技术领域technical field
本发明涉及一种丙烯酸酯光学胶的合成方法，具体是先合成丙烯酸酯预聚物，然后进行配方调试。The invention relates to a method for synthesizing an acrylate optical glue, specifically, first synthesizing an acrylate prepolymer, and then performing formula adjustment.
背景技术Background technique
紫外光固化胶黏剂是近年来发展较快的一种胶黏剂，它是利用紫外光引发具有化学活性的液态材料快速聚合交联，数秒内固化成膜，是一种高性能、高效率的胶黏剂，通过合成预聚物，用活性稀释剂进行改性，并配合加入各种光引发剂的方法，制备了UV系列紫外光固化胶黏剂，该系列紫外光固化胶黏剂具有固化速度快、粘接强度高、抗震性好等优点，已广泛应用于金属、玻璃、水晶、石材等多种材料的粘接，具有较好的社会经济效益，但现有的胶黏剂也存在很多不足之处，例如抗冲击性差，光、热稳定性较低等。UV-curable adhesive is a kind of adhesive that has developed rapidly in recent years. It uses ultraviolet light to trigger rapid polymerization and crosslinking of chemically active liquid materials, and solidifies into a film within a few seconds. It is a high-performance, high-efficiency adhesive. Adhesives, by synthesizing prepolymers, modifying with reactive diluents, and adding various photoinitiators, the UV series of ultraviolet curing adhesives are prepared. This series of ultraviolet curing adhesives have With the advantages of fast curing speed, high bonding strength, and good shock resistance, it has been widely used in the bonding of various materials such as metal, glass, crystal, and stone, and has good social and economic benefits. There are many shortcomings, such as poor impact resistance, low light and thermal stability, etc.
中国专利CN 102898980 A公开了一种紫外光胶黏剂的制备方法，以甲基丙烯酸甲酯、丙烯酸丁酯、醋酸乙烯酯、丙烯酸等为反应单体，过氧化苯甲酰为引发剂，四氢呋喃甲醇与甲苯为溶剂，过硫酸铵为链转移剂，在N2保护下，升温至80℃，采用分批加料的方法，反应2～3h后得到粘度合适的丙烯酸酯紫外光固化胶黏剂。用甲苯和四氢呋喃为溶剂，后期存留在预聚物中，毒性较大。Chinese patent CN 102898980 A discloses a preparation method of an ultraviolet light adhesive, using methyl methacrylate, butyl acrylate, vinyl acetate, acrylic acid, etc. as reaction monomers, benzoyl peroxide as an initiator, tetrahydrofuran Methanol and toluene are used as solvents, and ammonium persulfate is used as a chain transfer agent. Under the protection of N2 , the temperature is raised to 80°C, and the batch feeding method is adopted. After 2-3 hours of reaction, an acrylate UV-curable adhesive with a suitable viscosity is obtained. Toluene and tetrahydrofuran are used as solvents, which remain in the prepolymer in the later stage and are highly toxic.
中国专利CN 102477268 A公开了一种溶剂型丙烯酸酯胶黏剂的制备方法，按设定的配比量取丙烯酸酯类聚合物和溶剂乙酸乙酯，置于反应容器中，60℃下挥发乙酸乙酯，待乙酸乙酯挥发干净后，降温至40℃后，按配比量加入置换溶剂，搅拌均匀，得到一种溶液型丙烯酸酯胶黏剂。所述方法制备的胶黏剂的使用可将干燥工艺从传统的100～140℃下降至40～70℃，可节约能源，降低成本。但仍含有毒溶剂，非绿色环保胶黏剂。Chinese patent CN 102477268 A discloses a method for preparing a solvent-based acrylate adhesive. Acrylic polymers and solvent ethyl acetate are measured according to a set ratio, placed in a reaction vessel, and acetic acid is volatilized at 60°C. Ethyl acetate, after the ethyl acetate volatilizes completely, after cooling down to 40°C, add the displacement solvent according to the proportion, and stir evenly to obtain a solution-type acrylate adhesive. The use of the adhesive prepared by the method can reduce the drying process from the traditional 100-140°C to 40-70°C, which can save energy and reduce costs. However, it still contains toxic solvents and is not a green adhesive.
