CN1036404C - Polyurethane complementary networks adhesive and its preparing method - Google Patents

Polyurethane complementary networks adhesive and its preparing method Download PDF

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CN1036404C
CN1036404C CN 90103865 CN90103865A CN1036404C CN 1036404 C CN1036404 C CN 1036404C CN 90103865 CN90103865 CN 90103865 CN 90103865 A CN90103865 A CN 90103865A CN 1036404 C CN1036404 C CN 1036404C
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thermoplastic polyurethane
polyurethane elastomer
adhesive
organic
resin
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CN1056701A (en
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曾令培
孙向民
孙长发
胡文阁
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中国兵器工业第五三研究所
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Abstract

本发明公开了一种热塑性聚氨酯弹性体互贯网络胶粘剂。 The present invention discloses a thermoplastic polyurethane elastomer interpenetrating networks adhesives. 它包括由含活性双键的丙烯酸酯类单体、有机异氰酸酯、线性聚酯以及引发剂和催化剂合成而制得的热塑性聚氨酯弹性体和溶剂及其改性剂。 It comprises an acrylate monomer containing an active double bond, an organic isocyanate, a linear polyester and thermoplastic polyurethane elastomer and a solvent modifier and initiator and the catalyst synthesis prepared. 本发明主要用于粘接各种软材料(塑料、人造革、合成革、皮革、橡胶等),可以广泛用于制鞋开业,包装工业,橡胶和塑料制品工业,也可做密封剂,增韧剂。 The present invention is mainly used for bonding a variety of soft materials (plastic, leather, synthetic leather, leather, rubber, etc.), it can be opened widely used in footwear, packaging industry, industrial rubber and plastic products, also can sealants, toughening agents.

Description

聚氨酯互贯网络胶粘剂及制备方法 Interpenetrating network of polyurethane adhesive and method of preparation

本发明是一种聚氨酯互贯网络胶粘剂及制备方法。 The present invention is a polyurethane adhesive and a method for preparing cross-network penetration. 更详细地说,它是以异氰酸酯、聚酯与丙烯酸酯类为主要原料,制备成一种热塑性聚氨酯弹性体互贯网络胶粘剂。 More specifically, it is based on isocyanates, and polyester acrylates as main raw materials, to prepare a thermoplastic polyurethane elastomer interpenetrating networks adhesives. 主要用于粘接各种软材料(例如:塑料、人造革、合成革、皮革、橡胶、纸张等)。 Mainly used for bonding a variety of soft material (e.g.: plastic, leather, synthetic leather, leather, rubber, paper, etc.). 它可以广泛应用于制鞋工业、包装工业、橡胶、塑料制品工业。 It can be widely used in the footwear industry, packaging industry, rubber, plastic products industry. 本发明也可以粘接金属、木材等,也可以做密封剂和塑料的增韧剂。 The present invention may also be bonding metal, wood, etc., may be made of plastic sealant and toughener.

这种热塑性聚氨酯弹性体互贯网络胶粘剂具有固化快、粘接强度高、粘度可以调节、使用方便、贮存稳定性好、价格低等特点。 This thermoplastic polyurethane elastomer interpenetrating network having a fast curing adhesive, high bonding strength, viscosity can be adjusted, easy to use, good storage stability, and low prices.

目前,国内生产的聚氨酯胶粘剂品种、牌号甚多,但是都不能满足制鞋工业的需要,特别是没有一种胶粘剂能够满足注塑鞋、旅游鞋的需要。 At present, the domestic production of polyurethane adhesive variety, grade many, but can not meet the needs of the footwear industry, in particular, none of the adhesive to meet the injection shoes, sneakers required. 注塑鞋、旅游鞋大多是采用人造革、聚氯乙烯、聚氨酯加工而成。 Injection shoes, leather shoes are mostly employed, polyvinyl chloride, polyurethane processing. 目前国内生产的聚氨酯胶粘剂,其一是双组份聚氨酯胶粘剂。 Current domestic production of polyurethane adhesive, one is a two-component polyurethane adhesive. 使用时,需要不断地称量,不断配制胶粘剂,既不适于生产中大量应用,更不适于连续化生产。 In use, the need to continue to weigh constantly formulated adhesives, both suitable for the production of a large number of applications, more suitable for continuous production. 其二是单组份聚氨酯胶粘剂,采用本体聚合方法,粘接强度不高。 The second is a one-component polyurethane adhesive, bulk polymerization method, the bonding strength is not high. 聚氨酯胶粘剂的粘接强度是随反应程度增加、分子量增大而增加的。 Polyurethane adhesive bonding strength with the extent of reaction is increased, increasing the molecular weight increases. 但是本体聚合随反应程度增加,粘度急剧增大,搅拌十分困难,迫使反应中止,造成分子量不能增加到足够大,胶粘剂的粘接强度不高。 However, bulk polymerization increases with the degree of reaction, the viscosity increases sharply, stirring very difficult to force stop the reaction, resulting in the molecular weight can not be increased sufficiently large, the adhesive bonding strength is not high.

另外,由于反应体系粘度大,搅拌困难,体系内各部分的反应温度和反应程度不一致,反应不完全,残留的NCO根较多,严重地影响了胶粘剂的稳定性,贮存期短。 Further, due to the large viscosity of the reaction system, difficult to stir, the reaction temperature of each portion of the inconsistency in the system and the degree of reaction, the reaction is not complete, the residual NCO root more seriously affect the stability of the adhesive, short shelf life. 一般情况下,胶粘剂的贮存期少于六个月。 In general, the adhesive shelf life of less than six months.

