CN115717034A - Water-resistant adhesive based on hydrogen bond condensate and hydrophobic group and preparation method and application thereof - Google Patents
Water-resistant adhesive based on hydrogen bond condensate and hydrophobic group and preparation method and application thereof Download PDFInfo
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Abstract
本申请提供一种基于氢键凝聚物和疏水基团的耐水胶粘剂及其制备方法和应用,涉及材料领域。基于氢键凝聚物和疏水基团的耐水胶粘剂,其原料包括聚乙烯吡咯烷酮、丙烯酸类单体、甲基丙烯酸苄基酯类单体和引发剂。基于氢键凝聚物和疏水基团的耐水胶粘剂的制备方法,包括:将所述原料混合得到聚合前体,然后将所述聚合前体进行紫外辐射原位固化或加热反应。基于氢键凝聚物和疏水基团的耐水胶粘剂的应用,用于水下粘接。本申请提供的基于氢键凝聚物和疏水基团的耐水胶粘剂,具有优良的耐水、耐盐水、耐酸和耐高湿度特性。
The application provides a water-resistant adhesive based on hydrogen bond condensates and hydrophobic groups, its preparation method and application, and relates to the field of materials. A water-resistant adhesive based on hydrogen bond condensates and hydrophobic groups, whose raw materials include polyvinylpyrrolidone, acrylic monomers, benzyl methacrylate monomers and initiators. The preparation method of the water-resistant adhesive based on the hydrogen bond condensate and the hydrophobic group comprises: mixing the raw materials to obtain a polymeric precursor, and then subjecting the polymeric precursor to ultraviolet radiation in-situ curing or heating reaction. Application of water-resistant adhesives based on hydrogen-bonded condensates and hydrophobic groups for underwater bonding. The water-resistant adhesive based on hydrogen bond condensates and hydrophobic groups provided by the application has excellent water resistance, salt water resistance, acid resistance and high humidity resistance.
Description
技术领域technical field
本申请涉及材料领域,尤其涉及一种基于氢键凝聚物和疏水基团的耐水胶粘剂及其制备方法和应用。The present application relates to the field of materials, in particular to a water-resistant adhesive based on hydrogen bond condensates and hydrophobic groups and its preparation method and application.
背景技术Background technique
水下胶粘剂在日常生活和工业场景中起着重要的作用,包括创口敷料、水下机器人、水上能源设备、水下修复和海洋工业等。针对于不同基材,多种多样的高强度胶粘剂已被研发出来,然而绝大多数传统胶粘剂无法直接在水下使用,或者耐水性能较差。这是因为水下基材的表面会形成水合层,从而阻止胶粘剂和界面形成高强度的作用,使得粘接后易产生脱粘,强度减弱等问题。此外,在水环境中尤其是水下直接使用胶粘剂还要求胶粘剂具有一定的稳定性,而大部分传统胶粘剂粘度低、易扩散、易溶解,不能达到粘接效果就已经流失。传统的方法通常是使用带有疏水基团的化合物以达到排开水合层和耐水的效果,然而这些胶粘剂一般难以在多种基材如玻璃、金属等达到高强度的胶粘性能。Underwater adhesives play an important role in daily life and industrial scenarios, including wound dressings, underwater robots, aquatic energy devices, underwater repair, and marine industry, etc. A variety of high-strength adhesives have been developed for different substrates. However, most traditional adhesives cannot be used directly underwater, or have poor water resistance. This is because the surface of the underwater substrate will form a hydration layer, thereby preventing the adhesive and the interface from forming a high-strength effect, making it easy to cause problems such as debonding and weakening of the strength after bonding. In addition, direct use of adhesives in water environments, especially underwater, also requires adhesives to have certain stability, while most traditional adhesives have low viscosity, are easy to spread, and are easy to dissolve. If they cannot achieve the bonding effect, they will be lost. The traditional method is usually to use compounds with hydrophobic groups to achieve the effect of draining the hydration layer and water resistance. However, these adhesives are generally difficult to achieve high-strength adhesive properties on various substrates such as glass and metal.
近年来,受到生物体内黏附的启发,一系列基于邻苯二酚(catechol)基团的水下胶粘剂被开发出来。通过酚羟基和苯环的协同作用,该系列胶粘剂在不同基材上展现了优秀的粘接性能和耐水性。但是,这些胶粘剂需要复杂的前体合成步骤,大幅度提高了成本和商业化的难度。同时,此种胶粘剂在水下溶胀后硬度较低,不适合作为结构胶使用。另一方面,凝聚物(coacervate)也被广泛用于水下粘接。通过基团间的静电相互作用,凝聚物在水下也可保持稳定并达到良好的粘接强度。然而,大部分凝聚过程对于外界条件有不同的要求,如pH,离子键强度,离子浓度等,从而限制了凝聚物的应用场景。In recent years, inspired by the adhesion in organisms, a series of underwater adhesives based on catechol groups have been developed. Through the synergistic effect of phenolic hydroxyl groups and benzene rings, this series of adhesives exhibit excellent bonding performance and water resistance on different substrates. However, these adhesives require complex precursor synthesis steps, greatly increasing the cost and difficulty of commercialization. At the same time, this kind of adhesive has low hardness after swelling under water, so it is not suitable for use as a structural adhesive. On the other hand, coacervates are also widely used for underwater bonding. Through the electrostatic interaction between groups, the condensate can also maintain stability and achieve good bonding strength under water. However, most coagulation processes have different requirements for external conditions, such as pH, ionic bond strength, ion concentration, etc., which limit the application scenarios of condensates.