中国专利CN 103467668 A公开了一种耐水性的丙烯酸酯胶黏剂的制备方法，将多元醇聚合物、丙烯酸酯类单体、扩链剂脱水备用，向反应釜中通氮气，加入多元醇聚合物，另外添加催化剂，搅拌并滴加多异氰酸酯，升温至60～110℃，保温3～6小时，加入扩链剂，并加入丙烯酸酯类单体，当反应物中NCO基团的质量百分含量达到0.05～10％时，加入丙烯酸酯，然后将上述溶液降至室温，加入引发剂，并加到加有表面活性剂的去离子水溶液中，边滴加边搅拌，将其分散成一定粒径的聚氨酯预乳液，最后将上述预乳液加入到反应釜中，通入氮气，升温至50～80℃并反应3～6小时，然后降至室温出料。但该类丙烯酸胶黏剂固化后透明性较差，只能对一般的原件进行粘接，不能作为高精密仪器的粘结剂。Chinese patent CN 103467668 A discloses a method for preparing a water-resistant acrylate adhesive, which involves dehydrating polyol polymers, acrylate monomers, and chain extenders for later use, passing nitrogen into the reactor, and adding polyols to polymerize In addition, add catalyst, stir and drop polyisocyanate, heat up to 60-110°C, keep warm for 3-6 hours, add chain extender, and add acrylate monomer, when the mass percentage of NCO groups in the reactant When the content reaches 0.05-10%, add acrylate, then lower the above solution to room temperature, add the initiator, and add it to the deionized aqueous solution with surfactant, stir while adding dropwise, and disperse it into a certain particle A polyurethane pre-emulsion with diameter, and finally add the above-mentioned pre-emulsion into the reaction kettle, pass nitrogen gas, raise the temperature to 50-80°C and react for 3-6 hours, then cool down to room temperature and discharge. However, this type of acrylic adhesive has poor transparency after curing, and can only be used for bonding general originals, and cannot be used as an adhesive for high-precision instruments.
发明内容Contents of the invention
本发明针对现有技术反应温度高、反应压力大，对设备的要求高，生产投资大，常用水溶性醚类作反应溶剂，反应性能不佳，分离提纯不好等缺点，提供一种合成可有效控制聚合物粘度丙烯酸树脂的制备方法。该方法操作简单、成本低，避免了高温高压、散热困难的问题。The present invention aims at the disadvantages of the prior art, such as high reaction temperature, high reaction pressure, high requirements for equipment, large production investment, commonly used water-soluble ethers as reaction solvents, poor reaction performance, poor separation and purification, etc., and provides a synthetic method. A process for preparing an acrylic resin with effective polymer viscosity control. The method is simple in operation and low in cost, and avoids the problems of high temperature and high pressure and difficult heat dissipation.
为了获得组成均匀和分子量分布较窄的共聚物，通常采用连续聚合工艺。在聚合过程中，产物的组成随聚合过程而变化，最终得到一定粘度的丙烯酸酯聚合物。In order to obtain copolymers with uniform composition and narrow molecular weight distribution, a continuous polymerization process is usually used. During the polymerization process, the composition of the product changes with the polymerization process, and finally an acrylate polymer with a certain viscosity is obtained.
本发明首先通过半连续聚合工艺和溶液聚合法得到丙烯酸树脂聚合物溶液；然后将上述聚合物减压蒸馏去除残留溶剂，得到一种淡黄色黏稠树脂，将这种树脂与活性稀释剂、光引发剂按一定比例混配均匀，制成丙烯酸酯光学胶。The present invention first obtains the acrylic resin polymer solution through semi-continuous polymerization process and solution polymerization method; then the above-mentioned polymer is distilled under reduced pressure to remove the residual solvent to obtain a light yellow viscous resin, which is mixed with a reactive diluent, photoinitiated Agents are mixed evenly in a certain proportion to make acrylate optical glue.
本发明目的通过如下技术方案实现：The object of the invention is achieved through the following technical solutions:
一种丙烯酸树脂光学胶的合成方法，包括以下步骤：A kind of synthetic method of acrylic resin optical glue, comprises the following steps:
(1)以质量份计，将20～40份的单体、0.5～2份的引发剂和1～3份的分子量调节剂加入到溶剂丙酮中，搅拌使其充分混合，升温到70～80℃，反应10min；(1) In parts by mass, add 20-40 parts of monomer, 0.5-2 parts of initiator and 1-3 parts of molecular weight regulator into solvent acetone, stir to make it fully mixed, and heat up to 70-80 ℃, react for 10min;
(2)以质量份计，将60～80份的单体、0.5～2份的引发剂和0.5～2份的分子量调节剂混合，将混合溶液均匀滴加至步骤(1)反应后的溶液中，滴加时间1～3h，滴完后再加入0.2～0.5份的引发剂，于70～85℃保温1.0～5.0h，得到聚合物溶液；将得到的聚合物溶液在80℃条件下减压蒸馏除去杂质，得到丙烯酸酯预聚物；(2) In terms of parts by mass, mix 60-80 parts of monomer, 0.5-2 parts of initiator and 0.5-2 parts of molecular weight regulator, and evenly drop the mixed solution to the solution after the reaction in step (1) In the process, the dropping time is 1 to 3 hours, and then add 0.2 to 0.5 parts of initiator after the dropping, and keep warm at 70 to 85°C for 1.0 to 5.0 hours to obtain a polymer solution; reduce the obtained polymer solution at 80°C Impurities are removed by pressure distillation to obtain an acrylate prepolymer;
(3)以质量百分比计，将45～60％的丙烯酸酯预聚物、35～60％的活性稀释剂和1～5％的光引发剂均匀混配，即得到丙烯酸酯光学胶；(3) Evenly mix 45-60% of acrylate prepolymer, 35-60% of reactive diluent and 1-5% of photoinitiator in mass percentage to obtain acrylate optical glue;
步骤(1)(2)中所述单体为丙烯酸3，3，5-三甲基环己醇酯，所述分子量调节剂为含巯基的化合物，引发剂为有机过氧化物类引发剂或偶氮类引发剂。The monomer described in step (1)(2) is 3,3,5-trimethylcyclohexanol acrylate, the molecular weight regulator is a compound containing mercapto, and the initiator is an organic peroxide initiator or Azo initiators.
