WO2022237025A1 - 一种无皂乳液聚合法制备丙烯酸酯复合胶的方法 - Google Patents

一种无皂乳液聚合法制备丙烯酸酯复合胶的方法 Download PDF

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WO2022237025A1
WO2022237025A1 PCT/CN2021/118108 CN2021118108W WO2022237025A1 WO 2022237025 A1 WO2022237025 A1 WO 2022237025A1 CN 2021118108 W CN2021118108 W CN 2021118108W WO 2022237025 A1 WO2022237025 A1 WO 2022237025A1
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acrylate
emulsion
initiator
monomer
add
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PCT/CN2021/118108
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French (fr)
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孙大伟
杜志健
丁庄
高铨蔚
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江苏景宏新材料科技有限公司
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Priority to US17/762,661 priority Critical patent/US20240052215A1/en
Publication of WO2022237025A1 publication Critical patent/WO2022237025A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/006—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • 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
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]

Definitions

  • the invention belongs to the technical field of water-based pressure-sensitive adhesives, and in particular relates to a method for preparing acrylate composite adhesives by a soap-free emulsion polymerization method.
  • Water-based acrylic composite glue the dispersion medium is water, and the polymer is stably dispersed in water in the form of particles.
  • flexible packaging materials such as plastic-plastic and aluminum-plastic.
  • solvent-based polyurethane adhesives are mostly used in the lamination of such flexible packaging materials, but solvent-based polyurethane adhesives have potential safety risks for areas with strict safety requirements such as food, medicine and cosmetics.
  • people pay more attention to environmental protection, safety and energy saving Therefore, it is imminent to develop a flexible packaging water-based composite adhesive suitable for the above-mentioned fields.
  • Acrylic emulsion composite adhesives are a large category of green and environmentally friendly adhesives, but there are still some defects in water-based acrylic emulsion composite adhesives, such as composite strength and water resistance, which are not as good as solvent-based products, poor water resistance, or substrate.
  • the adaptation surface is very limited and other problems.
  • Patent CN 111440268 B adopts (meth)acrylic acid monomer, (meth)acrylate monomer, acrylonitrile monomer and vinyl oxidized starch as reaction monomers for emulsion copolymerization, and polymerizes with ⁇ , ⁇ -double active groups Siloxane is used as a crosslinking agent to prepare a water-based composite adhesive, which can be applied to the composite of plastic-plastic, aluminum-plastic, PET-aluminum foil and other flexible packaging materials, and has certain composite strength and water resistance.
  • emulsion polymerization still uses traditional small molecule emulsifiers, such as sodium alkylsulfonate, sodium alkylbenzenesulfonate, sodium vinylsulfonate, alkylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether ammonium sulfate, etc.
  • Small molecule emulsifiers are easy to migrate to the surface of the glue film, forming a weak interface layer, which will reduce the composite strength of the glue.
  • it uses ⁇ , ⁇ -bisactive polysiloxane as a crosslinking agent.
  • ⁇ , ⁇ -bisactive polysiloxane needs to be hydrolyzed into silicon hydroxyl groups, and then the silicon hydroxyl groups are condensed with the hydroxyl groups on the acrylate chain. Reaction, the efficiency and strength of the crosslinking reaction are not ideal, and its plastic-plastic composite strength does not exceed 2N/15mm, and the composite strength is relatively small. Compared with the strength of solvent-based composite adhesives, it is much worse.
  • Patent CN111269350 A adopts the pre-emulsification seed emulsion polymerization process, adopts the emulsification system compounded by traditional small molecule anionic emulsifiers and nonionic emulsifiers, and uses acetoacetoxyethyl methacrylate, glycidyl methacrylate, N - Isobutoxyacrylamide is used as a self-crosslinking monomer, and the obtained glue cannot be torn apart after being compounded on PE, and the composite strength on the PET film is not given. Strength and water resistance are yet to be verified.
  • Patent CN103059784 A adopts the pre-emulsified seed emulsion polymerization process, and adds the weaker polar monomer mixture and the stronger polar monomer mixture step by step to enhance the stability of the polymerization and make the surface layer of the polymer particles more distributed Polar groups, thereby improving the bonding strength of the substrate; using internal plasticizing monomers to improve the flexibility of the film and substrate adhesion; introducing monomers containing two or more double bonds as internal cross-linking Link monomers, increase the molecular weight of the polymer, and improve the cohesive strength of the film.
  • the water-based plastic-plastic composite adhesive for food and drug flexible packaging obtained in this patent does not contain organic solvents, does not release formaldehyde, has good adhesion, high peel strength and holding force, and can be applied to the flexible packaging industry.
