CN112724855A - Preparation method of improved degradable adhesive tape and adhesive tape - Google Patents
Preparation method of improved degradable adhesive tape and 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
- C09J7/20—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
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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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
- 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
- C09J151/08—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 macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/21—Paper; Textile fabrics
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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
- C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/241—Polyolefin, e.g.rubber
- C09J7/243—Ethylene or propylene polymers
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- 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
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
- C09J2400/28—Presence of paper
- C09J2400/283—Presence of paper in the substrate
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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
- C09J2423/00—Presence of polyolefin
- C09J2423/10—Presence of homo or copolymers of propene
- C09J2423/106—Presence of homo or copolymers of propene in the substrate
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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
- C09J2451/00—Presence of graft polymer
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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
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
Abstract
The invention relates to a preparation method of an improved degradable adhesive tape and the adhesive tape, and the preparation process comprises the following steps: preparing a modified polycaprolactone dimethylbenzene solution, synthesizing an improved degradable pressure-sensitive adhesive by using acrylic acid and ester monomers thereof and a modified polycaprolactone component together, preparing a coating liquid by using the improved degradable pressure-sensitive adhesive, and coating to obtain the adhesive tape. The preparation method is simple and easy to implement, and has good bearing performance compared with the traditional adhesive tape preparation process; the prepared pressure-sensitive adhesive and adhesive tape have good degradation performance under natural conditions.
Description
Technical Field
The invention relates to the field of pressure-sensitive adhesive products, in particular to a preparation method of an improved degradable adhesive tape and the adhesive tape.
Background
The adhesive tape used in the fields of medicine, electronics, electroplating, material processing and the like is obtained by coating a pressure-sensitive adhesive on a base material with a certain surface free energy and then carrying out drying curing and anti-sticking treatment, the adopted pressure-sensitive adhesive generally comprises polymethacrylates, rubbers, polyurethanes and the like, the raw materials are insoluble and infusible polymers, and the raw materials are difficult to remove from the base material by means of dissolution and the like. On one hand, the adhesive tape using these raw materials as the adhesive layer is usually discarded after use, and the base material thereof cannot be recycled, which not only wastes resources, but also causes environmental pollution; on the other hand, since the adhesive tapes are not used in a concentrated manner and are difficult to treat in a concentrated manner due to large use amount and scattered use occasions, the adhesive tapes are mixed in social waste and inevitably cause serious environmental problems. However, the existing adhesive tape processing methods inevitably have the defects of high cost, large limitation, potential safety hazard and incomplete processing. Therefore, it is necessary to solve the problem of environmental pollution of the pressure-sensitive adhesive product with urgency, both from the viewpoint of environmental protection and resource recycling.
Disclosure of Invention
The invention aims to provide a preparation method of an improved degradable adhesive tape and the adhesive tape.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a preparation method of an improved degradable adhesive tape, which comprises the following specific steps:
A. preparation of modified polycaprolactone xylene solution:
A1. adding a catalyst into xylene, stirring, standing for 60-80 min, filtering, and adjusting the concentration to obtain a 5% catalyst and xylene mixed solution;
A2. mixing xylene, caprolactone and a first initiator, heating to 140-150 ℃, and refluxing for 30-50 min;
A3. dropwise adding all the mixed solution of the catalyst and the xylene prepared in the step A1 into the mixed solution in the step A2 for 20-30 min, and refluxing for 5-6 h at 135-145 ℃ to prepare a modified polycaprolactone xylene solution;
B. synthesizing the improved degradable pressure-sensitive adhesive:
B1. adding a second initiator into an organic solvent, stirring, standing for 60-80 min, and removing water and impurities separated from the solution after the solution is layered, clarified and transparent to obtain a first initiator solution; adding a second initiator into an organic solvent, stirring, standing for 60-80 min, and removing water and impurities separated by layering after the solution is layered, clarified and transparent to obtain a second initiator solution; adding the second initiator into an organic solvent, stirring, standing for 60-80 min, and removing water and impurities separated by layering after the solution is layered, clarified and transparent to obtain a third initiator solution;
B2. mixing acrylic acid and ester monomers thereof with the all modified polycaprolactone xylene solution prepared in the step A3 to obtain a monomer mixed solution;
B3. adding the organic solution and all the second initiator solutions prepared in the step B1 into 75-80% of the total weight of the monomer mixed solution prepared in the step B2, and stirring for 5-10 min to prepare monomer dropping liquid;
B4. mixing the residual monomer mixed solution used in the step B3 with an organic solvent, heating to 78-82 ℃, and refluxing for 10-20 min; dropwise adding all the first initiator solution prepared in the step B1 for 10-15 min; refluxing for 30-50 min; dropwise adding all the monomer dropwise added liquid prepared in the step B3 for 180-200 min; preserving the heat for 60-80 min; dropwise adding all the third initiator solution prepared in the step B1 for 10-15 min; refluxing for 120-160 min at 80-88 ℃; adding an organic solvent, and dropwise adding for 5-10 min; cooling to 35-40 ℃ to obtain a pre-adhesive;
B5. filtering all the pre-adhesives obtained in the step B4, and hermetically storing to obtain an improved degradable pressure-sensitive adhesive with the solid content of 35%;
C. preparing an improved degradable pressure-sensitive adhesive coating liquid:
C1. mixing and stirring a curing agent and an organic solvent to obtain a cross-linking agent diluent;
C2. adding the improved degradable pressure-sensitive adhesive obtained in the step B5 into an organic solvent, and stirring for 30-50 min to obtain an adhesive diluent;
C3. adding all the cross-linking agent diluent obtained in the step C1 into the glue diluent obtained in the step C2, and stirring for 30-50 min to obtain an improved degradable pressure-sensitive adhesive coating liquid;
D. coating the improved degradable pressure-sensitive adhesive coating liquid:
and D, coating the improved degradable pressure-sensitive adhesive coating liquid prepared in the step C3 on the surface of the degradable base material, drying to obtain an improved degradable pressure-sensitive adhesive coating, attaching a degradable release film to the surface of the coating, and performing post-curing treatment to obtain an improved degradable adhesive tape.
Further, the steps A2, A3 and B4 are all carried out under the condition of introducing nitrogen; the operation of step B2 was performed in a stainless steel vessel; in the step B3, the organic solution and the second initiator solution are added into the monomer mixed solution in an amount which is 75-80% of the total weight of the monomer mixed solution, and the part of the monomer mixed solution is stirred; step C2, adding the improved degradable pressure-sensitive adhesive into the organic solvent and simultaneously stirring the organic solvent; c3, adding the cross-linking agent diluent into the glue diluent and stirring the glue diluent; in the step B4, the organic solvent added in the previous step is cooled, and before the organic solvent is added, the dropwise adding device is washed by the organic solvent; the caprolactone, the first initiator and all the xylene used in the preparation in step A2 are purified by rectification before use.
Further, in the step D, the surface of the degradable base material is subjected to corona treatment, and the corona value is not lower than 40 mN/m; the temperature of post-curing treatment is not lower than 50 ℃ and the time is not lower than 48 hours.
Further, the mass ratio of the organic solvent mixed with the second initiator in the step B1 to the second initiator is at least 10: 1; the dosage of the catalyst in the step A1 is 1/500-1/50 of the mole number of the caprolactone in the step A2; the mass of the first initiator in the step A2 is 20-50% of the mole number of caprolactone.
Further, the catalyst in the step a1 is an alkoxy metal compound or lewis acid; the first initiator in step a2 is hydroxyethyl acrylate; the caprolactone in the step A2 is epsilon-CL; the second initiators in step B1 are all AIBN; the organic solvent used in the preparation method of the improved degradable adhesive tape is ethyl acetate.
Further, the improved degradable pressure-sensitive adhesive comprises 60-90% of polyacrylate polymers polymerized by alpha-methyl-free acrylic acid with ester group carbon atom number not more than 4 and ester monomers thereof and 10-40% of polyacrylic acid hydroxy polycaprolactone polymers; the acrylic polymer includes: 15-30% of ethyl acrylate, 30-50% of methyl acrylate, less than or equal to 30% of butyl acrylate and 15-50% of mixture of acrylic acid and hydroxyethyl acrylate.
