阅读说明：本技术 一种植物油基uv树脂及压敏胶 (Plant oil-based UV resin and pressure-sensitive adhesive ) 是由 邵美忠 于 2020-05-14 设计创作，主要内容包括：本发明属于高分子材料领域。本发明涉及一种植物油基UV树脂及压敏胶,该方法以植物油(A)、氨基硫醇(B)、甲基丙烯酸缩水甘油酯(C)、多巴胺(D)作为原料,经点击反应、开环反应及迈克尔加成反应制备新型植物油基UV树脂,并将其制备成植物油基UV压敏胶。该新型材料有效解决了现有丙烯酸酯类压敏胶耐水性差,无法在潮湿环境中使用的问题,同时具有克服氧阻聚的优势,胶层表面效果更好。此外,该材料来源广泛、绿色环保,可生物降解。可以预见,该材料在胶黏剂、涂料(包括主体树脂和附着力促进剂等)等领域将会迎来广阔的市场前景。(The invention belongs to the field of high polymer materials. The invention relates to a vegetable oil-based UV resin and a pressure-sensitive adhesive, and the method is characterized in that vegetable oil (A), amino mercaptan (B), glycidyl methacrylate (C) and dopamine (D) are used as raw materials, the novel vegetable oil-based UV resin is prepared through click reaction, ring-opening reaction and Michael addition reaction, and the vegetable oil-based UV pressure-sensitive adhesive is prepared. The novel material effectively solves the problems that the existing acrylate pressure-sensitive adhesive is poor in water resistance and cannot be used in a humid environment, and has the advantage of overcoming oxygen inhibition, and the surface effect of an adhesive layer is better. In addition, the material has wide sources, is green and environment-friendly, and can be biodegraded. The material can be expected to have wide market prospect in the fields of adhesives, coatings (including main resin, adhesion promoters and the like) and the like.)

1. The plant oil-based UV resin is characterized by having a structural formula as follows:

wherein, -R₁-is-C₄H₈-、-C₅H₁₀-、-C₆H₁₂-、-C₇H₁₄-or-C₈H₁₆-；-R₂is-H or-OH; -R₃is-H or-CH₃；-R₄is-H or-COOH.

2. A preparation method of plant oil-based UV resin is characterized by comprising the following steps: comprises the following steps:

(1) dissolving vegetable oil containing 1mol of carbon-carbon double bonds, 1-1.2mol of aminothiol and 1 wt% of photoinitiator a in 80mol of dichloromethane, carrying out ultraviolet illumination reaction for 6-9h at room temperature, washing with deionized water for 3 times, separating liquid, drying a solvent phase with anhydrous sodium sulfate, and carrying out rotary evaporation to obtain an intermediate product I;

the usage amount of the photoinitiator a is the percentage of the total mass of the vegetable oil and the amino mercaptan;

(2) dissolving I containing 1mol of amino and 1.2-2mol of glycidyl methacrylate in 80mol of DMF, stirring at room temperature for 2-4h, and removing the solvent under reduced pressure to obtain an intermediate product II;

(3) placing II containing 1mol of carbon-carbon double bond structure and 0.1-0.3mol of dopamine in a mixed solvent of 60mol of DMF and 20mol of ethanol, stirring for 2-6h at 0-35 ℃, and after the reaction is finished, carrying out vacuum concentration; slowly adding 50mol of water, stirring for 30min, adding 80mol of BAc, stirring for 30min, standing for layering, taking an organic phase, drying with anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain a target product III.

3. The method of preparing a plant oil-based UV resin of claim 2, wherein: the iodine value of the vegetable oil is 100-160gI₂/100g。

4. The method of preparing a plant oil-based UV resin of claim 2, wherein: the photoinitiator a is 184, 1173, 2959 or TPO.

5. The method of preparing a plant oil-based UV resin of claim 2, wherein: the dopamine is dopamine hydrochloride, norepinephrine, levodopa or methyl dopamine.