  • this patent uses a small molecule reactive emulsifier, which can reduce the migration of traditional emulsifiers, only a part of the emulsifier can react with the monomer, and the remaining part of the emulsifier will still reduce the performance of the adhesive, so that the composite strength of the adhesive does not exceed 1.5 N/15mm, it cannot be applied in fields requiring high composite strength, such as the field of dry battery labels, which require that the film cannot be peeled off after lamination.
  • the purpose of the present invention is to provide a method for preparing acrylate composite glue by using soap-free emulsion polymerization.
  • another purpose of the present invention is to provide the above-mentioned acrylate water-based composite glue, which can be applied to soft packaging film materials.
  • Composite replacing solvent-based polyurethane compound adhesive.
  • step (1) Add butyl acrylate and initiator to the reactor in step (1), vacuumize nitrogen, react at 60-65°C for 12-72h, then remove ethanol by vacuuming at 60°C to obtain acrylic block Oligomer;
  • step (3) Add the acrylic block oligomer, deionized water, acrylic monomer, hydroxyl-containing monomer, carboxylic acid monomer, chain transfer agent and initiator obtained in step (2) to the emulsification tank , high-speed stirring and emulsification to obtain monomer pre-emulsion;
  • step (4) Stir and mix the acrylate composite collagen emulsion prepared in step (4) with the water-based curing agent evenly, and then it can be coated and composited on the film.
  • the mass ratio of acrylic acid, ethanol, RAFT chain transfer agent and initiator in the step (1) is 40-60:40-60:0.2-2:0.2-2;
  • the mass ratio of the ester to the initiator is 20-40:0.1-1.
  • the mass ratio of acrylic acid in step (1) to butyl acrylate in step (2) is 50-80:50-20.
  • the RAFT chain transfer agent in the step (1) is diisopropoxymethylsulfonyl persulfide; the initiators in the step (1) and the step (2) are both azobisisobutyronitrile.
  • the mass ratio of the acrylic block oligomer, deionized water, acrylate monomer, hydroxyl-containing monomer, carboxylic acid monomer, chain transfer agent and initiator is 0.4- 4: 30 ⁇ 60: 30 ⁇ 60: 1 ⁇ 5: 1 ⁇ 5: 0.2 ⁇ 2: 0.2 ⁇ 1.
  • the acrylic monomer in the step (3) is one or more of butyl acrylate, isooctyl acrylate, ethyl acrylate, methyl acrylate and methyl methacrylate.
  • the hydroxyl-containing monomer in the step (3) is hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl One or more of acrylate and hydroxyoctyl acrylate.
  • carboxylic acid monomer in the step (3) is ⁇ -acryloyloxypropionic acid.
  • the chain transfer agent in the step (3) is n-amyl alcohol.
  • the initiators in the step (3) and step (4) are independently ammonium persulfate, potassium persulfate or sodium persulfate.
  • the mass ratio of deionized water, monomer pre-emulsion, initiator, reducing agent, wetting agent and defoamer in the step (4) is 20-30:70-80:0.1-0.3:0.05 ⁇ 0.15: 0.1 ⁇ 0.5: 0.05 ⁇ 0.2.
  • the mass ratio of part of the monomer pre-emulsion to the remaining monomer pre-emulsion in the step (4) is 1-15:85-99.
  • the wetting agent in the step (4) is a silicone-based wetting agent or an acetylene glycol-based wetting agent.
  • the defoamer in the step (4) is a polyether modified silicone defoamer or a mineral oil defoamer.
  • the reducing agent in the step (4) is disodium glycolate sulfinate.
  • the water-based curing agent in the step (5) is a water-based polyisocyanate curing agent, and the addition amount is 1% to 10% of the mass of the acrylate composite latex emulsion.
  • the above-mentioned soap-free emulsion polymerization method to prepare acrylate composite glue is suitable for the composite of plastic-plastic, aluminum-plastic, PET-VMPET and other flexible packaging film materials.
  • the present invention adopts soap-free emulsion polymerization to prepare acrylate composite glue, synthesizes emulsifying acrylic block oligomers by using RAFT active free radical polymerization, and then uses acrylic block oligomers to emulsify acrylate monomers for semi-continuous emulsion polymerization , to solve the shortcomings of traditional small molecule emulsifiers that easily migrate to the surface of the film to form a weak interface layer, which leads to a decrease in bonding strength and poor water resistance. Improving the fluidity and compounding uniformity of the adhesive can reduce the surface tension of the emulsion and improve the coating wettability and leveling property of the acrylate compound latex.
  • the acrylic compound adhesive prepared by the present invention is suitable for compounding plastic-plastic, aluminum-plastic, PET-VMPET and other flexible packaging film materials. Can't tear it apart.