发明内容Contents of the invention
本申请的目的在于提供一种基于氢键凝聚物和疏水基团的耐水胶粘剂及其制备方法和应用,以解决上述问题。The purpose of this application is to provide a water-resistant adhesive based on hydrogen bond condensate and hydrophobic groups, its preparation method and application, so as to solve the above problems.
为实现以上目的,本申请采用以下技术方案:To achieve the above object, the application adopts the following technical solutions:
一种基于氢键凝聚物和疏水基团的耐水胶粘剂,其原料包括聚乙烯吡咯烷酮、丙烯酸类单体、甲基丙烯酸苄基酯类单体和引发剂。A water-resistant adhesive based on hydrogen bond condensates and hydrophobic groups, the raw materials of which include polyvinylpyrrolidone, acrylic monomers, benzyl methacrylate monomers and initiators.
优选地,所述丙烯酸类单体包括丙烯酸和/或甲基丙烯酸。Preferably, the acrylic monomer comprises acrylic acid and/or methacrylic acid.
优选地,所述甲基丙烯酸苄基酯类单体包括甲基丙烯酸苄基酯和/或丙烯酸苄基酯。Preferably, the benzyl methacrylate monomer includes benzyl methacrylate and/or benzyl acrylate.
优选地,所述甲基丙烯酸苄基酯类单体和所述丙烯酸类单体的质量比为(0.7-2.5):1。Preferably, the mass ratio of the benzyl methacrylate monomer to the acrylic monomer is (0.7-2.5):1.
优选地,所述引发剂包括光引发剂和热引发剂;Preferably, the initiator includes a photoinitiator and a thermal initiator;
所述光引发剂包括2,2-二乙氧基苯乙酮和/或1-羟基环己基苯基甲酮;The photoinitiator includes 2,2-diethoxyacetophenone and/or 1-hydroxycyclohexyl phenyl ketone;
所述热引发剂包括偶氮二异丁腈和/或过氧化苯甲酰。The thermal initiator includes azobisisobutyronitrile and/or benzoyl peroxide.
优选地,所述光引发剂或所述热引发剂的质量各自独立的为所述丙烯酸类单体和所述甲基丙烯酸苄基酯类单体的总质量的0.7-2%。Preferably, the mass of the photoinitiator or the thermal initiator is independently 0.7-2% of the total mass of the acrylic monomer and the benzyl methacrylate monomer.
优选地,所述聚乙烯吡咯烷酮中的乙烯吡咯烷酮单体与所述丙烯酸类单体摩尔比为1:1。Preferably, the molar ratio of the vinylpyrrolidone monomer in the polyvinylpyrrolidone to the acrylic monomer is 1:1.
本申请还提供一种所述的基于氢键凝聚物和疏水基团的耐水胶粘剂的制备方法,包括:The present application also provides a method for preparing the water-resistant adhesive based on hydrogen bond condensates and hydrophobic groups, including:
将所述原料混合得到聚合前体,然后将所述聚合前体进行紫外辐射原位固化或加热反应。The raw materials are mixed to obtain a polymeric precursor, and then the polymeric precursor is subjected to in-situ curing by ultraviolet radiation or heating reaction.
优选地,所述紫外辐射原位固化使用的紫外光源的功率密度为30-50mW/cm2,所述紫外辐射原位固化的时间为5-60min,所述加热反应的温度为65-80℃,时间为8-24h。Preferably, the power density of the ultraviolet light source used in the ultraviolet radiation in-situ curing is 30-50mW/cm 2 , the time of the ultraviolet radiation in-situ curing is 5-60min, and the temperature of the heating reaction is 65-80°C , the time is 8-24h.
本申请还提供一种所述的基于氢键凝聚物和疏水基团的耐水胶粘剂的应用,用于水下粘接。The present application also provides an application of the water-resistant adhesive based on hydrogen bond condensates and hydrophobic groups for underwater bonding.
与现有技术相比,本申请的有益效果包括:Compared with the prior art, the beneficial effects of the present application include:
本申请提供的基于氢键凝聚物和疏水基团的耐水胶粘剂,以聚乙烯吡咯烷酮、丙烯酸类单体、甲基丙烯酸苄基酯类单体和引发剂作为原料,利用聚乙烯吡咯烷酮、丙烯酸类单体之间的氢键作用获得凝聚效果,并以甲基丙烯酸苄基酯类单体作为疏水单体,与聚乙烯吡咯烷酮、丙烯酸类单体共聚而获得体系内的亲疏水协同作用;从而使得该胶粘剂在水下粘接中一方面可以同时吸收和排开基材上的水合层,另一方面可以在达到高强度粘接的同时保证耐水性。The water-resistant adhesive based on hydrogen bond condensates and hydrophobic groups provided by this application uses polyvinylpyrrolidone, acrylic monomers, benzyl methacrylate monomers and initiators as raw materials, and utilizes polyvinylpyrrolidone, acrylic monomers The coagulation effect can be obtained by the hydrogen bond between the bodies, and the benzyl methacrylate monomer is used as the hydrophobic monomer to copolymerize with polyvinylpyrrolidone and acrylic monomer to obtain the hydrophilic-hydrophobic synergy in the system; thus making the Adhesives can simultaneously absorb and drain the hydration layer on the substrate during underwater bonding, and on the other hand, can ensure water resistance while achieving high-strength bonding.
