CN110964458A - Preparation method of bio-based acrylate anti-warping adhesive tape - Google Patents
Preparation method of bio-based acrylate anti-warping adhesive tape Download PDFInfo
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- 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
- C09J2433/00—Presence of (meth)acrylic polymer
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- 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
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
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Abstract
The invention provides a preparation method of a bio-based acrylate anti-warping adhesive tape, and relates to the field of bio-based adhesive tapes. The preparation method comprises the following steps: 60-65 parts of bio-based methacrylate monomer, 4.5-10 parts of acrylate modified coumarin monomer, 30-40 parts of solvent and 0.1-0.5 part of thermal initiator are uniformly mixed, and a bio-based methacrylate resin solution is prepared by free radical polymerization at the temperature of 60-90 ℃; and finally, uniformly mixing 50-90 parts of bio-based methacrylate resin solution and 10-50 parts of bio-based tackifying resin, coating, drying, carrying out UV curing, and then attaching a release film or release paper to obtain the bio-based acrylate anti-warping adhesive tape. The content of biobased carbon in the adhesive layer of the biobased acrylate adhesive tape is 80-95%. And the high-viscosity bio-based anti-warping adhesive tape is prepared by UV curing by taking a carbon-carbon double bond functional group in coumarin as a photoreaction group. The product has excellent anti-warping performance and has wide application in the field of 3C electronic products.
Description
Technical Field
The invention relates to the field of bio-based adhesive tapes, and in particular relates to a preparation method of a bio-based acrylate anti-warping adhesive tape.
Background
The acrylate pressure-sensitive adhesive is also called acrylic pressure-sensitive adhesive and is a copolymer obtained by copolymerizing acrylate monomers. With the development of science and technology and the light and thin requirements of 3C electronic products, the acrylic pressure-sensitive adhesive has excellent weather resistance and high-strength adhesive property, and the consumption demand thereof is increasing greatly. The prior preparation process of various acrylate monomers comprises 6 methods, such as a cyanide method, a ketene method, an improved Reppe method, an acrylonitrile hydrolysis method, a propylene direct oxidation method, an esterification method and the like. The components are all from petroleum cracking products, the source cannot be continuously developed, and a great deal of pollution and toxicity are caused in the production process. With the demand of environmental protection and sustainable development, plant-extracted bio-based acrylate monomers are receiving more and more attention and development, and have been industrially produced. The side chain group of the acrylate monomer of biological origin has different structural units with petrochemical products, but has the same reactivity with the petrochemical products, so that the same synthetic process can be used for preparing the bio-based acrylate pressure-sensitive adhesive.
The main curing mode of the traditional petrochemical acrylate pressure-sensitive adhesive is thermosetting, namely, the curing and crosslinking reaction is carried out on carboxyl of acrylic acid or hydroxyl of acrylic hydroxyl ester, isocyanate, epoxy group and amino group under the condition of high temperature. The curing agent used by the method has high activity, is easy to deteriorate, is difficult to store for a long time, and has certain toxicity.
Disclosure of Invention
The invention aims to provide a preparation method for preparing a bio-based acrylate adhesive tape by using a bio-based acrylate monomer and a special crosslinking monomer as raw materials, and meanwhile, the adhesive tape can also solve the problems that the conventional petrochemical acrylate adhesive tape product is easy to warp, the raw materials are not available continuously, and the curing process is high in pollution and toxicity.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows.
Step 1 preparation of a bio-based acrylic resin solution: uniformly mixing 60-65 parts of bio-based acrylate monomer, 4.5-10 parts of acrylate modified coumarin, 0.1-0.5 part of thermal initiator and 30-40 parts of solvent; and carrying out free radical polymerization reaction at 60-90 ℃ in a manner of slowly dropping the mixed solution step by step.
The bio-based acrylate monomer comprises at least one of bio-based isobornyl methacrylate, bio-based isobornyl acrylate, bio-based tridecyl methacrylate and bio-based heptadecyl methacrylate, wherein the main component of the bio-based acrylate monomer is derived from pine resin and vegetable natural oil, and the bio-based carbon content is not lower than 70%. In addition, the bio-based monomers used are SARBIO5102, SARBIO6101, SARBIO6104, SARBIO6105, Terra C13-MA, Terra C17-MA, and Terra IBOMA.