之外,反应后期,反应釜内粘度很大,反应的终点难以控制,生产的胶粘剂质量不稳定。 Addition, post reaction, the reaction kettle large viscosity, the end of the reaction is difficult to control the quality of the adhesive unstable production. 又由于反应釜内粘度大,粘釜现象严重,影响热传导,清洗反应釜费工、费力,降低了生产效率。 Also, because the high viscosity reactor, sticky serious reactor, interfere with heat transfer, cleaning reactor of work, effort, reducing production efficiency.

采用溶液法制备聚氨酯胶粘剂,需要使用活性大的特种试剂。 Polyurethane adhesive prepared by solution method, requires the use of special-active agent. 文献USP 3,310,533,DE2149836,DE2515766,EP0007594等,曾披露采用高效催化剂乙酰丙酮铁等和一些活性很大的特种端氨基扩链剂,这些试剂价格都很贵,反应后期还需要减压蒸出原先的溶剂,换用强极性溶剂甲乙酮类。 Document USP 3,310,533, DE2149836, DE2515766, EP0007594, etc., have been disclosed using efficient catalysts such as iron acetylacetonate, and a large number of special active terminal amino chain extender, these agents are very expensive price, need to post reaction was distilled off under reduced pressure original The solvent switch to type strongly polar solvents of methyl ethyl ketone. 不仅提高了成本和设备投资,而且生产效率低。 Not only increases the cost and equipment investment and low productivity. 文献采用一元胺反应除去残留的极少量的NCO根,虽然可以提高产品的稳定性,但是对被粘接材料的表面活性降低了,粘接强度也降低了。 Document monoamine removed using a very small amount of remaining NCO root, increases the stability of the product, but the surfactant is reduced adhesive material, the adhesive strength is reduced.

有文献报导采用压延机将固体端羟基聚酯和固体二异氰酸酯进行混炼,然后加热聚合制得粘接型聚氨酯,其缺点是固体与固体反应,分子碰撞机会少,反应不均匀,分子量也上不去,劳动强度大,生产环境差,不适于生产。 There are literature reports using a calender and the solid was a hydroxyl terminated polyester diisocyanate solid kneaded, and then polymerized by heating to prepare polyurethane adhesive, the drawback is a solid with a solid reaction, less chance of molecular collision, heterogeneous reaction, but also the molecular weight not labor-intensive, poor production environment is not suitable for production.

本发明的目的在于克服上述现有技术的特点,提供一种能够粘接聚氨酯、聚氯乙烯的单组份聚氨酯胶粘剂,使用方便,不用经常称量配比,适用于生产大量应用和连续化生产需要的胶粘剂。 Object of the present invention to overcome the above-described characteristics of the prior art, to provide a polyurethane adhesive, a polyvinyl chloride-component polyurethane adhesive, easy to use, do not always weighed ratio, suitable for producing a large number of applications and continuous production require adhesive.

本发明的另一目的是在于能够提供一种粘接强度高、质量稳定的聚氨酯胶粘剂。 Another object of the present invention is to provide an adhesive of high strength, quality and stability of the polyurethane adhesive. 聚氨酯胶粘剂的粘接强度是随反应程度的增大而增大的。 Polyurethane adhesive bond strength is increased with increase of the degree of reaction. 在一定范围内,分子量增加,粘接强度增大。 Within a certain range, the molecular weight increases, the bonding strength increases. 由于本发明的反应前期,含有活性双键的单体(丙烯酸酯类)起稀释作用,反应体系粘度较低,容易搅拌,反应程度容易控制,生成聚氨酯预聚物和丙烯酸酯类预聚物的混合物以后,在高温下同时完成聚合反应,形成高分子量的聚氨酯中,贯穿着线性丙烯酸酯聚合物,所以本发明具有粘接强度高,质量稳定的优点。 Since the pre-reaction of the present invention, the double bond reactive monomer (acrylate esters) containing from dilution, the lower the viscosity of the reaction system, easily stirred, easy to control the extent of reaction, and to form a polyurethane acrylate prepolymer Prepolymer after the mixture was, at a high temperature while completing the polymerization reaction, a high molecular weight polyurethane is formed throughout the linear acrylate polymer, the present invention has high adhesive strength, quality and stability advantages.

本发明的又一目的是提供一种贮存稳定性好而又不降低其活性和粘接强度的聚氨酯胶粘剂。 A further object of the present invention is to provide one kind of good storage stability without reducing its activity and adhesion strength of polyurethane adhesive. 由于产品中存在极少量活性NCO基,所以保持了胶粘剂的活性。 Since a very small amount of active NCO groups in the product, so that the adhesive remains active. 胶粘剂中添加了特种复合稳定剂,使其又具有长期贮存稳定的特点。 A special adhesive compound stabilizer is added, it also has long-term storage stability characteristics.

为了达到上述目的,本发明的热塑性聚氨酯弹性体互贯网络胶粘剂包括含有有机异氰酸酯活性双键的单体丙烯酸酯类、与线性聚酯生成的聚氨酯弹性体预聚物、引发剂过氧化二异丙基苯、催化剂辛酸亚锡、无机填料气相二氧化硅、有机增粘剂过氯乙烯树脂、溶剂乙酸乙酯以及其它的改进剂。 To achieve the above object, the present invention is a thermoplastic polyurethane elastomer interpenetrating network of the monomer containing an acrylic adhesive comprising an organic isocyanate-reactive double bond, and the resulting linear polyester polyurethane elastomer prepolymer, diisopropyl peroxide initiator benzene, the catalyst stannous octoate, fumed silica inorganic filler, an organic resin tackifier perchlorethylene, ethyl acetate solvent, and other modifiers.