  • step (3) Weigh 30g of acrylic acid block oligomer in step (2), 1500g of deionized water, 2025g of butyl acrylate, 750g of methyl methacrylate, 60g of ⁇ -acryloxypropionic acid, 150g of hydroxyethyl methacrylate Ester, 60g of n-amyl alcohol, and 6g of potassium persulfate were added into an emulsification kettle, stirred and emulsified at a high speed to obtain a pre-emulsion of acrylate monomer.
  • the dosage ratio of the curing agent is 4% of the amount of the acrylate emulsion, which can be directly coated on the film for composite application .
  • step (3) Weigh 45g of acrylic acid block oligomer in step (2), 1500g of deionized water, 1995g of butyl acrylate, 750g of methyl methacrylate, 60g of ⁇ -acryloxypropionic acid, 180g of hydroxyethyl methacrylate Ester, 75g of n-amyl alcohol, and 6g of ammonium persulfate were added into an emulsification kettle, stirred and emulsified at a high speed to obtain a pre-emulsion of acrylate monomer.
  • the dosage ratio of the curing agent is 6% of the amount of the acrylate emulsion, which can be directly coated on the film for composite application .
  • step (3) Weigh 24g of acrylic acid block oligomer in step (2), 1500g of deionized water, 1245g of butyl acrylate, 600g of isooctyl acrylate, 900g of methyl methacrylate, 60g of ⁇ -acryloyloxypropionic acid, Add 150g of hydroxyethyl methacrylate, 60g of n-amyl alcohol, and 6g of sodium persulfate into an emulsification kettle, stir and emulsify at a high speed to obtain a pre-emulsion of acrylate monomers.
  • the dosage ratio of the curing agent is 5% of the amount of the acrylate emulsion, which can be directly coated on the film for composite application .
  • step (3) Weigh 60g of acrylic acid block oligomer in step (2), 1500g of deionized water, 1575g of butyl acrylate, 300g of isooctyl acrylate, 30g of hydroxyethyl acrylate, 840g of methyl methacrylate, and 90g of ⁇ -propylene
