CN114958300B - Bio-based pressure-sensitive adhesive and preparation method thereof - Google Patents
Bio-based pressure-sensitive adhesive and preparation method thereof 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
- C09J191/00—Adhesives based on oils, fats or waxes; Adhesives based on derivatives thereof
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
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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
- C09J7/38—Pressure-sensitive adhesives [PSA]
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
Abstract
The invention belongs to the technical field of pressure-sensitive adhesives, and particularly relates to a bio-based pressure-sensitive adhesive and a preparation method thereof. The preparation method of the bio-based pressure-sensitive adhesive comprises the following steps: 1) Mixing epoxy vegetable oil with ethyl acetate, adding rosin ester and antioxidant, and oscillating for dissolving to obtain a mixed solution; 2) Cooling the mixed solution to the temperature of-5 ℃ and keeping the temperature for 15-25 min, then adding phosphoric acid, and carrying out oscillation, heating and ultrasonic reaction to obtain a reaction solution; 3) Coating the reaction solution on a substrate, curing for 10-30 min at 22-28 ℃, and then performing constant temperature and humidity adjustment to obtain the catalyst. Compared with the bio-based pressure-sensitive adhesive in the prior art, the pressure-sensitive adhesive prepared by the method provided by the invention has the advantages that the peel strength, the initial adhesion and the ageing resistance are greatly improved, so that technical support can be provided for development and application of novel bio-based pressure-sensitive adhesive materials.
Description
Technical Field
The invention belongs to the technical field of pressure-sensitive adhesives, and particularly relates to a bio-based pressure-sensitive adhesive and a preparation method thereof.
Background
Pressure sensitive adhesives, i.e., pressure Sensitive Adhesives (PSAs), are adhesives that require little external force to adhere to a variety of substrates. The pressure-sensitive adhesive elastomer has both liquid viscosity and solid elasticity, and has the features of easy adhesion and easy uncovering, and may be used in expanding the contact area between adhesive and adhered matter due to the wetting property and plasticity of pressure-sensitive adhesive. In view of the excellent characteristics of pressure-sensitive adhesives, the global pressure-sensitive adhesives have rapidly increased in scale in recent years, and the asia-tai area is the most standard and fast-growing market in the global pressure-sensitive adhesives market, and pressure-sensitive adhesives are widely applied in various fields of automobiles, foods, packaging, electric and electronic, medical treatment and the like.
In commercial production, it is required that the pressure-sensitive adhesive be neither interfacial nor cohesive nor mixed. The interfacial failure means that in the peeling test, the pressure-sensitive adhesive has high bonding strength, but the bonding strength between the pressure-sensitive adhesive and the surface of the substrate is insufficient, so that the colloid is completely separated from the surface of the substrate, and the surface of the substrate is basically free of residual colloid; cohesive failure refers to that the cohesive force of the pressure-sensitive adhesive is smaller, so that the adhesive layer is internally damaged, and a part of residual adhesive is left on the surface of the substrate; hybrid failure is a phenomenon that combines two failure modes, interfacial failure and cohesive failure.
Currently, pressure sensitive adhesives are derived mainly from petrochemicals, in addition to traditional natural rubber, resins. However, due to the increasing shortage and non-renewable petroleum resources, sustainable new materials have more development prospects from the development strategy. Compared with the traditional petroleum-based pressure-sensitive adhesive, the bio-based pressure-sensitive adhesive can reduce the use amount of petroleum and the discharge amount of wastewater in the production process, protect the environment, save the cost and improve the economic benefit, so that the bio-based pressure-sensitive adhesive is paid attention to by students.
At present, the research of the bio-based pressure-sensitive adhesive takes vegetable oil as a matrix, and the method mainly comprises the steps of epoxy, ring-opening cross-linking and copolymerization of unsaturated double bonds in the vegetable oil under the action of a catalyst to prepare the pressure-sensitive adhesive. However, the existing vegetable oil pressure-sensitive adhesive is easy to have insufficient adhesive strength and aging phenomenon caused by the influence of environmental factors such as light, heat, oxygen and the like in the production, processing and actual use processes, and cannot meet the higher use requirements of pressure-sensitive adhesive products.