本发明采用的有机异氰酸酯的任何一种及其组合。 The present invention uses an organic isocyanate, and any combination thereof. 例如甲苯二异氰酸酯(纯2.4体或者2.4体与2.6体比例为80∶20或者2.4体与2.6体比例为65∶35)、二苯基甲烷二异氰酸酯、多苯基多次甲基异氰酸酯等。 Such as toluene diisocyanate (pure 2.4 2.6 body or the body and the body is 2.4 to 2.6 ratio of 80:20 or 2.4 member body 65:35), diphenylmethane diisocyanate, polyphenyl isocyanate polymethine.

本发明采用的含活性双键的单体是丙烯酸酯类、甲基丙烯酸低级烷基酯的一种及其组合。 Monomer employed in the present invention containing an active double bond are acrylates, methacrylates and a combination thereof lower alkyl ester. 例如,甲基丙烯酸甲酯、丙烯酸甲酯、苯乙烯、丙烯腈或者甲基丙烯酸等其中的一种及组合。 For example, methyl methacrylate, methyl acrylate, styrene, acrylonitrile or methacrylic acid type and the combination thereof. 其用量是含活性双键单体∶有机异氰酸酯与线性聚酯之和=1∶5~20。 In an amount of activated double bond-containing monomers: an organic polyisocyanate with a linear polyester sum = 1/5 to 20.

本发明采用的线性聚酯是饱和二元酸和二元醇缩聚而得。 Linear polyesters used in the present invention are saturated dibasic acid and a diol obtained by polycondensation. 饱和二元酸可以是己二酸、壬二酸等任何一种及其组合,二元醇可以是一缩二乙二醇、1,4丁二醇等任一种及其组合。 Unsaturated dibasic acid may be any one of adipic acid, azelaic acid, and combinations thereof, may be a diol, diethylene glycol, 1,4-butylene glycol, and any combination thereof. 聚酯的分子量为1000~5000,最好是1000~3000,其用量是NCO基∶OH基=(0.9~1.2)∶1。 Molecular weight polyesters of 1,000 to 5,000, preferably 1,000 to 3,000, in an amount of NCO groups :OH group = (0.9 to 1.2) to 1. 本发明采用的引发剂是在60~160℃能产生活性游历基的任一种引发剂及其组合。 Initiators used in the present invention is 60 ~ 160 ℃ travel any active group capable of producing an initiator, and combinations thereof. 例如有机过氧化物、偶氮化合物等任一种及其组合。 Such as any of organic peroxides, azo compounds and the like and combinations thereof. 引发剂用量是活性双键单体的0.5~5%重量,最好是1~2%重量。 The amount of initiator is 0.5 to 5% by weight of monomer reactive double bonds, preferably 1 to 2% by weight.

本发明采用的催化剂是各种叔胺类、锡、镍、钴、锌盐类化合物的一种及其组合,例如辛酸亚锡。 The catalyst employed in the present invention, a variety of tertiary amines, tin, nickel, cobalt, zinc compounds and combinations thereof, such as stannous octoate. 催化剂用量是反应物总和的0.01~0.1%重量。 The catalyst is used in an amount of 0.01 to 0.1% by weight of the total composition of the reaction.

本发明采用的无机填料是密度小的无机填料的任何一种及其组合。 The inorganic filler used in the present invention is a low density inorganic filler, and any combination thereof. 例如,气相二氧化硅、轻质碳酸钙等任一种及其组合。 For example, any one of fumed silica, precipitated calcium carbonate and the like and combinations thereof.

本发明采用的有机增粘剂是有机树脂或橡胶的任何一种及其组合。 The organic thickener employed in the present invention is any one of and a combination of organic resin or rubber. 例如过氯乙烯树脂、氯丁橡胶、古马龙树脂任何一种及其组合。 For example, vinyl chloride resin, chloroprene rubber, resin ancient Malone any combination thereof.

本发明采用的稳定剂是苯甲酰氯或双马来酰亚胺的任一种及其组合。 Stabilizer of the present invention uses a benzoyl chloride or any of the bismaleimides, and combinations thereof.

本发明采用的溶剂是能溶解聚氨酯树脂各种溶剂的任一种及其组合。 The solvent used in the present invention is capable of dissolving a polyurethane resin according to any of various solvents, and combinations thereof. 例如乙酸乙酯、甲苯、丙酮等任一种及其组合。 Such as any of ethyl acetate, toluene, acetone and the like, and combinations thereof.

另外,本发明可以根据具体的用途,加入其它各种改性剂,例如染料、颜色、润滑剂等。 Further, the present invention according to the specific purpose, the addition of other various modifiers, such as dyes, colors, lubricants and the like.

本发明的目的还可以通过以下措施来达到,即本发明的热塑性聚氨酯弹性体互贯网络胶粘剂的制备方法,包括下列各步骤:(1)线性聚酯树脂的熔融:在装有搅拌器和回流装置的反应器中,依次加入含活性双键单体,甲基丙烯酸甲酯、丙烯酸丁酯和1,4-丁二醇、乙二醇缩聚生成的线性聚酯以及催化剂辛酸亚锡、加热到70℃左右,使线性聚酯完全熔融并搅拌。 Object of the present invention can also be achieved by the following measures, i.e., the thermoplastic polyurethane elastomer of the present invention are interpenetrating network adhesive preparation, comprising the steps of: melt (1) linear polyester resin: equipped with a stirrer and a reflux reactor apparatus sequentially added monomers containing reactive double bonds, methyl methacrylate, butyl acrylate and 1,4-butanediol, linear polyesters and ethylene glycol generated by the polycondensation catalyst stannous octoate, heated to about 70 ℃, the linear polyester completely melted and stirred.

