WO2023071202A1 - 胶粘剂及其制备方法和用途 - Google Patents

胶粘剂及其制备方法和用途 Download PDF

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Publication number
WO2023071202A1
WO2023071202A1 PCT/CN2022/097317 CN2022097317W WO2023071202A1 WO 2023071202 A1 WO2023071202 A1 WO 2023071202A1 CN 2022097317 W CN2022097317 W CN 2022097317W WO 2023071202 A1 WO2023071202 A1 WO 2023071202A1
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Prior art keywords
adhesive
acid
hydrogen bond
adhesive according
hydrochloride
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PCT/CN2022/097317
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English (en)
French (fr)
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朱世平
黄帅帅
万一辰
张祺
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香港中文大学（深圳）
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Publication of WO2023071202A1 publication Critical patent/WO2023071202A1/zh

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    • 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
    • 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
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic

Definitions

  • the present disclosure relates to the field of materials, in particular to an adhesive and its preparation method and application.
  • many adhesives with unique uses have been successfully developed, including underwater adhesives, water-based adhesives, low-temperature resistant adhesives, etc.
  • glue it is necessary to use glue to firmly adhere the processed object to the bracket during processing. After that, the workpiece needs to be disengaged from the bracket under certain external stimuli.
  • methods such as immersion in organic solvents, heating, and UV irradiation are usually required to separate adhesives and adhesives, but this is not only energy-intensive and time-consuming, but also causes environmental problems. Not only that, heat-sensitive workpieces are often prone to surface damage and corrosion during the separation process.
  • Ionic gel adhesives based on polymers and ionic liquids may be a potential solution to this problem.
  • the strong bonding performance of ionic gel adhesives benefits from the rich interactions between polymer chain functional groups and ionic liquids. This weak interaction can maintain the integrity of the adhesive by dissipating mechanical forces when the adhesive is stretched.
  • the specimens bonded by ion gel often need to pass the above-mentioned trigger to make the workpiece peel off.
  • the high price and toxicity of ionogels also hinder the further commercialization of ionogel adhesives.
  • An adhesive whose raw materials are calculated by mass percentage including:
  • the acrylic monomer includes one or more of acrylic acid, methacrylic acid, ⁇ -(acryloxy)propionic acid, and hydroxyethyl methacrylate.
  • the hydrogen bond acceptors include choline chloride, lidocaine, betaine, choline fluoride, dimethylamine hydrochloride, methylamine hydrochloride, tetraethylammonium chloride, triethylammonium chloride, Amine hydrochloride, diethylamine hydrochloride, ethylamine hydrochloride, glycine, trimethylamine hydrochloride, tetramethylammonium chloride, (2-chloroethyl) trimethylammonium chloride, DL-proline One or more of amino acid, glycine and alanine.
  • the molar ratio of the acrylic monomer to the hydrogen bond acceptor is (1.5-2.5):1.
  • the adhesive further includes a non-polymerizable hydrogen bond donor.
  • the non-polymerizable hydrogen bond donors include urea, glucose, glycerol, 1,4-butanediol, malonic acid, ethylene glycol, adipic acid, acetamide, thiourea, Succinic acid, 1,3-dimethylurea, oxalic acid, lactic acid, citric acid, N-methylurea, 1,1-dimethylurea, capric acid, fructose, triethylene glycol, n-dodecanoic acid, One or more of menthol and 1-naphthol.
  • the initiator includes 1-hydroxycyclohexyl phenyl ketone, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide, 2-hydroxy-2-methyl- 1-Phenyl-1-propanone, 2-Hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, azobisisobutyronitrile, and Benzyl peroxide One or more of acyl.
  • the present disclosure also provides a preparation method of the adhesive, comprising:
  • the raw materials are mixed and reacted to obtain the adhesive.
  • the reaction includes a heating reaction or a UV curing reaction.
  • the temperature of the heating reaction is 60°C-80°C, and the time is 1h-24h.
  • the UV curing reaction time is 5 min-60 min.
  • the present disclosure also provides an application of the adhesive for the production of optical products.
  • the optical article includes an optical lens.
  • the present disclosure also provides the use of the adhesive in the medical, electronics, building construction or automotive fields.
  • Fig. 1 is a schematic photo of the performance of the adhesive obtained in Example 1 for lifting heavy objects.
  • compositions are synonymous with “comprising”.
  • the terms “comprises,” “including,” “has,” “containing,” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • a composition, step, method, article, or device comprising listed elements is not necessarily limited to those elements, but may include other elements not explicitly listed or inherent to such composition, step, method, article, or device. element.
  • Parts by mass refers to the basic measurement unit that expresses the mass ratio relationship of multiple components, and 1 part can represent any unit mass, such as 1g or 2.689g. If we say that the mass part of A component is a part, and the mass part of B component is b part, it means that the mass ratio of A component to B component is a:b. Alternatively, it means that the mass of component A is aK, and the mass of component B is bK (K is an arbitrary number, representing a multiple factor). It should not be misunderstood that, unlike the parts by mass, the sum of parts by mass of all components is not limited to 100 parts.
  • a and/or B includes (A and B) and (A or B).