步骤(1)所述分子量调节剂为十二烷基硫醇或巯基乙醇。The molecular weight regulator in step (1) is dodecyl mercaptan or mercaptoethanol.
步骤(1)所述引发剂为过氧化苯甲酸叔丁酯、过氧化(2-乙基)己酸叔丁酯、过氧化甲酸叔丁酯、偶氮二异丁腈、偶氮二异庚腈和偶氮二异丁酸二甲酯中的一种或两种以上。The initiator described in step (1) is tert-butyl peroxybenzoate, tert-butyl peroxy(2-ethyl)hexanoate, tert-butyl peroxyformate, azobisisobutyronitrile, azobisisoheptyl One or more of nitrile and dimethyl azobisisobutyrate.
步骤(3)所述的活性稀释剂为丙烯酸异冰片酯、二缩三丙二醇二丙烯酸酯、己二醇二丙烯酸酯、三羟甲基丙烷三丙烯酸酯和二丙二醇二丙烯酸酯中的一种或两种以上。本发明优选丙烯酸异冰片酯和二缩三丙二醇二丙烯酸酯中的一种或两种。The reactive diluent described in step (3) is one of isobornyl acrylate, tripropylene glycol diacrylate, hexanediol diacrylate, trimethylolpropane triacrylate and dipropylene glycol diacrylate or Two or more. The present invention is preferably one or both of isobornyl acrylate and tripropylene glycol diacrylate.
步骤(3)所述光引发剂为184光引发剂(1-羟基环己基苯基甲酮)或1173光引发剂(2-羟基-2-甲基-1-苯基-1-丙酮)。The photoinitiator in step (3) is 184 photoinitiator (1-hydroxycyclohexyl phenyl ketone) or 1173 photoinitiator (2-hydroxyl-2-methyl-1-phenyl-1-acetone).
步骤(1)加入的单体为30～40份；步骤(2)加入的单体为60～70份。The monomer added in the step (1) is 30-40 parts; the monomer added in the step (2) is 60-70 parts.
步骤(1)加入的引发剂为0.5～1份；步骤(2)前后两次加入的引发剂分别为0.5～1份，0.3～0.5份。The initiator added in step (1) is 0.5-1 part; the initiator added twice before and after step (2) is 0.5-1 part and 0.3-0.5 part respectively.
步骤(1)加入的分子量调节剂为1～2.5份；步骤(2)加入的分子量调节剂为0.5～1.5份。The molecular weight regulator added in the step (1) is 1-2.5 parts; the molecular weight regulator added in the step (2) is 0.5-1.5 parts.
步骤(3)中丙烯酸酯预聚物为50～60％，活性稀释剂为35～55％，光引发剂为1～3％。In the step (3), the content of the acrylate prepolymer is 50-60%, the content of the reactive diluent is 35-55%, and the content of the photoinitiator is 1-3%.
丙烯酸3,3,5-三甲基环己醇酯的合成方法，包括如下步骤：The synthetic method of 3,3,5-trimethylcyclohexanol acrylate comprises the steps:
(1)将丙烯酸和3,3,5-三甲基环己醇在插有冷凝管得烧瓶中混合，搅拌；升温进行回流冷凝，当温度达到稳定回流时，加入催化剂进行反应；其中，丙烯酸与3,3,5-三甲基环己醇的摩尔比为1：1.2～3.8；所述的催化剂为对甲苯磺酸，其用量为全部反应物总重量的0.5～2.0％；(1) Mix acrylic acid and 3,3,5-trimethylcyclohexanol in a flask with a condenser tube, stir; heat up for reflux condensation, and when the temperature reaches a stable reflux, add a catalyst to react; among them, acrylic acid The molar ratio to 3,3,5-trimethylcyclohexanol is 1:1.2-3.8; the catalyst is p-toluenesulfonic acid, and its dosage is 0.5-2.0% of the total weight of all reactants;
(2)反应4～6h后，取下冷凝管，安上分水器，继续升温到120～130℃，保温反应3～6h；反应结束后减压蒸馏出过量的醇，即得产物，其中，整个反应过程中通入氮气。(2) After reacting for 4 to 6 hours, remove the condenser tube, install a water separator, continue to heat up to 120 to 130 ° C, and keep the temperature for 3 to 6 hours; after the reaction is over, the excess alcohol is distilled off under reduced pressure to obtain the product, wherein , Nitrogen was introduced throughout the reaction.