Specifically, in the preparation process, hydroxyethyl acrylate is used as a first initiator, and caprolactone is subjected to ring opening polymerization in a xylene solution under the action of a catalyst in a nitrogen atmosphere to obtain a hydroxyl-terminated acrylate hydroxy polycaprolactone xylene solution; and in the coating and curing process, the end-capping group on the polyacrylic acid hydroxy polycaprolactone macromolecule in the copolymer structure and the functional group on the polyacrylic acid ester macromolecule are crosslinked with the curing agent together to form a stable pressure-sensitive adhesive coating.
On the basis, the invention also provides an adhesive tape, and the adhesive tape is prepared by the preparation method.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: 1. the preparation method is simple and easy to implement; 2. the prepared degradable pressure-sensitive adhesive and adhesive tape have good degradation performance under natural conditions; 3. compared with the traditional adhesive tape preparation process, the adhesive tape has good bearing performance.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention. In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
A. Preparation of modified polycaprolactone xylene solution:
A1. adding 1.4kg of triisopropoxyaluminum (catalyst) into 24kg of dimethylbenzene, stirring, standing for 60-80 min, filtering, and adjusting the concentration to obtain 25kg of a 5% triisopropoxyaluminum dimethylbenzene solution;
A2. mixing 47.1kg of dimethylbenzene, 70kg of epsilon-CL (caprolactone) and 4.25kg of hydroxyethyl acrylate (first initiator) under the condition of introducing nitrogen, heating to 140-150 ℃, and refluxing for 30-50 min;
A3. under the condition of introducing nitrogen, dropwise adding all the triisopropoxyaluminum xylene solutions prepared in the step A1 into the mixed solution in the step A2 for 20-30 min, and refluxing at 135-145 ℃ for 5-6 h to prepare about 180kg of modified acrylic acid hydroxy polycaprolactone xylene solution;
B. synthesizing the improved degradable pressure-sensitive adhesive:
B1. adding 0.2kg of AIBN (second initiator) into 7kg of ethyl acetate (organic solvent), stirring, standing for 60-80 min, and removing impurities separated out after the solution is layered, clarified and transparent to obtain a first initiator solution; adding 0.72kg of AIBN (second initiator) into 20kg of ethyl acetate (organic solvent), stirring, standing for 60-80 min, and removing water and impurities separated out after the solution is layered, clarified and transparent to obtain a second initiator solution; adding 0.3kg of AIBN (second initiator) into 10kg of ethyl acetate (organic solvent), stirring, standing for 60-80 min, and removing impurities separated by layering after the solution is layered, clarified and transparent to obtain a third initiator solution;
B2. mixing 60kg of methyl acrylate, 60kg of ethyl acrylate, 75kg of butyl acrylate, 15kg of acrylic acid (acrylic acid and ester monomers thereof) and all the acrylic acid hydroxy polycaprolactone xylene solution prepared in the step A3 to obtain 390kg of monomer mixed solution;
B3. adding 100kg of ethyl acetate (organic solution) and all the second initiator solution prepared in the step B1 into 312kg of monomer mixed solution, and stirring for 5-10 min to prepare monomer dropping liquid;