  • acyloxypropionic acid 180g hydroxyethyl methacrylate, 90g n-pentanol, and 6g ammonium persulfate into an emulsification kettle, stir and emulsify at a high speed to obtain an acrylate monomer pre-emulsion.
  • the test sample was a PET-VMPET composite film material obtained by coating, drying, pressing and aging with the composite glue.
  • the water resistance test is carried out as follows: test the peel strength after soaking the test sample in warm water at 60°C for 72 hours. The test results are shown in Table 1 below:
  • Table 1 The performance of the acrylic composite glue prepared by the soap-free emulsion polymerization method of embodiment 1-4
  • the acrylate composite adhesive emulsion prepared by soap-free emulsion polymerization of the present invention has excellent composite strength and water resistance, and the film cannot be peeled off after compounding, which is equivalent to solvent-based polyurethane composite adhesive, and can be widely used in plastic-plastic, Lamination of aluminum-plastic, PET-VMPET and other flexible packaging film materials.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

本发明公开了一种无皂乳液聚合法制备丙烯酸酯复合胶的方法，采用无皂乳液聚合制备丙烯酸酯复合胶，采用RAFT活性自由基聚合合成具有乳化性的丙烯酸嵌段低聚物，再以丙烯酸嵌段低聚物乳化丙烯酸酯单体进行半连续乳液聚合，解决了传统小分子乳化剂易向胶膜表面迁移形成弱界面层导致粘接强度下降、耐水差等缺陷，使用正戊醇作为链转移剂，既可以降低聚合物的分子量，提高胶黏剂的流动性和复合均匀性，又可以降低乳液的表面张力，提高丙烯酸酯复合胶乳液的涂布润湿性和流平性，丙烯酸酯复合胶适用于塑-塑、铝-塑、PET-VMPET等软包装膜材料复合，复合强度高，复合膜无法撕开，复合膜在60℃水浴中浸泡72h，复合膜仍撕不开。

Description

一种无皂乳液聚合法制备丙烯酸酯复合胶的方法
本申请要求于2021年05月11日提交中国专利局、申请号为202110508970.2、发明名称为“一种无皂乳液聚合法制备丙烯酸酯复合胶的方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明属于水性压敏胶技术领域，具体涉及一种无皂乳液聚合法制备丙烯酸酯复合胶的方法。
背景技术
水性丙烯酸酯复合胶，分散介质为水，聚合物是以微粒形式稳定地分散在水中。目前在电子产品、食品、药品和化妆品等包装领域，普遍需要对塑-塑、铝-塑等软包装材料进行复合。目前这类软包装材料的复合用胶大部分采用溶剂型聚氨酯胶粘剂，但溶剂型聚氨酯胶粘剂对于食品、药品和化妆品等安全性要求严格的领域来说，存在潜在的安全风险。另外，随着人们对环保、安全、节能的重视。因此，开发适合于上述领域的软包装水性复合胶迫在眉睫。
丙烯酸乳液复合胶是绿色环保型胶黏剂的一大类，但目前水性丙烯酸乳液复合胶还存在部分缺陷，比如复合强度、耐水性等不及溶剂型产品，耐水性能较差，或是对基材的适应面非常有限等问题。