(2)热塑性聚氨酯弹性体预聚物和丙烯酸酯预聚物的制备:在搅拌的条件下,不断加入有机二异氰酸酯,控制温度不超过110℃,有机二异氰酸酯加完之后,在60~110℃条件下,反应30~90分钟,控制NCO基含量小于2.5%重量。 (2) Preparation of thermoplastic polyurethane elastomer prepolymer and acrylate prepolymer: after under stirring, constantly adding an organic diisocyanate, to control the temperature does not exceed 110 deg.] C, an organic diisocyanate addition was completed, the 60 ~ 110 ℃ under the conditions, for 30 to 90 minutes, the control NCO group content of less than 2.5% by weight. 降温到70℃左右,加入游离基引发剂偶氮二异丁腈,在60~80℃条件下,搅拌均匀,反应10~40分钟,停止搅拌,出料,倒入料盘中,冷却后得到白色固体。 Cooled to about 70 ℃, was added to give the free radical initiator azobisisobutyronitrile, at 60 ~ 80 ℃, stir to react for 10 to 40 minutes, stirring was stopped, the material, is poured into trays, cooled white solid.

NCO含量测试方法:参照ASTM D1638标准方法测试。 NCO content Test Method: Standard reference to ASTM D1638 test method.

(3)热塑性聚氨酯弹性体的制备:将盛有白色固体的料盘,放入烘箱中,温度升至130~170℃,加热一小时至五小时,取出料盘,得到的白色或浅黄色固体,即为热塑性聚氨酯弹性体。 (3) Preparation of thermoplastic polyurethane elastomer: The white solid filled tray, placed in an oven, the temperature was raised to 130 ~ 170 ℃, is heated one to five hours, remove the tray, the resulting white or pale yellow solid , that is, the thermoplastic polyurethane elastomer.

(4)热塑性聚氨酯弹性体互贯网络胶粘剂的制备:将热塑性聚氨酯弹性体经炼胶机炼胶至门尼粘度40以下破碎后,放入溶剂乙酸乙酯中,密闭、室温浸泡一天以上,再搅拌3~12小时,使其完全溶解,如有少量未溶物,过滤除去。 Preparation of Adhesive network (4) Thermoplastic polyurethane elastomer interpenetrating: thermoplastic polyurethane elastomer by batch mixing machine to a Mooney viscosity of 40 or less after crushing, taken in ethyl acetate solvent, soaking closed more than a day at room temperature, and then stirred for 3 to 12 hours to completely dissolve, if a small amount of undissolved was removed by filtration. 再加入无机填料气相二氧化硅,有机增粘剂古马龙树脂,稳定剂苯甲酰氯以及其它各种改性剂。 Adding fumed silica inorganic filler, an organic tackifier resin ancient Malone, benzoyl chloride stabilizer and other various modifiers. 这样便得到了本发明的热塑性聚氨酯弹性体互贯网络胶粘剂。 This will give a thermoplastic polyurethane elastomer interpenetrating network of the present invention is an adhesive.

本发明制造的热塑性聚氨酯弹性体互贯网络胶粘剂,外观为白色的或淡黄色的液体。 The present invention is made of thermoplastic polyurethane elastomer interpenetrating networks adhesives, the appearance of white or pale yellow liquid. 常温储存期可达一年以上。 Room temperature storage period of up to one year. 与合成革粘接,180度剥离强度大于20N/cm,都是合成革破坏。 Synthetic leather and adhesive, 180 ° peel strength greater than 20N / cm, synthetic leather are destroyed. 与水龙带表面的粘接强度大于60N/cm。 And the adhesive strength of the surface of the hose is greater than 60N / cm.

本发明制造的热塑性聚氨酯弹性体互贯网络胶粘剂是能够粘接聚氨酯、聚氯乙烯的单组份聚氨酯胶粘剂,使用方便,不用经常称量配比,适于生产大量应用和连续化生产的需要。 The present invention is made of thermoplastic polyurethane elastomer interpenetrating network is capable of bonding a polyurethane adhesives, one-component polyurethane adhesive polyvinylchloride, easy to use, do not always weighed ratio, suitable for producing a large number of applications and require continuous production.

本发明制造的胶粘剂是一种粘接强度高,质量稳定的聚氨酯胶粘剂。 Adhesive manufactured by the present invention is a high bonding strength, quality and stability of polyurethane adhesive. 本发明的反应前期,含有活性双键的单体(丙烯酸酯类等) 起稀释作用,反应体系粘度低,容易搅拌,反应程度容易控制。 The reaction of the present invention early, active double bond-containing monomer (acrylate esters) from the dilution effect, the reaction system of low viscosity, easily stirred, easy to control the extent of reaction. 生成聚氨酯预聚物和丙烯酸酯类预聚物的混合物,在高温下同时完成聚合反应,形成了粘接强度高、质量稳定的聚氨酯胶粘剂。 Generating a mixture of the polyurethane prepolymer and the acrylate prepolymer, at a high temperature while the polymerization reaction is completed, to form a high bonding strength, quality and stability of the polyurethane adhesive.

本发明制造的胶粘剂是一种贮存稳定性好而又不降低活性和粘接强度的聚氨酯胶粘剂。 Adhesives of the present invention produced a good storage stability without decreasing the activity and polyurethane adhesive bonding strength. 由于产品中存在极少量的活性NCO基,保持了胶粘剂的活性。 Due to the presence of very small amounts of active NCO groups of the product, to maintain the activity of the adhesive. 胶粘剂中又添加了特种复合稳定剂,使其又具有长期贮存稳定的特点。 Has added a special adhesive composite stabilizer, it also has long-term storage stability characteristics.

本发明制造的弹性体具有一定的活性和高韧性,与各种热塑性材料有良好的相容性,可以作为高分子材料的增韧剂,各种涂料,密封剂和热熔胶粘剂等。 The present invention is produced elastomers have some activity and high toughness, and various thermoplastic materials have good compatibility, as a toughening agent can be a polymer material, various coatings, adhesives and hot melt sealants.

