CN108395847B - A kind of high-intensity light, heat curing polyurethane adhesive and its preparation method and use method - Google Patents
A kind of high-intensity light, heat curing polyurethane adhesive and its preparation method and use methodDownload PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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Abstract
Translated fromChineseDescription
Translated fromChinese技术领域technical field
本发明涉及聚氨酯粘合剂领域，具体涉及具有高强度、光热双重固化的聚氨酯粘合剂领域，还涉及具体的制备方法和使用方法。The invention relates to the field of polyurethane adhesives, in particular to the field of polyurethane adhesives with high strength and dual curing of light and heat, and also to a specific preparation method and use method.
背景技术Background technique
聚氨酯树脂属于一类优质的高分子树脂类物质，广泛应用于各个领域：如聚氨酯人造革广泛用于皮草、衣物的制作，聚氨酯粘合剂、聚氨酯涂料和聚氨酯地坪材料都有应用。Polyurethane resin belongs to a class of high-quality polymer resins and is widely used in various fields: for example, polyurethane artificial leather is widely used in the production of fur and clothing, and polyurethane adhesives, polyurethane coatings and polyurethane floor materials are also used.
自1937年，聚氨酯材料首次合成后，发展十分快，各品类的聚氨酯层出不穷，20年代中叶，出现热塑性聚氨酯粘合剂，1968年出现了无溶剂聚氨酯粘合剂，1978年出现了湿固化聚氨酯粘合剂，1984年出现了反应型热熔聚氨酯粘合剂。基础类聚氨酯粘合剂在20世纪已经基本完成，近二十年的研究主要集中在高性能、复合型聚氨酯粘合剂，都是针对具体应用的粘合剂品类，通用型粘合剂的研究难度逐渐增大。Since the first synthesis of polyurethane materials in 1937, the development has been very rapid, and various types of polyurethane have emerged one after another. In the mid-1920s, thermoplastic polyurethane adhesives appeared, solvent-free polyurethane adhesives appeared in 1968, and moisture-curing polyurethane adhesives appeared in 1978. Mixtures, reactive hot melt polyurethane adhesives appeared in 1984. Basic polyurethane adhesives have been basically completed in the 20th century, and the research in the past two decades has mainly focused on high-performance, composite polyurethane adhesives, all of which are adhesive types for specific applications and research on general-purpose adhesives. Difficulty gradually increases.
对于高分子材料使用，发明人针对光热、湿热和湿光的固化方式都进行了细节研究，并分别进行了专利申请。对于实际使用中如何得到一类适合光热条件下使用的高强度、耐高温的聚氨酯粘合剂是待开发的产品品类。For the use of polymer materials, the inventor has carried out detailed research on the curing methods of light heat, damp heat and wet light, and filed patent applications respectively. How to obtain a type of high-strength, high-temperature-resistant polyurethane adhesive suitable for use under light and heat conditions in actual use is a product category to be developed.
针对上述技术问题，发明人企业进行了长期研究，得到本发明。In view of the above technical problems, the inventor enterprise has conducted long-term research and obtained the present invention.
发明内容SUMMARY OF THE INVENTION
发明目的：针对背景技术中介绍的技术问题，本发明通过对聚氨酯组分的选择，以端NCO聚氨酯低聚物为基础，得到一种通过光快速固化、多阶段固化的设计，实现了高温下快速、稳定固化，高温下固化程度增高，可以实现粘合结构高强度粘结、耐高温性能且快速固化优异的效果。Purpose of the invention: In view of the technical problems introduced in the background technology, the present invention obtains a design of rapid curing through light and multi-stage curing through the selection of polyurethane components and based on the terminal NCO polyurethane oligomer, which realizes high temperature curing. Fast and stable curing, high curing degree at high temperature, can achieve high-strength bonding of bonding structure, high temperature resistance and excellent fast curing effect.
本发明另一目的是提供了高强度光、热固化聚氨酯粘合剂的制备方法。Another object of the present invention is to provide a preparation method of a high-intensity light, heat-curing polyurethane adhesive.
本发明另一目的是提供高强度光、热固化聚氨酯粘合剂的使用方法。Another object of the present invention is to provide a method of using a high-intensity light, heat-curing polyurethane adhesive.
为了实现上述技术效果，采用了如下的技术方案。In order to achieve the above technical effects, the following technical solutions are adopted.
一种高强度光、热固化聚氨酯粘合剂的制备方法，包括如下步骤：A preparation method of a high-intensity light and heat-curing polyurethane adhesive, comprising the steps of:
(1)端NCO聚氨酯预聚物(1) Terminal NCO polyurethane prepolymer
将聚碳酸酯多元醇、聚醚多元醇和异氰酸酯分别进行真空干燥；Vacuum-drying polycarbonate polyol, polyether polyol and isocyanate respectively;
将干燥后的聚碳酸酯多元醇、聚醚多元醇和异氰酸酯搅拌均匀，加入催化剂，在70-100℃下反应1-5h，降温至60-80℃，加入扩链剂反应0.5-2h，加入溶剂稀释，得到NCO含量约为5-10％的端NCO聚氨酯预聚物。Stir the dried polycarbonate polyol, polyether polyol and isocyanate evenly, add catalyst, react at 70-100℃ for 1-5h, cool down to 60-80℃, add chain extender and react for 0.5-2h, add solvent Dilution yields an NCO-terminated polyurethane prepolymer with an NCO content of about 5-10%.
(2)光固化组分加入(2) Addition of light-curing components
在上述预聚物降温至50℃以下，在避光条件下，向预聚物中依次加入含羟基丙烯酸酯单体和光引发剂、阻聚剂，搅拌均匀。The above prepolymer is cooled to below 50°C, and under light-proof conditions, hydroxy-containing acrylate monomer, photoinitiator and polymerization inhibitor are sequentially added to the prepolymer, and the mixture is uniformly stirred.
(3)封闭剂的加入(3) Addition of sealing agent
在避光条件下，向步骤(2)混合均匀的混合物中依次加入己内酰胺、亚硫酸氢钠和甲基乙基酮肟，搅拌均匀，并根据粘度需要加入溶剂，即得产品。Add caprolactam, sodium bisulfite and methyl ethyl ketoxime to the mixture uniformly mixed in step (2) in order under light-proof conditions, stir evenly, and add solvent according to the viscosity to obtain the product.
作为优选技术方案，所述聚醚多元醇为聚醚三元醇，分子量在1000-5000，所述聚碳酸酯多元醇为聚碳酸酯二元醇，分子量在1000-2000。As a preferred technical solution, the polyether polyol is a polyether triol with a molecular weight of 1000-5000, and the polycarbonate polyol is a polycarbonate diol with a molecular weight of 1000-2000.
作为优选技术方案，所述聚碳酸酯多元醇和聚醚多元醇的摩尔比为3-5：1。As a preferred technical solution, the molar ratio of the polycarbonate polyol and the polyether polyol is 3-5:1.
作为优选技术方案，所述聚碳酸酯多元醇和聚醚多元醇的总摩尔比与异氰酸酯摩尔比为1：(1.2-2.3)。As a preferred technical solution, the total molar ratio of the polycarbonate polyol and the polyether polyol to the isocyanate molar ratio is 1:(1.2-2.3).
作为优选技术方案，所述异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯或异佛尔酮二异氰酸酯。As a preferred technical solution, the isocyanate is toluene diisocyanate, diphenylmethane diisocyanate or isophorone diisocyanate.
作为优选技术方案，所述溶剂为甲苯、二甲苯或丙酮。As a preferred technical solution, the solvent is toluene, xylene or acetone.