专利CN 111440268 B采用(甲基)丙烯酸单体、(甲基)丙烯酸酯类单体、丙烯腈单体以及乙烯基氧化淀粉作为乳液共聚合的反应单体，以α,ω-双活性基聚硅氧烷作为交联剂制备得到了水性复合胶黏剂，可应用于塑-塑、铝-塑、PET-铝箔等软包装材料的复合，具有一定的复合强度和耐水性。但是乳液聚合仍采用了传统小分子乳化剂，如烷基磺酸钠、烷基苯磺酸钠、乙烯基磺酸钠、烷基酚聚氧乙烯醚、脂肪醇聚氧乙烯醚硫酸铵等，小分子乳化剂易向胶膜表面迁移，形成弱界面层，会降低胶水的复合强度。另外，其采用α,ω-双活性基聚硅氧烷作为交联剂，α,ω-双活性基聚硅氧烷需要水解成硅羟基，然后硅羟基再与丙烯酸酯链上的羟基进行缩合反应，该交联反应效率和强度都不够理想，其塑-塑复合强度没有超过 2N/15mm，复合强度比较小，与溶剂型复合胶的强度相比，还差较多。
专利CN111269350 A通过采用预乳化种子乳液聚合工艺，采用传统小分子阴离子乳化剂和非离子乳化剂复配的乳化体系，并使用甲基丙烯酸乙酰乙酰氧基乙酯、甲基丙烯酸缩水甘油酯、N-异丁氧基丙烯酰胺作为自交联单体，得到的胶水在PE上复合后撕不开，没有给出在PET膜上的复合强度，另外，采用小分子乳化剂合成的复合胶其复合强度和耐水性有待考证。
专利CN103059784 A采用预乳化种子乳液聚合工艺，将极性较弱的单体混合物与极性较强的单体混合物分步滴加，增强聚合的稳定性，并使聚合物胶粒表层分布更多的极性基团，从而提高基材粘结强度；采用内增塑单体，提高胶膜的柔韧性和基材粘附性；引入含两个或两个以上双键的单体作为内交联单体，增大聚合物分子量，提高胶膜内聚强度。该专利得到的食品药品软包装用水性塑-塑复合胶粘剂不含有机溶剂，不释放甲醛，粘附性好，剥离强度与持粘力高，可应用于软包装行业。虽然该专利采用小分子反应型乳化剂，能够减少传统乳化剂迁移性，但只有一部分乳化剂可以与单体反应，另一部分残留乳化剂仍会降低胶粘剂的性能，使得胶粘剂的复合强度没有超过1.5N/15mm，无法在复合强度要求高的领域应用，如干电池标签领域，要求复合后膜无法剥离。
发明内容
针对背景技术提出的问题，本发明目的在于提供一种采用无皂乳液聚合法制备丙烯酸酯复合胶的方法。
针对现有水性复合胶在塑-塑、铝-塑、PET-VMET等上复合强度低、耐水差等缺陷，本发明的另一目的在于提供上述丙烯酸酯水性复合胶，应用于软包装膜材料的复合，替代溶剂型聚氨酯复合胶。
本发明无皂乳液聚合法丙烯酸酯复合胶的制备方法通过以下技术方案来具体实现：
(1)将丙烯酸、乙醇、RAFT链转移剂、引发剂加入到反应器中，然后抽真空，通入高纯氮气，在60～65℃反应24～72h；
(2)将丙烯酸丁酯、引发剂加入到步骤(1)反应器中，抽真空通氮气， 在60～65℃反应12～72h，然后在60℃抽真空脱除乙醇，得到丙烯酸类嵌段低聚物；
(3)将步骤(2)中得到的丙烯酸类嵌段低聚物、去离子水、丙烯酯类单体、含羟基单体、羧酸单体、链转移剂、引发剂加入到乳化釜中，高速搅拌乳化得到单体预乳化液；
(4)将去离子水加入到反应釜中并加热至80～82℃，加入部分步骤(3)制得的单体预乳化液、引发剂，反应20～30min；然后将剩余单体预乳化液在2～4h时间内滴加至反应釜中，滴加结束后在80～82℃保温1h，降温至65℃，滴加还原剂水溶液进行后处理；然后降温至45℃以下，加入氨水调pH值至7～8，最后加入润湿剂、消泡剂，搅拌均匀，过滤出料，即得丙烯酸酯复合胶原乳液；
(5)将步骤(4)中制得的丙烯酸酯复合胶原乳液与水性固化剂搅拌混合均匀，即可在薄膜上进行涂布复合应用。
进一步地，所述步骤(1)中丙烯酸、乙醇、RAFT链转移剂和引发剂的质量比为40～60：40～60：0.2～2：0.2～2；所述步骤(2)中丙烯酸丁酯、引发剂的质量比为20～40：0.1～1。
进一步地，所述步骤(1)中丙烯酸和步骤(2)中丙烯酸丁酯的质量比为50～80：50～20。
进一步地，所述步骤(1)中RAFT链转移剂为过硫化二异丙氧基甲硫酰；所述步骤(1)和步骤(2)中的引发剂均为偶氮二异丁腈。
进一步地，所述步骤(3)中丙烯酸类嵌段低聚物、去离子水、丙烯酯类单体、含羟基单体、羧酸单体、链转移剂和引发剂的质量比为0.4～4：30～60：30～60：1～5：1～5：0.2～2：0.2～1。
进一步地，所述步骤(3)中丙烯酯类单体为丙烯酸丁酯、丙烯酸异辛酯、丙烯酸乙酯、丙烯酸甲酯和甲基丙烯酸甲酯中的一种或多种。
进一步地，所述步骤(3)中的含羟基单体为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸-2-羟基丙酯、甲基丙烯酸-2-羟基丙酯、4-羟基丁基丙烯酸酯和羟辛基丙烯酸酯中的一种或多种。
