制备,步骤如下:
A组份的制备:
取100份的羟基树脂(40份聚醚多元醇(巴斯夫sovermol 805,25℃下粘度3500cps)、40份聚酯多元醇(巴斯夫sovermol 818,25℃下粘度750cps)以及20份改性多元醇(斯泰潘PS-1752,25℃下粘度3800cps))、2份助剂(消泡剂BYK-A500)、100份氢氧化铝、5份分子筛粉末加入到反应釜中,常温搅拌20分钟。之后往反应釜中加入实施例1中制备的光响应性树脂50份以及1份的二月桂酸丁基锡。常温下高速搅拌分散1个小时,真空脱泡。
上述A组份在25℃下的粘度为60000cps。
B组份的制备:
取100份MDI预聚体(异氰酸封端的预聚体,25℃下粘度17000cps),5份的噁唑烷,10份TCPP阻燃剂,常温搅拌分散30分钟。之后真空脱泡。
上述B组份在25℃下的粘度为16500cps。
实施例3
本实施例一种光响应性粘结胶的制备,步骤如下:
A组份的制备:
取100份的羟基树脂(40份聚醚多元醇(巴斯夫sovermol 805,25℃下粘度3500cps)、40份聚酯多元醇(巴斯夫sovermol 818,25℃下粘度750cps)以及20份改性多元醇(斯泰潘PS-1752,25℃下粘度3800cps))、2份助剂(消泡剂BYK-A500)、80份氢氧化铝、5份分子筛粉末加入到反应釜中,常温搅拌20分钟。之后往反应釜中加入实施例1中制备的光响应性树脂90份以及1份的二月桂酸丁基锡。常温下高速搅拌分散1个小时,真空脱泡。
上述A组份在25℃下的粘度为56500cps。
B组份的制备:
取100份液化MDI(异氰酸封端的预聚体,25℃下粘度17000cps),5份的噁唑烷,15份TCPP阻燃剂,常温搅拌分散30分钟。之后真空脱泡。
上述B组份在25℃下的粘度为16000cps。
对比例1
本对比例一种光响应性粘结胶的制备,其采用的原料及制备方法同实施例3,区别在于:未采用所述光响应性树脂,相应制得的A组份在25℃下的粘度在56000cps。
对比例2
本对比例一种光响应性粘结胶的制备,其采用的原料及制备方法同实施例3,区别在于:以氢化双酚A环氧树脂(斯泰潘EPALLOY 5000)代所述光响应性树脂。
将所述上述实施例2-3和对比例1-2的A组分和B组分按照体积比混合并温室固化168小时后,测试其性能,具体方法如下:
硬度测试的方法为:GB/T 531-1999橡胶袖珍硬度计压入硬度试验方法;
粘接力测试方法为:GB/T 13936-1992硫化橡胶与金属粘接拉伸剪切强度测定方法;
阻燃性测试方法为:GB/24267-2009建筑用阻燃密封胶。
测试结果如下表1所示:
表1
Figure PCTCN2018124514-appb-000007
光响应性测试方法如下:
方法一;上述实施例3和对比例1-2温室固化168小时之后的胶切割成2mm厚,20mm×20mm的方形胶块,放入二氯甲烷溶剂中。将胶块暴露在波长为365nm的紫外光(100w)下照射8分钟,之后取出胶块测试其硬度;
方法二;将上述实施例3和对比例1的胶混合后均匀涂覆在透明的PVC和PC板上,固化168小时,按GB/T 13936-1992硫化橡胶与金属粘接拉伸剪切强 度测定方法测定光照前的剪切强度测定;将胶固化好的PVC和PC板放置在二氯甲烷溶剂中,在波长为365nm的紫外光(100w)下照射8分钟,按GB 7124-86胶粘剂拉伸剪切强度的测试方法测定光照后的剪切强度测定。
方法一测试结果如下表2所示:
表2
实施例 光照前硬度 光照后硬度
实施例2 92HA 39HA
实施例3 90HA 30HA
对比例1 89HA 87HA
对比例2 86HA 85HA
方法二测试结果如下表3所示:
表3
Figure PCTCN2018124514-appb-000008
由表1可知引入光响应性树脂并不会造成聚氨酯胶硬度粘接性能、阻燃性能等变化。而表2和表3则表明引入光引发树脂的聚氨酯胶在紫外光照的条件下,胶的物性发生的巨大变化。具体的说,在经过紫外光照射下,聚氨酯胶的硬度和剪切强度明显降低,能够方便的去除,而对比没有引入光响应性树脂的对比例1,聚氨酯胶在短时间内紫外光照下并未出现明显的物性变化,难以去除。
以上所述实施例的各技术特征可以进行任意的组合,为使描述简洁,未对上述实施例中的各个技术特征所有可能的组合都进行描述,然而,只要这些技术特征的组合不存在矛盾,都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。因此,本发明专利的保护范围应以所附权利要求为准。