作为优选方案，所述扩链剂为1,4-丁二醇、二甘醇、1,6-己二醇，三羟甲基丙烷，蓖麻油等。As a preferred solution, the chain extender is 1,4-butanediol, diethylene glycol, 1,6-hexanediol, trimethylolpropane, castor oil and the like.
作为优选技术方案，所述光引发剂为2,4,6(三甲基苯甲酰基)二苯基氧化膦或2,4,6-三甲基苯甲酰基膦酸乙酯。As a preferred technical solution, the photoinitiator is 2,4,6(trimethylbenzoyl)diphenylphosphine oxide or 2,4,6-trimethylbenzoylphosphonate ethyl ester.
作为优选技术方案，所述阻聚剂为对苯二酚或对苯醌。As a preferred technical solution, the polymerization inhibitor is hydroquinone or p-benzoquinone.
作为优选技术方案，所述己内酰胺、亚硫酸氢钠和甲基乙基酮肟的总质量占粘合剂固体成分的3-10wt％，己内酰胺、亚硫酸氢钠和甲基乙基酮肟的重量比为1：(2-3)：1。As a preferred technical solution, the total mass of the caprolactam, sodium bisulfite and methyl ethyl ketoxime accounts for 3-10wt% of the solid content of the adhesive, and the weight of the caprolactam, sodium bisulfite and methyl ethyl ketoxime The ratio is 1:(2-3):1.
作为优选技术方案，所述含羟基丙烯酸酯单体为丙烯酸羟乙酯、苯基缩水甘油醚丙烯酸酯和环己烷二甲氧基二丙烯酸酯比例为1:(0.8-1.5)：(0.2-0.5)(摩尔比)的混合物，上述单体总质量占粘合剂固体成分的10-25％，可进一步优选11％，13％，15％，17％，19％，21％，23％。As a preferred technical solution, the hydroxyl-containing acrylate monomers are hydroxyethyl acrylate, phenyl glycidyl ether acrylate and cyclohexanedimethoxydiacrylate in a ratio of 1:(0.8-1.5):(0.2- 0.5) (molar ratio) mixture, the total mass of the above monomers accounts for 10-25% of the solid content of the adhesive, more preferably 11%, 13%, 15%, 17%, 19%, 21%, 23%.
一种高强度光、热固化聚氨酯粘合剂的制备方法得到高强度光、热固化聚氨酯粘合剂。A preparation method of a high-intensity light and heat-curing polyurethane adhesive obtains the high-intensity light and heat-curing polyurethane adhesive.
一种高强度光、热固化聚氨酯粘合剂的使用方法，将粘合剂涂附在被粘物一表面，将被粘物二压实在涂附有粘合剂的被粘物一表面，使用夹子夹持连接部，紫外光照射3-10min，进而置于温度60-80℃固化1-3h，即可。A method for using a high-intensity light and heat-curing polyurethane adhesive, which comprises applying the adhesive on one surface of an adherend, and pressing the second adherend on the other surface of the adherend coated with the adhesive, Use a clip to hold the connection part, irradiate it with ultraviolet light for 3-10 minutes, and then place it at a temperature of 60-80 °C to cure for 1-3 hours.
所述被粘物一和被粘物二中至少一个为紫光线可透过的材料制得。作为优选被粘物一和被粘物二为玻璃或耐高温塑料，耐高温塑料优选为PMMA、PC、PS、PPS等。At least one of the first adherend and the second adherend is made of a material that can transmit purple light. The first and second adherends are preferably glass or high-temperature-resistant plastics, and the high-temperature-resistant plastics are preferably PMMA, PC, PS, PPS, and the like.
具体实施方式Detailed ways
为了使技术人员和公众更加充分的理解本发明的技术方案，下面对反应的机理和实施例方式进行了介绍。In order to make the technical solution of the present invention more fully understood by the skilled person and the public, the reaction mechanism and the embodiment mode are introduced below.
本发明通过分步法制备高强度光、热双重固固化的聚氨酯粘合剂，下面分别对两个步骤中的重点技术点进行介绍。The present invention prepares a high-intensity light and heat dual-curing polyurethane adhesive by a step-by-step method, and the key technical points in the two steps are respectively introduced below.
端NCO聚氨酯预聚物Terminated NCO Polyurethane Prepolymer
端NCO聚氨酯预聚物制备是将干燥后的聚碳酸酯多元醇、聚醚多元醇和异氰酸酯搅拌均匀，在70-100℃下反应1-5h，降温至60-80℃，加入扩链剂反应0.5-2h，加入溶剂稀释，得到NCO含量约5-10％的湿固化预聚物，其相对于本发明人其他专利来看，其端基含量低，主要是由于不需要湿固化性，端基大幅度的降低，但本发明不排除最终产品中含有NCO基团，使其具有湿固化特性。The preparation of NCO-terminated polyurethane prepolymer is to stir the dried polycarbonate polyol, polyether polyol and isocyanate evenly, react at 70-100℃ for 1-5h, cool down to 60-80℃, add chain extender to react for 0.5 hours -2h, add solvent to dilute to obtain a moisture-curing prepolymer with an NCO content of about 5-10%. Compared with other patents of the inventor, its end group content is low, mainly because it does not require moisture curability, and the end group Significant reduction, but the present invention does not exclude NCO groups in the final product, making it moisture-curable.
聚碳酸酯多元醇和聚醚多元醇配合使用，聚醚多元醇具有较好的柔韧性，聚碳酸酯多元醇具有较好的刚性，两者通过合适的摩尔比配合，得到的粘合剂具有较好的强度，较好的柔韧性保证了粘合剂的贴合性和粘合性。Polycarbonate polyol and polyether polyol are used together, polyether polyol has good flexibility, polycarbonate polyol has good rigidity, and the combination of the two is in a suitable molar ratio, and the obtained adhesive has a relatively high performance. Good strength and good flexibility ensure the fit and adhesion of the adhesive.
由于本发明粘合剂的使用时粘接高强度的材料，固化后要具有较大的机械强度和粘合强度，其中所述聚碳酸酯多元醇和聚醚多元醇的摩尔比为3-5:1，聚碳酸酯多元醇占主体，其使用保证了机械强度，如果不在该范围内，聚醚多元醇量增大后，粘合强度有所提升，但机械强度大幅度的下降；如果不使用聚醚多元醇或使用量过小，机械强度增大但由于与基材的亲和力过低，粘合强度降低，且在连接体在发生横向移动或弯曲时，极易断裂。Since the adhesive of the present invention is used to bond high-strength materials, it will have greater mechanical strength and adhesive strength after curing, wherein the molar ratio of the polycarbonate polyol and the polyether polyol is 3-5: 1. Polycarbonate polyol is the main body, and its use ensures mechanical strength. If it is not within this range, after the amount of polyether polyol increases, the adhesive strength will be improved, but the mechanical strength will be greatly reduced; if it is not used If the amount of polyether polyol used is too small, the mechanical strength will increase, but because the affinity with the substrate is too low, the adhesive strength will be reduced, and when the connecting body moves or bends laterally, it is very easy to break.
所述聚醚多元醇为聚醚三元醇，分子量在1000-5000，分子量优选2500-3500，所述聚碳酸酯多元醇为聚碳酸酯二元醇，分子量在1000-2000。上述选择分子量不宜过大，分子量过大，羟值较低，后期交联程度低，机械强度降低，如果分子量过小，交联程度过大，粘合强度有降低的趋势。The polyether polyol is a polyether triol with a molecular weight of 1000-5000, preferably 2500-3500, and the polycarbonate polyol is a polycarbonate diol with a molecular weight of 1000-2000. The above-mentioned selection of molecular weight should not be too large, the molecular weight is too large, the hydroxyl value is low, the degree of cross-linking in the later stage is low, and the mechanical strength is reduced.