The acrylate modified coumarin comprises methacrylate coumarin, acrylate coumarin, methacrylate-4-methylcoumarin, acrylate-4-methylcoumarin, methacrylate-4, 8-dimethoxycoumarin, acrylate-4, 8-dimethoxycoumarin; and the carbon-carbon double bond functional group contained in the coumarin can generate a crosslinking reaction under the irradiation of UV light and can be used as a photoinitiated crosslinking monomer.
The selected thermal initiator can generate efficient cracking reaction at 60-90 ℃ to meet the requirement of polymerization reaction, and further comprises at least one of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, lauroyl peroxide and tert-butyl peroxybenzoate.
The solvent with a low chain transfer constant is selected from at least one of toluene, ethyl acetate, butanone, isopropanol, methanol and ethanol, so that the reaction rate can be accelerated, and the molecular weight of the bio-based acrylate resin can be improved.
The method for slowly dripping the mixed solution step by step is characterized in that 1/3-3/5 mixture is added in advance to react for 2-4 hours, the rest mixture is dripped within 2-4 hours, and the reaction is carried out for at least 4 hours. The method of dripping the mixed solution can accelerate the reaction rate, improve the molecular weight of the acrylate resin and reduce the monomer residue.
Step 2, preparation of bio-based acrylate adhesive tape: and (3) uniformly mixing 50-90 parts of the bio-based acrylate resin solution obtained in the step (1) with 10-50 parts of bio-based tackifying resin, coating, drying, UV curing, and attaching and releasing to obtain the bio-based acrylate anti-warping adhesive tape.
The glass transition temperature range of the bio-based acrylate resin is-48 to-22 ℃, the number average molecular weight range is 20 to 100 ten thousand, the molecular weight distribution is 2.3 to 4.8, and the viscosity range is 1000-4500cps under the condition of 40 percent of solid content in ethyl acetate solvent.
The bio-based tackifying resin is at least one of rosin resin with a softening point of 60-150 ℃, terpene resin with a softening point of 90-130 ℃ and polymerized rosin resin with a softening point of 105-150 ℃. The tackifying resins are all from plant extracts, and the content of bio-based carbon is 100%.
The drying temperature in the preparation of the bio-based acrylate adhesive tape is 100-120 ℃, the curing is performed for 3-50 s by using a high-pressure mercury lamp, and the power of a UV curing machine is 100 mW/cm2-1000 mW/cm2。
As a preferable embodiment of the present invention, the acrylate-modified coumarin monomer in step 1 can be synthesized by the following steps: dissolving 25-30 parts by mass of coumarin containing hydroxyl in 30-50 parts by mass of solvent, dropwise adding 30-35 parts by mass of acyl chloride at the temperature of-20 ℃, heating to 15-35 ℃ after dropwise adding, continuously reacting for 2-4 h, and recrystallizing at the temperature of-30 to-20 ℃ by using a mixed solvent of anhydrous ether and methanol according to the mass ratio of 1: 2-1: 3 to obtain the acrylate modified coumarin.
The coumarin containing hydroxyl comprises one or two of 7-hydroxycoumarin, 7-hydroxy-4-methylcoumarin, and 7-hydroxy-4, 8-dimethoxycoumarin, and hydroxyl group is used as modification reaction functional group. Wherein the coumarin is extracted from black cumin, and the content of bio-based carbon is 100%.
The acyl chloride is acryloyl chloride and/or methacryloyl chloride, and can perform nucleophilic reaction with the hydroxyl of coumarin at low temperature.
The solvent comprises one or more of acetonitrile, methanol, isopropanol, or dichloromethane in combination.
Further, the bio-based acrylic adhesive tape prepared in step 2 has a bio-based carbon content of not less than 80% in the adhesive layer, and the carbon content is measured by measuring radioactive carbon isotope (C-14, C14 or 14C), which is a naturally occurring isotope having radioactivity and gradually decaying to disappear after death of animals and plants, for about 45,000 years. The content of biobased carbon in the adhesive layer of the biobased acrylic adhesive tape was determined by the American BETA laboratory using the ASTM D6866-18 method.
Further, the anti-warping performance in step 2 is represented by a constant load of 90 °, as shown in fig. 3, a sample bar with a specification of 150 mm × 25.4mm is attached to the steel plate, the attachment length is 100mm, and the mark is made. Two passes were stitched using a 2kg stitching stick at a rate of 600mm/min and left for 20 min. And then hanging 500g-2000g of weight on the non-joint end of the sample strip, and testing for 48h to obtain the sliding distance of the sample strip. Falling within 48h indicates poor warp resistance. The material does not fall after 48 hours and has small sliding distance, which indicates that the anti-warping property is strong.