该耐水胶粘剂在固化完成后具有长时间的耐水效果,可以满足长期使用的需要;并且不受使用条件和环境的限制,粘接过程可以完全在水下进行,包括涂抹前体和光聚合,丰富了应用场景。具有优秀的耐水、耐盐水、耐酸、耐高湿度的性能。以耐水为例,将样品泡水30天后仍能保持7MPa的粘接强度。The water-resistant adhesive has a long-term water-resistant effect after curing, which can meet the needs of long-term use; and is not limited by the conditions of use and the environment, and the bonding process can be completely carried out underwater, including the application of precursors and photopolymerization, enriched Application scenarios. It has excellent water resistance, salt water resistance, acid resistance and high humidity resistance. Taking water resistance as an example, the adhesive strength of 7MPa can still be maintained after the sample is soaked in water for 30 days.
本申请提供的基于氢键凝聚物和疏水基团的耐水胶粘剂,对于不同基材表面都有着超高的粘接强度,包括玻璃、陶瓷、金属、聚氯乙烯、有机玻璃等。The water-resistant adhesive based on hydrogen bond condensate and hydrophobic groups provided by this application has super high bonding strength for different substrate surfaces, including glass, ceramics, metal, polyvinyl chloride, organic glass, etc.
附图说明Description of drawings
为了更清楚地说明本申请实施例的技术方案,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申请的某些实施例,因此不应被看作是对本申请范围的限定。In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following will briefly introduce the accompanying drawings used in the embodiments. It should be understood that the following drawings only show some embodiments of the present application, so should be considered as limiting the scope of the application.
图1为丙烯酸、聚乙烯吡咯烷酮、甲基丙烯酸苄基酯前体原位凝聚和光固化及胶粘剂本体内部作用力示意图以及胶粘剂与不同基材可能形成的作用力示意图;Figure 1 is a schematic diagram of the in-situ condensation and photocuring of the precursors of acrylic acid, polyvinylpyrrolidone, and benzyl methacrylate, as well as the internal forces of the adhesive body and the possible forces formed between the adhesive and different substrates;
图2为实施例1所得胶粘剂、聚乙烯吡咯烷酮、丙烯酸-甲基丙烯酸苄基酯共聚物三者红外图谱对比;Fig. 2 is the comparison of the infrared spectra of the obtained adhesive in Example 1, polyvinylpyrrolidone, and acrylic acid-benzyl methacrylate copolymer;
图3为实施例1所得胶粘剂及其在不同环境处理30天后的红外谱图;Fig. 3 is the adhesive obtained in embodiment 1 and its infrared spectrogram after being processed in different environments for 30 days;
图4展示了实施例4、5分别在水和盐水环境中长时间悬挂重物的图片。Figure 4 shows the pictures of Examples 4 and 5 hanging heavy objects for a long time in water and salt water environment respectively.
具体实施方式Detailed ways
如本文所用之术语:As used herein:
“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。"Prepared from" is synonymous with "comprising". As used herein, the terms "comprises," "including," "has," "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, 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. elements.
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。The conjunction "consisting of" excludes any unspecified elements, steps or components. If used in a claim, this phrase will make the claim closed so that it does not contain material other than those described except for the customary impurities associated therewith. When the phrase "consisting of" appears in a clause of the subject of a claim rather than immediately following the subject matter, it only defines the elements described in that clause; other elements are not excluded from the claims as a whole. beyond the claims.
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。When amounts, concentrations, or other values or parameters are expressed in terms of ranges, preferred ranges, or ranges bounded by a series of upper preferred values and lower preferred values, it is to be understood that any range upper or preferred value combined with any lower range limit is specifically disclosed. All ranges formed by any pairing of values or preferred values, whether or not such ranges are individually disclosed. For example, when the range "1-5" is disclosed, the described range should be construed to include the ranges "1-4", "1-3", "1-2", "1-2 and 4-5" , "1 ~ 3 and 5" and so on. When a numerical range is described herein, unless otherwise stated, that range is intended to include its endpoints and all integers and fractions within the range.
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。In these examples, unless otherwise specified, the stated parts and percentages are by mass.
“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。"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.
“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)。"And/or" is used to indicate that one or both of the stated situations may occur, for example, A and/or B includes (A and B) and (A or B).
一种基于氢键凝聚物和疏水基团的耐水胶粘剂,其原料包括聚乙烯吡咯烷酮、丙烯酸类单体、甲基丙烯酸苄基酯类单体和光引发剂。A water-resistant adhesive based on hydrogen bond condensate and hydrophobic groups, its raw materials include polyvinylpyrrolidone, acrylic monomers, benzyl methacrylate monomers and photoinitiators.