B4. mixing the residual monomer mixed solution used in the step B3 with an organic solvent under the condition of introducing nitrogen, heating to 78-82 ℃, and refluxing for 10-20 min; dropwise adding all the first initiator solution prepared in the step B1 for 10-15 min; refluxing for 30-50 min; dropwise adding all the monomer dropwise added liquid prepared in the step B3 for 180-200 min; preserving the heat for 60-80 min; dropwise adding all the third initiator solution prepared in the step B1 for 10-15 min; refluxing for 120-160 min at 80-88 ℃; adding 20kg of ethyl acetate (organic solvent), and dripping for 5-10 min; cooling to 35-40 ℃ to obtain a pre-adhesive;
B5. filtering all the pre-adhesives obtained in the step B4, and hermetically storing to obtain an improved degradable pressure-sensitive adhesive with the solid content of 35%;
C. preparing an improved degradable pressure-sensitive adhesive coating liquid:
C1. 1kg of HDI dimer (curing agent) and 10kg of ethyl acetate (organic solvent) were mixed and stirred to obtain a crosslinking agent diluent;
C2. adding 100kg of the improved degradable pressure-sensitive adhesive obtained in the step B5 into 34kg of (organic solvent), and stirring for 30-50 min to obtain a glue diluent;
C3. adding all the cross-linking agent diluent obtained in the step C1 into the glue diluent obtained in the step C2, and stirring for 30-50 min to obtain an improved degradable pressure-sensitive adhesive coating liquid;
D. coating the improved degradable pressure-sensitive adhesive coating liquid:
and D, coating the improved degradable pressure-sensitive adhesive coating liquid prepared in the step C3 on the anti-sticking surface of the degradable BOPP release film, wherein the coating thickness is about 20 micrometers, drying for 1 minute by using an oven at 100 ℃ to obtain a degradable pressure-sensitive adhesive coating, attaching a degradable polylactic acid PLA film to the surface of the coating, and performing post-curing treatment at 50 ℃ for not less than 48 hours to obtain the improved degradable PLA adhesive tape.
And D, performing performance test on the improved degradable PLA adhesive tape prepared in the step D according to the standard in the table 1.
| Item | Unit of | Reference value | Test standard |
| Appearance of the product | --- | Smooth surface, no spot, impurity, dirt, scratch, and no adhesive migration | Visualization |
| Total thickness of | μm | 110±5 | GB/T 7125-2014 |
| Thickness of the substrate | μm | 50±3 | GB/T 7125-2014 |
| Thickness of release film | μm | 40±2 | GB/T 7125-2014 |
| 180 degree peel force | gf/25mm | 700±200 | GB/T 2792-2014 |
| Viscosity-holding property | Hour(s) | ≥120 | GB/T 4851-2014 |
| Temperature resistanceCan be used for | 100℃/30min | No crack, no residual glue, no falling off and no cracking | Enterprise standard |
TABLE 1
And D, performing a degradation test on the used improved degradable PLA adhesive tape prepared in the step D, wherein the degradation test comprises the following steps: cutting the improved degradable PLA adhesive tape into 25mm multiplied by 25mm, counting 100 pieces, and weighing; burying the 100 improved degradable PLA adhesive tapes and domestic garbage into fertile soil, keeping the temperature between 20 and 30 ℃, and ventilating well; and observing the residual condition of the improved degradable PLA adhesive tape after 6 months.
The basic performance of the improved degradable PLA adhesive tape prepared in the embodiment 1 meets the use requirement of the adhesive tape; the observations after 6 months were: the 100 improved degradable PLA adhesive tapes are reduced by more than 95% or basically disappear, and have good degradation performance in a simulated natural environment.