Advantages of the invention compared to the prior art include.
1. The raw materials used in the invention are all derived from plant extract components, and the sources are environment-friendly and pollution-free, and the development is sustainable.
2. According to the invention, the acrylate modified coumarin monomer is used as a UV curing group to replace the traditional isocyanate curing, so that the UV curing agent is non-toxic and high in curing efficiency.
3. The bio-based acrylate adhesive tape developed by the invention has excellent anti-warping capability and excellent bonding performance with adherends made of different materials.
Drawings
FIG. 1 is the molecular structure of a biobased acrylate resin and the biological origin of the components.
FIG. 2 is a cross-linking cure of coumarin functional groups after UV curing.
FIG. 3 is a schematic view of a warpage resistance test.
Detailed Description
The present invention will be described in detail with reference to specific embodiments. Of course, the following embodiments are only some of the examples of the present invention.
Example 1.
Firstly, 100g of 7-hydroxycoumarin is added into a 1000 mL three-neck flask, 70g of methanol is added, and the three-neck flask is placed into a low-temperature tank to be cooled to-20 DEGoAnd C, stirring for 10 min. Adding 120 g of acryloyl chloride and 70g of dichloromethane mixed solution into a constant-pressure funnel, slowly dropwise adding (6-7 d/s), continuing to react for 2 hours at 25 ℃ after dropwise adding is finished, and then, reducing pressure and rotatably removing residual organic solvent. Dissolving the mixture by using 300g of anhydrous ether and methanol in a mixed solvent according to the mass ratio of 1:2, carrying out suction filtration to obtain a filtrate, recrystallizing at-30 to-20 ℃, carrying out suction filtration, and carrying out vacuum drying at room temperature for 48h to obtain the acrylate modified 7-hydroxycoumarin.
50g of biobased isobornyl methacrylate (brand: SARBIO 6105), 35 g of biobased isobornyl methacrylate (brand: SARBIO 5102), 410 g of biobased tridecyl methacrylate (brand: SARBIO 6101), 105 g of biobased heptadecyl methacrylate (brand: SARBIO 6104), 50g of acrylate-modified 7-hydroxycoumarin, 3 g of benzoyl peroxide, 1.5 g of azobisisobutyronitrile, 100g of toluene, and 300g of ethyl ester were uniformly mixed. Adding 1/2 mixed solution into a 2000 mL four-neck flask with a mechanical stirrer, a condenser tube and a constant pressure titration funnel, then putting the flask into a constant temperature oil bath, carrying out free radical polymerization reaction for 2h at the temperature of 75 ℃, then slowly dripping the rest mixed solution and finishing dripping within 3h, and carrying out constant temperature reaction for 4h to obtain the bio-based propionate resin solution. The glass transition temperature range of the prepared bio-based propionate resin is-42 ℃, the number average molecular weight range is 55 ten thousand, and the molecular weight distribution is 3.5; it has a viscosity range of 3200cps at 40% solids in ethyl acetate solvent.
Adding 240 g of rosin resin with the softening point of 75 ℃ into the prepared bio-based propionate resin solution, stirring for 20min, uniformly mixing, coating 25um dry glue with 25um transparent PET by a scraper type coating machine, and coating the mixture at 100 umoDrying for 3 min under C, and then using power of 300 mW/cm2The UV curing machine irradiates for 5 seconds, and then 50um PET release film is attached to the UV curing machine, and finallyObtaining the bio-based acrylate anti-warping adhesive tape A.
And (3) testing results: the steel plate was peeled off at 180 ℃ with a force of 2000. + -. 200gf, subjected to a constant load of 500g at 23 ℃ and 50% humidity, and slipped down by 2mm after 48 hours.
Example 2.
Firstly, 100g of 7-hydroxycoumarin is added into a 1000 mL three-neck flask, 70g of methanol is added, and the three-neck flask is placed into a low-temperature tank to be cooled to-20 DEGoAnd C, stirring for 10 min. Adding 120 g of methacryloyl chloride and 70g of dichloromethane mixed solution into a constant-pressure funnel, slowly dropwise adding (6-7 d/s), continuing to react for 2 hours at 25 ℃ after dropwise adding is finished, and then, reducing pressure and rotatably removing residual organic solvent. Dissolving the raw materials in a mixed solvent of 300g of anhydrous ether and methanol according to the mass ratio of 1:3, carrying out suction filtration to obtain a filtrate, recrystallizing at-30 to-20 ℃, carrying out suction filtration, and carrying out vacuum drying at room temperature for 48h to obtain the methacrylate modified 7-hydroxycoumarin.