Disclosure of Invention
In order to solve the problems, one of the purposes of the invention is to provide a preparation method of a bio-based pressure-sensitive adhesive, which has simple process and can effectively improve the initial adhesion, the peeling strength and the ageing resistance of the bio-based pressure-sensitive adhesive.
The second object of the present invention is to provide a bio-based pressure-sensitive adhesive which has excellent initial adhesion, peel strength and aging resistance.
In order to achieve the above purpose, the preparation method of the bio-based pressure-sensitive adhesive of the invention adopts the following technical scheme:
a method for preparing a bio-based pressure-sensitive adhesive, comprising the following steps:
1) Mixing epoxy vegetable oil with ethyl acetate, adding rosin ester and antioxidant, and oscillating for dissolving to obtain a mixed solution;
2) Cooling the mixed solution to the temperature of-5 ℃ and keeping the temperature for 15-25 min, then adding phosphoric acid, and carrying out oscillation, heating and ultrasonic reaction to obtain a reaction solution;
3) Coating the reaction solution on a substrate, curing for 10-30 min at 22-28 ℃, and then performing constant temperature and humidity adjustment to obtain the catalyst;
wherein, the dosage of the corresponding ethyl acetate is 0.8-1.2 mL and the dosage of the corresponding phosphoric acid is 0.051-0.0595 g; the mass ratio of the epoxy vegetable oil to the rosin ester to the antioxidant is 1:0.65-0.75:0.006-0.009; the antioxidant is one of caffeic acid, di-tert-butyl-p-cresol, tert-butyl hydroxy anisole, propyl gallate and tea polyphenol palmitate.
When the bio-based pressure-sensitive adhesive is prepared, the crosslinking copolymerization is carried out between partial phenolic hydroxyl groups and/or carboxyl groups of a plurality of specific antioxidants and epoxy groups of epoxy vegetable oil and phosphoric acid through esterification and etherification, so that the cohesive strength of the pressure-sensitive adhesive is enhanced; at the same time, unreacted phenolic hydroxyl and/or carboxyl polar functional groups enhance the wettability of the pressure sensitive adhesive. The aging resistance of unreacted phenolic hydroxyl groups on the antioxidant and the ability of the benzene ring to absorb ultraviolet rays in the pressure-sensitive adhesive greatly delay the aging problem of the pressure-sensitive adhesive in indoor and outdoor environment use.
The preparation method of the bio-based pressure-sensitive adhesive provided by the invention has the advantages that the adopted raw materials are simple and easy to obtain, the process operation difficulty is low, and particularly, the performance test experiment shows that the pressure-sensitive adhesive prepared by the method does not generate interfacial damage and cohesive failure, the 180-degree peel strength is 0.967-2.460N/cm, the annular initial adhesion is 0.97-3.10N, and the 180-degree peel strength residual rate after aging is 157-366%. The invention can well balance the crosslinking degree and wettability of the pressure-sensitive adhesive, and compared with the bio-based pressure-sensitive adhesive in the prior art, the peel strength, the initial adhesion and the ageing resistance are greatly improved.
In the invention, the types of the epoxy vegetable oil are not particularly limited, and the epoxy vegetable oil with relatively large unsaturation degree is only needed to ensure the performance of the bio-based pressure-sensitive adhesive. Preferably, in the step 1), the epoxy vegetable oil is one of epoxy soybean oil, epoxy sunflower oil, epoxy rapeseed oil, epoxy Canola oil, epoxy castor oil and epoxy linseed oil; more preferably, the epoxidized vegetable oil is epoxidized soybean oil having an epoxy value of 6.1 to 6.5%.
The purpose of heating ultrasound is to promote mass and heat transfer between the reaction substance and phosphoric acid in the reaction system and accelerate the reaction. Preferably, in the step 2), the temperature of the heating ultrasonic reaction is 48-52 ℃.
The oscillating and heating ultrasonic reaction in the step 2) is preferably specifically carried out for the purpose of promoting the conversion of raw materials, balancing the crosslinking degree and wettability of the polymer and improving the pressure-sensitive adhesive performance: vortex oscillation for 25-35 s, heating ultrasonic for 25-35 s, and circulating for 5-6 times; more preferably, the ultrasonic wave is heated for 30 seconds by vortex oscillation for 30 seconds, and circulated for 5 to 6 times.