进一步地，所述步骤(3)中的羧酸单体为β-丙烯酰氧基丙酸。
进一步地，所述步骤(3)中的链转移剂为正戊醇。
进一步地，所述步骤(3)和步骤(4)中的引发剂独立地为过硫酸铵、过硫酸钾或过硫酸钠。
进一步地，所述步骤(4)中去离子水、单体预乳化液、引发剂、还原剂、润湿剂和消泡剂的质量比为20～30：70～80：0.1～0.3：0.05～0.15：0.1～0.5：0.05～0.2。
进一步地，所述步骤(4)中部分单体预乳化液与剩余单体预乳化液的质量比为1～15：85～99。
进一步地，所述步骤(4)中润湿剂为有机硅类润湿剂或炔二醇类润湿剂。
进一步地，所述步骤(4)中消泡剂为聚醚改性有机硅类消泡剂或矿物油类消泡剂。
进一步地，所述步骤(4)中的还原剂为羟乙酸亚磺酸二钠。
进一步地，所述步骤(5)中的水性固化剂为水性多异氰酸酯固化剂，添加量为丙烯酸酯复合胶乳液质量的1％～10％。
上述无皂乳液聚合法制备丙烯酸酯复合胶适合应用于塑-塑、铝-塑、PET-VMPET等软包装膜材料的复合。
与现有技术相比，本发明有益效果是：
本发明采用无皂乳液聚合制备丙烯酸酯复合胶，通过采用RAFT活性自由基聚合合成具有乳化性的丙烯酸嵌段低聚物，再以丙烯酸嵌段低聚物乳化丙烯酸酯单体进行半连续乳液聚合，解决了传统小分子乳化剂易向胶膜表面迁移形成弱界面层导致粘接强度下降、耐水差等缺陷，同时配方中创新使用正戊醇作为链转移剂，既可以降低聚合物的分子量，提高胶黏剂的流动性和复合均匀性，又可以降低乳液的表面张力，提高丙烯酸酯复合胶乳液的涂布润湿性和流平性。本发明制备的丙烯酸酯复合胶适用于塑-塑、铝-塑、PET-VMPET等软包装膜材料复合，复合强度高，复合膜无法撕开，复合膜在60℃水浴中浸泡72h，复合膜仍撕不开。
具体实施方式
以下通过具体实施例对本发明做进一步说明。
实施例1
(1)将65g丙烯酸、60g乙醇、0.9g过硫化二异丙氧基甲硫酰、0.52g偶氮二异丁腈加到反应器中，室温下抽真空并通入氮气，在60℃反应48h。
(2)降至室温，再加入35g丙烯酸丁酯、0.28g偶氮二异丁腈，抽真空并通氮气，在65℃反应18h，然后在60℃抽真空脱除乙醇，得到丙烯酸嵌段低聚物。
(3)称取30g步骤(2)中丙烯酸嵌段低聚物、1500g去离子水、2025g丙烯酸丁酯、750g甲基丙烯酸甲酯、60gβ-丙烯酰氧基丙酸、150g甲基丙烯酸羟乙酯、60g正戊醇、6g过硫酸钾加入到乳化釜中，高速搅拌乳化，得到丙烯酸酯单体预乳化液。
(4)将去离子水加入到反应釜中并加热至80～82℃，加入225g步骤(3)中单体预乳化液和0.9g过硫酸钾，反应20～30min；然后将剩余单体预乳化液在2～4h时间内滴加至反应釜中，滴加结束后在80～82℃保温1h，降温至65℃，滴加还原剂水溶液进行后处理；然后降温至45℃以下，加入氨水调pH值至5～7，最后加入炔二醇类润湿剂15g、矿物油类消泡剂3g，搅拌均匀，过滤出料，即得丙烯酸酯复合胶原乳液。
(5)将丙烯酸酯复合胶原乳液与水性多异氰酸酯固化剂搅拌混合均匀，即得丙烯酸酯复合胶乳液，固化剂用量比为丙烯酸酯乳液量的4％，可直接在薄膜上进行涂布复合应用。
实施例2
(1)将70g丙烯酸、60g乙醇、0.9g过硫化二异丙氧基甲硫酰、0.56g偶氮二异丁腈加到反应器中，室温下抽真空并通入氮气，在60℃反应48h。
(2)降至室温，再加入30g丙烯酸丁酯、0.24g偶氮二异丁腈，抽真空并通氮气，在60℃反应36h，然后在60℃抽真空脱除乙醇得到丙烯酸嵌段低聚物。
(3)称取45g步骤(2)中丙烯酸嵌段低聚物、1500g去离子水、1995g丙烯酸丁酯、750g甲基丙烯酸甲酯、60gβ-丙烯酰氧基丙酸、180g甲基丙烯酸羟乙酯、75g正戊醇、6g过硫酸铵加入到乳化釜中，高速搅拌乳化，得到丙烯酸酯单体预乳化液。
(4)将去离子水加入到反应釜中并加热至80～82℃，加入270g步骤(3)中单体预乳化液和0.6g过硫酸铵，反应20～30min；然后将剩余单体预 乳化液在2～4h时间内滴加至反应釜中，滴加结束后在80～82℃保温1h，降温至65℃，滴加还原剂水溶液进行后处理；然后降温至45℃以下，加入氨水调pH值至5～7，最后加入有机硅类润湿剂12g、聚醚改性有机硅类消泡剂1.5g，搅拌均匀，过滤出料，即得丙烯酸酯复合胶原乳液。
(5)将丙烯酸酯复合胶原乳液与水性多异氰酸酯固化剂搅拌混合均匀，即得丙烯酸酯复合胶乳液，固化剂用量比为丙烯酸酯乳液量的6％，可直接在薄膜上进行涂布复合应用。
实施例3