  • One embodiment of the present disclosure provides an adhesive, the raw materials of which are calculated by mass percentage, including:
  • the adhesive does not include a non-polymerizable hydrogen bond donor, the hydrogen bond acceptor and the acrylic monomer actually constitute a polymerizable deep eutectic solvent, wherein the acrylic monomer acts as A hydrogen bond donor is present.
  • the hydrogen bond interaction is provided by the hydroxyl group and the hydrogen bond acceptor of the acrylic polymer obtained by the polymerization of the acrylic monomer.
  • the acrylic polymer is a good water-absorbing material, and the hydrogen bond acceptor is well compatible with water. As a result, the adhesive can be well dissolved and released by water.
  • the raw material of the adhesive is calculated by mass percentage, and the amount of the acrylic monomer can be, for example, 50%-80%, 55%-75% or 60%-70%, such as 40%, 50%, 60%, 70% %, 80%, 90%, or any value between 40% and 90%.
  • the amount of hydrogen bond acceptor can be, for example, 10%-45%, 15%-40% or 20%-35%, such as 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, or any value between 5% and 50%.
  • the amount of the initiator can be, for example, 1.5%-4.5%, 2%-4% or 2.5%-3.5%, such as 1%, 2%, 3%, 4%, 5% or 1%-5% any value in between.
  • the acrylic monomer includes but not limited to one or more of acrylic acid, methacrylic acid, ⁇ -(acryloyloxy)propionic acid and hydroxyethyl methacrylate.
  • hydrogen bond acceptors include but are not limited to choline chloride, lidocaine, betaine, choline fluoride, dimethylamine hydrochloride, methylamine hydrochloride, tetraethyl chloride Ammonium Chloride, Triethylamine Hydrochloride, Diethylamine Hydrochloride, Ethylamine Hydrochloride, Glycine, Trimethylamine Hydrochloride, Tetramethylammonium Chloride, (2-Chloroethyl) Trimethyl Chloride One or more of ammonium, DL-proline, glycine and alanine.
  • the molar ratio of the acrylic monomer to the hydrogen bond acceptor is (1.5-2.5):1.
  • the molar ratio of the acrylic monomer to the hydrogen bond acceptor may be any value between 1.5:1, 2:1, 2.5:1 or (1.5-2.5):1.
  • the adhesive further includes, but is not limited to, non-polymerizable hydrogen bond donors.
  • the adhesive when the adhesive also includes a non-polymerizable hydrogen bond donor, the adhesive is composed of an acrylic monomer, a deep eutectic solvent containing a hydrogen bond acceptor and a non-polymerizable hydrogen bond donor.
  • the hydrogen bond interaction is provided by the hydroxyl group of the high molecular polymer polymerized by the acrylic monomer and the hydrogen bond donor and hydrogen bond acceptor in the deep eutectic solvent.
  • High molecular polymers containing acrylic acid groups are good water-absorbing materials, and the deep eutectic solvent can be well compatible with water, so that the adhesive can be well dissolved by water and the adhesive can be separated from the adhered substrate.
  • non-polymerizable hydrogen bond donors include, but are not limited to, urea, glucose, glycerol, 1,4-butanediol, malonic acid, ethylene glycol, adipic acid, ethylene Amide, thiourea, succinic acid, 1,3-dimethylurea, oxalic acid, lactic acid, citric acid, N-methylurea, 1,1-dimethylurea, capric acid, fructose, triethylene glycol, n- One or more of dodecanoic acid, menthol and 1-naphthol.
  • the initiator includes but not limited to 1-hydroxycyclohexyl phenyl ketone, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide, 2-hydroxy- 2-methyl-1-phenyl-1-propanone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, azobisisobutyronitrile and one or more of benzoyl peroxide.
  • One embodiment of the present disclosure also provides a method for preparing an adhesive, including:
  • the raw materials are mixed and reacted to obtain an adhesive.
  • the reaction includes heating reaction or ultraviolet curing reaction.
  • the temperature of the heating reaction is 60°C-80°C, and the time is 1h-24h;
  • the ultraviolet curing reaction time is 5 min-60 min.
  • the temperature of the heating reaction can be, for example, 62°C-78°C, 64°C-75°C or 66°C-72°C, such as 60°C, 65°C, 70°C, 75°C, 80°C or 60°C-80°C any value in between.
  • the time may be, for example, 4h-20h, 8h-18h or 10h-15h, such as 1h, 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h or 1h-24h any value in between.
  • the UV curing reaction time can be, for example, 10min-50min, 15min-55min or 20min-50min, such as 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min or 5min-60min any value.
  • An embodiment of the present disclosure also provides an application of an adhesive for the production of optical products.
  • a transparent, UV-curable, and strong adhesive adhesive is needed to fix the workpiece so that it can be modified and processed, but after the processing is completed, it needs to be borrowed in time.
  • the workpiece is taken down by external action.
  • the adhesive needs to reduce the bonding strength under some specific stimuli so that the workpiece can be detached smoothly.
  • used adhesives need to use some destructive methods, such as soaking in organic solvents, heating and other strong external effects, so that not only can not get a good debonding effect, but also consume time and energy, and also pollute the environment.