多元醇选择优选为：聚碳酸酯多元醇为聚碳酸酯二醇(PCDL)，可选择旭化成牌号为L6001，分子量1000，羟值110±10，酸值0.05mgKOH/g，粘度1100-2300mPas(55℃)；L5651，分子量1000，羟值110±10，酸值0.05mgKOH/g，粘度1200-2400mPas(55℃)；聚醚多元醇为聚醚三元醇，可以选择N330，分子量3000±200，羟值56±3，酸值≤0.1mgKOH/g，粘度500±75mPas。The polyol selection is preferably: polycarbonate polyol is polycarbonate diol (PCDL), and the Asahi Kasei brand can be selected as L6001, molecular weight 1000, hydroxyl value 110±10, acid value 0.05mgKOH/g, viscosity 1100-2300mPas (55 ℃); L5651, molecular weight 1000, hydroxyl value 110±10, acid value 0.05mgKOH/g, viscosity 1200-2400mPas (55℃); polyether polyol is polyether triol, N330 can be selected, molecular weight 3000±200, The hydroxyl value is 56±3, the acid value is ≤0.1mgKOH/g, and the viscosity is 500±75mPas.
异氰酸酯没有明确的限制，可以为常见的任何异氰酸酯，作为优选方案，所述异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯或异佛尔酮二异氰酸酯，进一步优选为甲苯二异氰酸酯或二苯基甲烷二异氰酸酯或与异佛尔酮二异氰酸酯的混合物，进一步的优选为芳香族的异氰酸酯与非芳香族异氰酸酯的复配，平衡强度和柔韧性。The isocyanate is not specifically limited and can be any common isocyanate. As a preferred solution, the isocyanate is toluene diisocyanate, diphenylmethane diisocyanate or isophorone diisocyanate, more preferably toluene diisocyanate or diphenylmethane Diisocyanate or a mixture with isophorone diisocyanate, more preferably a compound of aromatic isocyanate and non-aromatic isocyanate, balances strength and flexibility.
在多元醇和异氰酸酯的反应中，所述聚碳酸酯多元醇和聚醚多元醇的总摩尔比与异氰酸酯摩尔比为1：(1.2-2.3)，其旨在得到的NCO含量约为5-10％的端NCO聚氨酯预聚物，该NCO含量可以保证后面可以与下一步使用的含有活泼氢的光固化基团和封端剂进行反应。In the reaction of polyol and isocyanate, the total molar ratio of the polycarbonate polyol and polyether polyol to the isocyanate molar ratio is 1:(1.2-2.3), which aims to obtain an NCO content of about 5-10%. NCO-terminated polyurethane prepolymer, the NCO content can ensure that it can react with the photocurable group containing active hydrogen and the end-capping agent used in the next step.
光固化基团的引入Introduction of photocurable groups
在上述端NCO聚氨酯预聚物是具有大量的异氰酸酯端基，其可以通过含有羟基的丙烯酸酯或封闭剂与异氰酸酯反应。The above-mentioned terminal NCO polyurethane prepolymers have a large number of isocyanate end groups, which can be reacted with isocyanates through hydroxyl-containing acrylates or blocking agents.
预聚物中依次加入含羟基丙烯酸酯单体和光引发剂、阻聚剂，搅拌均匀，并根据粘度需要加入溶剂，即得产品。Add hydroxyl-containing acrylate monomer, photoinitiator and polymerization inhibitor to the prepolymer in turn, stir evenly, and add solvent according to the viscosity to obtain the product.
涉及到单体选择，丙烯酸羟乙酯作为主单体，作为最常用的基础型含羟基丙烯酸酯，综合性能优异；苯基缩水甘油醚丙烯酸酯含有苯基，可以提供强度，同时，羟基可以与环氧基缓慢反应，固化，提高后期交联程度；由于前期湿固化以及含苯类丙烯酸酯固化，都不断提高了强度，但粘附力下降较为明显；环辛己烷二甲氧基二丙烯酸酯作为附着力增强型单体，可以采用SR406，其具有固化快，附着力强，抗光解，耐高温，对塑料的附着能力强，耐化学腐蚀，该单体的选择用以弥补上述区别。When it comes to monomer selection, hydroxyethyl acrylate as the main monomer is the most commonly used basic hydroxyl-containing acrylate with excellent comprehensive properties; phenyl glycidyl ether acrylate contains phenyl, which can provide strength, and at the same time, hydroxyl can be combined with The epoxy group reacts slowly and cures to improve the degree of cross-linking in the later stage; due to the moisture curing in the early stage and the curing of benzene-containing acrylates, the strength is continuously improved, but the adhesion decreases significantly; cyclooctane hexanedimethoxydiacrylic acid Ester as an adhesion-enhancing monomer can use SR406, which has the advantages of fast curing, strong adhesion, resistance to photolysis, high temperature resistance, strong adhesion to plastics, and resistance to chemical corrosion. The choice of this monomer is used to make up for the above differences. .
作为优选技术方案，所述含羟基丙烯酸酯单体为丙烯酸羟乙酯、苯基缩水甘油醚丙烯酸酯和环己烷二甲氧基二丙烯酸酯比例为1:(0.8-1.5)：(0.2-0.5)(摩尔比)的混合物。由于本发明针对性的使用方面是高强度材料的粘结，故苯基缩水甘油醚丙烯酸酯的使用量较大，其可以大幅度提高粘合剂的自身强度，如果使用量过小，强度增强不足；但由于上述的对粘附性能的影响，本发明创造性的选择了环己烷二甲氧基二丙烯酸酯，其弥补了上述不足，但也不宜过大，过大则强度降低，如果不加入或者加入量最小，则粘合剂粘附性能下降。其总质量以保证最终含羟基单体和封闭剂可以把所有NCO反应完全，不排除最终产品中含有NCO基团的情形。As a preferred technical solution, the hydroxyl-containing acrylate monomers are hydroxyethyl acrylate, phenyl glycidyl ether acrylate and cyclohexanedimethoxydiacrylate in a ratio of 1:(0.8-1.5):(0.2- 0.5) (molar ratio) of the mixture. Since the targeted use aspect of the present invention is the bonding of high-strength materials, the use amount of phenyl glycidyl ether acrylate is large, which can greatly improve the strength of the adhesive itself. If the use amount is too small, the strength will be enhanced. However, due to the above-mentioned influence on the adhesion performance, the present invention creatively selects cyclohexanedimethoxydiacrylate, which makes up for the above-mentioned shortcomings, but it should not be too large, and the strength will be reduced if it is not too large. Addition or the amount of addition is minimal, the adhesive adhesion performance is reduced. Its total mass is to ensure that the final hydroxyl-containing monomer and blocking agent can completely react all NCO, and the situation that NCO groups are contained in the final product is not excluded.
封闭剂的加入Addition of blocking agent
本发明中一个重要的发明点就在于封闭剂的选择，通过封闭剂的选择得到一种可以实现分段热固化的粘合剂，其分为低温段、中温段和高温段封闭剂，其中低温段封闭剂是在初步固化中就发生固化反应，保证粘合过程中的强度，中温段和高温段的封闭剂在高温下解封闭发生固化反应，提高了交联程度，提高了耐高温性能。An important inventive point of the present invention lies in the selection of the sealing agent. Through the selection of the sealing agent, a kind of adhesive that can realize segmental thermal curing is obtained, which is divided into low temperature section, medium temperature section and high temperature section sealing agent. The blocker in the middle temperature section and the blocker in the high temperature section is deblocked at high temperature and the curing reaction occurs, which improves the degree of crosslinking and improves the high temperature resistance.