65 g of biobased isobornyl methacrylate (brand: SARBIO 6105), 20g of biobased isobornyl methacrylate (brand: SARBIO 5102), 450 g of biobased tridecyl methacrylate (brand: SARBIO 6101), 95 g of biobased heptadecyl methacrylate (brand: SARBIO 6104), 80 g of methacrylate-modified coumarin, 2 g of benzoyl peroxide, 2 g of azobisisobutyronitrile, 100g of toluene and 300g of ethyl ester were uniformly mixed. Adding 1/3 mixed solution into a 2000 mL four-neck flask with a mechanical stirrer, a condenser tube and a constant pressure titration funnel, then putting the flask into a constant temperature oil bath, carrying out free radical polymerization reaction for 2h at the temperature of 85 ℃, slowly dripping the residual mixed solution and finishing dripping within 4h, and carrying out constant temperature reaction for 4h to obtain the bio-based propionate resin solution. The glass transition temperature range of the prepared bio-based propionate resin is-46 ℃, the number average molecular weight range is 65 ten thousand, and the molecular weight distribution is 3.0; it has a viscosity range of 3600cps at 40% solids in ethyl acetate solvent.
Adding 150 g of rosin resin with the softening point of 115 ℃ into the prepared bio-based propionate resin solution, stirring for 20min, uniformly mixing, coating 50um dry glue with 50um transparent PET (polyethylene terephthalate) by a scraper coater, and coating the mixture at 110 umoDrying for 3 min under C, and then using power of 300 mW/cm2The UV curing machine irradiates for 20 seconds, and then a 50um PET release film is attached to the UV curing machine, so that the bio-based acrylate warping-resistant adhesive tape B is finally obtained.
And (3) testing results: the steel plate was peeled off at 180 ℃ with a force of 4200. + -. 300gf, and suspended at 23 ℃ under a constant load of 50% humidity by a weight of 1kg, and after 48 hours, it slipped down only 6 mm.
Example 3.
Firstly, 90g of 7-hydroxy-4-methylcoumarin is added into a 1000 mL three-neck flask, 60 g of methanol is added, and the three-neck flask is placed into a low-temperature tank to be cooled to-20%oAnd C, stirring for 10 min. Adding 110 g of acryloyl chloride and 80 g of dichloromethane mixed solution into a constant-pressure funnel, slowly dropwise adding (6-7 d/s), continuing to react for 2 hours at 20 ℃ after dropwise adding is finished, and then, decompressing and rotatably removing residual organic solvent. Dissolving the mixture by using 300g of anhydrous ether and methanol in a mixed solvent according to the mass ratio of 1:2, carrying out suction filtration to obtain a filtrate, recrystallizing at-30 to-20 ℃, carrying out suction filtration, and carrying out vacuum drying at room temperature for 48h to obtain the acrylate modified 7-hydroxy-4-methylcoumarin.
115 g of biobased isobornyl methacrylate (brand: SARBIO 6105), 70g of biobased isobornyl acrylate (brand: SARBIO 5102), 350 g of biobased tridecyl methacrylate (brand: Terra C13-MA), 105 g of biobased heptadecyl methacrylate (brand: Terra C17-MA), 60 g of acrylate-modified 7-hydroxy-4-methylcoumarin, 3 g of benzoyl peroxide, 2 g of azobisisobutyronitrile, 50g of toluene and 350 g of ethyl ester are uniformly mixed. Adding 1/2 mixed solution into a 2000 mL four-neck flask with a mechanical stirrer, a condenser tube and a constant pressure titration funnel, then putting the flask into a constant temperature oil bath, carrying out free radical polymerization reaction for 2h at the temperature of 85 ℃, slowly dripping the residual mixed solution and finishing dripping within 2h, and carrying out constant temperature reaction for 4h to obtain the bio-based propionate resin solution. The glass transition temperature range of the prepared bio-based propionate resin is-36 ℃, the number average molecular weight range is 45 ten thousand, and the molecular weight distribution is 3.8; it has a viscosity range of 2800cps at 40% solids in ethyl acetate solvent.