  • the adhesive provided by the present disclosure, the workpiece can be easily peeled off by soaking in water.
  • Some embodiments of the present disclosure also provide the use of the adhesive in the medical, electronics, building construction or automotive fields.
  • the adhesive provided by the present disclosure selects acrylic monomers, hydrogen bond acceptors and initiators as raw materials, and uses hydrogen bond acceptors and polymers formed by acrylic monomers to form a hydrogen bond network to achieve the effect of dissipating mechanical forces , so that the adhesive has the advantages of high bonding strength and trigger release, and becomes a low-cost, high-strength, and easy-to-debond adhesive; at the same time, the above-mentioned raw materials are easy to obtain, which reduces the cost of raw materials while improving performance and safety. The cost has great application prospects.
  • the preparation method of the adhesive provided by the disclosure has simple process, low cost and can be produced in a large-scale industrialized manner.
  • the adhesive provided by the present disclosure has a wide range of applications, especially for the production of optical products.
  • the present embodiment provides a kind of adhesive and preparation method thereof, as follows:
  • Fig. 1 is the photograph showing the performance of the adhesive used in Example 1 to lift a heavy object (the bonding area of the adhesive is approximately 7 square centimeters, and the suspended heavy object weighs about 24 kg).
  • Figure 1 shows that the adhesive obtained in the present disclosure has excellent adhesive properties. It should be noted that the present disclosure only uses Example 1 as an example to describe the adhesive performance of the adhesive, and the adhesive prepared from Examples 2-11 of the present disclosure has similar technical effects to the adhesive performance of Example 1.
  • the present embodiment provides a kind of adhesive and preparation method thereof, as follows:
  • the present embodiment provides a kind of adhesive and preparation method thereof, as follows:
  • the present embodiment provides a kind of adhesive and preparation method thereof, as follows:
  • the present embodiment provides a kind of adhesive and preparation method thereof, as follows:
  • the present embodiment provides a kind of adhesive and preparation method thereof, as follows:
  • the present embodiment provides a kind of adhesive and preparation method thereof, as follows:
  • This embodiment provides an adhesive and its preparation method as follows: 2.8g of acrylic acid, 1.2g of deep eutectic solution mixed with ethylene glycol and choline chloride at a molar ratio of 2:1 and 79mg of 1-hydroxycyclohexyl Phenyl ketone (PI184) was mixed evenly, vacuum degassed for 30s, and then the precursor liquid was coated on the substrate and cured by ultraviolet light.
  • the power density of the light source is 50mW/cm 2 , and the time is 10min.
  • the present embodiment provides a kind of adhesive and preparation method thereof, as follows:
  • the precursor liquid is coated on the substrate and cured by ultraviolet light.
  • the power density of the light source is 50mW/cm 2 , and the time is 10min.
  • the present embodiment provides a kind of adhesive and preparation method thereof, as follows:
  • the present embodiment provides a kind of adhesive and preparation method thereof, as follows:
  • the different substrates (glass, metal, ceramic, plastic) were bonded using commercial 3M instant adhesive (model CA40H) to measure their lap shear strength with different substrates of the present disclosure hereinafter.
  • test method is as follows:
  • a glass substrate (substrates are not limited to glass substrates, and can also be metal, ceramic and other substrates.
  • the test method in this disclosure takes glass substrates as an example), and use soapy water, ethanol and acetone to clean the substrate thoroughly in sequence before testing surface. Leave the substrate overnight to evaporate residual solvent from the surface.
  • the adhesives from Examples 1-11 and Comparative Example 1 were UV cured between two glass substrates to obtain test strips. Subsequently, lap shear experiments were carried out on the prepared test strips, and three parallel tests were carried out on the samples of each embodiment or comparative example. The experiment is based on the ASTMD1002 test method, and the Shenzhen Sansi UTM 6104 tensile machine is used to test the adhesive performance at room temperature. The tensile machine stretches the test sample at a rate of 2 mm/min until failure, and simultaneously records the maximum shear force and the overlapping area of the two substrates.
  • Example 1 Water immersion degumming time (min) Example 1 12.5 ⁇ 1.23 10 Example 2 6.56 ⁇ 1.63 10 Example 3 8.3 ⁇ 1.87 10 Example 4 9.91 ⁇ 1.32 10 Example 5 10.14 ⁇ 0.52 10 Example 6 7.91 ⁇ 1.24 10 Example 7 12.78 ⁇ 2.73 10 Example 8 4.66 ⁇ 0.75 10 Example 9 4.79 ⁇ 1.00 10 Example 10 9.73 ⁇ 2.86 10 Example 11 6.44 ⁇ 1.02 10 Comparative example 1 2.00 ⁇ 0.40 /
  • the bonding performance of the commercial 3M quick-drying adhesive provided in Comparative Example 1 on glass is only 2MPa, which is less than 20% of the adhesive prepared by the present disclosure.
  • the bond strength of the adhesive prepared by the present disclosure is significantly improved compared to the comparative examples.
  • the adhesive prepared in the present disclosure can be quickly debonded under water immersion: after the adhesive provided in the present disclosure is immersed in water for ten minutes, the bonding strength immediately decreases by more than 80%, which facilitates the debonding of optical lenses after processing.