本发明中端NCO聚氨酯预聚物在加入光固化基团后，在避光条件下，依次加入己内酰胺、亚硫酸氢钠和甲基乙基酮肟，搅拌均匀，并根据粘度需要加入溶剂，即得产品。其中低温段封闭剂为亚硫酸氢钠的解离温度在60℃，中温段封闭剂为甲基乙基酮肟的解离温度在125-130℃，高温段封闭剂为己内酰胺，其解离温度为160℃。上述三者封闭剂在不同温度下解封闭，后实现了本发明分段固化的效果。In the present invention, after adding the photocurable group, the mid-end NCO polyurethane prepolymer of the present invention sequentially adds caprolactam, sodium bisulfite and methyl ethyl ketoxime under the condition of avoiding light, stirs evenly, and adds solvent according to the viscosity, namely get product. Wherein the low temperature section sealing agent is sodium bisulfite, the dissociation temperature is 60 ° C, the dissociation temperature of the middle temperature section sealing agent is methyl ethyl ketoxime is 125-130 ° C, the high temperature section sealing agent is caprolactam, and its dissociation temperature is is 160°C. The above-mentioned three blocking agents are deblocked at different temperatures, and then the effect of segmented curing of the present invention is achieved.
所述己内酰胺、亚硫酸氢钠和甲基乙基酮肟的重量比为1：(2-3)：1，其中亚硫酸氢钠的使用量最大，保证了初步的基础粘合力，同时，也保证了机械强度，后续的甲基乙基酮肟和己内酰胺的摩尔量逐渐减少。所述己内酰胺、亚硫酸氢钠和甲基乙基酮肟的总质量占粘合剂固体成分的3-10wt％，其用量根据使用产品的强度要求选择。The weight ratio of described caprolactam, sodium bisulfite and methyl ethyl ketoxime is 1: (2-3): 1, wherein the usage amount of sodium bisulfite is the largest, which ensures the preliminary basic adhesive force, and meanwhile, The mechanical strength is also ensured, and the molar amounts of subsequent methyl ethyl ketoxime and caprolactam are gradually reduced. The total mass of the caprolactam, sodium bisulfite and methyl ethyl ketoxime accounts for 3-10 wt % of the solid content of the adhesive, and the amount thereof is selected according to the strength requirements of the product used.
由于在后续步骤中加入的光固化单体和封端剂的用量，部分情况下有残留的NCO，但残留量不大，不影响整体性能。实质上本发明在高温下，也依靠部分水实现再次的交联。Due to the amount of photocurable monomer and end-capping agent added in the subsequent steps, there is residual NCO in some cases, but the residual amount is not large and does not affect the overall performance. In essence, the present invention also relies on partial water to achieve re-crosslinking at high temperatures.
同时，本发明中在实施例中光固化组分以及分段固化的实施例和对比例在同日的其他专利中有详细的记载，证明效果，本申请中不在赘述。Meanwhile, in the present invention, the examples and comparative examples of the photocurable components and staged curing in the examples are described in detail in other patents of the same day to prove the effect, and will not be repeated in this application.
使用方法Instructions
本发明提供了一种具体的使用方法，其根据粘合剂的基本性能选择得到，具体为：由于该粘合剂的固化需要一段较长的时间，故将粘合剂涂附在被粘物一表面，将被粘物二压实在涂附有粘合剂的被粘物一表面，需使用夹子夹持连接部，保证其不会发生偏移。The present invention provides a specific use method, which is selected according to the basic properties of the adhesive, specifically: since the curing of the adhesive requires a long period of time, the adhesive is coated on the adherend. On one surface, the adherend 2 is pressed on the surface of the adherend coated with the adhesive, and the connecting part needs to be clamped with a clip to ensure that it will not be offset.
对于光固化条件，使用时间较为常规，紫外光照射3-10min，后续自由基聚合交联可以在后续热固化中完成。对于热固化条件，由于需要湿固化和保证初步的热固化(低温段封闭剂为亚硫酸氢钠的解离温度在60℃)，选择温度60-80℃固化1-3h。For light curing conditions, the use time is relatively conventional, and the ultraviolet light is irradiated for 3-10 minutes, and the subsequent free radical polymerization and crosslinking can be completed in the subsequent thermal curing. For thermal curing conditions, due to the need for moisture curing and to ensure preliminary thermal curing (the dissociation temperature of sodium bisulfite in the low temperature section is 60 °C), the temperature of 60-80 °C is selected for curing for 1-3 hours.
对于被粘物的选择，粘物一和被粘物二可以为紫外透过性材料，作为优选被粘物一和被粘物二为玻璃或耐高温塑料，耐高温塑料优选为PMMA、PC、PS、PPS等。For the selection of the adherend, the first and second adherends can be UV-transmitting materials, and preferably the first and second adherends are glass or high-temperature-resistant plastics, and the high-temperature-resistant plastics are preferably PMMA, PC, PS, PPS, etc.
有益的技术效果beneficial technical effect
本发明的结构设计主体是通过NCO封端的预聚物引入含羟基光固化单体和封端剂，使其具有光固化和分段固化的粘合剂，两者相互配合，光固化可以实现快速固化，封端固化可以实现分段的高温固化，提高耐高温性能。The main body of the structural design of the present invention is to introduce a hydroxyl group-containing photocurable monomer and an end capping agent through an NCO-terminated prepolymer, so that it has photocurable and segmented curing adhesives. The two cooperate with each other, and photocuring can achieve rapid Curing and end-capping curing can achieve segmented high-temperature curing and improve high-temperature resistance.
本发明中端NCO湿固化预聚物选择了特定用量和分子量的聚碳酸酯多元醇、聚醚多元醇，实现了机械强度和附着力的平衡；引入光固化基团，主要选择了特定比例的丙烯酸单体丙烯酸羟乙酯、苯基缩水甘油醚丙烯酸酯和环己烷二甲醇二丙烯酸酯，进一步平衡了机械强度和附着力；引入封端剂，选择在避光条件下，依次加入己内酰胺、亚硫酸氢钠和甲基乙基酮肟，实现了三段固化。同时本发明还优选提供了配合上述组成的使用方法，使其更好了的实现了上述效果。The mid-end NCO moisture-curing prepolymer of the present invention selects polycarbonate polyol and polyether polyol with specific dosage and molecular weight, so as to realize the balance of mechanical strength and adhesion; The acrylic monomers hydroxyethyl acrylate, phenyl glycidyl ether acrylate and cyclohexane dimethanol diacrylate further balance the mechanical strength and adhesion; introduce end-capping agent, choose to add caprolactam, Sodium bisulfite and methyl ethyl ketoxime to achieve three-stage curing. At the same time, the present invention also preferably provides a use method in conjunction with the above composition, so that the above effect can be better achieved.
为了使技术人员更加直观的了解本发明的技术方案，下面选择典型实施例和对比例进行介绍，这些实施例不构成对本发明保护范围的限制，今后任何不背离本发明基本构思的实施方案都在本发明保护范围内。In order to make the technical solution of the present invention more intuitively understood by the technical personnel, typical examples and comparative examples are selected below for introduction. These examples do not constitute a limitation on the protection scope of the present invention. within the protection scope of the present invention.