Claims (10)

  1. 一种光响应性粘结胶,其特征在于,包括A组分和B组分:
    以重量份数计,所述A组分由包括如下组分的原料制备而成:
    Figure PCTCN2018124514-appb-100001
    其中,所述光响应性树脂由带有偶氮苯基的丙烯酸单体与带有羟基的丙烯酸单体共聚而成;
    以重量份数计,所述B组分由包括如下组分的原料制备而成:
    异氰酸树脂            100份
    除水剂B               1~8份
    阻燃剂B               10~15份。
  2. 根据权利要求1所述的光响应性粘结胶,其特征在于,所述带有偶氮苯基的丙烯酸单体具有如式(I)所示结构:
    Figure PCTCN2018124514-appb-100002
    所述带有羟基的丙烯酸单体为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯中的一种或多种。
  3. 根据权利要求2所述的光响应性粘结胶,其特征在于,所述光响应性树 脂具有式II所示结构:
    Figure PCTCN2018124514-appb-100003
    其中,n=10~50,m=10~30。
  4. 根据权利要求1所述的光响应性粘结胶,其特征在于,所述的羟基树脂为聚醚多元醇、聚酯多元醇、改性多元醇、1,4-丁二醇、三羟甲基丙烷、1,6-己二醇中的一种或者多种混合,粘度在750~20000cps之间,固含量100%;及/或,
    所述的异氰酸树脂为HDI、HDI预聚体、聚合MDI、液化MDI、MDI预聚体中的一种或者多种混合,粘度在100~30000cps。
  5. 根据权利要求1所述的光响应性粘结胶,其特征在于,所述阻燃剂A、阻燃剂B分别独立的选自磷酸酯、氢氧化铝、硼酸锌、三氧化二锑、聚磷酸酯、甲基磷酸二甲酯、FR-109、TCPP、Weston 430、ExoIit OP550中的一种或几种;及/或,
    所述除水剂A、除水剂B分别独立的选自分子筛粉末、氯化钙、硫酸铝、噁唑烷中的一种或几种;及/或,
    所述催化剂为有机锡类催化剂、叔胺类催化剂中的一种或多种。
  6. 根据权利要求5所述的光响应性粘结胶,其特征在于,所述阻燃剂A为氢氧化铝;所述阻燃剂B为TCPP;及/或,
    所述除水剂A为分子筛粉末;所述除水剂B为噁唑烷。
  7. 根据权利要求1-6任一项所述的光响应性粘结胶,其特征在于,所述A组分粘度在8000~100000cps;所述B组分粘度在100~20000cps。
  8. 权利要求1-7任一项所述的光响应性粘结胶的制备方法,其特征在于,包括如下步骤:
    A组份的制备:
    将所述羟基树脂、阻燃剂A、除水剂A混合,搅拌;
    所得混合物中加入所述光响应性树脂和催化剂,搅拌,脱泡,即可;
    B组份的制备:
    将所述异氰酸树脂、除水剂B和阻燃剂B混合,搅拌、脱泡,即可。
  9. 一种具有如式II所示结构的光响应性树脂:
    Figure PCTCN2018124514-appb-100004
    其中,n=10~50,m=10~30。
  10. 权利要求9所述的光响应性树脂在制备粘结胶中的应用。
PCT/CN2018/124514 2018-12-21 2018-12-27 光响应性粘结胶及其制备方法 WO2020124666A1 (zh)

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