  • the adhesive provided by the present disclosure is completely soluble in water, has low cost and is environmentally friendly.
  • the present disclosure provides an adhesive and its preparation method and use.
  • the adhesive disclosed in the present disclosure has the advantages of high bonding strength and triggering release, and can be well dissolved by water so that the adhesive is released from the adhered substrate, improving performance. At the same time, it also reduces the cost and safety of raw materials, so it has excellent application performance and a wide range of applications, especially for the production of optical products.

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Abstract

本公开提供一种胶粘剂及其制备方法和用途。胶粘剂，其原料以质量百分比计算，包括：丙烯酸类单体40％-90％、氢键受体5％-50％和引发剂1％-5％。其中丙烯酸类单体和氢键受体组成可聚合的深共融溶剂。胶粘剂的制备方法，包括：将所述原料混合，反应得到所述胶粘剂。胶粘剂的用途，用于光学产品的生产。本公开提供的胶粘剂，能很好地被水溶解致使胶粘剂与被粘基材脱开，在提升性能的同时也降低了原材料的成本和安全性。

Description

胶粘剂及其制备方法和用途
相关申请的交叉引用
本公开要求于2021年10月29日提交中国专利局的申请号为CN202111268968.9、名称为“胶粘剂及其制备方法和用途”的中国专利申请的优先权，其全部内容通过引用结合在本公开中。
技术领域
本公开涉及材料领域，尤其涉及一种胶粘剂及其制备方法和用途。
背景技术
胶粘剂在日常生活中起着重要的作用，如医疗、电子、房屋建筑和汽车。在过去的十年中，有很多具有独特用途的胶粘剂被成功开发了出来，包括水下胶粘剂、水基胶粘剂、耐低温胶粘剂等。然而在其他特殊领域，如在钻孔、切片光学透镜过程中，加工时需要用胶水将被加工物体牢固地粘在支架上。之后，工件需要在一定的外界刺激作用下与支架脱开。传统上，通常需要使用诸如有机溶剂浸泡、加热和UV照射等方法来分离粘合剂和粘合剂，但这不仅耗能又耗时，而且还会导致环境问题。不仅如此，热敏性工件在往往容易在分离过程发生表面破坏和腐蚀。
基于聚合物和离子液体(ILs)组成的离子凝胶胶粘剂可能是解决这一难题的潜在方法，离子凝胶胶粘剂的强粘结性能得益于聚合物链官能团与离子液体间丰富的相互作用，这种弱的相互作用可以在拉伸胶粘剂时通过耗散机械力来保持胶粘剂的完整性。然而，在触发剥离方面，离子凝胶粘接的试件往往需要通过上述触发才能使工件剥离。不仅如此，离子凝胶昂贵的价格和毒性也阻碍了离子凝胶胶粘剂的进一步商业化。
发明内容
一种胶粘剂，其原料以质量百分比计算，包括：
丙烯酸类单体40％-90％、氢键受体5％-50％和引发剂1％-5％。
在一些实施方式中，所述丙烯酸类单体包括丙烯酸、甲基丙烯酸、β-(丙 烯酰氧)丙酸和甲基丙烯酸羟乙酯中的一种或多种。
在一些实施方式中，所述氢键受体包括氯化胆碱、利多卡因、甜菜碱、氟化胆碱、盐酸二甲胺、甲胺盐酸盐、四乙基氯化铵、三乙胺盐酸盐、二乙胺盐酸盐、乙胺盐酸盐、甘氨酸、三甲胺盐酸盐、四甲基氯化铵、(2-氯乙基)三甲基氯化铵、DL-脯氨酸、甘氨酸和丙氨酸中的一种或多种。
在一些实施方式中，所述丙烯酸类单体与所述氢键受体的摩尔比为(1.5-2.5)：1。
在一些实施方式中，所述胶粘剂还包括不可聚合的氢键供体。
在一些实施方式中，所述不可聚合的氢键供体包括尿素、葡萄糖、丙三醇、1,4-丁二醇、丙二酸、乙二醇、己二酸、乙酰胺、硫脲、丁二酸、1,3-二甲基脲、草酸、乳酸、柠檬酸、N-甲基脲、1,1-二甲基脲、葵酸、果糖、三甘醇、正十二烷酸、薄荷醇和1-萘酚中的一种或多种。
在一些实施方式中，所述引发剂包括1-羟基环己基苯基甲酮、苯基双(2，4，6-三甲基苯甲酰基)氧化膦、2-羟基-2-甲基-1-苯基-1-丙酮、2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮、偶氮二异丁腈和过氧化苯甲酰中的一种或多种。