具体实施例和对比例如下：Specific examples and comparative examples are as follows :
实施例1Example 1
(1)湿固化预聚物(1) Moisture curing prepolymer
将聚碳酸酯二醇(PCDL，L6001，分子量1000，羟值110±10，酸值0.05mgKOH/g，粘度1100-2300mPas)、聚醚三元醇N330(分子量3000±200，羟值56±3，酸值≤0.1mgKOH/g，粘度500±75mPas)和二苯基甲烷二异氰酸酯分别进行真空干燥；Polycarbonate diol (PCDL, L6001, molecular weight 1000, hydroxyl value 110±10, acid value 0.05mgKOH/g, viscosity 1100-2300mPas), polyether triol N330 (molecular weight 3000±200, hydroxyl value 56±3 , acid value ≤ 0.1mgKOH/g, viscosity 500±75mPas) and diphenylmethane diisocyanate were vacuum dried;
将干燥后的40g聚碳酸酯二醇L6001、30g聚醚三元醇N330和40g二苯基甲烷二异氰酸酯搅拌均匀，加入催化剂二月桂酸二丁基锡0.5g，在80℃下反应1-5h，降温至60℃，加入扩链剂1,4-丁二醇4g反应1h，加入二甲苯稀释，得到NCO含量约为8％的湿固化预聚物(NCO含量为占预聚物的质量含量，下同)。Stir the dried 40g polycarbonate diol L6001, 30g polyether triol N330 and 40g diphenylmethane diisocyanate evenly, add 0.5g catalyst dibutyltin dilaurate, react at 80°C for 1-5h, cool down At 60°C, 4 g of chain extender 1,4-butanediol was added to react for 1 h, and xylene was added to dilute to obtain a moisture-cured prepolymer with an NCO content of about 8% (the NCO content is the mass content of the prepolymer, and the following same).
(2)光固化基团的加入(2) Addition of photocurable groups
在上述湿固化预聚物降温至50℃以下，在避光条件下，向预聚物中依次加入8g丙烯酸羟乙酯、20g苯基缩水甘油醚丙烯酸酯和7g环己烷二甲醇二丙烯酸酯和光引发剂2,4,6(三甲基苯甲酰基)二苯基氧化膦0.5g、阻聚剂对苯二酚0.3g，搅拌均匀。The above moisture-cured prepolymer was cooled to below 50°C, and 8 g of hydroxyethyl acrylate, 20 g of phenyl glycidyl ether acrylate and 7 g of cyclohexane dimethanol diacrylate were sequentially added to the prepolymer under the condition of avoiding light. and photoinitiator 2,4,6(trimethylbenzoyl)diphenylphosphine oxide 0.5g, polymerization inhibitor hydroquinone 0.3g, stir uniformly.
(3)封端剂的加入(3) Addition of end-capping agent
在避光条件下向上述湿固化预聚物中依次加入3.5g己内酰胺、7g亚硫酸氢钠和3.5g甲基乙基酮肟，搅拌均匀，并根据粘度需要加入二甲苯，即得高强度多重固化的聚氨酯粘合剂。Add 3.5g of caprolactam, 7g of sodium bisulfite and 3.5g of methyl ethyl ketoxime to the above moisture-cured prepolymer in order under light-proof conditions, stir evenly, and add xylene according to the viscosity to obtain a high-strength multi-layer Cured polyurethane adhesive.
对比例1Comparative Example 1
(1)湿固化预聚物(1) Moisture curing prepolymer
将聚碳酸酯二醇(PCDL，L6001，分子量1000，羟值110±10，酸值0.05mgKOH/g，粘度1100-2300mPas)和二苯基甲烷二异氰酸酯分别进行真空干燥；Polycarbonate diol (PCDL, L6001, molecular weight 1000, hydroxyl value 110±10, acid value 0.05mgKOH/g, viscosity 1100-2300mPas) and diphenylmethane diisocyanate were vacuum dried;
将干燥后的62g聚碳酸酯二醇L6001和40g二苯基甲烷二异氰酸酯搅拌均匀，加入催化剂二月桂酸二丁基锡0.5g，在80℃下反应1-5h，降温至60℃，加入扩链剂1,4-丁二醇4g反应1h，加入二甲苯稀释，得到NCO含量约为8％的湿固化预聚物(NCO含量为占预聚物的含量)。Stir the dried 62g polycarbonate diol L6001 and 40g diphenylmethane diisocyanate evenly, add 0.5g catalyst dibutyltin dilaurate, react at 80℃ for 1-5h, cool down to 60℃, add chain extender 4 g of 1,4-butanediol was reacted for 1 h, and diluted with xylene to obtain a moisture-cured prepolymer with an NCO content of about 8% (the NCO content is the content of the prepolymer).
(2)光固化基团的加入(2) Addition of photocurable groups
在上述湿固化预聚物降温至50℃以下，在避光条件下，向预聚物中依次加入8g丙烯酸羟乙酯、20g苯基缩水甘油醚丙烯酸酯和7g环己烷二甲醇二丙烯酸酯和光引发剂2,4,6(三甲基苯甲酰基)二苯基氧化膦0.5g、阻聚剂对苯二酚0.3g，搅拌均匀。The above moisture-cured prepolymer was cooled to below 50°C, and 8 g of hydroxyethyl acrylate, 20 g of phenyl glycidyl ether acrylate and 7 g of cyclohexane dimethanol diacrylate were sequentially added to the prepolymer under the condition of avoiding light. and photoinitiator 2,4,6(trimethylbenzoyl)diphenylphosphine oxide 0.5g, polymerization inhibitor hydroquinone 0.3g, stir uniformly.
(3)封端剂的加入(3) Addition of end-capping agent
在避光条件下向上述湿固化预聚物中依次加入3.5g己内酰胺、7g亚硫酸氢钠和3.5g甲基乙基酮肟，搅拌均匀，并根据粘度需要加入二甲苯，即得高强度多重固化的聚氨酯粘合剂。Add 3.5g of caprolactam, 7g of sodium bisulfite and 3.5g of methyl ethyl ketoxime to the above moisture-cured prepolymer in order under light-proof conditions, stir evenly, and add xylene according to the viscosity to obtain a high-strength multi-layer Cured polyurethane adhesive.
对比例2Comparative Example 2
(1)湿固化预聚物(1) Moisture curing prepolymer
将聚碳酸酯二醇(PCDL，L6001，分子量1000，羟值110±10，酸值0.05mgKOH/g，粘度1100-2300mPas)、聚醚三元醇N330(分子量3000±200，羟值56±3，酸值≤0.1mgKOH/g，粘度500±75mPas)和二苯基甲烷二异氰酸酯分别进行真空干燥；Polycarbonate diol (PCDL, L6001, molecular weight 1000, hydroxyl value 110±10, acid value 0.05mgKOH/g, viscosity 1100-2300mPas), polyether triol N330 (molecular weight 3000±200, hydroxyl value 56±3 , acid value ≤ 0.1mgKOH/g, viscosity 500±75mPas) and diphenylmethane diisocyanate were vacuum dried;
将干燥后的30g聚碳酸酯二醇L6001、43g聚醚三元醇N330和40g二苯基甲烷二异氰酸酯搅拌均匀，加入催化剂二月桂酸二丁基锡0.5g，在80℃下反应1-5h，降温至60℃，加入扩链剂1,4-丁二醇4g反应1h，加入二甲苯稀释，得到NCO含量约为8％的湿固化预聚物(NCO含量为占预聚物的含量)。Stir the dried 30g polycarbonate diol L6001, 43g polyether triol N330 and 40g diphenylmethane diisocyanate evenly, add the catalyst 0.5g dibutyltin dilaurate, react at 80°C for 1-5h, cool down At 60°C, 4 g of chain extender 1,4-butanediol was added to react for 1 h, and xylene was added to dilute to obtain a moisture-cured prepolymer with an NCO content of about 8% (NCO content is the content of the prepolymer).