本发明热塑性聚氨酯弹性体互贯网络胶粘剂实施例如下:实施例1在装有搅拌器和回流冷凝管的三口烧瓶中,依次加入15.5克甲基丙烯酸甲酯、由1,4-丁二醇、乙二醇和己二酸制备的、羟值为35.42,酸值为3.60的端羟基聚酯(牌号SBG型-3,产地无锡县张泾聚氨酯材料厂)287.7克(约0.1MOL),辛酸亚锡0.03克。 The thermoplastic polyurethane elastomers of the invention interpenetrating network embodiment of the adhesive are as follows: Example 1 three-necked flask equipped with a stirrer and a reflux condenser, were added 15.5 g of methyl methacrylate, 1,4-butanediol, preparation of ethylene glycol and adipic acid, hydroxyl value of 35.42, an acid value of 3.60 of a hydroxyl terminated polyester (SBG type designation -3 origin Wuxi County Zhangjing polyurethane materials plant) 287.7 g (about 0.1 mol), stannous octoate 0.03 g. 加热到70℃,使端羟基聚酯完全熔融,并不断搅拌。 It was heated to 70 ℃, so that a hydroxyl terminated polyester completely melted, stirring constantly. 在不断搅拌条件下,加入甲苯二异氰酸酯(TDI)(2.4体与2.6体的重量比为80∶20的混合物)20.9克(约0.12MOL),控制加料速度,使反应温度不超过110℃,加完TDI后,升温、在100~110℃继续反应30分钟,待NCO含量小于2.5%重量,停止加热,温度降至70℃,加入引发剂过氧化苯甲酰0.15克,搅拌均匀,在70~80℃反应30分钟,停止搅拌,倒入料盘中,冷却后得到白色固体。 Under continued stirring, toluene diisocyanate (the TDI) (weight ratio of 2.4 to 2.6 body member 80:20 mixture) 20.9 g (about 0.12 mol), feed speed control, so that the reaction temperature does not exceed 110 deg.] C, was added after TDI, heating, the reaction was continued at 100 ~ 110 ℃ 30 minutes until the NCO content is less than 2.5% by weight, heating was stopped, temperature lowered to 70 ℃, benzoyl peroxide initiator was added 0.15 g, stir at 70 ~ 80 deg.] C for 30 minutes, stirring was stopped, poured into trays, cooled to give a white solid.

NCO含量测试方法:参照ASTM D1638标准方法测试。 NCO content Test Method: Standard reference to ASTM D1638 test method.

将盛有白色固体的料盘,放入烘箱中,温度升至160~170℃,加热一小时,取出料盘,得到的白色固体,即为本发明的热塑性聚氨酯弹性体。 The white solid filled tray, placed in an oven, the temperature was raised to 160 ~ 170 ℃, heated for one hour, remove the tray, a white solid was obtained, that is, the thermoplastic polyurethane elastomer of the present invention. NCO含量0.29%,分子量五万以上。 An NCO content of 0.29%, a molecular weight of more than 50,000.

将热塑性聚氨酯弹性体160克经炼胶机炼胶至门尼粘度40以下破碎后,放入840克溶剂乙酸乙酯中,密闭,室温下浸泡一天后,搅拌4小时,使其完全溶解,若有少量未溶物,可过滤除去。 The thermoplastic polyurethane elastomer 160 g batch after mixing machine to break a Mooney viscosity of 40 or less, 840 g ethyl acetate solvent was placed in a sealed, one day after soaking at room temperature, stirred for 4 hours to completely dissolve, if a small amount of undissolved material, may be removed by filtration. 再加入无机填料气相二氧化硅5.6克,613粉(5%甲基丙烯酸和95%甲基丙烯酸甲酯的二元共聚物,上海制笔化工厂生产)20%氯仿溶液10克,稳定剂苯甲酰氯1.0克,充分搅拌均匀,便可得到热塑性聚氨酯弹性体互贯网络胶粘剂。 Was added 5.6 g fumed silica inorganic filler, (a binary copolymer of methacrylic acid and 5% of 95% methyl methacrylate, Shanghai chemical plant pen) 613 powder 20% chloroform solution of 10 grams benzene stabilizer chloride 1.0 g, fully stirred, to obtain a thermoplastic polyurethane elastomer can be interpenetrating networks adhesives.

上述所得到的热塑性聚氨酯弹性体互贯网络胶粘剂外观为白色的透明液体,常温贮存期可达一年以上,与合成革粘接,180度剥离粘接强度大于20N/cm,合成革被破坏。 The above-obtained thermoplastic polyurethane elastomer interpenetrating network of adhesive is white transparent liquid, room temperature storage period of up to one year, and synthetic leather bonding, 180-degree peel strength greater than 20N / cm, synthetic leather is destroyed. 与水龙带表面的粘接强度大于60N/cm。 And the adhesive strength of the surface of the hose is greater than 60N / cm.

实施例2在装有搅拌器和回流冷凝管的三口烧瓶中,依次加入甲基丙烯酸丁酯21.0克、由1,4-丁二醇、乙二醇和己二酸制备的、羟值52.31,酸值为4.12的羟基聚酯(牌号CMA-244,产地烟台合成革总厂)210.7克(约0.1MOL),辛酸亚锡0.23克,加热到60~70℃,使聚酯完全熔融。 Example 2 A three-necked flask equipped with a stirrer and a reflux condenser, were added 21.0 g of butyl methacrylate, was prepared from 1,4-butanediol, ethylene glycol and adipic acid, hydroxyl value of 52.31, an acid the hydroxyl value of the polyester 4.12 (trademark CMA-244, synthetic leather Yantai plant origin) 210.7 g (about 0.1 mol), 0.23 g of stannous octoate, heated to 60 ~ 70 ℃, the polyester completely melted.