本公开还提供一种所述的胶粘剂的制备方法，包括：
将所述原料混合，反应得到所述胶粘剂。
在一些实施方式中，所述反应包括加热反应或紫外固化反应。
在一些实施方式中，所述加热反应的温度为60℃-80℃，时间为1h-24h。
在一些实施方式中，所述紫外固化反应时间为5min-60min。
本公开还提供一种所述的胶粘剂的用途，用于光学产品的生产。
在一些实施方式中，所述光学产品包括光学透镜。
本公开还提供所述胶粘剂在医疗、电子、房屋建筑或汽车领域中的用途。
附图说明
为了更清楚地说明本公开实施例的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，应当理解，以下附图仅示出了本公开的某些 实施例，因此不应被看作是对本公开范围的限定。
图1为实施例1得到的胶粘剂吊起重物的性能示意照片。
具体实施方式
如本文所用之术语：
“由……制备”与“包含”同义。本文中所用的术语“包含”、“包括”、“具有”、“含有”或其任何其它变形，意在覆盖非排它性的包括。例如，包含所列要素的组合物、步骤、方法、制品或装置不必仅限于那些要素，而是可以包括未明确列出的其它要素或此种组合物、步骤、方法、制品或装置所固有的要素。
连接词“由……组成”排除任何未指出的要素、步骤或组分。如果用于权利要求中，此短语将使权利要求为封闭式，使其不包含除那些描述的材料以外的材料，但与其相关的常规杂质除外。当短语“由……组成”出现在权利要求主体的子句中而不是紧接在主题之后时，其仅限定在该子句中描述的要素；其它要素并不被排除在作为整体的所述权利要求之外。
当量、浓度、或者其它值或参数以范围、优选范围、或一系列上限优选值和下限优选值限定的范围表示时，这应当被理解为具体公开了由任何范围上限或优选值与任何范围下限或优选值的任一配对所形成的所有范围，而不论该范围是否单独公开了。例如，当公开了范围“1～5”时，所描述的范围应被解释为包括范围“1～4”、“1～3”、“1～2”、“1～2和4～5”、“1～3和5”等。当数值范围在本文中被描述时，除非另外说明，否则该范围意图包括其端值和在该范围内的所有整数和分数。
在这些实施例中，除非另有指明，所述的份和百分比均按质量计。
“质量份”指表示多个组分的质量比例关系的基本计量单位，1份可表示任意的单位质量，如可以表示为1g，也可表示2.689g等。假如我们说A组分的质量份为a份，B组分的质量份为b份，则表示A组分的质量和B组分的质量之比a：b。或者，表示A组分的质量为aK，B组分的质量为bK(K为任意数，表示倍数因子)。不可误解的是，与质量份数不同的是，所有组分的质量份之和并不受限于100份之限制。
“和/或”用于表示所说明的情况的一者或两者均可能发生，例如，A 和/或B包括(A和B)和(A或B)。
本公开一实施方式提供一种胶粘剂，其原料以质量百分比计算，包括：
丙烯酸类单体40％-90％、氢键受体5％-50％和引发剂1％-5％。
据信，不受理论的约束，当胶粘剂不包括不可聚合的氢键供体时，氢键受体和丙烯酸类单体实际上构成了可聚合的深共融溶剂，其中，丙烯酸类单体作为氢键供体存在。氢键相互作用由含有丙烯酸类单体聚合得到的丙烯酸类聚合物的羟基与氢键受体提供，丙烯酸类聚合物是很好的吸水材料，氢键受体能与水很好的相容，从而导致胶粘剂能很好地被水溶解和脱开。
可选的，胶粘剂的原料以质量百分比计算，丙烯酸类单体的用量可以是例如50％-80％、55％-75％或60％-70％，诸如40％、50％、60％、70％、80％、90％或者40％-90％之间的任一值。可选的，氢键受体的用量可以是例如10％-45％、15％-40％或20％-35％，诸如5％、10％、15％、20％、25％、30％、35％、40％、45％、50％或者5％-50％之间的任一值。可选的，引发剂的用量可以是例如1.5％-4.5％、2％-4％或2.5％-3.5％，诸如1％、2％、3％、4％、5％或者1％-5％之间的任一值。
在一种可选的实施方式中，丙烯酸类单体包括但不限于丙烯酸、甲基丙烯酸、β-(丙烯酰氧)丙酸和甲基丙烯酸羟乙酯中的一种或多种。
在一种可选的实施方式中，氢键受体包括但不限于氯化胆碱、利多卡因、甜菜碱、氟化胆碱、盐酸二甲胺、甲胺盐酸盐、四乙基氯化铵、三乙胺盐酸盐、二乙胺盐酸盐、乙胺盐酸盐、甘氨酸、三甲胺盐酸盐、四甲基氯化铵、(2-氯乙基)三甲基氯化铵、DL-脯氨酸、甘氨酸和丙氨酸中的一种或多种。
在一种可选的实施方式中，丙烯酸类单体与氢键受体的摩尔比为(1.5-2.5)：1。
可选的，丙烯酸类单体与氢键受体的摩尔比可以为1.5：1、2：1、2.5：1或者(1.5-2.5)：1之间的任一值。
在一种可选的实施方式中，胶粘剂还包括但不限于不可聚合的氢键供体。