In the bio-based propionate resin solution prepared aboveAdding 220 g rosin resin with softening point of 100 deg.C, stirring for 20min, mixing, coating 10 um dry glue with 25um transparent PET by a scraper coater at 100%oDrying for 3 min under C, and then using power of 300 mW/cm2The UV curing machine irradiates for 5 seconds, and then a 50um PET release film is attached to the UV curing machine, so that the bio-based acrylate warping-resistant adhesive tape C is finally obtained.
And (3) testing results: the steel plate was peeled off at 180 ℃ with a force of 1100. + -. 100gf, subjected to a constant load of 500g at 23 ℃ and 50% humidity, and slipped down only 5mm after 48 hours.
Example 4.
Firstly, 100g of 7-hydroxy-4, 8-dimethoxy coumarin is added into a 1000 mL three-neck flask, 70g of methanol is added, and the three-neck flask is placed into a low-temperature tank to be cooled to-20%oAnd C, stirring for 10 min. Adding 120 g of acryloyl chloride and 70g of dichloromethane mixed solution into a constant-pressure funnel, slowly dropwise adding (6-7 d/s), continuing to react for 2 hours at 20 ℃ after dropwise adding is finished, and then, reducing pressure and rotatably removing residual organic solvent. Dissolving the mixture by using 300g of anhydrous ether and methanol according to the mass ratio of 1:3, carrying out suction filtration to obtain a filtrate, recrystallizing at-30 to-20 ℃, carrying out suction filtration, and carrying out vacuum drying at room temperature for 48h to obtain the methacrylate modified 7-hydroxy-4, 8-dimethoxycoumarin.
65 g of biobased isobornyl methacrylate (trade name: Terra IBOMA), 70g of biobased isobornyl acrylate (trade name: SARBIO 5102), 400g of biobased tridecyl methacrylate (trade name: Terra C13-MA), 85 g of biobased heptadecyl methacrylate (trade name: Terra C17-MA), 75g of methacrylate-modified 7-hydroxy-4, 8-dimethoxycoumarin, 3 g of benzoyl peroxide, 0.5 g of azobisisobutyronitrile, 50g of toluene and 350 g of ethyl ester are uniformly mixed. Adding 1/2 mixed solution into a 2000 mL four-neck flask with a mechanical stirrer, a condenser tube and a constant pressure titration funnel, then putting the flask into a constant temperature oil bath, carrying out free radical polymerization reaction for 2h at the temperature of 75 ℃, slowly dripping the residual mixed solution and finishing dripping within 2h, and carrying out constant temperature reaction for 4h to obtain the bio-based propionate resin solution. The glass transition temperature range of the prepared bio-based propionate resin is-39 ℃, the number average molecular weight range is 53 ten thousand, and the molecular weight distribution is 3.3; it has a viscosity range of 3100cps at 40% solids in ethyl acetate solvent.
Adding 120 g of terpene resin with softening point of 125 ℃ into the prepared bio-based propionate resin solution, stirring for 20min, uniformly mixing, coating 100 um dry glue with 25um transparent PET by a scraper coater, and coating 120 um dry glueoDrying for 3 min under C, and then using power of 600 mW/cm2The UV curing machine irradiates for 25 seconds, and then 50um PET release film is attached to obtain the bio-based acrylate anti-warping adhesive tape D.
And (3) testing results: the steel plate was peeled from the steel plate at 180 ℃ with a peeling force of 5200. + -. 300gf, and suspended at 23 ℃ under a constant load of 50% humidity by a weight of 1kg, and after 48 hours, the steel plate slipped only 1 mm.
Example 5.
Firstly, 100g of 7-hydroxy-4, 8-dimethoxy coumarin is added into a 1000 mL three-neck flask, 70g of methanol is added, and the three-neck flask is placed into a low-temperature tank to be cooled to-20%oAnd C, stirring for 10 min. Adding 110 g of methacryloyl chloride and 70g of dichloromethane mixed solution into a constant-pressure funnel, slowly dropwise adding (6-7 d/s), continuing to react for 2 hours at 25 ℃ after dropwise adding is finished, and then carrying out rotary removal on residual organic solvent under reduced pressure. Dissolving the mixture by using 300g of anhydrous ether and methanol according to the mass ratio of 1:3, carrying out suction filtration to obtain a filtrate, recrystallizing at-30 to-20 ℃, carrying out suction filtration, and carrying out vacuum drying at room temperature for 48h to obtain the methacrylate modified 7-hydroxy-4, 8-dimethoxycoumarin.