The invention does not limit the types of the base materials used for coating, and the base materials only need to meet the coating requirement. Preferably, in step 3), the substrate is one of PET, PI, PVC, nonwoven fabric, aluminum foil, copper foil, and PET aluminizer. More preferably a PET substrate.
Preferably, in step 3), the constant temperature and humidity adjustment is: regulating the mixture for 20 to 28 hours in a constant temperature and humidity box with the temperature of 22 to 24 ℃ and the humidity of 45 to 55 percent; more preferably at 23℃and 50% humidity for 24 hours.
The technical scheme adopted by the bio-based pressure-sensitive adhesive is as follows:
the bio-based pressure-sensitive adhesive is prepared by adopting the method.
Compared with the traditional petroleum-based pressure-sensitive adhesive, the biological-based pressure-sensitive adhesive is more environment-friendly, and the pressure-sensitive adhesive performance test experiment shows that the 180-degree peel strength of the pressure-sensitive adhesive is 0.967-2.460N/cm, the annular initial adhesion is 0.97-3.10N, and the 180-degree peel strength residual rate after aging is 157-366%, which is far better than the existing biological-based pressure-sensitive adhesive material, so that the biological-based pressure-sensitive adhesive can provide technical support for development and application of novel biological-based pressure-sensitive adhesive materials.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples, which should not be construed as limiting the invention. The equipment and reagents used in the examples and test examples were commercially available, except as specifically indicated. Wherein: in the following examples and test examples, the test apparatus involved were as follows: normal temperature tape holding power tester (HTS-BCL 2220): the middlefield instrument equipment, inc; full function materials tester (LT-1000): the Jinan Chi test instruments Co., ltd; applicator (1806F/100): guangzhou City Shenghua practice Co., ltd; vortex oscillator (XW-80A): the company of Haimen City, inc. of Linbell instruments; ultrasonic cleaner (KQ-300B): kunshan, ultrosophy, inc.
The invention provides a preparation method of a bio-based pressure-sensitive adhesive, which comprises the following steps:
1) Mixing epoxy vegetable oil with ethyl acetate, adding rosin ester and antioxidant, and oscillating for dissolving to obtain a mixed solution;
2) Cooling the mixed solution to the temperature of-5 ℃ and keeping the temperature for 15-25 min, then adding phosphoric acid, and carrying out oscillation, heating and ultrasonic reaction to obtain a reaction solution;
3) Coating the reaction solution on a substrate, curing for 10-30 min at 22-28 ℃, and then performing constant temperature and humidity adjustment to obtain the catalyst;
wherein, in the step 1), the dosage of the corresponding ethyl acetate is 0.8-1.2 mL per gram of epoxy vegetable oil, more preferably 1mL per gram of epoxy vegetable oil. The mass ratio of the epoxy vegetable oil to the rosin ester to the antioxidant is 1:0.65-0.75:0.006-0.009; more preferably, the mass ratio of the epoxy vegetable oil to the rosin ester to the antioxidant is 1:0.7:0.006-0.009. The antioxidant is one of caffeic acid, di-tert-butyl-p-cresol, tert-butyl hydroxy anisole, propyl gallate and tea polyphenol palmitate.
In the invention, the choice of the epoxy vegetable oil is not specially limited, and the performance of the bio-based pressure-sensitive adhesive is ensured by adopting the epoxy vegetable oil with larger unsaturation degree. Preferably, in the step 1), the epoxy vegetable oil is one of epoxy soybean oil, epoxy sunflower oil, epoxy rapeseed oil, epoxy Canola oil, epoxy castor oil and epoxy linseed oil; more preferably, the epoxidized vegetable oil is epoxidized soybean oil having an epoxy value of 6.1 to 6.5%. In the following examples of the present invention, the epoxidized vegetable oil used in particular was epoxidized soybean oil available from microphone company with an epoxy value of 6.12%.
In the invention, in the step 2), the phosphoric acid is a catalyst and a reaction raw material, the adding amount of the phosphoric acid can be determined according to the reaction effect between the phosphoric acid, the epoxy vegetable oil and the antioxidant, and preferably, the corresponding phosphoric acid is used in an amount of 0.051-0.0595 g per gram of epoxy vegetable oil. In the following examples, the phosphoric acid is commercially available at a concentration of 85% and the amount of 85% phosphoric acid added per gram of epoxidized vegetable oil is 0.06 to 0.07g, more preferably 0.07g.