在不断搅拌条件下,加入甲苯二异氰酸酯(TDI)(2.4体与2.6体的重量比为80∶20的混合物)17.4克(0.1MOL),控制加料速度,使反应温度不超过80℃。 Under continued stirring, toluene diisocyanate (the TDI) (2.4 weight body and the body is 2.6 ratio of 80:20) 17.4 g (0.1 mol), feed speed control, the reaction temperature did not exceed 80 ℃. 加完TDI之后,升温,在80~90℃条件下,反应50分钟,停止加热。 After completion of TDI, warmed, at 80 ~ 90 ℃, 50 min heating was stopped. 加入过氧化二异丙基苯(CUP)0.35克,搅拌均匀后,在60~70℃反应40分钟,停止搅拌,出料,倒入料盘中,冷却后得到白色固体。 Diisopropylbenzene peroxide was added (CUP) 0.35 grams, stir for 40 min at 60 ~ 70 ℃, stirring was stopped, the material, is poured into trays, cooled to give a white solid.

将盛有白色固体的料盘放入烘箱中,温度升至140~150℃,加热2小时,取出料盘,得到浅黄色固体,即为热塑性聚氨酯弹性体。 The white solid filled tray into the oven, the temperature was raised to 140 ~ 150 ℃, heating for 2 hours, remove the tray, to give a pale yellow solid, that is, the thermoplastic polyurethane elastomer. 分析得出:NCO含量0.02%,分子量7万以上。 Analysis of results: NCO content of 0.02%, a molecular weight of 70,000 or more.

将热塑性聚氨酯弹性体,经炼胶机炼胶至门尼粘度40以下粉碎为粒料,取出160克,加入840克工业乙酸乙酯中,密闭,室温下浸泡一天后,搅拌4小时,使其完全溶解。 The thermoplastic polyurethane elastomers, by batch mixing machine 40 to the Mooney viscosity pulverized into pellets, remove 160 g, 840 g of ethyl acetate were added industry, closed, one day after soaking at room temperature, stirred for 4 hours, allowed completely dissolved. 若有少量未溶物,可过滤除去。 If a small amount of undissolved material, may be removed by filtration. 再加入气相二氧化硅6克,过氯乙烯树脂(锦西化工厂生产,涂料用HG2-344-66),20%丙酮溶液24克,稳定剂双马来酰亚胺0.036克,充分搅拌均匀,便可得到热塑性聚氨酯弹性体互贯网络胶粘剂。 Was added 6 g of fumed silica, a vinyl chloride resin (Jinxi Chemical Plant, coating HG2-344-66), 24 grams of a 20% acetone solution, the stabilizer bismaleimide 0.036 g, stir, can be obtained a thermoplastic polyurethane elastomer interpenetrating networks adhesives.

实施例2的使用效果与实施例1基本相同。 Example 2 using the effect of Example 1 is substantially the same.

NCO含量测试方法:参照ASTM D1638标准方法测试。 NCO content Test Method: Standard reference to ASTM D1638 test method.

实施例3将甲基丙烯酸甲酯23.0克,苯乙烯5.0克,甲基丙烯酸3.0克,由1,4-丁二醇∶一缩二乙二醇=3∶1(重量比)的混合二元醇和己二酸制备的羟值为78.25、酸值为4.51的线性聚酯149.4克(约0.1MOL)和辛酸亚锡0.1克,三乙胺0.03克,加入装有搅拌器和回流冷凝管的三口瓶中,加热到60~70℃,使线性聚酯(烟台合成革总厂生产,牌号MX-706)完全熔融。 Diethylene glycol = 3 (weight ratio) Mixed Dibasic: 3 23.0 g of methyl methacrylate, 5.0 g of styrene, 3.0 g of methacrylic acid, from 1,4-butanediol Example preparation of a hydroxyl value of 78.25 and adipic acid, an acid number of 4.51 to 149.4 g of linear polyester (about 0.1 mol) and 0.1 g of stannous octoate, 0.03 g of triethylamine was added three equipped with stirrer and reflux condenser bottle, heated to 60 ~ 70 ℃, the linear polyester (Yantai synthetic leather production plant, grade MX-706) completely melted.

在搅拌条件下,加入甲苯二异氰酸酯(TDI,纯2,4体)15.7克(0.09mol),控制加料速度,使反应温度不超过70℃,加完TDI后,在60~70℃条件下,反应90分钟,加入偶氮二异丁腈0.2克,搅拌均匀后,70~80℃反应10分钟,停止搅拌,出料,倒入料盘中,冷却后得到白色固体。 Under stirring, toluene diisocyanate (TDI, 2,4 body pure) 15.7 g (0.09 mol), feed speed control, so that the reaction temperature did not exceed 70 ℃, After the addition of TDI, at 60 ~ 70 ℃, for 90 minutes, was added 0.2 g of azobisisobutyronitrile, stir the reaction 70 ~ 80 ℃ 10 minutes stirring was stopped, the material, is poured into trays, cooled to give a white solid.

将白色蜡状固体放入烘箱中,温度升至130~140℃,加热5小时,取出料盘,得到白色固体。 The white, waxy solid was placed in an oven, the temperature was raised to 130 ~ 140 ℃, for 5 hours, remove the tray, to give a white solid. 即为热塑性聚氨酯弹性体。 It is the thermoplastic polyurethane elastomer.

分析得出:NCO含量0.01%,分子量6万以上。 Analysis of results: NCO content of 0.01%, a molecular weight of 60,000 or more.