据信，不受理论的约束，当胶粘剂还包括不可聚合的氢键供体时，该胶粘剂由丙烯酸类单体、含有氢键受体和不可聚合的氢键供体的深共融溶剂构成。其中氢键相互作用由丙烯酸类单体聚合得到的高分子聚合物的羟基与深共融溶剂中的氢键供体和氢键受体提供。含有丙烯酸基团的高分子聚合物是很好的吸水材料，深共融溶剂能与水很好的相容，从而导致胶粘剂能很好地被水溶解致使胶粘剂与被粘基材脱开。
在一种可选的实施方式中，不可聚合的氢键供体包括但不限于尿素、葡萄糖、丙三醇、1,4-丁二醇、丙二酸、乙二醇、己二酸、乙酰胺、硫脲、丁二酸、1,3-二甲基脲、草酸、乳酸、柠檬酸、N-甲基脲、1,1-二甲基脲、葵酸、果糖、三甘醇、正十二烷酸、薄荷醇和1-萘酚中的一种或多种。
在一种可选的实施方式中，引发剂包括但不限于1-羟基环己基苯基甲酮、苯基双(2，4，6-三甲基苯甲酰基)氧化膦、2-羟基-2-甲基-1-苯基-1-丙酮、2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮、偶氮二异丁腈和过氧化苯甲酰中的一种或多种。
本公开一实施方式还提供一种的胶粘剂的制备方法，包括：
将原料混合，反应得到胶粘剂。
在一种可选的实施方式中，反应包括加热反应或紫外固化反应。
在一种可选的实施方式中，加热反应的温度为60℃-80℃，时间为1h-24h；
在一种可选的实施方式中，紫外固化反应时间为5min-60min。
可选的，加热反应的温度可以为例如62℃-78℃、64℃-75℃或66℃-72℃，诸如60℃、65℃、70℃、75℃、80℃或者60℃-80℃之间的任一值。可选的，时间可以为例如4h-20h、8h-18h或10h-15h，诸如1h、2h、4h、6h、8h、10h、12h、14h、16h、18h、20h、22h、24h或者1h-24h之间的任一值。紫外固化反应时间可以为例如10min-50min、15min-55min或20min-50min，诸如5min、10min、15min、20min、25min、30min、35min、40min、45min、50min、55min、60min或者5min-60min之间的任一值。
本公开一实施方式还提供一种胶粘剂的用途，用于光学产品的生产。
例如，在光学透镜钻孔，加工时，需要一种透明的，紫外光可固化的，而且具有强黏附力的胶粘剂固定工件以便对其进行修饰和加工，但在加工完成之后，需要及时地借用外界作用将工件拿下来，这时候就需要胶粘剂在一些特定的刺激下降低粘接强度以便工件的顺利脱离。传统使用的胶粘剂都需要使用一些破坏性的方法，例如有机溶剂浸泡，加热等强外界作用，这样不仅得不到很好的脱粘效果，而且耗时耗能，同时还会污染环境。而采用本公开提供的胶粘剂，用水浸泡即可使工件很轻易地被剥离下来。
本公开的一些实施方式还提供胶粘剂在医疗、电子、房屋建筑或汽车领域中的用途。
本公开提供的胶粘剂，选择丙烯酸类单体、氢键受体和引发剂作为原料，利用氢键受体与丙烯酸类单体形成的聚合物之间产生氢键网络，达到耗散机械力的作用，从而使得胶粘剂具有高粘接强度且触发脱开的优势，成为一种低成本、高强度、易脱粘的胶粘剂；同时，上述原料易得，在提升性能和安全性的同时也降低了原材料的成本，有着很大的应用前景。
本公开提供的胶粘剂的制备方法，工艺简单，成本低，可大规模工业化生产。
本公开提供的胶粘剂，应用广泛，尤其可以用于光学产品的生产。
实施例
下面将结合具体实施例对本公开的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本公开，而不应视为限制本公开的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
实施例1
本实施例提供一种胶粘剂及其制备方法，如下：
将2.8g丙烯酸，1.2g由尿素和氯化胆碱以摩尔比为2：1混合而成的深共融溶液和79mg 1-羟基环己基苯基甲酮(PI184)混合均匀，真空脱气30s，后将前体液涂敷在基材后通过紫外固化。光源功率密度为50 mW/cm 2,时间10min。
图1为实施例1得到的胶粘剂吊起重物的性能示意照片(胶粘剂胶粘面积大致为7平方厘米，吊起的重物重约24kg)。图1表明，本公开获得的胶粘剂具有优异的黏合性能。需要说明的是，本公开仅以实施例1为例，对胶粘剂的黏合性能进行说明，由本公开实施例2-11制备的胶粘剂具备与实施例1黏合性能相近的技术效果。
实施例2
本实施例提供一种胶粘剂及其制备方法，如下：
将2.8g丙烯酸，1.2g由1,4-丁二醇和氯化胆碱以摩尔比为2：1混合而成的深共融溶液和79mg1-羟基环己基苯基甲酮(PI184)混合均匀，真空脱气30s，后将前体液涂敷在基材后通过紫外固化。光源功率密度为50mW/cm 2,时间10min。
实施例3
本实施例提供一种胶粘剂及其制备方法，如下：