(1)将65g丙烯酸、60g乙醇、1.2g化二异丙氧基甲硫酰、0.65g偶氮二异丁腈加到反应器中，室温下抽真空并通入氮气，在60℃反应48h。
(2)降至室温，再加入35g丙烯酸丁酯、0.35g偶氮二异丁腈，抽真空并通氮气，在62℃反应24h，然后在60℃抽真空脱除乙醇，得到丙烯酸嵌段低聚物。
(3)称取24g步骤(2)中丙烯酸嵌段低聚物、1500g去离子水、1245g丙烯酸丁酯、600g丙烯酸异辛酯、900g甲基丙烯酸甲酯、60gβ-丙烯酰氧基丙酸、150g甲基丙烯酸羟乙酯、60g正戊醇、6g过硫酸钠加入到乳化釜中，高速搅拌乳化，得到丙烯酸酯单体预乳化液。
(4)将去离子水加入到反应釜中并加热至80～82℃，360g部分步骤(3)中单体预乳化液和9g过硫酸钠，反应20～30min；然后将剩余单体预乳化液在2～4h时间内滴加至反应釜中，滴加结束后在80～82℃保温1h，降温至65℃，滴加还原剂水溶液进行后处理；然后降温至45℃以下，加入氨水调pH值至5～7，最后加入炔二醇类润湿剂21g、矿物油类消泡剂6g，搅拌均匀，过滤出料，即得丙烯酸酯复合胶原乳液。
(5)将丙烯酸酯复合胶原乳液与水性多异氰酸酯固化剂搅拌混合均匀，即得丙烯酸酯复合胶乳液，固化剂用量比为丙烯酸酯乳液量的5％，可直接在薄膜上进行涂布复合应用。
实施例4
(1)将70g丙烯酸、60g乙醇、1.5g过硫化二异丙氧基甲硫酰、0.7g偶氮二异丁腈加到反应器中，室温下抽真空并通入氮气，在60℃反应48h。
(2)降至室温，再加入30g丙烯酸丁酯、0.36g偶氮二异丁腈，抽真空 并通氮气，在65℃反应24h，然后在60℃抽真空脱除乙醇，得到丙烯酸嵌段低聚物。
(3)称取60g步骤(2)中丙烯酸嵌段低聚物、1500g去离子水、1575g丙烯酸丁酯、300g丙烯酸异辛酯、30g丙烯酸羟乙酯、840g甲基丙烯酸甲酯、90gβ-丙烯酰氧基丙酸、180g甲基丙烯酸羟乙酯、90g正戊醇、6g过硫酸铵加入到乳化釜中，高速搅拌乳化，得到丙烯酸酯单体预乳化液。
(4)将去离子水加入到反应釜中并加热至80～82℃，加入180g步骤(3)中单体预乳化液和6g过硫酸铵，反应20～30min；然后将剩余单体预乳化液在2～4h时间内滴加至反应釜中，滴加结束后在80～82℃保温1h，降温至65℃，滴加还原剂水溶液进行后处理；然后降温至45℃以下，加入氨水调pH值至5～7，最后加入有机硅类润湿剂18g、聚醚改性有机硅类消泡剂3g，搅拌均匀，过滤出料，即得丙烯酸酯复合胶原乳液。
(5)将丙烯酸酯复合胶原乳液与水性多异氰酸酯固化剂搅拌混合均匀，即得丙烯酸酯复合胶乳液，固化剂用量比为丙烯酸酯乳液量的3％，可直接在薄膜上进行涂布复合应用。
对以上实施例所得丙烯酸酯复合胶乳液进行复合强度和耐水性测试，测试样品为经复合胶进行涂布、干燥、压合、熟化得到的PET-VMPET复合膜材料。
复合强度按GB/T8808软质复合塑料材料剥离试验方法进行测试；
耐水性测试按如下方法进行：将测试样品在60℃温水中浸泡72h后测试剥离强度。测试结果如下表1所示：
表1 实施例1-4无皂乳液聚合法制备的丙烯酸酯复合胶的性能
项目 剥离强度(N/15mm) 耐水性
实施例1 膜断、无法剥离 不泛白、无法剥离
实施例2 膜断、无法剥离 不泛白、无法剥离
实施例3 膜断、无法剥离 不泛白、无法剥离
实施例4 4.8 不泛白、剥离力4.6
由上表可知，本发明无皂乳液聚合制备的丙烯酸酯复合胶乳液具有优异的复合强度和耐水性，复合后膜无法剥离，与溶剂型聚氨酯复合胶性能相当，可以广泛应用于塑-塑、铝-塑、PET-VMPET等软包装膜材料的复 合。

Claims (16)

  1. 一种无皂乳液聚合法制备丙烯酸酯复合胶原乳液的方法，其特征在于，包括如下制备步骤：
    (1)将丙烯酸、乙醇、RAFT链转移剂、引发剂加入到反应器中后抽真空，通入高纯氮气，在60～65℃反应24～72h；
    (2)将丙烯酸丁酯、引发剂加入到步骤(1)反应器中，抽真空通氮气，在60～65℃反应12～72h后在60℃抽真空脱除乙醇，得到丙烯酸类嵌段低聚物；
    (3)将步骤(2)中得到的丙烯酸类嵌段低聚物、去离子水、丙烯酯类单体、含羟基单体、羧酸单体、链转移剂、引发剂加入到乳化釜中，高速搅拌乳化得到单体预乳化液；
    (4)将去离子水加入到反应釜中并加热至80～82℃，加入部分步骤(3)制得的单体预乳化液、引发剂，反应20～30min；然后将剩余单体预乳化液在2～4h时间内滴加至反应釜中，滴加结束后在80～82℃保温1h，降温至65℃，滴加还原剂水溶液进行后处理；降温至45℃以下，加入氨水调pH值至7～8，最后加入润湿剂、消泡剂，搅拌均匀，过滤出料，得到丙烯酸酯复合胶原乳液。