In the step 2), the mixed solution is directly reacted with phosphoric acid, and the epoxy bond of the epoxy vegetable oil is active, so that the reaction effect is seriously affected, and therefore, the reaction speed after the phosphoric acid is added is reduced by cooling in advance. Preferably, in the invention, the mixed solution is cooled to the temperature of-5 ℃ and kept for 15-25 min, and then phosphoric acid is added for reaction, more preferably: cooling the mixed solution to 0 ℃ and keeping the temperature for 20min, and adding phosphoric acid for reaction.
The purpose of heating ultrasound is to promote mass transfer and heat transfer between the reaction substances and the catalyst in the reaction system and accelerate the reaction. Preferably, in step 2), the temperature of the heated ultrasonic reaction is between 48 and 52 ℃, more preferably 50 ℃.
The oscillating and heating ultrasonic reaction in the step 2) is preferably specifically carried out for the purpose of promoting the conversion of raw materials, balancing the crosslinking degree and wettability of the polymer and improving the pressure-sensitive adhesive performance: vortex oscillation for 25-35 s, heating ultrasonic for 25-35 s, and circulating for 5-6 times; more preferably, the ultrasonic wave is heated for 30 seconds by vortex oscillation for 30 seconds, and circulated for 5 to 6 times.
The invention does not limit the types of the base materials used for coating, and the base materials only need to meet the coating requirement. Preferably, in step 3), the substrate is one of PET, PI, PVC, nonwoven fabric, aluminum foil, copper foil, and PET aluminizer. More preferably a PET substrate.
Preferably, in step 3), the constant temperature and humidity adjustment is: the temperature and humidity are adjusted in a constant temperature and humidity box with the temperature of 22-24 ℃ and the humidity of 50% for 20-28 hours, more preferably in a constant temperature and humidity box with the temperature of 23 ℃ and the humidity of 50% for 24 hours.
1. Examples
Example 1
The preparation method of the bio-based pressure-sensitive adhesive of the embodiment adopts the following steps:
1) 10g of epoxidized soybean oil (the epoxy value is 6.12%, the same applies below) is taken and placed in a 50mL centrifuge tube, 10mL of ethyl acetate is added, then 7g of rosin ester and 0.09g of caffeic acid are accurately added, and vortex oscillation dissolution is carried out, so that mixed solution is obtained;
2) Cooling the mixed solution to 0 ℃, keeping for 20min, then adding 0.7g of 85% phosphoric acid, carrying out vortex oscillation for 30s, heating and ultrasonic treatment at 50 ℃ for 30s, and repeating the operation for 5 times to obtain a reaction solution;
3) And (3) coating the reaction solution by using a coater, curing for 20min at 25 ℃, and regulating for 24h in a constant temperature and humidity box at 23 ℃ and 50% humidity to obtain the bio-based pressure-sensitive adhesive.
The bio-based pressure-sensitive adhesive of the embodiment is prepared by adopting the preparation method.
Example 2
The preparation method of the bio-based pressure-sensitive adhesive of the embodiment adopts the following steps:
1) 10g of epoxidized soybean oil is taken and placed in a 50mL centrifuge tube, 10mL of ethyl acetate is added, then 7g of rosin ester and 0.09g of di-tert-butyl-p-cresol (BHT) are accurately added, and vortex oscillation dissolution is carried out, so that a mixed solution is obtained;
2) Cooling the mixed solution to 0 ℃, keeping for 20min, then adding 0.7g of 85% phosphoric acid, carrying out vortex oscillation for 30s, heating and ultrasonic treatment at 50 ℃ for 30s, and repeating the operation for 5 times to obtain a reaction solution;
3) And (3) coating the reaction solution by using a coater, curing for 20min at 25 ℃, and regulating for 24h in a constant temperature and humidity box at 23 ℃ and 50% humidity to obtain the bio-based pressure-sensitive adhesive.
The bio-based pressure-sensitive adhesive of the embodiment is prepared by adopting the preparation method.