较强的氢键给体(如丙烯酸、甲基丙烯酸等)和较强的氢键受体(例如聚乙烯吡咯烷酮等)之间也可以产生凝聚。相比静电作用凝聚过程,基于氢键作用的凝聚有着显著的优势,例如对外界环境要求很低、操作简单、成本低且适合大规模生产等。以聚丙烯酸和聚乙烯吡咯烷酮为例,其各自在水溶液中与水分子的氢键作用强度分别约为-22.28kJ/mol和-24.59kJ/mol,而二者之间的氢键作用约为-35.86kJ/mol,使得简单混合其水溶液即可达到凝聚效果。同时,水下聚合过程中原位凝聚可使其在界面上达到很高的粘接强度。此外,在原位凝聚过程中可以和疏水单体(如甲基丙烯酸苄基酯,丙烯酸苄基酯等)共聚,使得体系内亲疏水协同作用。在水下粘接中一方面可以同时吸收和排开基材上的水合层,另一方面可以在达到高强度粘接的同时保证耐水性。本申请提供了基于氢键凝聚物和疏水基团协同作用的胶粘剂的制备原理和方法,为需要在水下完成高强度粘接和长期耐水耐酸使用的场景提供了适合解决方案,原料简单廉价且易商业化。Agglomeration can also occur between stronger hydrogen bond donors (such as acrylic acid, methacrylic acid, etc.) and stronger hydrogen bond acceptors (such as polyvinylpyrrolidone, etc.). Compared with the electrostatic condensation process, condensation based on hydrogen bonding has significant advantages, such as low requirements on the external environment, simple operation, low cost, and suitable for large-scale production. Taking polyacrylic acid and polyvinylpyrrolidone as an example, the strengths of their hydrogen bonds with water molecules in aqueous solution are about -22.28kJ/mol and -24.59kJ/mol respectively, and the hydrogen bonds between them are about - 35.86kJ/mol, so that the coagulation effect can be achieved simply by mixing its aqueous solution. At the same time, the in-situ coagulation during the underwater polymerization can make it achieve high bonding strength on the interface. In addition, it can be copolymerized with hydrophobic monomers (such as benzyl methacrylate, benzyl acrylate, etc.) during the in-situ coagulation process, so that the hydrophilic and hydrophobic synergies in the system can be achieved. In underwater bonding, on the one hand, it can simultaneously absorb and drain the hydration layer on the substrate, and on the other hand, it can ensure water resistance while achieving high-strength bonding. This application provides the principle and method for the preparation of adhesives based on the synergistic effect of hydrogen bond condensates and hydrophobic groups, and provides a suitable solution for scenarios that require high-strength bonding and long-term water and acid resistance under water. The raw materials are simple, cheap and Easy to commercialize.
图1中,a)表示丙烯酸(AA)、聚乙烯吡咯烷酮(PVP)、甲基丙烯酸苄基酯(BzMA)前体原位凝聚和光固化;b)表示胶粘剂与不同基材可能形成的界面作用力及胶粘剂内部形成的非共价作用。In Figure 1, a) represents the in-situ condensation and photocuring of the precursors of acrylic acid (AA), polyvinylpyrrolidone (PVP), and benzyl methacrylate (BzMA); b) represents the possible interfacial forces between the adhesive and different substrates And the non-covalent interaction formed inside the adhesive.
在一个可选的实施方式中,所述丙烯酸类单体包括丙烯酸和/或甲基丙烯酸。In an optional embodiment, the acrylic monomer includes acrylic acid and/or methacrylic acid.
在一个可选的实施方式中,所述甲基丙烯酸苄基酯类单体包括甲基丙烯酸苄基酯和/或丙烯酸苄基酯。In an optional embodiment, the benzyl methacrylate monomer includes benzyl methacrylate and/or benzyl acrylate.
在一个可选的实施方式中,所述甲基丙烯酸苄基酯类单体和所述丙烯酸类单体的质量比为(0.7-2.5):1。In an optional embodiment, the mass ratio of the benzyl methacrylate monomer to the acrylic monomer is (0.7-2.5):1.
通过调节此质量比可改变聚合前体的粘度从而使前体在水下保持短时间稳定以完成光聚合。By adjusting this mass ratio, the viscosity of the polymerization precursor can be changed so that the precursor remains stable under water for a short time to complete photopolymerization.
可选的,所述甲基丙烯酸苄基酯类单体和所述丙烯酸类单体的质量比可以为0.7:1、1:1、1.5:1、2:1、2.5:1或者(0.7-2.5):1之间的任一值。Optionally, the mass ratio of the benzyl methacrylate monomer to the acrylic monomer may be 0.7:1, 1:1, 1.5:1, 2:1, 2.5:1 or (0.7- 2.5): Any value between 1.
在一个可选的实施方式中,所述引发剂包括光引发剂和热引发剂;In an optional embodiment, the initiator includes a photoinitiator and a thermal initiator;
所述光引发剂包括2,2-二乙氧基苯乙酮和/或1-羟基环己基苯基甲酮;The photoinitiator includes 2,2-diethoxyacetophenone and/or 1-hydroxycyclohexyl phenyl ketone;
所述热引发剂包括偶氮二异丁腈和/或过氧化苯甲酰。The thermal initiator includes azobisisobutyronitrile and/or benzoyl peroxide.
在一个可选的实施方式中,所述光引发剂的质量为所述丙烯酸类单体和所述甲基丙烯酸苄基酯类单体的总质量的0.7-2%。In an optional embodiment, the mass of the photoinitiator is 0.7-2% of the total mass of the acrylic monomer and the benzyl methacrylate monomer.