步骤(1)中的丙烯酸与3,3,5-三甲基环己醇的摩尔比为1：1.2～2.0。The molar ratio of acrylic acid to 3,3,5-trimethylcyclohexanol in step (1) is 1:1.2-2.0.
步骤(1)中搅拌的速度为300～500转/分。The stirring speed in the step (1) is 300-500 rpm.
步骤(1)中催化剂的用量为全部反应物总重量的0.5～1.5％。The amount of catalyst used in step (1) is 0.5-1.5% of the total weight of all reactants.
步骤(2)中减压蒸馏的条件为温度为80～100℃，压力为－0.099～－0.06Mpa。The conditions for vacuum distillation in step (2) are that the temperature is 80-100° C., and the pressure is -0.099--0.06Mpa.
本发明所述反应溶剂为丙酮作溶剂，避免了在其他溶剂中，单体的反应性能不佳，反应后溶剂分离提纯不好等缺点。溶剂丙酮和水的混合物溶液经过精馏系统，分离出溶剂丙酮；步骤(3)中得到的丙烯酸树脂溶液，粘度较大，不能进行高温蒸馏，选择丙酮作为溶剂，可以在相对较低的温度下将杂质及溶剂出去，得到丙烯酸树脂。该种固体树脂在分离提纯后颜色淡黄、透明，为下一步的配方调配提供良好的预聚物。The reaction solvent of the present invention is acetone as a solvent, which avoids the disadvantages of poor reaction performance of monomers and bad solvent separation and purification after reaction in other solvents. The mixture solution of solvent acetone and water passes through the rectification system to separate the solvent acetone; the acrylic resin solution obtained in step (3) has a high viscosity and cannot be distilled at high temperature. Acetone is selected as the solvent, which can be distilled at a relatively low temperature. Impurities and solvents are removed to obtain acrylic resin. The color of this solid resin is light yellow and transparent after separation and purification, which provides a good prepolymer for the next step of formulating.
相对于现有技术，本发明的优点是：Compared with the prior art, the advantages of the present invention are:
(1)本发明聚合反应在常压较低温度下进行，避免了高温带来的能量损耗和高压带来的不安全因素，聚合工艺简单易操作。(1) The polymerization reaction of the present invention is carried out at normal pressure and relatively low temperature, which avoids energy loss caused by high temperature and unsafe factors caused by high pressure, and the polymerization process is simple and easy to operate.
(2)本发明采用溶液聚合，反应介质特别是丙酮的加入有效地提高聚合反应中的散热效果，降低了聚合物溶液的粘度，使得反应设备比较容易清理。(2) The present invention adopts solution polymerization, and the addition of the reaction medium, especially acetone, effectively improves the heat dissipation effect in the polymerization reaction, reduces the viscosity of the polymer solution, and makes the reaction equipment easier to clean.
(3)本发明用丙烯酸酯为主要原料，采用丙酮为溶剂，在较低的温度和常压条件下反应，通过采用半连续滴加工艺、引发剂和分子量调节剂的协同作用，有效地调节了所得聚合物产品的分子量大小和分子量分布，合成出分子量可控、分子量分布窄、玻璃化温度可调节的丙烯酸树脂，然后将合成的聚合物与活性稀释剂等进行混配，得到丙烯酸酯光学胶，使得最后调配的光学胶性能稳定。(3) the present invention is main raw material with acrylate, adopts acetone to be solvent, reacts under lower temperature and normal pressure condition, by adopting the synergistic effect of semi-continuous dripping process, initiator and molecular weight regulator, regulates effectively The molecular weight and molecular weight distribution of the obtained polymer product are studied, and an acrylic resin with controllable molecular weight, narrow molecular weight distribution and adjustable glass transition temperature is synthesized, and then the synthesized polymer is mixed with a reactive diluent to obtain an acrylate optical resin. Glue, so that the performance of the final deployment of optical glue is stable.
(4)本发明的合成方法以丙烯酸、3,3,5-三甲基环己醇及催化剂为原料，可使丙烯酸的转化率达到90％以上，丙烯酸3,3,5-三甲基环己醇酯的直收率在94％以上；并且具有所得的产物颜色较浅，产品质量好，回收醇品质好，可多次套用等优点。(4) The synthesis method of the present invention uses acrylic acid, 3,3,5-trimethylcyclohexanol and catalyst as raw materials, so that the conversion rate of acrylic acid can reach more than 90%, and acrylic acid 3,3,5-trimethylcyclohexanol The direct yield of hexanol ester is above 94%; and the obtained product has the advantages of light color, good product quality, good quality of recovered alcohol, and can be applied mechanically for many times.
附图说明Description of drawings
图1为丙烯酸酯预聚物的FT-IR曲线。Figure 1 is the FT-IR curve of acrylate prepolymer.