Example 3
The preparation method of the bio-based pressure-sensitive adhesive of the embodiment adopts the following steps:
1) 10g of epoxidized soybean oil is taken and placed in a 50mL centrifuge tube, 10mL of ethyl acetate is added, 7g of rosin ester and 0.09g of tert-Butyl Hydroxy Anisole (BHA) are accurately added, and vortex oscillation dissolution is carried out, so that a mixed solution is obtained;
2) Cooling the mixed solution to 0 ℃, keeping for 20min, then adding 0.7g of 85% phosphoric acid, carrying out vortex oscillation for 30s, heating and ultrasonic treatment at 50 ℃ for 30s, and repeating the operation for 6 times to obtain a reaction solution;
3) And (3) coating the reaction solution by using a coater, curing for 20min at 25 ℃, and regulating for 24h in a constant temperature and humidity box at 23 ℃ and 50% humidity to obtain the bio-based pressure-sensitive adhesive.
The bio-based pressure-sensitive adhesive of the embodiment is prepared by adopting the preparation method.
Example 4
The preparation method of the bio-based pressure-sensitive adhesive of the embodiment adopts the following steps:
1) 10g of epoxidized soybean oil is taken and placed in a 50mL centrifuge tube, 10mL of ethyl acetate is added, then 7g of rosin ester and 0.09g of propyl gallate are accurately added, and vortex oscillation dissolution is carried out, so that mixed solution is obtained;
2) Cooling the mixed solution to 0 ℃, keeping for 20min, then adding 0.7g of 85% phosphoric acid, carrying out vortex oscillation for 30s, heating and ultrasonic treatment at 50 ℃ for 30s, and repeating the operation for 5 times to obtain a reaction solution;
3) And (3) coating the reaction solution by using a coater, curing for 20min at 25 ℃, and regulating for 24h in a constant temperature and humidity box at 23 ℃ and 50% humidity to obtain the bio-based pressure-sensitive adhesive.
The bio-based pressure-sensitive adhesive of the embodiment is prepared by adopting the preparation method.
Example 5
The preparation method of the bio-based pressure-sensitive adhesive of the embodiment adopts the following steps:
1) 10g of epoxidized soybean oil is taken and placed in a 50mL centrifuge tube, 10mL of ethyl acetate is added, then 7g of rosin ester and 0.09g of tea polyphenol palmitate are accurately added, and vortex oscillation dissolution is carried out, so that mixed solution is obtained;
2) Cooling the mixed solution to 0 ℃, keeping for 20min, then adding 0.7g of 85% phosphoric acid, carrying out vortex oscillation for 30s, heating and ultrasonic treatment at 50 ℃ for 30s, and repeating the operation for 5 times to obtain a reaction solution;
3) And (3) coating the reaction solution by using a coater, curing for 20min at 25 ℃, and regulating for 24h in a constant temperature and humidity box at 23 ℃ and 50% humidity to obtain the bio-based pressure-sensitive adhesive.
The bio-based pressure-sensitive adhesive of the embodiment is prepared by adopting the preparation method.
Example 6
The preparation method of the bio-based pressure-sensitive adhesive of the embodiment adopts the following steps:
1) 10g of epoxidized soybean oil is taken and placed in a 50mL centrifuge tube, 10mL of ethyl acetate is added, 7g of rosin ester and 0.06g of caffeic acid are accurately added, and vortex oscillation dissolution is carried out, so that mixed solution is obtained;
2) Cooling the mixed solution to 0 ℃, keeping for 20min, then adding 0.7g of 85% phosphoric acid, carrying out vortex oscillation for 30s, heating and ultrasonic treatment at 50 ℃ for 30s, and repeating the operation for 6 times to obtain a reaction solution;
3) And (3) coating the reaction solution by using a coater, curing for 20min at 25 ℃, and regulating for 24h in a constant temperature and humidity box at 23 ℃ and 50% humidity to obtain the bio-based pressure-sensitive adhesive.
The bio-based pressure-sensitive adhesive of the embodiment is prepared by adopting the preparation method.
2. Comparative example
Comparative example 1
The preparation method of the bio-based pressure-sensitive adhesive of this comparative example is substantially the same as in example 1, except that: no antioxidant caffeic acid was added.
Comparative example 2
The preparation method of the bio-based pressure-sensitive adhesive of this comparative example is substantially the same as in example 6, except that: no antioxidant caffeic acid was added.