在一个可选的实施方式中,所述聚乙烯吡咯烷酮中的乙烯吡咯烷酮单体与所述丙烯酸类单体摩尔比为1:1。In an optional embodiment, the molar ratio of the vinylpyrrolidone monomer in the polyvinylpyrrolidone to the acrylic monomer is 1:1.
本申请还提供一种所述的基于氢键凝聚物和疏水基团的耐水胶粘剂的制备方法,包括:The present application also provides a method for preparing the water-resistant adhesive based on hydrogen bond condensates and hydrophobic groups, including:
将所述原料混合得到聚合前体,然后将所述聚合前体进行紫外辐射原位固化或加热反应。The raw materials are mixed to obtain a polymeric precursor, and then the polymeric precursor is subjected to in-situ curing by ultraviolet radiation or heating reaction.
在一个可选的实施方式中,所述紫外辐射原位固化使用的紫外光源的功率密度为30-50mW/cm2,所述紫外辐射原位固化的时间为5-60min,所述加热反应的温度为65-80℃,时间为8-24h。In an optional embodiment, the power density of the ultraviolet light source used in the ultraviolet radiation in-situ curing is 30-50mW/cm 2 , the time for the ultraviolet radiation in-situ curing is 5-60min, and the heating reaction The temperature is 65-80°C, and the time is 8-24h.
可选的,所述紫外辐射原位固化使用的紫外光源的功率密度可以为30mW/cm2、40mW/cm2、50mW/cm2或者30-50mW/cm2之间的任一值,所述紫外辐射原位固化的时间可以为5min、10min、15min、20min、25min、30min、35min、40min、45min、50min、55min、60min或者5-60min之间的任一值,所述加热反应的温度可以为65℃、70℃、75℃、80℃或者65-80℃之间的任一值,时间可以为8h、12h、16h、20h、24h或者8-24h之间的任一值。Optionally, the power density of the ultraviolet light source used in the in-situ curing of ultraviolet radiation can be 30mW/cm 2 , 40mW/cm 2 , 50mW/cm 2 or any value between 30-50mW/cm 2 , the The time of in-situ curing by ultraviolet radiation can be any value between 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min or 5-60min, and the temperature of the heating reaction can be It can be any value between 65°C, 70°C, 75°C, 80°C or 65-80°C, and the time can be any value between 8h, 12h, 16h, 20h, 24h or 8-24h.
本申请还提供一种所述的基于氢键凝聚物和疏水基团的耐水胶粘剂的应用,用于水下粘接。The present application also provides an application of the water-resistant adhesive based on hydrogen bond condensates and hydrophobic groups for underwater bonding.
下面将结合具体实施例对本申请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申请,而不应视为限制本申请的范围。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。The implementation of the present application will be described in detail below in conjunction with specific examples, but those skilled in the art will understand that the following examples are only used to illustrate the present application, and should not be considered as limiting the scope of the present application. Those who do not indicate the specific conditions in the examples are carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments used were not indicated by the manufacturer, and they were all conventional products that could be purchased from the market.
实施例1Example 1
本实施例提供一种基于氢键凝聚物和疏水基团的耐水胶粘剂,其制备方法具体如下:This embodiment provides a water-resistant adhesive based on hydrogen bond condensates and hydrophobic groups, and its preparation method is as follows:
将1g丙烯酸,1.54g聚乙烯吡咯烷酮,1.5g甲基丙烯酸苄基酯和25mg的光引发剂2,2-二乙氧基苯乙酮混合均匀,在空气中将前体均匀涂在基材上,以50mW/cm2功率密度的紫外光源照射30min完成固化。Mix 1g of acrylic acid, 1.54g of polyvinylpyrrolidone, 1.5g of benzyl methacrylate and 25mg of photoinitiator 2,2-diethoxyacetophenone, and evenly coat the precursor on the substrate in the air , irradiating with a UV light source with a power density of 50mW/cm 2 for 30min to complete the curing.
图2为实施例1所得胶粘剂、聚乙烯吡咯烷酮、丙烯酸-甲基丙烯酸苄基酯共聚物三者红外图谱对比。实施例中的聚丙烯酸特征峰由1703cm-1移动至1720cm-1,聚乙烯吡咯烷酮特征峰由1645cm-1移动至1630cm-1,表明二者之间的强氢键作用。Fig. 2 is the comparison of the infrared spectra of the adhesive obtained in Example 1, polyvinylpyrrolidone, and acrylic acid-benzyl methacrylate copolymer. In the examples, the characteristic peak of polyacrylic acid moves from 1703cm -1 to 1720cm -1 , and the characteristic peak of polyvinylpyrrolidone moves from 1645cm -1 to 1630cm -1 , indicating the strong hydrogen bond between the two.
图3为实施例1所得胶粘剂及其在不同环境处理30天后的红外谱图对比。实施例1处理前后的PAA和PVP的红外特征峰移动均保持相近的结果,表明了处理后的样品中PAA与PVP之间的氢键作用没有受到影响。Figure 3 is a comparison of the infrared spectrum of the adhesive obtained in Example 1 and its treatment in different environments for 30 days. The results of Example 1 that the infrared characteristic peaks of PAA and PVP before and after treatment remained similar, indicating that the hydrogen bond between PAA and PVP in the treated sample was not affected.