图2为实施例6合成的丙烯酸3,3,5-三甲基环己醇酯的红外谱图。Fig. 2 is the infrared spectrogram of 3,3,5-trimethylcyclohexanol acrylate synthesized in Example 6.
具体实施方式Detailed ways
以下结合具体实施例来对本发明作进一步说明，但本发明所要求保护的范围并不局限于实施例所涉及之范围。The present invention will be further described below in conjunction with specific examples, but the protection scope of the present invention is not limited to the scope involved in the examples.
实施例1Example 1
步骤1)在N2保护下，常压的条件下，称取40.00g丙烯酸3，3，5-三甲基环己醇酯单体、0.50g偶氮二异丁腈、3.00g十二烷基硫醇溶于40.00g丙酮溶剂中得到混合溶液，搅拌使其充分混合，升温到80℃，反应10min；Step 1) Under the protection ofN2 , under the condition of normal pressure, weigh 40.00g 3,3,5-trimethylcyclohexyl acrylate monomer, 0.50g azobisisobutyronitrile, 3.00g dodecane Dissolve mercaptan in 40.00g of acetone solvent to obtain a mixed solution, stir to make it fully mixed, heat up to 80°C, and react for 10min;
步骤2)将60g丙烯酸3，3，5-三甲基环己醇酯单体、0.50g偶氮二异丁腈和1g十二烷基硫醇混合，将混合溶液均匀滴加至步骤1反应后的溶液中，匀速滴加1.5h，滴完后加入0.50g偶氮二异丁腈，80℃保温3h后，得到的聚合物在80℃条件下减压蒸馏出去杂质与溶剂，得到丙烯酸酯预聚物；Step 2) Mix 60g of 3,3,5-trimethylcyclohexanol acrylate monomer, 0.50g of azobisisobutyronitrile and 1g of dodecyl mercaptan, and evenly drop the mixed solution to the step 1 reaction Add 0.50 g of azobisisobutyronitrile to the final solution at a constant speed for 1.5 hours, and then add 0.50 g of azobisisobutyronitrile. After 3 hours of heat preservation at 80 ° C, the obtained polymer is distilled under reduced pressure at 80 ° C to remove impurities and solvents to obtain acrylate prepolymer;
步骤3)将2.0g丙烯酸酯预聚物、1.0g丙烯酸异冰片酯(IBOA，)、l.0g二缩三丙二醇二丙烯酸酯(TPGDA)、0.10g184光引发剂混合均匀，并避光保存。将混合均匀的胶液倒入铝箔中，使其均匀平铺，用紫外光照射20分钟完全固化后脱膜，测试折射率与透光率。树脂的红外光谱图如图1所示。2950、2869、2837cm-1处是-CH3、-CH2的伸缩振动特征吸收峰。1730cm-1处是羰基的特征吸收峰。1638、811cm-1处是伸缩振动和弯曲振动吸收峰C＝C双键的特征吸收峰，表明反应产物中还有部分双键，并未完全聚合。分子中含有C＝C与羰基，达到了光敏预聚物的预期结构。Step 3) Mix 2.0g acrylate prepolymer, 1.0g isobornyl acrylate (IBOA,), 1.0g tripropylene glycol diacrylate (TPGDA), 0.10g184 photoinitiator, and store in the dark. Pour the evenly mixed glue solution into the aluminum foil, spread it evenly, irradiate with ultraviolet light for 20 minutes to completely cure, then remove the film, and test the refractive index and light transmittance. The infrared spectrum of the resin is shown in Figure 1. The stretching vibration characteristic absorption peaks of -CH3 and -CH2 are at 2950, 2869, and 2837 cm-1 . 1730cm-1 is the characteristic absorption peak of carbonyl. The stretching vibration and bending vibration absorption peaks at 1638 and 811 cm-1 are the characteristic absorption peaks of the C=C double bond, indicating that there are still some double bonds in the reaction product, which are not completely polymerized. The molecule contains C=C and carbonyl groups, and the expected structure of the photosensitive prepolymer is achieved.
使用粘度计测得预聚物的粘度达到了14000mpa.s，调配的固化胶的固化时间为20s，折射率达到了1.50，透光率在一定波长范围内达到了90％以上，附着力为良好，剥离强度达到了188N/20mm。The viscosity of the prepolymer measured by a viscometer has reached 14000mpa.s, the curing time of the prepared curing glue is 20s, the refractive index has reached 1.50, the light transmittance has reached more than 90% in a certain wavelength range, and the adhesion is excellent. , The peel strength reached 188N/20mm.