将该热塑性聚氨酯弹性体150克,经炼胶机炼胶至门尼粘度40以下并破碎,加入850克丙酮中,密闭、室温浸泡2天后,搅拌8小时,使其完全溶解,若有少量不溶物,可过滤除去。 The 150 g of thermoplastic polyurethane elastomer, in 40 the following batch mixing mill and crushed to a Mooney viscosity, 850 g of acetone was added, sealed, soaked for 2 days at room temperature, stirred for 8 hours, to completely dissolve, if a small amount of insoluble thereof, may be removed by filtration. 再加入气相二氧化硅10克、LDJ-240氯丁橡胶20%、甲苯溶液55克,稳定剂双马来酰亚胺0.02克、硫化促进剂二硫化四甲基秋兰姆0.1克,充分搅拌均匀,便可得到热塑性聚氨酯弹性体互贯网络胶粘剂。 10 grams of fumed silica was added, LDJ-240 Neoprene 20% toluene solution of 55 g, stabilizers bismaleimide 0.02 g, vulcanization accelerator tetramethylthiuram disulfide 0.1 g, sufficiently stirred uniform, can be obtained a thermoplastic polyurethane elastomer interpenetrating networks adhesives.

实施例3的使用效果与实施例1基本相同。 Use Example 3 Effect of Example 1 is substantially the same embodiment.

NCO含量测试方法:参照ASTM D1638标准方法测试。 NCO content Test Method: Standard reference to ASTM D1638 test method.

Claims (5)

1.一种热塑性聚氨酯弹性体互贯网络胶粘剂,其特征在于含有重量百分比热塑性聚氨酯弹性体14.08%~15.74%、无机填料0.55%~0.94%、有机增粘剂0.19%~1.03%、稳定剂0.002%~0.1%、溶剂80.59%~81.76%;以上所述的热塑性聚氨酯弹性体是由有机异氰酸酯、含活性双键的单体、线性聚酯、引发剂、催化剂制得,其质量份数为:含活性双键单体∶有机异氰酸酯与线性聚酯之和=1∶5~20、引发剂∶含活性双键单体=0.5~5∶100、催化剂∶反应物总和=0.001~0.1∶100;其中的有机异氰酸酯纯2、4体、2、4体∶2、6体=80∶20,2、4体∶2、6体=65∶35的甲苯二异氰酸酯,二苯基甲烷二异氰酸酯,多苯基多次甲基异氰酸酯;其中的含活性双键的单体是丙烯酸酯类、甲基丙烯酸低级烷基酯的一种,有甲基丙烯酸甲酯、丙烯酸甲酯或者苯乙烯、丙烯腈、甲基丙烯酸其中 A thermoplastic polyurethane elastomer interpenetrating network of adhesive, characterized in that the 14.08% ~ 15.74% thermoplastic polyurethane elastomer, comprising by weight, the inorganic filler is 0.55% ~ 0.94%, 0.19% organic thickener to 1.03% stabilizer 0.002 to 0.1%, solvent 80.59% ~ 81.76%; the above-described thermoplastic polyurethane elastomer is an organic isocyanate, a monomer containing an active double bond, linear polyesters, an initiator, a catalyst was prepared, as its parts by mass: activated double bond-containing monomer: an organic polyisocyanate with a linear polyester sum = 1/5 to 20, initiator: activated double bond-containing monomer is 0.5 to 5:100, the catalyst: reactant sum = 0.001 ~ 0.1:100; wherein the organic isocyanate body pure 2,4, 2,4 toluene diisocyanate isomer = 80:20,2,4 :2,6 body member :2,6 isomer = 65:35, diphenylmethane diisocyanate, multiple polymethine phenyl isocyanate; wherein the activated double bond-containing monomers are acrylic acid esters, methacrylic acid lower alkyl ester, methyl methacrylate, methyl acrylate or styrene, acrylonitrile, methacrylic acid wherein 一种;其中的线性聚酯是饱和二元酸和二元醇缩聚而得,饱和二元酸是己二酸、壬二酸任一种及其组合,二元醇是一缩二乙二醇、1、4丁二醇任一种及其组合,线性聚酯的分子含量为1000~5000;其中的引发剂是在60~160℃能产生活性游离基的任一种引发剂,有有机过氧化物、偶氮化合物任一种;其中的催化剂是各种叔胺类、锡盐化合物辛酸亚锡;所说的有机增粘剂是有机树脂或橡胶任一种,有过氯乙烯树脂、氯丁橡胶、古马龙树脂任一种;所说的稳定剂是苯甲酰氯或双马来酰亚胺的任一种。 One kind; wherein the polyester is a linear saturated dibasic acid and a diol obtained by polycondensation of a saturated dibasic acid is adipic acid, azelaic acid, and any combination thereof, glycols are diethylene glycol , any one of 1,4-butanediol, and combinations thereof, the content of linear polyester molecules of 1000 to 5000; wherein the initiator is 60 ~ 160 ℃ any activity can produce a free radical initiator, an organic too oxide, any one azo compound; wherein the catalyst is a variety of tertiary amines, stannous octoate, tin salts of compounds; said organic resin or an organic tackifier is any one of rubber, had a vinyl chloride resin, chlorine butadiene rubber, either ancient Malone resin; said stabilizer is either benzoyl chloride or bismaleimides.
2.根据权利要求1所述的热塑性聚氨酯弹性体互贯网络胶粘剂,其特征在于它所说的无机填料是密度小的无机填料气相二氧化硅、轻质碳酸钙任一种及其组合。 The thermoplastic polyurethane elastomer as claimed in claim 1, said interpenetrating network of adhesive, characterized in that it said inorganic filler is a low density inorganic filler is fumed silica, calcium carbonate, and any combination thereof.
3.根据权利要求1所述的热塑性聚氨酯弹性体互贯网络胶粘剂,其特征在于它所说的溶剂是能溶解聚氨酯树脂的各种溶剂乙酸乙酯、甲苯、丙酮任一种及其组合。 The thermoplastic polyurethane elastomer as claimed in claim 1, said interpenetrating network of adhesive, characterized in that it said solvent is ethyl acetate various solvents capable of dissolving the polyurethane resin, toluene, acetone, and any combination thereof.
4.根据权利要求1所述的热塑性聚氨酯弹性体互贯网络胶粘剂,其特征在于它可加入各种改性剂,有染料、颜料、润滑剂、硫化促进剂。 The thermoplastic polyurethane elastomer as claimed in claim 1, said interpenetrating network of adhesive, characterized in that it can be added a variety of modifiers, dye, pigments, lubricants, vulcanization accelerator.
5.一种热塑性聚氨酯弹性体互贯网络胶粘剂的制备方法,其特征由下列各步骤组成:(1)线性聚酯树脂的熔融:在装有搅拌器和回流装置的反应器中,依次加入含活性双键单体甲基丙烯酸甲酯、丙烯酸丁酯和由1,4-丁二醇、乙二醇、己二酸缩聚生成的线性聚酯以及催化剂辛酸亚锡,加热到70℃,使线性聚酯完全熔融;(2)热塑性聚氨酯弹性体预聚物和丙烯酸酯预聚物的制备:在搅拌的条件下,不断加入有机二异氰酸酯,控制温度不超过110℃,有机二异氰酸酯加完之后,在60~110℃条件下,反应30~90分钟,控制NCO基含量小于2.5%重量,降温到70℃,加入引发剂偶氮二异丁腈,在60~80℃条件下,搅拌均匀,反应10~40分钟,停止搅拌,出料,倒入料盘中,冷却后得到白色固体;(3)热塑性聚氨酯弹性体的制备:将盛有白色固体的料盘,放入烘箱中,温度升至130 A thermoplastic polyurethane elastomer interpenetrating network adhesive preparation, wherein the composition consists of the following steps: (1) linear polyester resin was melt: In a reactor equipped with a stirrer and a reflux device, comprising successively added activated double bond monomers methyl methacrylate, butyl acrylate, and the polycondensation of 1,4-butanediol, ethylene glycol, adipic acid and linear polyesters stannous octoate catalyst, was heated to 70 ℃, the linear polyester completely melted; preparation of (2) a thermoplastic polyurethane elastomer prepolymer and acrylate prepolymer: under stirring, continuously adding an organic diisocyanate, to control the temperature does not exceed 110 deg.] C, an organic diisocyanate addition was complete after at 60 ~ 110 ℃, for 30 to 90 minutes, the control NCO group content of less than 2.5% by weight, cooled to 70 ℃, azobisisobutyronitrile was added an azo initiator, at 60 ~ 80 ℃, stir the reaction 10 to 40 minutes, stirring was stopped, the material, is poured into trays, cooled to give a white solid; (3) preparation of thermoplastic polyurethane elastomer: the white solid filled tray, placed in an oven, the temperature was raised 130 170℃,加热1小时至5小时,取出料盘,得到的白色或淡黄色固体,即为热塑性聚氨酯弹性体;(4)热塑性聚氨酯弹性体互贯网络胶粘剂的制备:将热塑性聚氨酯弹性体炼胶至门尼粘度40以下破碎后,放入溶剂乙酸乙酯中,密闭,室温条件下浸泡一天,再搅拌3~12小时,使其完全溶解,如有少量未溶物,过滤除去,再加入无机填料气相二氧化硅,有机增粘剂古马龙树脂、稳定剂苯甲酰氯、硫化促进剂二硫化四甲基秋兰姆以及其它各种改性剂,搅拌均匀,这样便得到了热塑性聚氨酯弹性体互贯网络胶粘剂。 170. deg.] C, for 1 hour to 5 hours, remove the tray, to give a white or pale yellow solid, that is, the thermoplastic polyurethane elastomer; Preparation of adhesive network (4) Thermoplastic polyurethane elastomer interpenetrating: thermoplastic polyurethane elastomer batch after 40 to Mooney viscosity less broken, taken in ethyl acetate solvent, soaking confined one day, room temperature, stirred for 3 to 12 hours to completely dissolve, if a small amount of undissolved was removed by filtration, then add an inorganic fumed silica filler, an organic tackifier resin ancient Malone, benzoyl chloride stabilizer, a vulcanization accelerator tetramethylthiuram disulfide and various other modifiers, stir, thus obtained thermoplastic polyurethane elastomer interpenetrating networks adhesives.
CN 90103865 1990-05-22 1990-05-22 Polyurethane complementary networks adhesive and its preparing method CN1036404C (en)