实施例2Example 2
本实施例提供一种基于氢键凝聚物和疏水基团的耐水胶粘剂,其制备方法具体如下:This embodiment provides a water-resistant adhesive based on hydrogen bond condensates and hydrophobic groups, and its preparation method is as follows:
将1.2g甲基丙烯酸,1.54g聚乙烯吡咯烷酮,1.8g甲基丙烯酸苄基酯和30mg的光引发剂2,2-二乙氧基苯乙酮混合均匀,在空气中将前体均匀涂在基材上,以50mW/cm2功率密度的紫外光源照射30min完成固化。Mix 1.2g of methacrylic acid, 1.54g of polyvinylpyrrolidone, 1.8g of benzyl methacrylate and 30mg of photoinitiator 2,2-diethoxyacetophenone, and evenly coat the precursor in the air On the substrate, irradiate with an ultraviolet light source with a power density of 50mW/cm 2 for 30min to complete the curing.
实施例3Example 3
本实施例提供一种基于氢键凝聚物和疏水基团的耐水胶粘剂,其制备方法具体如下:This embodiment provides a water-resistant adhesive based on hydrogen bond condensates and hydrophobic groups, and its preparation method is as follows:
将1g丙烯酸,1.54g聚乙烯吡咯烷酮,1.5g丙烯酸苄基酯和25mg的光引发剂2,2-二乙氧基苯乙酮混合均匀,在空气中将前体均匀涂在基材上,以50mW/cm2功率密度的紫外光源照射30min完成固化。Mix 1g of acrylic acid, 1.54g of polyvinylpyrrolidone, 1.5g of benzyl acrylate and 25mg of photoinitiator 2,2-diethoxyacetophenone, and evenly coat the precursor on the substrate in the air to 50mW/cm 2 power density of ultraviolet light source irradiation for 30min to complete the curing.
实施例4Example 4
本实施例提供一种基于氢键凝聚物和疏水基团的耐水胶粘剂,其制备方法具体如下:This embodiment provides a water-resistant adhesive based on hydrogen bond condensates and hydrophobic groups, and its preparation method is as follows:
将1g丙烯酸,1.54g聚乙烯吡咯烷酮,1.5g甲基丙烯酸苄基酯和25mg的光引发剂2,2-二乙氧基苯乙酮混合均匀,在空气中将前体均匀涂在基材上,以50mW/cm2功率密度的紫外光源照射30min完成固化。将得到的样品泡入水中保持30天。Mix 1g of acrylic acid, 1.54g of polyvinylpyrrolidone, 1.5g of benzyl methacrylate and 25mg of photoinitiator 2,2-diethoxyacetophenone, and evenly coat the precursor on the substrate in the air , irradiating with a UV light source with a power density of 50mW/cm 2 for 30min to complete the curing. The obtained samples were soaked in water for 30 days.
实施例5Example 5
本实施例提供一种基于氢键凝聚物和疏水基团的耐水胶粘剂,其制备方法具体如下:This embodiment provides a water-resistant adhesive based on hydrogen bond condensates and hydrophobic groups, and its preparation method is as follows:
将1g丙烯酸,1.54g聚乙烯吡咯烷酮,1.5g甲基丙烯酸苄基酯和25mg的光引发剂2,2-二乙氧基苯乙酮混合均匀,在空气中将前体均匀涂在基材上,以50mW/cm2功率密度的紫外光源照射30min完成固化。将得到的样品泡入1mol/L氯化钠水溶液保持30天。Mix 1g of acrylic acid, 1.54g of polyvinylpyrrolidone, 1.5g of benzyl methacrylate and 25mg of photoinitiator 2,2-diethoxyacetophenone, and evenly coat the precursor on the substrate in the air , irradiating with a UV light source with a power density of 50mW/cm 2 for 30min to complete the curing. Soak the obtained sample in 1mol/L sodium chloride aqueous solution for 30 days.
图4为实施例4和实施例5分别在水和1M盐水中悬挂5kg重物保持两个月的照片。表明了各自良好的耐水、耐盐水粘接性能(粘接面积约4cm2)。Fig. 4 is the photograph that embodiment 4 and embodiment 5 hang 5kg weight in water and 1M saline respectively and keep for two months. It shows good water resistance and salt water resistance bonding performance (the bonding area is about 4 cm 2 ).
实施例6Example 6
本实施例提供一种基于氢键凝聚物和疏水基团的耐水胶粘剂,其制备方法具体如下:This embodiment provides a water-resistant adhesive based on hydrogen bond condensates and hydrophobic groups, and its preparation method is as follows:
将1g丙烯酸,1.54g聚乙烯吡咯烷酮,1.5g甲基丙烯酸苄基酯和25mg的光引发剂2,2-二乙氧基苯乙酮混合均匀,在空气中将前体均匀涂在基材上,以50mW/cm2功率密度的紫外光源照射30min完成固化。将得到的样品泡入pH=1的氯化氢水溶液保持30天。Mix 1g of acrylic acid, 1.54g of polyvinylpyrrolidone, 1.5g of benzyl methacrylate and 25mg of photoinitiator 2,2-diethoxyacetophenone, and evenly coat the precursor on the substrate in the air , irradiating with a UV light source with a power density of 50mW/cm 2 for 30min to complete the curing. The obtained sample was soaked in an aqueous hydrogen chloride solution with pH=1 for 30 days.