6. The vegetable oil-based UV pressure-sensitive adhesive is prepared from the following raw materials in parts by weight: 50-70 parts of vegetable oil-based UV resin, 15-30 parts of reactive diluent, 5-20 parts of tackifying resin and 1-5 parts of photoinitiator b;

under a yellow light, mixing the plant oil-based UV resin, the reactive diluent, the tackifying resin and the photoinitiator b, dispersing for 30min by using a high-speed dispersion machine, properly adjusting the system viscosity, and filtering to obtain the plant oil-based pressure-sensitive adhesive.

7. The vegetable oil-based UV pressure-sensitive adhesive of claim 6, wherein: the active diluent is a mixture of trimethylolpropane triacrylate, tripropylene glycol diacrylate, 1, 6-hexanediol diacrylate, butyl acrylate, isooctyl acrylate, acrylamide or acrylic acid.

8. The vegetable oil-based UV pressure-sensitive adhesive of claim 6, wherein: the tackifying resin is one or a mixture of rosin glyceride, rosin pentaerythritol ester, polymerized rosin ester, disproportionated rosin ester, hydrogenated modified rosin ester or rosin modified phenolic resin.

9. The vegetable oil-based UV resin coating of claim 6, wherein: the photoinitiator b is 184, 1173, TPO, BP or ITX.

Technical Field

The invention relates to plant oil-based UV resin and a pressure-sensitive adhesive. The invention belongs to the field of high polymer materials.

Background

With the gradual depletion of petroleum fossil resources worldwide, the development and utilization of biomass resources are receiving much attention. Vegetable oils are triglycerides of long carbon chain acids containing double bonds, which are widely distributed in nature, and among them, tung oil, soybean oil, linseed oil, olive oil, palm oil, castor oil, and the like are common. Due to the special structure and degradability, the obtained polymer is low in cost, environment-friendly and widely applied to multiple fields of the industries such as coatings, printing ink, plastics and the like.

On the other hand, in recent years, many reports have been made on photocurable adhesives in which an acrylate or acrylamide is modified and introduced into a hydroxyl group or a mercapto group to form an amide bond, a urethane bond, a urea bond, or the like, and then photopolymerization is performed to form a nonpolar group to impart adhesiveness to the material itself. However, most of the acrylate pressure-sensitive adhesives have unsatisfactory adhesion performance in a humid environment.

The super strong adhesion capability of marine organism mussels is impressive, and mussel adhesion protein secreted by byssus can be adhered to the surface of a rough object, metal, glass and other materials, and even can be adhered to the surface of polytetrafluoroethylene which is extremely difficult to adhere. The mussel adhesive protein has the characteristics of super-strong waterproof adhesive capacity, wide adhesive base material applicability, good cell compatibility, biodegradability, nontoxicity and the like, so that the mussel adhesive protein has wide application prospects in the fields of biomedicine, national defense and ocean engineering. With further research, it was found that the catechol group and the amino group contained in the mussel adhesive protein are the main reasons for its universal adhesion.

In view of the above factors, scientific researchers need to actively research and develop a bio-based adhesive material capable of meeting the use requirements in a humid environment, and the dopamine modified vegetable oil-based UV resin can effectively solve the above problems, is green, environmentally friendly and biodegradable, and further meets the national call for energy conservation, emission reduction and recycling green economy.

Disclosure of Invention

The invention aims to solve the problems that the existing acrylate pressure-sensitive adhesive is poor in water resistance and cannot be used in a humid environment, and provides a plant oil-based UV resin and a pressure-sensitive adhesive.

The technical scheme adopted by the invention for solving the technical problems is as follows:

the plant oil-based UV resin is characterized by having a structural formula as follows:

wherein, -R₁-is-C₄H₈-、-C₅H₁₀-、-C₆H₁₂-、-C₇H₁₄-or-C₈H₁₆-；-R₂is-H or-OH; -R₃is-H or-CH₃；-R₄is-H or-COOH.