将2.8g丙烯酸，1.2g由丙三醇和氯化胆碱以摩尔比为2：1混合而成的深共融溶液和79mg1-羟基环己基苯基甲酮(PI184)混合均匀，真空脱气30s，后将前体液涂敷在基材后通过紫外固化。光源功率密度为50mW/cm 2，时间10min。
实施例4
本实施例提供一种胶粘剂及其制备方法，如下：
将3.8g甲基丙烯酸羟乙酯，0.2g由丙三醇和氯化胆碱以摩尔比为2：1混合而成的深共融溶液和59mg1-羟基环己基苯基甲酮(PI184)混合均匀，真空脱气30s，后将前体液涂敷在基材后通过紫外固化。光源功率密度为50mW/cm 2,时间10min。
实施例5
本实施例提供一种胶粘剂及其制备方法，如下：
将1.44g丙烯酸，1.39g氯化胆碱和40mg 1-羟基环己基苯基甲酮(PI184)混合均匀，在80℃油浴下搅拌5-10min，静置至室温后真空脱气30s，后将前体液涂敷在基材后通过紫外固化。光源功率密度为50 mW/cm 2,时间10min。
实施例6
本实施例提供一种胶粘剂及其制备方法，如下：
将1.44g丙烯酸，0.8154g乙胺盐酸盐和40mg 1-羟基环己基苯基甲酮(PI184)混合均匀，在80℃油浴下搅拌5-10min，静置至室温后真空脱气30s，后将前体液涂敷在基材后通过紫外固化。光源功率密度为50mW/cm 2,时间10min。
实施例7
本实施例提供一种胶粘剂及其制备方法，如下：
将1.44g丙烯酸，0.956g三甲胺盐酸盐和40mg 1-羟基环己基苯基甲酮(PI184)混合均匀，在80℃油浴下搅拌5-10min，静置至室温后真空脱气30s，后将前体液涂敷在基材后通过紫外固化。光源功率密度为50mW/cm 2,时间10min。
实施例8
本实施例提供一种胶粘剂及其制备方法，如下：将2.8g丙烯酸，1.2g由乙二醇和氯化胆碱以摩尔比为2：1混合而成的深共融溶液和79mg1-羟基环己基苯基甲酮(PI184)混合均匀，真空脱气30s，后将前体液涂敷在基材后通过紫外固化。光源功率密度为50mW/cm 2,时间10min。
实施例9
本实施例提供一种胶粘剂及其制备方法，如下：
将2.8g丙烯酸，1.2g由丙二酸和氯化胆碱以摩尔比为1：1混合而成的深共融溶液和66mg1-羟基环己基苯基甲酮(PI184)混合均匀，真空脱气30s，后将前体液涂敷在基材后通过紫外固化。光源功率密度为50mW/cm 2,时间10min。
实施例10
本实施例提供一种胶粘剂及其制备方法，如下：
将1.44g丙烯酸，1.657g四乙基氯化铵和40mg 1-羟基环己基苯基甲酮(PI184)混合均匀，在80℃油浴下搅拌5-10min，静置至室温后真空脱气30s，后将前体液涂敷在基材后通过紫外固化。光源功率密度为50mW/cm 2, 时间10min。
实施例11
本实施例提供一种胶粘剂及其制备方法，如下：
将1.44g丙烯酸，1.096g甲基氯化铵和40mg 1-羟基环己基苯基甲酮(PI184)混合均匀，在80℃油浴下搅拌5-10min，静置至室温后真空脱气30s，后将前体液涂敷在基材后通过紫外固化。光源功率密度为50mW/cm 2,时间10min。
对比例1
使用商用3M快干胶(型号CA40H)粘结不同的基材(玻璃，金属，陶瓷，塑料)，以在下文中测量其与本公开不同基材的搭接剪切强度。
实验例1胶黏剂的性能测试
测试上述实施例1-11和对比例1得到的胶粘剂的胶粘性能和水浸泡脱胶时间，测试方法如下：
(1)胶粘性能测试：
选择玻璃基材(基材不限于玻璃基材，也可以为金属、陶瓷等基材，本公开测试方法以玻璃基材为例)，在测试之前使用肥皂水、乙醇和丙酮依次彻底清洗基材表面。将基材放置隔夜以挥发表面残留溶剂。将来自实施例1-11和对比例1得到的胶粘剂在两个玻璃基材之间进行紫外固化，得到测试样条。随后针对已制备的测试样条进行搭接剪切实验，每个实施例或对比例的样品进行三次平行测试。该实验基于ASTMD1002测试方法，采用深圳三思UTM 6104拉力机，在室温条件下进行胶粘性能测试。拉力机以2mm/min的速率拉伸测试样条直至失效，同时记录最大剪切力和两块基材的重叠区域面积。
(2)水浸泡脱胶时间测试：
将上述所制备的测试样条在室温(25℃)的条件下直接置于去离子水中进行浸泡，并按照不同浸泡时间将上述测试样条分为7组，分别将测试样条浸泡2min、4min、6min、8min、10min、12min和14min，随后取出测试样条，使用吹风机快速除掉表面残存的水分，随后立即用深圳三思UTM6104拉力机根据上述测试条件获得搭接剪切强度。将搭接剪切强度为0MPa 时的时间定义为水浸泡脱胶时间，每组中对应每个测试样进行三次平行测试。
测试结果如下表1所示：
表1测试结果
样品 粘接强度(MPa) 水浸泡脱胶时间(min)
实施例1 12.5±1.23 10
实施例2 6.56±1.63 10