实施例7Example 7
本实施例提供一种基于氢键凝聚物和疏水基团的耐水胶粘剂,其制备方法具体如下:This embodiment provides a water-resistant adhesive based on hydrogen bond condensates and hydrophobic groups, and its preparation method is as follows:
将1g丙烯酸,1.54g聚乙烯吡咯烷酮,1.5g甲基丙烯酸苄基酯和25mg的光引发剂2,2-二乙氧基苯乙酮混合均匀,在空气中将前体均匀涂在基材上,以50mW/cm2功率密度的紫外光源照射30min完成固化。将得到的样品置于90%相对湿度的湿度箱内保持30天。Mix 1g of acrylic acid, 1.54g of polyvinylpyrrolidone, 1.5g of benzyl methacrylate and 25mg of photoinitiator 2,2-diethoxyacetophenone, and evenly coat the precursor on the substrate in the air , irradiating with a UV light source with a power density of 50mW/cm 2 for 30min to complete the curing. The obtained samples were kept in a humidity chamber at 90% relative humidity for 30 days.
通过调节胶粘剂组分中甲基丙烯酸苄基酯的含量,可以改变前体的粘度,从而让前体在水下保持短时间稳定,使得该胶粘剂可以直接于水下涂于基材表面并完成聚合,具体为:By adjusting the content of benzyl methacrylate in the adhesive component, the viscosity of the precursor can be changed, so that the precursor can remain stable under water for a short time, so that the adhesive can be directly coated on the surface of the substrate under water and complete polymerization ,Specifically:
实施例8Example 8
本实施例提供一种基于氢键凝聚物和疏水基团的耐水胶粘剂,其制备方法具体如下:This embodiment provides a water-resistant adhesive based on hydrogen bond condensates and hydrophobic groups, and its preparation method is as follows:
将1g丙烯酸,1.54g聚乙烯吡咯烷酮,0.7g甲基丙烯酸苄基酯和17mg的光引发剂2,2-二乙氧基苯乙酮混合均匀,将前体直接均匀涂在水下的基材上,以50mW/cm2功率密度的紫外光源照射30min在水环境中完成固化。Mix 1g of acrylic acid, 1.54g of polyvinylpyrrolidone, 0.7g of benzyl methacrylate and 17mg of photoinitiator 2,2-diethoxyacetophenone, and evenly coat the precursor directly on the substrate under water On the surface, irradiate with a UV light source with a power density of 50mW/cm 2 for 30min in a water environment to complete the curing.
对比例1Comparative example 1
使用商用3M快干胶(型号CA40H)粘结玻璃基材,测量其搭接剪切强度。The glass substrates were bonded using commercial 3M quick-drying adhesive (model CA40H) and their lap shear strength was measured.
对比例2Comparative example 2
将2g丙烯酸,1.54g聚乙烯吡咯烷酮,25mg的光引发剂2,2-二乙氧基苯乙酮混合均匀,在空气中将前体均匀涂在基材上,以50mW/cm2功率密度的紫外光源照射30min完成固化。2g of acrylic acid, 1.54g of polyvinylpyrrolidone, and 25mg of photoinitiator 2,2-diethoxyacetophenone were mixed evenly, and the precursor was evenly coated on the substrate in the air, with a power density of 50mW/cm The UV light source was irradiated for 30 minutes to complete the curing.
测试其初始状态的粘接性能数据,然后将得到的样品分别泡入水中7天,测试其粘接性能。Test the adhesive performance data of its initial state, and then soak the obtained samples in water for 7 days to test their adhesive performance.
对比例3Comparative example 3
将相同质量的10wt%聚丙烯酸水溶液和15wt%聚乙烯吡咯烷酮水溶液混合振荡均匀,以7000rpm的转速离心10min,取得白色凝聚物后在空气中均匀涂在基材上,在空气中干燥3天直至凝聚物变为透明,测试其粘接性能。Mix and shake the same mass of 10wt% polyacrylic acid aqueous solution and 15wt% polyvinylpyrrolidone aqueous solution, centrifuge at a speed of 7000rpm for 10min, obtain a white condensate, apply it evenly on the substrate in the air, and dry it in the air for 3 days until condensed The object becomes transparent, and its adhesive performance is tested.
对比例4Comparative example 4
将1g丙烯酸,1.5g甲基丙烯酸苄基酯和25mg的光引发剂2,2-二乙氧基苯乙酮混合均匀,在空气中将前体均匀涂在基材上,以50mW/cm2功率密度的紫外光源照射30min完成固化。将得到的样品泡入水中30天。Mix 1g of acrylic acid, 1.5g of benzyl methacrylate and 25mg of photoinitiator 2,2-diethoxyacetophenone evenly, and evenly coat the precursor on the substrate in the air at 50mW/cm 2 The UV light source of power density was irradiated for 30 minutes to complete the curing. The obtained samples were soaked in water for 30 days.
除特殊说明之外,实施例和对比例测试使用的基材均为玻璃。Unless otherwise specified, the substrates used in the tests of the examples and comparative examples are all glass.
表1对比了实施例1-3不同配方和对比例1的胶粘性能。Table 1 compares the adhesive properties of different formulations of Examples 1-3 and Comparative Example 1.
表1实施例1-3和对比例1玻璃基材搭接剪切测试性能对比(未泡水)Table 1 Example 1-3 and Comparative Example 1 glass substrate lap shear test performance comparison (not soaked in water)
表2对比了实施例4-7不同配方和对比例2-3的胶粘性能。Table 2 compares the adhesive properties of different formulations of Examples 4-7 and Comparative Examples 2-3.