A preparation method of plant oil-based UV resin is characterized by comprising the following steps: comprises the following steps:

(1) dissolving vegetable oil (A) containing 1mol of carbon-carbon double bonds, 1-1.2mol of aminothiol (B) and 1 wt% of photoinitiator a in 80mol of dichloromethane, carrying out ultraviolet illumination reaction for 6-9h at room temperature, washing for 3 times by using deionized water, separating liquid, drying a solvent phase by using anhydrous sodium sulfate, and carrying out rotary evaporation to obtain an intermediate product I;

the using amount of the photoinitiator a is A, B percent of the total mass;

(2) dissolving I containing 1mol of amino and 1.2-2mol of glycidyl methacrylate (C) in 80mol of DMF, stirring at room temperature for 2-4h, and removing the solvent under reduced pressure to obtain an intermediate product II;

(3) placing II containing 1mol of carbon-carbon double bond structure and 0.1-0.3mol of dopamine (D) in a mixed solvent of 60mol of DMF and 20mol of ethanol, stirring for 2-6h at 0-35 ℃, and after the reaction is finished, carrying out vacuum concentration; slowly adding 50mol of water, stirring for 30min, adding 80mol of BAc, stirring for 30min, standing for layering, taking an organic phase, drying with anhydrous sodium sulfate, filtering, and performing rotary evaporation to obtain a target product III.

Preferably, the iodine value of the vegetable oil is 100-160gI₂/100g。

Preferably, the photoinitiator a is 184, 1173, 2959 or TPO.

Preferably, the dopamine is dopamine hydrochloride, norepinephrine, levodopa or methyldopamine.

The vegetable oil-based UV pressure-sensitive adhesive is prepared from the following raw materials in parts by weight: 50-70 parts of vegetable oil-based UV resin, 15-30 parts of reactive diluent, 5-20 parts of tackifying resin and 1-5 parts of photoinitiator b;

under a yellow light, mixing the plant oil-based UV resin, the reactive diluent, the tackifying resin and the photoinitiator b, dispersing for 30min by using a high-speed dispersion machine, properly adjusting the system viscosity, and filtering to obtain the plant oil-based pressure-sensitive adhesive.

Preferably, the reactive diluent is a mixture of trimethylolpropane triacrylate (TMTPA), tripropylene glycol diacrylate (TPGDA), 1, 6-hexanediol diacrylate (HDDA), butyl acrylate, isooctyl acrylate, acrylamide or acrylic acid.

Preferably, the tackifying resin is one or a mixture of rosin glyceride, rosin pentaerythritol ester, polymerized rosin ester, disproportionated rosin ester, hydrogenated modified rosin ester or rosin modified phenolic resin.

Preferably, the photoinitiator b is 184, 1173, TPO, BP or ITX.

The novel plant oil-based UV resin provided by the invention has the following preparation process:

the invention has the beneficial effects that:

(1) the invention provides a preparation method of vegetable oil-based UV resin and pressure-sensitive adhesive, which adopts vegetable oil (A), amino mercaptan (B), glycidyl methacrylate (C) and dopamine (D) as raw materials to prepare novel vegetable oil-based UV resin, solves the defects that the existing acrylate pressure-sensitive adhesive has poor water resistance and cannot be used in a humid environment, and has wide raw material sources and easy operation.

(2) The invention provides vegetable oil-based UV resin and a pressure-sensitive adhesive, wherein a target product takes vegetable oil as a basic structure. On one hand, the vegetable oil structure has multifunctional carbon-carbon double bonds which can be used as a hyperbranched active center; on the other hand, the vegetable oil has wide sources, is green and environment-friendly and can be biologically degraded.

(3) The invention provides a vegetable oil-based UV resin and a pressure-sensitive adhesive, wherein a target product contains a catechol structure. The catechol structures have excellent adhesion properties in humid environments and even underwater.

(4) The invention provides a vegetable oil-based UV resin, which solves the problems that the existing acrylate pressure-sensitive adhesive has poor water resistance and cannot be used in a humid environment by molecular design and a chemical modification means. In addition, the target product contains a tertiary amine structure, does not need to add an auxiliary initiator when a II type photoinitiator is used for UV curing, and has excellent oxygen resistant polymerization inhibition. The material can be expected to have wide market prospect in the fields of adhesives, coatings (including main resin, adhesion promoters and the like) and the like.

The specific implementation mode is as follows:

the present invention will be described in detail with reference to examples. It is to be understood, however, that the following examples are illustrative of embodiments of the present invention and are not to be construed as limiting the scope of the invention.