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CN 90103865 CN1036404C (en) 1990-05-22 1990-05-22 Polyurethane complementary networks adhesive and its preparing method

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CN 90103865 CN1036404C (en) 1990-05-22 1990-05-22 Polyurethane complementary networks adhesive and its preparing method

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CN1056701A CN1056701A (en) 1991-12-04
CN1036404C true CN1036404C (en) 1997-11-12

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Publication number Priority date Publication date Assignee Title
CN1045971C (en) * 1993-01-19 1999-10-27 江苏石油化工学院 Method for preparing polyurethane acrylic ester copolymerized emulsion
CN1095492C (en) * 1997-03-19 2002-12-04 湖北大学 Process for producing adhesive for polyurethane shoes by solution method
US6892725B2 (en) * 2002-04-26 2005-05-17 Mine Safety Appliances Company Protective hoods and neck seals for use therein
CN1322970C (en) * 2003-03-14 2007-06-27 姚禹肃 Conveyer belt connecting method
CN106118171A (en) * 2016-07-19 2016-11-16 董芬芳 Heavy-duty anticorrosive and antirust paint for metals
CN106497038A (en) * 2016-11-02 2017-03-15 安徽隆宇塑业有限公司 Nylon 66 composite
CN107254025A (en) * 2017-06-29 2017-10-17 阜南县中信柳木工艺品有限公司 Artwork adhesive

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