表2实施例4-7和对比例2-3玻璃基材搭接剪切性能对比Table 2 Example 4-7 and Comparative Example 2-3 Comparison of lap shear performance of glass substrates
表3对比了对比例2和对比例4未泡水的胶粘性能。Table 3 compares the adhesive properties of Comparative Example 2 and Comparative Example 4 without soaking in water.
表3对比例2和对比例4玻璃基材搭接剪切性能对比Table 3 Comparative Example 2 and Comparative Example 4 Comparison of Lap Shear Performance of Glass Substrates
由表3和表2对比可知,当缺少聚乙烯吡咯烷酮或甲基丙烯酸苄基酯之后,虽然初始剪切强度很高,但是其泡水后的剪切强度大幅度下降,不适合用于水下。From the comparison of Table 3 and Table 2, it can be seen that when the lack of polyvinylpyrrolidone or benzyl methacrylate, although the initial shear strength is very high, the shear strength after soaking in water is greatly reduced, and it is not suitable for underwater use. .
更重要的是,聚丙烯酸和聚乙烯吡咯烷酮之间的超强氢键作用带来的凝聚可以与疏水的基团协同,内部氢键的保护使其在水中长时间保持低溶胀,保证了长时间耐水使用。而对比例2、3中当组分中缺少疏水基团或氢键凝聚时,耐水性能显著下降。More importantly, the aggregation brought about by the super-strong hydrogen bond between polyacrylic acid and polyvinylpyrrolidone can cooperate with the hydrophobic group, and the protection of the internal hydrogen bond keeps it low in water for a long time, ensuring a long-term Resistant to water use. However, in Comparative Examples 2 and 3, when the components lacked hydrophobic groups or hydrogen bonds condensed, the water resistance decreased significantly.
此外,本胶粘剂由于能和不同基材的表面形成非共价作用,使得该胶粘剂在不同基材展现了良好的粘接强度。In addition, since the adhesive can form non-covalent interactions with the surfaces of different substrates, the adhesive exhibits good bonding strength on different substrates.
表4对比了实施例1、实施例8在不同基材的胶粘性能。Table 4 compares the adhesive properties of Example 1 and Example 8 on different substrates.
表4实施例1和实施例8在不同基材的搭接剪切性能Table 4 embodiment 1 and embodiment 8 in the lap shear performance of different substrates
需要说明的是,以上所述实施方法中聚合方法均为紫外光聚合,要求紫外线穿过基材引发聚合。对于不透明基材的粘接,以上方法受到限制。而本申请配方可以通过热引发聚合产生粘接强度,从而解决此问题。It should be noted that the polymerization methods in the above-mentioned implementation methods are all ultraviolet light polymerization, which requires ultraviolet rays to pass through the substrate to initiate polymerization. For the bonding of opaque substrates, the above methods are limited. The formulation of the present application can solve this problem by generating adhesive strength through thermally induced polymerization.
具体的:保持胶粘剂其他成分不变,使用热引发剂代替光引发剂,通过加热至一定温度使前体聚合。热引发剂可为偶氮二异丁腈、过氧化苯甲酰等,热固化时间不等。Specifically: keep the other components of the adhesive unchanged, use a thermal initiator instead of a photoinitiator, and polymerize the precursor by heating to a certain temperature. The thermal initiator can be azobisisobutyronitrile, benzoyl peroxide, etc., and the thermal curing time varies.
具体方案为:The specific plan is:
实施例9Example 9
将1g丙烯酸,1.54g聚乙烯吡咯烷酮,1.5g甲基丙烯酸苄基酯和50mg的偶氮二异丁腈混合均匀,置于圆底瓶通氮气除氧20min,先在瓶中逐渐加热至60℃保持30min,然后将前体均匀涂在基材上加热至70℃保持10h。Mix 1g of acrylic acid, 1.54g of polyvinylpyrrolidone, 1.5g of benzyl methacrylate and 50mg of azobisisobutyronitrile evenly, put in a round-bottom bottle to remove oxygen for 20min, and gradually heat to 60°C in the bottle Keep it for 30min, then evenly coat the precursor on the substrate and heat it to 70°C for 10h.
上述实施例在玻璃基材上完成固化后,经过搭接剪切实验测得粘接强度为8.03±1.14MPa,与光固化粘接效果接近。After the above embodiments are cured on the glass substrate, the bonding strength measured by the lap shear test is 8.03±1.14 MPa, which is close to the bonding effect of light curing.
最后应说明的是:以上各实施例仅用以说明本申请的技术方案,而非对其限制;尽管参照前述各实施例对本申请进行了详细的说明,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申请各实施例技术方案的范围。Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present application, and are not intended to limit it; although the application has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: It is still possible to modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the various embodiments of the present application. scope.
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申请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申请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。In addition, those skilled in the art will appreciate that although some embodiments herein include some features included in other embodiments but not others, combinations of features from different embodiments are meant to be within the scope of the present application. And form different embodiments. For example, in the following claims, any one of the claimed embodiments may be used in any combination. The information disclosed in the background technology section is only intended to deepen the understanding of the general background technology of the application, and should not be regarded as an acknowledgment or any form of suggestion that the information constitutes the prior art known to those skilled in the art.
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