(2)光固化基团的加入(2) Addition of photocurable groups
在上述湿固化预聚物降温至50℃以下，在避光条件下，向预聚物中依次加入8g丙烯酸羟乙酯、20g苯基缩水甘油醚丙烯酸酯和7g环己烷二甲醇二丙烯酸酯和光引发剂2,4,6(三甲基苯甲酰基)二苯基氧化膦0.5g、阻聚剂对苯二酚0.3g，搅拌均匀。The above moisture-cured prepolymer was cooled to below 50°C, and 8 g of hydroxyethyl acrylate, 20 g of phenyl glycidyl ether acrylate and 7 g of cyclohexane dimethanol diacrylate were sequentially added to the prepolymer under the condition of avoiding light. and photoinitiator 2,4,6(trimethylbenzoyl)diphenylphosphine oxide 0.5g, polymerization inhibitor hydroquinone 0.3g, stir uniformly.
(3)封端剂的加入(3) Addition of end-capping agent
在避光条件下向上述湿固化预聚物中依次加入3.5g己内酰胺、7g亚硫酸氢钠和3.5g甲基乙基酮肟，搅拌均匀，并根据粘度需要加入二甲苯，即得高强度多重固化的聚氨酯粘合剂。Add 3.5g of caprolactam, 7g of sodium bisulfite and 3.5g of methyl ethyl ketoxime to the above moisture-cured prepolymer in order under light-proof conditions, stir evenly, and add xylene according to the viscosity to obtain a high-strength multi-layer Cured polyurethane adhesive.
对比例3Comparative Example 3
(1)湿固化预聚物将聚碳酸酯二醇(PCDL，L6001，分子量1000，羟值110±10，酸值0.05mgKOH/g，粘度1100-2300mPas)、聚醚二元醇VORANOL3010(分子量3000)和二苯基甲烷二异氰酸酯分别进行真空干燥；(1) Moisture-curing prepolymer polycarbonate diol (PCDL, L6001, molecular weight 1000, hydroxyl value 110±10, acid value 0.05mgKOH/g, viscosity 1100-2300mPas), polyether diol VORANOL3010 (molecular weight 3000 ) and diphenylmethane diisocyanate are respectively vacuum-dried;
将干燥后的40g聚碳酸酯二醇L6001、35g聚醚二元醇VORANOL3010和40g二苯基甲烷二异氰酸酯搅拌均匀，加入催化剂二月桂酸二丁基锡0.5g，在80℃下反应1-5h，降温至60℃，加入扩链剂1,4-丁二醇4g反应1h，加入二甲苯稀释，得到NCO含量约为8％的湿固化预聚物(NCO含量为占预聚物的含量)。Stir the dried 40g polycarbonate diol L6001, 35g polyether diol VORANOL3010 and 40g diphenylmethane diisocyanate evenly, add catalyst 0.5g dibutyltin dilaurate, react at 80°C for 1-5h, cool down At 60°C, 4 g of chain extender 1,4-butanediol was added to react for 1 h, and xylene was added to dilute to obtain a moisture-cured prepolymer with an NCO content of about 8% (NCO content is the content of the prepolymer).
(2)光固化基团的加入(2) Addition of photocurable groups
在上述湿固化预聚物降温至50℃以下，在避光条件下，向预聚物中依次加入8g丙烯酸羟乙酯、20g苯基缩水甘油醚丙烯酸酯和7g环己烷二甲醇二丙烯酸酯和光引发剂2,4,6(三甲基苯甲酰基)二苯基氧化膦0.5g、阻聚剂对苯二酚0.3g，搅拌均匀。The above moisture-cured prepolymer was cooled to below 50°C, and 8 g of hydroxyethyl acrylate, 20 g of phenyl glycidyl ether acrylate and 7 g of cyclohexane dimethanol diacrylate were sequentially added to the prepolymer under the condition of avoiding light. and photoinitiator 2,4,6(trimethylbenzoyl)diphenylphosphine oxide 0.5g, polymerization inhibitor hydroquinone 0.3g, stir uniformly.
(3)封端剂的加入(3) Addition of end-capping agent
在避光条件下向上述湿固化预聚物中依次加入3.5g己内酰胺、7g亚硫酸氢钠和3.5g甲基乙基酮肟，搅拌均匀，并根据粘度需要加入二甲苯，即得高强度多重固化的聚氨酯粘合剂。Add 3.5g of caprolactam, 7g of sodium bisulfite and 3.5g of methyl ethyl ketoxime to the above moisture-cured prepolymer in order under light-proof conditions, stir evenly, and add xylene according to the viscosity to obtain a high-strength multi-layer Cured polyurethane adhesive.
对比例4Comparative Example 4
(1)湿固化预聚物(1) Moisture curing prepolymer
将聚碳酸酯二醇(PCDL，L6001，分子量1000，羟值110±10，酸值0.05mgKOH/g，粘度1100-2300mPas)、聚醚三元醇N330(分子量3000±200，羟值56±3，酸值≤0.1mgKOH/g，粘度500±75mPas)和二苯基甲烷二异氰酸酯分别进行真空干燥；Polycarbonate diol (PCDL, L6001, molecular weight 1000, hydroxyl value 110±10, acid value 0.05mgKOH/g, viscosity 1100-2300mPas), polyether triol N330 (molecular weight 3000±200, hydroxyl value 56±3 , acid value ≤ 0.1mgKOH/g, viscosity 500±75mPas) and diphenylmethane diisocyanate were vacuum dried;
将干燥后的40g聚碳酸酯二醇L6001、30g聚醚三元醇N330和40g二苯基甲烷二异氰酸酯搅拌均匀，加入催化剂二月桂酸二丁基锡0.5g，在80℃下反应1-5h，降温至60℃，加入扩链剂1,4-丁二醇4g反应1h，加入二甲苯稀释，得到NCO含量约为8％的湿固化预聚物(NCO含量为占预聚物的含量)。Stir the dried 40g polycarbonate diol L6001, 30g polyether triol N330 and 40g diphenylmethane diisocyanate evenly, add 0.5g catalyst dibutyltin dilaurate, react at 80°C for 1-5h, cool down At 60°C, 4 g of chain extender 1,4-butanediol was added to react for 1 h, and xylene was added to dilute to obtain a moisture-cured prepolymer with an NCO content of about 8% (NCO content is the content of the prepolymer).
(2)光固化基团的加入(2) Addition of photocurable groups
在上述湿固化预聚物降温至50℃以下，在避光条件下，向预聚物中依次加入10g丙烯酸羟乙酯、23g苯基缩水甘油醚丙烯酸酯和光引发剂2,4,6(三甲基苯甲酰基)二苯基氧化膦0.5g、阻聚剂对苯二酚0.3g，搅拌均匀。The above moisture-cured prepolymer was cooled to below 50°C, and 10 g of hydroxyethyl acrylate, 23 g of phenyl glycidyl ether acrylate and photoinitiator 2, 4, 6 (three 0.5 g of methylbenzoyl) diphenyl phosphine oxide and 0.3 g of hydroquinone as a polymerization inhibitor were stirred uniformly.
(3)封端剂的加入(3) Addition of end-capping agent
在避光条件下向上述湿固化预聚物中依次加入3.5g己内酰胺、7g亚硫酸氢钠和3.5g甲基乙基酮肟，搅拌均匀，并根据粘度需要加入二甲苯，即得高强度多重固化的聚氨酯粘合剂。Add 3.5g of caprolactam, 7g of sodium bisulfite and 3.5g of methyl ethyl ketoxime to the above moisture-cured prepolymer in order under light-proof conditions, stir evenly, and add xylene according to the viscosity to obtain a high-strength multi-layer Cured polyurethane adhesive.