实施例2Example 2
步骤1)在N2保护下，常压的条件下，称量100.00g丙烯酸3，3，5-三甲基环己醇酯单体，取单体的30.00g、0.50g偶氮二异丁腈、2.00g十二烷基硫醇溶于30.00g丙酮溶剂中得到混合溶液，搅拌使其充分混合，升温到70℃，反应10min；Step 1) Under the protection ofN2 , under the condition of normal pressure, weigh 100.00g of 3,3,5-trimethylcyclohexyl acrylate monomer, take 30.00g of the monomer, 0.50g of azobisisobutyl Nitrile and 2.00g of dodecylmercaptan were dissolved in 30.00g of acetone solvent to obtain a mixed solution, stirred to make it fully mixed, heated to 70°C, and reacted for 10 minutes;
步骤2)将配方中剩余的70g单体、0.50g偶氮二异丁腈和1g十二烷基硫醇混合，将混合溶液均匀滴加至步骤1反应后的溶液中，匀速滴加1h，滴完后加入0.50g偶氮二异丁腈，70℃保温2h后，得到的聚合物在80℃条件下减压蒸馏出去杂质与溶剂，得到丙烯酸酯预聚物；Step 2) Mix the remaining 70g of monomer, 0.50g of azobisisobutyronitrile and 1g of dodecylmercaptan in the formula, and evenly add the mixed solution dropwise to the solution after the reaction in step 1, and add dropwise at a constant speed for 1h, After dripping, add 0.50 g of azobisisobutyronitrile, keep warm at 70°C for 2 hours, and distill the obtained polymer under reduced pressure at 80°C to remove impurities and solvents to obtain an acrylate prepolymer;
步骤3)将2.0g丙烯酸酯预聚物、1.5g丙烯酸异冰片酯(IBOA，)、0.5g二缩三丙二醇二丙烯酸酯(TPGDA)、0.10g184光引发剂混合均匀，并避光保存。将混合均匀的胶液倒入铝箔中，使其均匀平铺，用紫外光照射20分钟完全固化后脱膜，测试折射率与透光率。Step 3) Mix 2.0 g of acrylate prepolymer, 1.5 g of isobornyl acrylate (IBOA,), 0.5 g of tripropylene glycol diacrylate (TPGDA), and 0.10 g of 184 photoinitiator, and store in the dark. Pour the evenly mixed glue solution into the aluminum foil, spread it evenly, irradiate with ultraviolet light for 20 minutes to completely cure, then remove the film, and test the refractive index and light transmittance.
使用粘度计测得预聚物的粘度达到了8600mpa.s，调配的固化胶固化时间30s，折射率达到了1.493，透光率在一定波长范围内达到了88％以上，附着力为良好，剥离强度达到了184N/20mm。The viscosity of the prepolymer measured by a viscometer has reached 8600mpa.s, the curing time of the prepared curing glue is 30s, the refractive index has reached 1.493, the light transmittance has reached more than 88% in a certain wavelength range, and the adhesion is good. The strength reached 184N/20mm.
实施例3Example 3
步骤1)在N2保护下，常压的条件下，称量100.00g丙烯酸3，3，5-三甲基环己醇酯单体，取单体的30.00g、0.50g偶氮二异丁腈、3.00g十二烷基硫醇溶于40.00g丙酮溶剂中得到混合溶液，搅拌使其充分混合，升温到70℃，反应10min；Step 1) Under the protection ofN2 , under the condition of normal pressure, weigh 100.00g of 3,3,5-trimethylcyclohexyl acrylate monomer, take 30.00g of the monomer, 0.50g of azobisisobutyl Nitrile and 3.00g of dodecyl mercaptan were dissolved in 40.00g of acetone solvent to obtain a mixed solution, stirred to make it fully mixed, heated to 70°C, and reacted for 10 minutes;
步骤2)将配方中剩余的70g单体、0.50g偶氮二异丁腈和1g十二烷基硫醇混合，将混合溶液均匀滴加至步骤1反应后的溶液中，匀速滴加1.5h，滴完后加入0.50g偶氮二异丁腈，70℃保温3h后，得到的聚合物在80℃条件下减压蒸馏出去杂质与溶剂，得到丙烯酸酯预聚物；Step 2) Mix the remaining 70g of monomer, 0.50g of azobisisobutyronitrile and 1g of dodecylmercaptan in the formula, and evenly drop the mixed solution into the solution after the reaction in step 1, and add dropwise at a constant speed for 1.5h After dropping, add 0.50 g of azobisisobutyronitrile, keep warm at 70°C for 3 hours, and distill the obtained polymer under reduced pressure at 80°C to remove impurities and solvents to obtain an acrylate prepolymer;
步骤3)将2.0g丙烯酸酯预聚物、1.0g丙烯酸异冰片酯(IBOA，)、1.0g二缩三丙二醇二丙烯酸酯(TPGDA)、0.10g1173光引发剂混合均匀，并避光保存。将混合均匀的胶液倒入铝箔中，使其均匀平铺，用紫外光照射20分钟完全固化后脱膜，测试折射率与透光率。Step 3) Mix 2.0 g of acrylate prepolymer, 1.0 g of isobornyl acrylate (IBOA,), 1.0 g of tripropylene glycol diacrylate (TPGDA), and 0.10 g of 1173 photoinitiator, and store in the dark. Pour the evenly mixed glue solution into the aluminum foil, spread it evenly, irradiate with ultraviolet light for 20 minutes to completely cure, then remove the film, and test the refractive index and light transmittance.