Comparative example 3
The preparation method of the bio-based pressure-sensitive adhesive of this comparative example is substantially the same as in example 1, except that: 0.09g of ferulic acid was used instead of 0.09g of caffeic acid in example 1.
Comparative example 4
The preparation method of the bio-based pressure-sensitive adhesive of this comparative example is substantially the same as in example 2, except that: instead of 0.09g of di-tert-butyl-p-cresol (BHT) in example 2, 0.09g of tert-butylhydroquinone (TBHQ) was used.
Comparative example 5
The preparation method of the bio-based pressure-sensitive adhesive of this comparative example is substantially the same as in example 4, except that: 0.09g of gallic acid was used instead of 0.09g of propyl gallate in example 4.
Comparative example 6
The preparation method of the bio-based pressure-sensitive adhesive of this comparative example is substantially the same as in example 5, except that: 0.09g of tea polyphenol palmitate was used instead of 0.09g of tea polyphenol palmitate in example 5.
Comparative example 7
The preparation method of the bio-based pressure-sensitive adhesive of this comparative example is substantially the same as in example 5, except that: 0.09g of beta-carotene was used instead of 0.09g of tea polyphenol palmitate in example 5.
Comparative example 8
The preparation method of the bio-based pressure-sensitive adhesive of this comparative example is substantially the same as in example 5, except that: the amount of tea polyphenol palmitate was reduced from 0.09g to 0.03g.
Comparative example 9
The preparation method of the bio-based pressure-sensitive adhesive of this comparative example is substantially the same as in example 5, except that: the amount of tea polyphenol palmitate was reduced from 0.09g to 0.06g.
Comparative example 10
The preparation method of the bio-based pressure-sensitive adhesive of this comparative example is substantially the same as in example 5, except that: the amount of tea polyphenol palmitate was increased from 0.09g to 0.12g.
Comparative example 11
The preparation method of the bio-based pressure-sensitive adhesive of this comparative example is substantially the same as in example 5, except that: the amount of tea polyphenol palmitate was increased from 0.09g to 0.15g.
Comparative example 12
The preparation method of the bio-based pressure-sensitive adhesive of this comparative example is substantially the same as in example 5, except that: the amount of 85% phosphoric acid was reduced from 0.7g to 0.6g.
Comparative example 13
The preparation method of the bio-based pressure-sensitive adhesive of this comparative example is substantially the same as in example 5, except that: the amount of 85% phosphoric acid was reduced from 0.7g to 0.65g.
Comparative example 14
The preparation method of the bio-based pressure-sensitive adhesive of this comparative example is substantially the same as in example 5, except that: the amount of 85% phosphoric acid was increased from 0.7g to 0.75g.
Comparative example 15
The preparation method of the bio-based pressure-sensitive adhesive of this comparative example is substantially the same as in example 5, except that: the amount of 85% phosphoric acid was increased from 0.7g to 0.8g.
Comparative example 16
The preparation method of the bio-based pressure-sensitive adhesive of this comparative example is substantially the same as in example 5, except that: the rosin ester dosage was reduced from 7g to 6g.
Comparative example 17
The preparation method of the bio-based pressure-sensitive adhesive of this comparative example is substantially the same as in example 5, except that: the rosin ester dosage was reduced from 7g to 6.5g.
Comparative example 18
The preparation method of the bio-based pressure-sensitive adhesive of this comparative example is substantially the same as in example 5, except that: the rosin ester dosage was increased from 7g to 7.5g.
Comparative example 19
The preparation method of the bio-based pressure-sensitive adhesive of this comparative example is substantially the same as in example 5, except that: the rosin ester dosage was increased from 7g to 8g.
Comparative example 20
The preparation method of the bio-based pressure-sensitive adhesive of this comparative example is substantially the same as in example 5, except that: vortex shaking was carried out for 30s and heating was carried out at 50℃for 30s, and the number of repetitions was reduced from 5 to 3.
Comparative example 21
The preparation method of the bio-based pressure-sensitive adhesive of this comparative example is substantially the same as in example 5, except that: vortex shaking was carried out for 30s and heating was carried out at 50℃for 30s, and the number of repetitions was reduced from 5 to 4.
Comparative example 22
The preparation method of the bio-based pressure-sensitive adhesive of this comparative example is substantially the same as in example 5, except that: vortex vibration was carried out for 30s and ultrasound was applied at 50 ℃ for 30s, and the number of repetitions was increased from 5 to 6.