85 g of biobased isobornyl methacrylate (brand: Terra IBOMA), 90g of biobased isobornyl acrylate (brand: SARBIO 5102), 300g of biobased tridecyl methacrylate (brand: Terra C13-MA), 145 g of biobased heptadecyl methacrylate (brand: Terra C17-MA), 55 g of methacrylate-modified-hydroxy-4, 8-dimethoxycoumarin, 3 g of benzoyl peroxide, 1.5 g of azobisisobutyronitrile, 100g of toluene and 300g of ethyl ester are uniformly mixed. Adding 1/3 mixed solution into a 2000 mL four-neck flask with a mechanical stirrer, a condenser tube and a constant pressure titration funnel, then putting the flask into a constant temperature oil bath, carrying out free radical polymerization reaction at the temperature of 70 ℃ for 2h, slowly dripping the residual mixed solution and finishing dripping within 3h, and carrying out constant temperature reaction for 4h to obtain the bio-based propionate resin solution. The glass transition temperature range of the prepared bio-based propionate resin is-33 ℃, the number average molecular weight range is 75 ten thousand, and the molecular weight distribution is 4.0; it has a viscosity range of 4100cps at 40% solids in ethyl acetate solvent.
Adding 200g of polymerized rosin resin with a softening point of 105 ℃ into the prepared bio-based propionate resin solution, stirring for 20min, uniformly mixing, coating 150 um dry glue with 25um transparent PET by a scraper type coating machine, and coating at 100 umoDrying for 3 min under C, and then using power of 600 mW/cm2The UV curing machine irradiates for 40 seconds, and then a 50um PET release film is attached to the UV curing machine, so that the bio-based acrylate anti-warping adhesive tape E is finally obtained.
And (3) testing results: the steel plate was peeled from the steel plate at 180 ℃ with a peel force of 5900. + -. 400gf, a weight of 1kg was applied at 23 ℃ and a constant load of 50% humidity, and the steel plate slipped down only 2mm after 48 hours.
Comparative example.
50g of petroleum-based isobornyl methacrylate, 35 g of isobornyl acrylate, 410 g of tridecyl methacrylate, 105 g of heptadecyl methacrylate, 50g of hydroxyethyl acrylate, 3 g of benzoyl peroxide, 1.5 g of azobisisobutyronitrile, 100g of toluene and 300g of ethyl ester were uniformly mixed. Adding 1/2 mixed solution into a 2000 mL four-neck flask with a mechanical stirrer, a condenser tube and a constant pressure titration funnel, then putting the flask into a constant temperature oil bath, carrying out free radical polymerization reaction at the temperature of 85 ℃ for 2h, then slowly dripping the rest mixed solution and finishing dripping within 2h, and carrying out constant temperature reaction for 4h to obtain the propionate resin solution. The prepared propionate resin has the glass transition temperature range of-44 ℃, the number average molecular weight range of 58 ten thousand and the molecular weight distribution of 3.3; it has a viscosity range of 3400cps at 40% solids in ethyl acetate solvent.
Adding 240 g of rosin resin with the softening point of 75 ℃ and 20g L-75 isocyanate curing agent into the prepared propionate resin solution, stirring for 20min, uniformly mixing, coating 25um dry glue with 25um transparent PET by a scraper type coating machine, and coating at 100 umoC is belowDrying for 3 min, and attaching a 50um PET release film to finally obtain the petroleum-based acrylate adhesive tape with the similar molecular structure and composition with the biological acrylate.
And (3) testing results: the steel plate was peeled from the steel plate at 180 ℃ with a force of 1700. + -. 200gf, and a constant load of 500g was applied at 23 ℃ and 50% humidity, and the plate was completely dropped after 1 hour.
The foregoing is only a preferred embodiment of the present invention. The scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution of the present invention and the inventive concept within the technical scope of the present invention.