使用粘度计测得预聚物的粘度达到了9600mpa.s，调配的固化胶固化时间20s，折射率达到了1.48，透光率在一定波长范围内达到了89％以上，附着力为良好，剥离强度达到了194N/20mm。The viscosity of the prepolymer measured by a viscometer has reached 9600mpa.s, the curing time of the prepared curing glue is 20s, the refractive index has reached 1.48, the light transmittance has reached more than 89% in a certain wavelength range, and the adhesion is very good. The strength reached 194N/20mm.
实施例4Example 4
步骤1)在N2保护下，常压的条件下，称量100.00g丙烯酸3，3，5-三甲基环己醇酯单体，取单体的30.00g、0.50g偶氮二异丁腈、2.00g十二烷基硫醇溶于30.00g丙酮溶剂中得到混合溶液，搅拌使其充分混合，升温到70℃，反应10min；Step 1) Under the protection ofN2 , under the condition of normal pressure, weigh 100.00g of 3,3,5-trimethylcyclohexyl acrylate monomer, take 30.00g of the monomer, 0.50g of azobisisobutyl Nitrile and 2.00g of dodecylmercaptan were dissolved in 30.00g of acetone solvent to obtain a mixed solution, stirred to make it fully mixed, heated to 70°C, and reacted for 10 minutes;
步骤2)将配方中剩余的70g单体、0.50g偶氮二异丁腈和1g十二烷基硫醇混合，将混合溶液均匀滴加至步骤1反应后的溶液中，匀速滴加1h，滴完后加入0.50g偶氮二异丁腈，70℃保温2h后，得到的聚合物在80℃条件下减压蒸馏出去杂质与溶剂，得到丙烯酸酯预聚物；Step 2) Mix the remaining 70g of monomer, 0.50g of azobisisobutyronitrile and 1g of dodecylmercaptan in the formula, and evenly add the mixed solution dropwise to the solution after the reaction in step 1, and add dropwise at a constant speed for 1h, After dripping, add 0.50 g of azobisisobutyronitrile, keep warm at 70°C for 2 hours, and distill the obtained polymer under reduced pressure at 80°C to remove impurities and solvents to obtain an acrylate prepolymer;
步骤3)将2.0g丙烯酸酯预聚物、1.0g丙烯酸异冰片酯(IBOA，)、1.0g二缩三丙二醇二丙烯酸酯(TPGDA)、0.10g1173光引发剂混合均匀，并避光保存。将混合均匀的胶液倒入铝箔中，使其均匀平铺，用紫外光照射20分钟完全固化后脱膜，测试折射率与透光率。Step 3) Mix 2.0 g of acrylate prepolymer, 1.0 g of isobornyl acrylate (IBOA,), 1.0 g of tripropylene glycol diacrylate (TPGDA), and 0.10 g of 1173 photoinitiator, and store in the dark. Pour the evenly mixed glue solution into the aluminum foil, spread it evenly, irradiate with ultraviolet light for 20 minutes to completely cure, then remove the film, and test the refractive index and light transmittance.
使用粘度计测得预聚物的粘度达到了12800mpa.s，调配的固化胶固化时间28s，折射率达到了1.48，透光率在一定波长范围内达到了89％以上，附着力为良好，剥离强度达到了189N/20mm。The viscosity of the prepolymer measured by a viscometer has reached 12800mpa.s, the curing time of the prepared curing glue is 28s, the refractive index has reached 1.48, the light transmittance has reached more than 89% in a certain wavelength range, the adhesion is good, and the peeling The strength reached 189N/20mm.