Comparative example 23
The preparation method of the bio-based pressure-sensitive adhesive of this comparative example is substantially the same as in example 5, except that: vortex vibration was carried out for 30s and ultrasound was applied at 50 ℃ for 30s, and the number of repetitions was increased from 5 to 7.
Comparative example 24
The preparation method of the bio-based pressure-sensitive adhesive of this comparative example is substantially the same as in example 5, except that: the ultrasonic heating temperature was reduced from 50 ℃ to 40 ℃.
Comparative example 25
The preparation method of the bio-based pressure-sensitive adhesive of this comparative example is substantially the same as in example 5, except that: the ultrasonic heating temperature was reduced from 50 ℃ to 45 ℃.
Comparative example 26
The preparation method of the bio-based pressure-sensitive adhesive of this comparative example is substantially the same as in example 5, except that: the ultrasonic heating temperature is increased from 50 ℃ to 55 ℃.
3. Test examples
This test example was conducted to determine 180 ° peel strength, initial adhesion and aging resistance of the bio-based pressure-sensitive adhesives prepared in examples 1 to 6 and comparative examples 1 to 26, respectively. The specific test process is as follows: the reaction solutions of examples 1 to 6 and comparative examples 1 to 26, which were prepared in step 2), were coated on PET films by a coater to a thickness of 80. Mu.m, cured at room temperature for 20 minutes, and then placed in a constant temperature and humidity cabinet at a temperature of 23℃and a humidity of 50% for 24 hours, and then 180℃peel strength, initial adhesion and aging resistance were measured. The testing method comprises the following steps: measurement of 180 ° peel strength of pressure sensitive adhesives is referred to method a in ASTM D3330/D3330M-04 (2018). Measurement of pressure sensitive adhesive initial adhesion refers to method A in ASTM D6195-03 (2019). The aging test of the pressure-sensitive adhesive was a reinforced destructive aging test (aging temperature 60 ℃, relative humidity 50%, aging time 4 days), and was performed with reference to ASTM D3611-06 (2019). The calculation formula of 180 ° peel strength residual rate after aging refers to the prior art, and is specifically shown below.
·
Table 1 180 ° peel strength before aging, loop tack and 180 ° peel strength residual ratio after aging for examples and comparative examples
As is clear from Table 1, examples 1 to 6 provided by the present invention have 180℃peel strengths of 0.967 to 2.460N/cm, ring-shaped primary adhesion of 0.97 to 3.10N, 180℃peel strength residual ratios of 157 to 366% after aging, and overall properties superior to those of comparative examples 1 to 26.
From the comparison results of comparative example 1 and examples 1 to 6 of the present invention, it is understood that the present invention applies specific types of antioxidants (caffeic acid, di-t-butyl-p-cresol, t-butyl hydroxy anisole, propyl gallate, tea polyphenol palmitate) to the synthesis reaction of the pressure-sensitive adhesive, which can not only significantly improve the anti-aging performance of the pressure-sensitive adhesive, but also improve the 180 degree peel strength of the pressure-sensitive adhesive by 2.4 to 6.0 times and the initial adhesion by 2.3 to 7.2 times. Therefore, the specific antioxidant is added in the invention, so that the peel strength, initial adhesion and ageing resistance of the pressure-sensitive adhesive are greatly improved in a synergic manner.
Further, as is clear from the comparison of comparative examples 3 to 7 with the examples of the present invention, if the antioxidant is improperly used, it is inferior in either peel strength, initial adhesion or aging resistance, and even cohesive failure occurs in the epoxidized soybean oil pressure-sensitive adhesive (comparative examples 3, 5) added with ferulic acid or gallic acid, and even interfacial failure occurs in the epoxidized soybean oil pressure-sensitive adhesive (comparative example 7) added with β -carotene, and the pressure-sensitive adhesive cannot meet the use requirement at all.
As can be seen from the performance test results of examples 5 and comparative examples 8 to 26, the various performances of the pressure-sensitive adhesive were adversely affected to different degrees by changing the addition amount of tea polyphenol palmitate (comparative examples 8 to 11), or the amount of phosphoric acid (comparative examples 12 to 15), rosin ester (comparative examples 16 to 19), or the number of heating ultrasonic cycles or the temperature (comparative examples 20 to 26). The pressure sensitive adhesive of the partial comparison group has interfacial failure or cohesive failure phenomenon, and can not meet the use requirement any more.