对比例5Comparative Example 5
(1)湿固化预聚物(1) Moisture curing prepolymer
将聚碳酸酯二醇(PCDL，L6001，分子量1000，羟值110±10，酸值0.05mgKOH/g，粘度1100-2300mPas)、聚醚三元醇N330(分子量3000±200，羟值56±3，酸值≤0.1mgKOH/g，粘度500±75mPas)和二苯基甲烷二异氰酸酯分别进行真空干燥；Polycarbonate diol (PCDL, L6001, molecular weight 1000, hydroxyl value 110±10, acid value 0.05mgKOH/g, viscosity 1100-2300mPas), polyether triol N330 (molecular weight 3000±200, hydroxyl value 56±3 , acid value ≤ 0.1mgKOH/g, viscosity 500±75mPas) and diphenylmethane diisocyanate were vacuum dried;
将干燥后的40g聚碳酸酯二醇L6001、30g聚醚三元醇N330和40g二苯基甲烷二异氰酸酯搅拌均匀，加入催化剂二月桂酸二丁基锡0.5g，在80℃下反应1-5h，降温至60℃，加入扩链剂1,4-丁二醇4g反应1h，加入二甲苯稀释，得到NCO含量约为8％的湿固化预聚物(NCO含量为占预聚物的含量)。Stir the dried 40g polycarbonate diol L6001, 30g polyether triol N330 and 40g diphenylmethane diisocyanate evenly, add 0.5g catalyst dibutyltin dilaurate, react at 80°C for 1-5h, cool down At 60°C, 4 g of chain extender 1,4-butanediol was added to react for 1 h, and xylene was added to dilute to obtain a moisture-cured prepolymer with an NCO content of about 8% (NCO content is the content of the prepolymer).
(2)光固化基团的加入(2) Addition of photocurable groups
在上述湿固化预聚物降温至50℃以下，在避光条件下，向预聚物中依次加入20g丙烯酸羟乙酯、5g苯基缩水甘油醚丙烯酸酯和10g环己烷二甲醇二丙烯酸酯和光引发剂2,4,6(三甲基苯甲酰基)二苯基氧化膦0.5g、阻聚剂对苯二酚0.3g，搅拌均匀。The above moisture-cured prepolymer was cooled to below 50°C, and 20 g of hydroxyethyl acrylate, 5 g of phenyl glycidyl ether acrylate and 10 g of cyclohexane dimethanol diacrylate were added to the prepolymer in sequence under the condition of avoiding light. and photoinitiator 2,4,6(trimethylbenzoyl)diphenylphosphine oxide 0.5g, polymerization inhibitor hydroquinone 0.3g, stir uniformly.
(3)封端剂的加入(3) Addition of end-capping agent
在避光条件下向上述湿固化预聚物中依次加入3.5g己内酰胺、7g亚硫酸氢钠和3.5g甲基乙基酮肟，搅拌均匀，并根据粘度需要加入二甲苯，即得高强度多重固化的聚氨酯粘合剂。Add 3.5g of caprolactam, 7g of sodium bisulfite and 3.5g of methyl ethyl ketoxime to the above moisture-cured prepolymer in order under light-proof conditions, stir evenly, and add xylene according to the viscosity to obtain a high-strength multi-layer Cured polyurethane adhesive.
对比例6Comparative Example 6
(1)湿固化预聚物(1) Moisture curing prepolymer
将聚碳酸酯二醇(PCDL，L6001，分子量1000，羟值110±10，酸值0.05mgKOH/g，粘度1100-2300mPas)、聚醚三元醇N330(分子量3000±200，羟值56±3，酸值≤0.1mgKOH/g，粘度500±75mPas)和二苯基甲烷二异氰酸酯分别进行真空干燥；Polycarbonate diol (PCDL, L6001, molecular weight 1000, hydroxyl value 110±10, acid value 0.05mgKOH/g, viscosity 1100-2300mPas), polyether triol N330 (molecular weight 3000±200, hydroxyl value 56±3 , acid value ≤ 0.1mgKOH/g, viscosity 500±75mPas) and diphenylmethane diisocyanate were vacuum dried;
将干燥后的40g聚碳酸酯二醇L6001、30g聚醚三元醇N330和40g二苯基甲烷二异氰酸酯搅拌均匀，加入催化剂二月桂酸二丁基锡0.5g，在80℃下反应1-5h，降温至60℃，加入扩链剂1,4-丁二醇4g反应1h，加入二甲苯稀释，得到NCO含量约为8％的湿固化预聚物(NCO含量为占预聚物的含量)。Stir the dried 40g polycarbonate diol L6001, 30g polyether triol N330 and 40g diphenylmethane diisocyanate evenly, add 0.5g catalyst dibutyltin dilaurate, react at 80°C for 1-5h, cool down At 60°C, 4 g of chain extender 1,4-butanediol was added to react for 1 h, and xylene was added to dilute to obtain a moisture-cured prepolymer with an NCO content of about 8% (NCO content is the content of the prepolymer).
(2)光引发基团加入(2) Addition of photoinitiating groups
在上述湿固化预聚物降温至50℃以下，在避光条件下，向预聚物中依次加入8g丙烯酸羟乙酯、20g苯基缩水甘油醚丙烯酸酯和7g环己烷二甲醇二丙烯酸酯和光引发剂2,4,6(三甲基苯甲酰基)二苯基氧化膦0.5g、阻聚剂对苯二酚0.3g，搅拌均匀，并根据粘度需要加入二甲苯，即得高强度湿热双重固化的聚氨酯粘合剂。The above moisture-cured prepolymer was cooled to below 50°C, and 8 g of hydroxyethyl acrylate, 20 g of phenyl glycidyl ether acrylate and 7 g of cyclohexane dimethanol diacrylate were sequentially added to the prepolymer under the condition of avoiding light. and photoinitiator 2,4,6(trimethylbenzoyl)diphenylphosphine oxide 0.5g, polymerization inhibitor hydroquinone 0.3g, stir evenly, and add xylene according to the viscosity to obtain high-strength damp heat Dual cure polyurethane adhesive.
对比例7Comparative Example 7
(1)湿固化预聚物(1) Moisture curing prepolymer
将聚碳酸酯二醇(PCDL，L6001，分子量1000，羟值110±10，酸值0.05mgKOH/g，粘度1100-2300mPas)、聚醚三元醇N330(分子量3000±200，羟值56±3，酸值≤0.1mgKOH/g，粘度500±75mPas)和二苯基甲烷二异氰酸酯分别进行真空干燥；Polycarbonate diol (PCDL, L6001, molecular weight 1000, hydroxyl value 110±10, acid value 0.05mgKOH/g, viscosity 1100-2300mPas), polyether triol N330 (molecular weight 3000±200, hydroxyl value 56±3 , acid value ≤ 0.1mgKOH/g, viscosity 500±75mPas) and diphenylmethane diisocyanate were vacuum dried;
将干燥后的40g聚碳酸酯二醇L6001、30g聚醚三元醇N330和40g二苯基甲烷二异氰酸酯搅拌均匀，加入催化剂二月桂酸二丁基锡0.5g，在80℃下反应1-5h，降温至60℃，加入扩链剂1,4-丁二醇4g反应1h，加入二甲苯稀释，得到NCO含量约为8％的湿固化预聚物(NCO含量为占预聚物的含量)。Stir the dried 40g polycarbonate diol L6001, 30g polyether triol N330 and 40g diphenylmethane diisocyanate evenly, add 0.5g catalyst dibutyltin dilaurate, react at 80°C for 1-5h, cool down At 60°C, 4 g of chain extender 1,4-butanediol was added to react for 1 h, and xylene was added to dilute to obtain a moisture-cured prepolymer with an NCO content of about 8% (NCO content is the content of the prepolymer).