实施例5Example 5
步骤1)在N2保护下，常压的条件下，称量100.00g丙烯酸3，3，5-三甲基环己醇酯单体，取单体的40.00g、0.50g偶氮二异丁腈、3.00g十二烷基硫醇溶于40.00g丙酮溶剂中得到混合溶液，搅拌使其充分混合，升温到75℃，反应10min；Step 1) Under the protection ofN2 , under the condition of normal pressure, weigh 100.00g of 3,3,5-trimethylcyclohexyl acrylate monomer, take 40.00g of the monomer, 0.50g of azobisisobutyl Nitrile and 3.00g of dodecylmercaptan were dissolved in 40.00g of acetone solvent to obtain a mixed solution, stirred to make it fully mixed, heated to 75°C, and reacted for 10 minutes;
步骤2)将配方中剩余的60g单体、0.50g偶氮二异丁腈和1g十二烷基硫醇混合，将混合溶液均匀滴加至步骤1反应后的溶液中，匀速滴加1.5h，滴完后加入0.50g偶氮二异丁腈，75℃保温3h后，得到的聚合物在80℃条件下减压蒸馏出去杂质与溶剂，得到丙烯酸酯预聚物；Step 2) Mix the remaining 60g of monomer, 0.50g of azobisisobutyronitrile and 1g of dodecylmercaptan in the formula, and evenly add the mixed solution dropwise to the solution after the reaction in step 1, and add dropwise at a constant speed for 1.5h After dropping, add 0.50 g of azobisisobutyronitrile, keep warm at 75° C. for 3 hours, and distill the obtained polymer under reduced pressure at 80° C. to remove impurities and solvents to obtain an acrylate prepolymer;
步骤3)将2.0g丙烯酸酯预聚物、0.67g丙烯酸异冰片酯(IBOA，)、0.67g二缩三丙二醇二丙烯酸酯(TPGDA)、0.67三羟甲基丙烷三丙烯酸酯(TMPTA)、0.10g184光引发剂混合均匀，并避光保存。将混合均匀的胶液倒入铝箔中，使其均匀平铺，用紫外光照射20分钟完全固化后脱膜，测试折射率与透光率。Step 3) 2.0g acrylate prepolymer, 0.67g isobornyl acrylate (IBOA,), 0.67g tripropylene glycol diacrylate (TPGDA), 0.67 trimethylolpropane triacrylate (TMPTA), 0.10 Mix the g184 photoinitiator evenly and keep it away from light. Pour the evenly mixed glue solution into the aluminum foil, spread it evenly, irradiate with ultraviolet light for 20 minutes to completely cure, then remove the film, and test the refractive index and light transmittance.
使用粘度计测得预聚物的粘度达到了14000mpa.s，调配的固化胶的固化时间为20s，由于固化后整个体系发白，导致折射率与透光率严重下降且无法测试，附着力为良好，剥离强度达到了195N/20mm。The viscosity of the prepolymer measured by a viscometer reached 14000mpa.s, and the curing time of the prepared cured adhesive was 20s. Since the whole system turned white after curing, the refractive index and light transmittance decreased severely and could not be tested. The adhesion was Good, the peel strength reached 195N/20mm.
实施例6Example 6
丙烯酸3,3,5-三甲基环己醇酯的合成方法，包括如下步骤：The synthetic method of 3,3,5-trimethylcyclohexanol acrylate comprises the steps:
1、在装有搅拌器、冷凝回流管、温度计、N2管的四口烧瓶内通入氮气，并加入丙烯酸及3,3,5-三甲基环己醇，丙烯酸与3,3,5-三甲基环己醇的摩尔比为1：1.2，搅拌，搅拌的速度为300转/分，升温；2、继续升温到118℃，稳定冷凝回流，加入催化剂，保温反应4h；然后取出冷凝管，安上分水器，在125℃反应3h，停止通氮气；然后在温度为80℃，压力为－0.099Mpa的条件下减压蒸馏，即得到淡黄色透明产物，丙烯酸转化率94.6％，收率为85.14％。所述的催化剂为对甲苯磺酸，用量为全部反应物总重量的1.0％。1. Introduce nitrogen into a four-necked flask equipped with a stirrer, condensing reflux tube, thermometer andN2 tube, and add acrylic acid and 3,3,5-trimethylcyclohexanol, acrylic acid and 3,3,5 - The molar ratio of trimethylcyclohexanol is 1:1.2, stir, the stirring speed is 300 rpm, and heat up; 2. Continue to heat up to 118°C, stabilize the condensing reflux, add catalyst, keep warm for 4 hours; then take out the condensing tube, install a water separator, react at 125°C for 3 hours, stop nitrogen; then distill under reduced pressure at a temperature of 80°C and a pressure of -0.099Mpa to obtain a light yellow transparent product with a conversion rate of acrylic acid of 94.6%. The yield is 85.14%. The catalyst is p-toluenesulfonic acid, and the consumption is 1.0% of the total weight of all reactants.
所得产品的检测和分析Detection and analysis of the resulting product
制备的产物，用红外光谱进行检测，结果见图2。The prepared product was detected by infrared spectroscopy, and the results are shown in Figure 2.
从谱图上分析：图2中可知2951、2912、2870、2838cm-1处是-CH3、-CH2的伸缩振动特征吸收峰。1722cm-1处是羰基的特征吸收峰。1637、1619、811cm-1处是伸缩振动和弯曲振动吸收峰C＝C双键的特征吸收峰，1472～1406cm-1处是六元环的特征峰，谱图说明反应产物中含有酯基、六元环、碳碳双键，达到了产物的预期效果。Analysis from the spectrum: Figure 2 shows that 2951, 2912, 2870, and 2838 cm-1 are the characteristic absorption peaks of stretching vibration of -CH3 and -CH2 . 1722cm-1 is the characteristic absorption peak of carbonyl. 1637, 1619, 811cm-1 are the characteristic absorption peaks of stretching vibration and bending vibration absorption peak C=C double bond, and 1472～1406cm-1 is the characteristic peak of six-membered ring. The spectrogram shows that the reaction product contains ester group, The six-membered ring and carbon-carbon double bond have achieved the expected effect of the product.
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