In summary, the preparation method of the bio-based pressure-sensitive adhesive can prepare the bio-based pressure-sensitive adhesive with excellent peel strength, initial adhesion and ageing resistance, shows good pressure-sensitive adhesive development and application potential, and provides a brand new idea for the preparation and industrial application of novel bio-based pressure-sensitive adhesives.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (5)
1. A method for preparing a bio-based pressure-sensitive adhesive, which is characterized by comprising the following steps:
1) Mixing epoxy vegetable oil with ethyl acetate, adding rosin ester and antioxidant, and oscillating for dissolving to obtain a mixed solution;
2) Cooling the mixed solution to the temperature of-5 ℃ and keeping the temperature for 15-25 min, then adding phosphoric acid, and carrying out oscillation, heating and ultrasonic reaction to obtain a reaction solution;
3) Coating the reaction liquid on a substrate, curing for 10-30 min at 22-28 ℃, and then performing constant temperature and humidity adjustment to obtain the catalyst;
wherein, the dosage of the corresponding ethyl acetate is 0.8-1.2 mL and the dosage of the corresponding phosphoric acid is 0.051-0.0595 g; the mass ratio of the epoxy vegetable oil to the rosin ester to the antioxidant is 1:0.65-0.75:0.006-0.009; the antioxidant is one of caffeic acid, di-tert-butyl-p-cresol, tert-butyl hydroxy anisole, propyl gallate and tea polyphenol palmitate;
in the step 1), the epoxidized vegetable oil is epoxidized soybean oil, and the epoxy value of the epoxidized soybean oil is 6.1-6.5%; in the step 2), the temperature of the heating ultrasonic reaction is 48-52 ℃; in the step 2), the specific process of oscillating and heating ultrasonic reaction is as follows: vortex oscillation is carried out for 25-35 s, heating ultrasonic is carried out for 25-35 s, and circulation is carried out for 5 times.
2. The method for preparing a bio-based pressure-sensitive adhesive as claimed in claim 1, wherein in the step 2), the specific process of oscillating and heating ultrasonic reaction is as follows: vortex for 30s, heat ultrasonic for 30s, and circulate 5 times.
3. The method for preparing a bio-based pressure-sensitive adhesive as claimed in claim 1, wherein in the step 3), the substrate is one of PET, PI, PVC, non-woven fabric, aluminum foil, copper foil and PET aluminized film.
4. The method of preparing a bio-based pressure sensitive adhesive as claimed in claim 1, wherein in the step 3), the constant temperature and humidity is adjusted to: and (3) regulating the temperature in a constant-temperature and constant-humidity box with the temperature of 22-24 ℃ and the humidity of 45-55% for 20-28 h.
5. The bio-based pressure-sensitive adhesive is characterized by being prepared by adopting the preparation method of the bio-based pressure-sensitive adhesive as claimed in any one of claims 1-4.
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| CN104968742A (en) * | 2012-12-05 | 2015-10-07 | 艾利丹尼森公司 | Pressure sensitive adhesives prepared from maleated vegetable oils and expoxidized vegetable oils |
| CN113316624A (en) * | 2018-11-20 | 2021-08-27 | 俄勒冈州立大学 | Ultraviolet radiation cured pressure sensitive adhesives from vegetable oils or animal fats |
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| WO2012100171A2 (en) * | 2011-01-20 | 2012-07-26 | Kansas State University Research Foundation | Pressure sensitive adhesives, coatings, and films from plant oils |
| WO2015112492A1 (en) * | 2014-01-24 | 2015-07-30 | Oregon State University | Pressure-sensitive adhesives based on carboxylic acids and epoxides |
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| CN104968742A (en) * | 2012-12-05 | 2015-10-07 | 艾利丹尼森公司 | Pressure sensitive adhesives prepared from maleated vegetable oils and expoxidized vegetable oils |
| CN113316624A (en) * | 2018-11-20 | 2021-08-27 | 俄勒冈州立大学 | Ultraviolet radiation cured pressure sensitive adhesives from vegetable oils or animal fats |
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