实施例3 8.3±1.87 10
实施例4 9.91±1.32 10
实施例5 10.14±0.52 10
实施例6 7.91±1.24 10
实施例7 12.78±2.73 10
实施例8 4.66±0.75 10
实施例9 4.79±1.00 10
实施例10 9.73±2.86 10
实施例11 6.44±1.02 10
对比例1 2.00±0.40 /
由上表1可知，以粘接基材都为玻璃举例，对比例1提供的商用的3M快干胶在玻璃上的粘接性能只有2MPa，只有本公开制备的胶粘剂的20％不到，与对比例相比，由本公开制备的胶粘剂的粘接强度显著提高。
本公开制备的胶粘剂可以在水的浸泡下迅速脱粘：将本公开提供的胶粘剂浸入水中十分钟后，粘接强度立即有了大于80％的下降，便于光学镜片加工后的脱粘。
本公开提供的胶粘剂可完全溶于水中，成本较低且对环境友好。
最后应说明的是：以上各实施例仅用以说明本公开的技术方案，而非对其限制；尽管参照前述各实施例对本公开进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进 行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本公开各实施例技术方案的范围。
此外，本领域的技术人员能够理解，尽管在此的一些实施例包括其它实施例中所包括的某些特征而不是其它特征，但是不同实施例的特征的组合意味着处于本公开的范围之内并且形成不同的实施例。例如，在上面的权利要求书中，所要求保护的实施例的任意之一都可以以任意的组合方式来使用。公开于该背景技术部分的信息仅仅旨在加深对本公开的总体背景技术的理解，而不应当被视为承认或以任何形式暗示该信息构成已为本领域技术人员所公知的现有技术。
工业实用性
本公开提供一种胶粘剂及其制备方法和用途，本公开的胶粘剂具有高粘接强度且触发脱开的优势，同时能很好地被水溶解致使胶粘剂与被粘基材脱开，在提升性能的同时也降低了原材料的成本和安全性，因此具有优异的应用性能，应用领域广泛，尤其可以用于光学产品的生产。

Claims (12)

  1. 一种胶粘剂，其特征在于，其原料以质量百分比计算，包括：
    丙烯酸类单体40％-90％、氢键受体5％-50％和引发剂1％-5％。
  2. 根据权利要求1所述的胶粘剂，其特征在于，所述丙烯酸类单体包括丙烯酸、甲基丙烯酸、β-(丙烯酰氧)丙酸和甲基丙烯酸羟乙酯中的一种或多种。
  3. 根据权利要求1或2所述的胶粘剂，其特征在于，所述氢键受体包括氯化胆碱、利多卡因、甜菜碱、氟化胆碱、盐酸二甲胺、甲胺盐酸盐、四乙基氯化铵、三乙胺盐酸盐、二乙胺盐酸盐、乙胺盐酸盐、甘氨酸、三甲胺盐酸盐、四甲基氯化铵、(2-氯乙基)三甲基氯化铵、DL-脯氨酸、甘氨酸和丙氨酸中的一种或多种。
  4. 根据权利要求3所述的胶粘剂，其特征在于，所述丙烯酸类单体与所述氢键受体的摩尔比为(1.5-2.5)：1。
  5. 根据权利要求1-4中任一项所述的胶粘剂，其特征在于，所述胶粘剂还包括不可聚合的氢键供体。
  6. 根据权利要求5所述的胶粘剂，其特征在于，所述不可聚合的氢键供体包括尿素、葡萄糖、丙三醇、1,4-丁二醇、丙二酸、乙二醇、己二酸、乙酰胺、硫脲、丁二酸、1,3-二甲基脲、草酸、乳酸、柠檬酸、N-甲基脲、1,1-二甲基脲、葵酸、果糖、三甘醇、正十二烷酸、薄荷醇和1-萘酚中的一种或多种。
  7. 根据权利要求1-6任一项所述的胶粘剂，其特征在于，所述引发剂包括1-羟基环己基苯基甲酮、苯基双(2，4，6-三甲基苯甲酰基)氧化膦、2-羟基-2-甲基-1-苯基-1-丙酮、2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮、偶氮二异丁腈和过氧化苯甲酰中的一种或多种。
  8. 一种权利要求1-7任一项所述的胶粘剂的制备方法，其特征在于，包括：
    将所述原料混合，反应得到所述胶粘剂。
  9. 根据权利要求8所述的制备方法，其特征在于，所述反应包括加热反应或紫外固化反应；
    优选地，所述加热反应的温度为60℃-80℃，时间为1h-24h；
    优选地，所述紫外固化反应时间为5min-60min。
  10. 一种权利要求1-7任一项所述的胶粘剂的用途，其特征在于，用于光学产品的生产。
  11. 根据权利要求10所述的用途，其特征在于，所述光学产品包括光学透镜。
  12. 一种权利要求1-7任一项所述的胶粘剂在医疗、电子、房屋建筑或汽车领域中的用途。
PCT/CN2022/097317 2021-10-29 2022-06-07 胶粘剂及其制备方法和用途 WO2023071202A1 (zh)

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