  2. 权利要求1所述方法制备得到的丙烯酸酯复合胶原乳液。
  3. 一种无皂乳液聚合法制备丙烯酸酯复合胶的方法，其特征在于：包括如下制备步骤：
    (1)将丙烯酸、乙醇、RAFT链转移剂、引发剂加入到反应器中后抽真空，通入高纯氮气，在60～65℃反应24～72h；
    (2)将丙烯酸丁酯、引发剂加入到步骤(1)反应器中，抽真空通氮气，在60～65℃反应12～72h后在60℃抽真空脱除乙醇，得到丙烯酸类嵌段低聚物；
    (3)将步骤(2)中得到的丙烯酸类嵌段低聚物、去离子水、丙烯酯类单体、含羟基单体、羧酸单体、链转移剂、引发剂加入到乳化釜中，高速搅拌乳化得到单体预乳化液；
    (4)将去离子水加入到反应釜中并加热至80～82℃，加入部分步骤(3) 制得的单体预乳化液、引发剂，反应20～30min；然后将剩余单体预乳化液在2～4h时间内滴加至反应釜中，滴加结束后在80～82℃保温1h，降温至65℃，滴加还原剂水溶液进行后处理；降温至45℃以下，加入氨水调pH值至7～8，最后加入润湿剂、消泡剂，搅拌均匀，过滤出料，即得丙烯酸酯复合胶原乳液；
    (5)将步骤(4)中制得的丙烯酸酯复合胶原乳液与水性固化剂搅拌混合均匀，得到丙烯酸酯复合胶。
  4. 如权利要求1或3所述的方法，其特征在于：所述步骤(1)中丙烯酸、乙醇、RAFT链转移剂和引发剂的质量比为40～60：40～60：0.2～2：0.2～2；所述步骤(2)中丙烯酸丁酯和引发剂的质量比为20～40：0.1～1。
  5. 如权利要求1或3所述的方法，其特征在于：所述步骤(1)中RAFT链转移剂为过硫化二异丙氧基甲硫酰；所述步骤(1)和步骤(2)中的引发剂均为偶氮二异丁腈。
  6. 如权利要求1或3所述的方法，其特征在于：所述步骤(3)中丙烯酸类嵌段低聚物、去离子水、丙烯酯类单体、含羟基单体、羧酸单体、链转移剂和引发剂的质量比为0.4～4：30～60：30～60：1～5：1～5：0.2～2：0.2～1。
  7. 如权利要求1或3所述的方法，其特征在于，所述步骤(3)中丙烯酸类嵌段低聚物、去离子水、丙烯酯类单体、含羟基单体、羧酸单体、链转移剂和引发剂的质量比为30g：1500g：2775g：150g：60g：60g：6g、或45g：1500g：2745g：180g：60g：75g：6g或24g：1500g：2745g：150g：60g：60g：6g。
  8. 如权利要求1或3所述的方法，其特征在于：所述步骤(3)中丙烯酯类单体为丙烯酸丁酯、丙烯酸异辛酯、丙烯酸乙酯、丙烯酸甲酯和甲基丙烯酸甲酯中的一种或多种。
  9. 如权利要求1或3所述的方法，其特征在于：所述步骤(3)中的含羟基单体为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸-2-羟基丙酯、甲基丙烯酸-2-羟基丙酯、4-羟基丁基丙烯酸酯和羟辛基丙烯酸酯中的一种或多种；所述步骤(3)中的羧酸单体为β-丙烯酰氧基丙酸；所述步骤(3)中的链转移剂为正戊醇；所述步骤(3)和步骤(4)中的引发剂独立地为过硫酸铵、 过硫酸钾或过硫酸钠。
  10. 如权利要求1或3所述的方法，其特征在于：所述步骤(4)中去离子水、单体预乳化液、引发剂、还原剂、润湿剂和消泡剂的质量比为20～30：70～80：0.1～0.3：0.05～0.15：0.1～0.5：0.05～0.2。
  11. 如权利要求1或3所述的方法，其特征在于：所述步骤(4)中部分单体预乳化液与剩余单体预乳化液的质量比为1～15：85～99。
  12. 如权利要求1或3所述的方法，其特征在于：所述步骤(4)中润湿剂为有机硅类润湿剂或炔二醇类润湿剂；所述步骤(4)中消泡剂为聚醚改性有机硅类消泡剂或矿物油类消泡剂；所述步骤(4)中的还原剂为羟乙酸亚磺酸二钠。
  13. 如权利要求1或3所述的方法，其特征在于：所述步骤(4)中加入氨水调pH值至7～8替换为加入氨水调pH值至5～7。
  14. 如权利要求3所述一种无皂乳液聚合法制备丙烯酸酯复合胶的方法，其特征在于：所述步骤(5)中的水性固化剂为水性多异氰酸酯固化剂，添加量为丙烯酸酯复合胶原乳液质量的1％～10％。
  15. 权利要求3或14所述方法制备得到的丙烯酸酯复合胶。
  16. 权利要求15所述丙烯酸酯复合胶在软包装膜材料复合中的应用，所述应用是在薄膜上涂布复合。
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