(2)光固化基团的加入(2) Addition of photocurable groups
在上述湿固化预聚物降温至50℃以下，在避光条件下，向预聚物中依次加入8g丙烯酸羟乙酯、20g苯基缩水甘油醚丙烯酸酯和7g环己烷二甲醇二丙烯酸酯和光引发剂2,4,6(三甲基苯甲酰基)二苯基氧化膦0.5g、阻聚剂对苯二酚0.3g，搅拌均匀。The above moisture-cured prepolymer was cooled to below 50°C, and 8 g of hydroxyethyl acrylate, 20 g of phenyl glycidyl ether acrylate and 7 g of cyclohexane dimethanol diacrylate were sequentially added to the prepolymer under the condition of avoiding light. and photoinitiator 2,4,6(trimethylbenzoyl)diphenylphosphine oxide 0.5g, polymerization inhibitor hydroquinone 0.3g, stir uniformly.
(3)封端剂的加入(3) Addition of end-capping agent
在避光条件下向上述湿固化预聚物中依次加入14g亚硫酸氢钠，搅拌均匀，并根据粘度需要加入二甲苯，即得高强度多重固化的聚氨酯粘合剂。Add 14 g of sodium bisulfite to the above moisture-cured prepolymer in sequence under light-proof conditions, stir evenly, and add xylene according to the viscosity to obtain a high-strength multi-curing polyurethane adhesive.
对比例8Comparative Example 8
(1)湿固化预聚物(1) Moisture curing prepolymer
将聚碳酸酯二醇(PCDL，L6001，分子量1000，羟值110±10，酸值0.05mgKOH/g，粘度1100-2300mPas)、聚醚三元醇N330(分子量3000±200，羟值56±3，酸值≤0.1mgKOH/g，粘度500±75mPas)和二苯基甲烷二异氰酸酯分别进行真空干燥；Polycarbonate diol (PCDL, L6001, molecular weight 1000, hydroxyl value 110±10, acid value 0.05mgKOH/g, viscosity 1100-2300mPas), polyether triol N330 (molecular weight 3000±200, hydroxyl value 56±3 , acid value ≤ 0.1mgKOH/g, viscosity 500±75mPas) and diphenylmethane diisocyanate were vacuum dried;
将干燥后的40g聚碳酸酯二醇L6001、30g聚醚三元醇N330和40g二苯基甲烷二异氰酸酯搅拌均匀，加入催化剂二月桂酸二丁基锡0.5g，在80℃下反应1-5h，降温至60℃，加入扩链剂1,4-丁二醇4g反应1h，加入二甲苯稀释，得到NCO含量约为8％的湿固化预聚物(NCO含量为占预聚物的含量)。Stir the dried 40g polycarbonate diol L6001, 30g polyether triol N330 and 40g diphenylmethane diisocyanate evenly, add 0.5g catalyst dibutyltin dilaurate, react at 80°C for 1-5h, cool down At 60°C, 4 g of chain extender 1,4-butanediol was added to react for 1 h, and xylene was added to dilute to obtain a moisture-cured prepolymer with an NCO content of about 8% (NCO content is the content of the prepolymer).
(2)封闭剂的加入(2) Addition of sealing agent
在上述湿固化预聚物依次加入3.5g己内酰胺、7g亚硫酸氢钠和3.5g甲基乙基酮肟，搅拌均匀，并根据粘度需要加入二甲苯，即得高强度湿光双重固化的聚氨酯粘合剂。Add 3.5g of caprolactam, 7g of sodium bisulfite and 3.5g of methyl ethyl ketoxime to the above-mentioned moisture-curing prepolymer in turn, stir evenly, and add xylene according to the viscosity to obtain a high-strength wet-light dual-curing polyurethane adhesive mixture.
【测试方法】【testing method】
1.拉伸剪切强度1. Tensile shear strength
测试标准参考GB/T13936-92进行，以PMMA测试片替换金属片，以本发明实施例和对比例的粘合剂替换硫化橡胶，其他条件同GB/T13936-92，并记录破裂面的破坏形式。The test standard is carried out with reference to GB/T13936-92, the metal sheet is replaced with PMMA test piece, and the vulcanized rubber is replaced with the adhesive of the embodiment of the present invention and the comparative example, other conditions are the same as GB/T13936-92, and the failure mode of the rupture surface is recorded.
样品固化方法1：将粘合剂涂附在PMMA测试片，将另一PMMA测试片压实在涂附有粘合剂的PMMA测试片表面，使用夹子夹持连接部，紫外线光照10min，置于湿度50，65℃下，固化2h，即可按照上述方法进行测试，得到低温拉伸剪切强度并记录破裂情况。Sample curing method 1: apply the adhesive to the PMMA test piece, press another PMMA test piece on the surface of the PMMA test piece coated with the adhesive, use a clip to hold the connection part, expose it to ultraviolet light for 10 minutes, and place it on the surface of the PMMA test piece. Under the humidity of 50 and 65 ℃, after curing for 2 hours, the test can be carried out according to the above method to obtain the low temperature tensile shear strength and record the rupture.
样品固化方法2：将粘合剂涂附在PMMA测试片，将被粘物二压实在涂附有粘合剂的PMMA测试片表面，使用夹子夹持连接部，紫外线光照10min，置于湿度50，65℃下，固化2h，进而再次置于湿度50，160℃下固化30分钟，即可按照上述方法进行测试，得到高温拉伸剪切强度。Sample curing method 2: Apply the adhesive to the PMMA test piece, press the adherend 2 on the surface of the PMMA test piece coated with the adhesive, use a clip to hold the connection part, expose it to ultraviolet light for 10 minutes, and place it in the humidity. After curing for 2 hours at 50 and 65 °C, and then curing at a humidity of 50 and 160 °C for 30 minutes, the test can be carried out according to the above method to obtain the high temperature tensile shear strength.
2.三点塑料弯曲试验2. Three-point plastic bending test
三点测试测试标准参考GB/T9341-2000进行，测试片通过如下方法制备：将粘合剂涂布在离型膜上，另一侧覆盖离型膜，采用上述固化方法，得到厚4mm，宽10mm，长80mm的样品。记录弯曲模量(MPa)和弯曲强度(MPa)。Three-point test The test standard is carried out with reference to GB/T9341-2000. The test piece is prepared by the following method: coating the adhesive on the release film, covering the release film on the other side, and using the above curing method to obtain a thickness of 4mm and a width of 4mm. 10mm, 80mm long sample. The flexural modulus (MPa) and flexural strength (MPa) were recorded.
【试验结果】【test results】
备注：对比例8前期固化慢，强度上升很慢。Remarks: Comparative Example 8 was cured slowly in the early stage, and the strength increased very slowly.
由上述实验数据验证了说明书的内容，其聚碳酸酯多元醇和聚醚多元醇的比例、光固化单体的种类选择以及封闭剂种类的选择都会对最终产品的性能有重要影响，如果不在本发明的技术范围内，难以平衡剪切强度、模量、强度以及固化速率，难以适应高强度、快速固化的需求。The content of the specification is verified by the above experimental data. The ratio of polycarbonate polyol and polyether polyol, the selection of light-curing monomers and the selection of sealing agents will have an important impact on the performance of the final product. If not in the present invention It is difficult to balance the shear strength, modulus, strength and curing rate within the technical range of 100%, and it is difficult to meet the needs of high strength and fast curing.
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| US6562881B2 (en)* | 2001-05-30 | 2003-05-13 | Henkel Loctite Corporation | Liquified polyols, urethane acrylate resins prepared therewith and curable compositions employing such resins |
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| CN103703087A (en)* | 2011-07-22 | 2014-04-02 | H.B.富勒公司 | A one-component, dual-cure adhesive for use on electronics |
| CN103173179A (en)* | 2013-03-07 | 2013-06-26 | 常州大学 | Preparation method of aqueous polyurethane adhesive for laminated composite fabrics |
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| CN108395847A (en) | 2018-08-14 |
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