Claims (12)
1. A preparation method of a bio-based acrylate anti-warping adhesive tape is characterized by comprising the following steps:
s1: preparing a bio-based acrylate resin solution;
uniformly mixing the following components and raw materials in parts by mass, and performing free radical polymerization reaction at 60-90 ℃ in a manner of slowly dropping a mixed solution step by step;
60-65 parts of a bio-based acrylate monomer;
4.5-10 parts of acrylate modified coumarin;
0.1-0.5 part of thermal initiator;
30-40 parts of a solvent;
s2: preparing a bio-based acrylate adhesive tape;
uniformly mixing 50-90 parts of the bio-based acrylate resin solution prepared in the step S1 with 10-50 parts of bio-based tackifying resin, coating, drying, UV curing, and attaching and releasing to obtain a bio-based acrylate anti-warping adhesive tape;
the content of biobased carbon in the biobased acrylate monomer is not lower than 70 percent;
the acrylate-modified coumarin is at least one of methacrylate coumarin, acrylate coumarin, methacrylate-4-methylcoumarin, acrylate-4-methylcoumarin, methacrylate-4, 8-dimethoxycoumarin and acrylate-4, 8-dimethoxycoumarin;
the content of biobased carbon in an adhesive layer of the biobased acrylate adhesive tape is not less than 80%.
2. The method for preparing the bio-based acrylate warp-resistant adhesive tape according to claim 1, wherein: the bio-based acrylate monomer is at least one of bio-based isobornyl methacrylate, bio-based isobornyl acrylate, bio-based tridecyl methacrylate and bio-based heptadecyl methacrylate.
3. The method for preparing the bio-based acrylate warp-resistant adhesive tape according to claim 1, wherein: the thermal initiator comprises at least one of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, lauroyl peroxide and tert-butyl peroxybenzoate.
4. The method for preparing the bio-based acrylate warp-resistant adhesive tape according to claim 1, wherein: the solvent is at least one of toluene, ethyl acetate, butanone, isopropanol, methanol and ethanol.
5. The method for preparing the bio-based acrylate warp-resistant adhesive tape according to claim 1, wherein: the method for slowly dripping the mixed solution step by step is characterized in that 1/3-3/5 mixture is added in advance to react for 2-4 hours, the rest mixture is dripped within 2-4 hours, and the reaction is carried out for at least 4 hours.
6. The method for preparing the bio-based acrylate warp-resistant adhesive tape according to claim 1, wherein: the glass transition temperature range of the prepared bio-based acrylic resin is-48 to-22 ℃, the number average molecular weight range is 20 to 100 ten thousand, and the molecular weight distribution is 2.3 to 4.8; the viscosity range is 1000-4500cps at 40% solid content in ethyl acetate solvent.
7. The method for preparing the bio-based acrylate warp-resistant adhesive tape according to claim 1, wherein: the bio-based tackifying resin is at least one of rosin resin with a softening point of 60-150 ℃, terpene resin with a softening point of 90-130 ℃ and polymerized rosin resin with a softening point of 105-150 ℃.
8. The method for preparing the bio-based acrylate warp-resistant adhesive tape according to claim 1, wherein: the drying temperature in the preparation of the bio-based acrylate adhesive tape is 100-120 ℃; the UV curing is carried out for 3-50 s by using a high-pressure mercury lamp, and the power of the UV curing machine is 100 mW/cm2-1000 mW/cm2。
9. The method for preparing the bio-based acrylate warp-resistant adhesive tape according to claim 1, wherein: the acrylate modified coumarin can also be obtained by adopting the following preparation method: dissolving 25-30 parts by mass of coumarin in 30-50 parts by mass of solvent, dropwise adding 30-35 parts by mass of acyl chloride at the temperature of-20 ℃, heating to 15-35 ℃ after dropwise adding, continuously reacting for 2-4 h, and recrystallizing at the temperature of-30 to-20 ℃ by using mixed solvent to obtain the coumarin;
the mixed solvent is formed by mixing anhydrous ether and methanol according to the mass ratio of 1: 2-1: 3.
10. The method for preparing the bio-based acrylate warp-resistant adhesive tape according to claim 9, wherein: the coumarin includes one or two of 7-hydroxycoumarin, 7-hydroxy-4-methylcoumarin, and 7-hydroxy-4, 8-dimethoxycoumarin.
11. The method for preparing the bio-based acrylate warp-resistant adhesive tape according to claim 9, wherein: the solvent is one or more of acetonitrile, methanol, isopropanol or dichloromethane.
12. The method for preparing the bio-based acrylate warp-resistant adhesive tape according to claim 9, wherein: the acyl chloride is acryloyl chloride and/or methacryloyl chloride.
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