Example 2
A. Preparation of modified polycaprolactone xylene solution:
A1. adding 1.4kg of triisopropoxyaluminum (catalyst) into 24kg of dimethylbenzene, stirring, standing for 60-80 min, filtering, and adjusting the concentration to obtain 25kg of a 5% triisopropoxyaluminum dimethylbenzene solution;
A2. mixing 47.1kg of dimethylbenzene, 70kg of epsilon-CL (caprolactone) and 4.25kg of hydroxyethyl acrylate (first initiator) under the condition of introducing nitrogen, heating to 140-150 ℃, and refluxing for 30-50 min;
A3. under the condition of introducing nitrogen, dropwise adding all the triisopropoxyaluminum xylene solutions prepared in the step A1 into the mixed solution in the step A2 for 20-30 min, and refluxing at 135-145 ℃ for 5-6 h to prepare about 180kg of modified acrylic acid hydroxy polycaprolactone xylene solution;
B. synthesizing the improved degradable pressure-sensitive adhesive:
B1. adding 0.2kg of AIBN (second initiator) into 7kg of ethyl acetate (organic solvent), stirring, standing for 60-80 min, and removing water and impurities separated out after the solution is layered, clarified and transparent to obtain a first initiator solution; adding 0.72kg of AIBN (second initiator) into 20kg of ethyl acetate (organic solvent), stirring, standing for 60-80 min, and removing impurities separated by layering after the solution is layered, clarified and transparent to obtain a second initiator solution; adding 0.3kg of AIBN (second initiator) into 10kg of ethyl acetate (organic solvent), stirring, standing for 60-80 min, and removing impurities separated by layering after the solution is layered, clarified and transparent to obtain a third initiator solution;
B2. mixing 60kg of methyl acrylate, 60kg of ethyl acrylate, 75kg of butyl acrylate, 15kg of acrylic acid (acrylic acid and ester monomers thereof) and all the acrylic acid hydroxy polycaprolactone xylene solution prepared in the step A3 to obtain 390kg of monomer mixed solution;
B3. adding 100kg of ethyl acetate (organic solution) and all the second initiator solution prepared in the step B1 into 312kg of monomer mixed solution, and stirring for 5-10 min to prepare monomer dropping liquid;
B4. mixing the residual monomer mixed solution used in the step B3 with an organic solvent under the condition of introducing nitrogen, heating to 78-82 ℃, and refluxing for 10-20 min; dropwise adding all the first initiator solution prepared in the step B1 for 10-15 min; refluxing for 30-50 min; dropwise adding all the monomer dropwise added liquid prepared in the step B3 for 180-200 min; preserving the heat for 60-80 min; dropwise adding all the third initiator solution prepared in the step B1 for 10-15 min; refluxing for 120-160 min at 80-88 ℃; adding 20kg of ethyl acetate (organic solvent), and dripping for 5-10 min; cooling to 35-40 ℃ to obtain a pre-adhesive;
B5. filtering all the pre-adhesives obtained in the step B4, and hermetically storing to obtain an improved degradable pressure-sensitive adhesive with the solid content of 35%;
C. preparing an improved degradable pressure-sensitive adhesive coating liquid:
C1. mixing 0.4kg of HDI dimer (curing agent) and 10kg of ethyl acetate (organic solvent), and stirring to obtain a crosslinking agent diluent;
C2. adding 50kg of the improved degradable pressure-sensitive adhesive obtained in the step B5 into 25kg of (organic solvent), and stirring for 30-50 min to obtain a glue diluent;
C3. adding all the cross-linking agent diluent obtained in the step C1 into the glue diluent obtained in the step C2, adding 0.57kg of tributyl citrate, and stirring for 30-50 min to obtain an improved degradable pressure-sensitive adhesive coating liquid;
D. coating the improved degradable pressure-sensitive adhesive coating liquid:
and D, coating the improved degradable pressure-sensitive adhesive coating liquid prepared in the step C3 on the surface of the degradable BOPP base material, wherein the corona value of the surface is not lower than 40mN/m, the coating thickness is about 15 microns, drying is carried out for 1 minute by using an oven at 100 ℃ to obtain a degradable pressure-sensitive adhesive coating, a degradable BOPP release film is attached to the surface of the coating, and post-curing treatment is carried out at 50 ℃ for not lower than 48 hours to obtain the improved degradable BOPP adhesive tape.
And D, performing performance test on the improved degradable BOPP adhesive tape prepared in the step D according to the standard in the table 2.
| Item | Unit of | Reference value | Test standard |
| Appearance of the product | --- | Smooth surface, no spot, impurity, dirt, scratch, and no adhesive migration | Visualization |
| Total thickness of | μm | 105±3 | GB/T 7125-2014 |
| Thickness of the substrate | μm | 50±2 | GB/T 7125-2014 |
| Thickness of release film | μm | 40±1 | GB/T 7125-2014 |
| 180 degree peel force | gf/25mm | 300±100 | GB/T 2792-2014 |
| Viscosity-holding property | Hour(s) | ≥120 | GB/T 4851-2014 |
| Temperature resistance | 105℃/30min | No crack, no residual glue, no falling off and no cracking | Enterprise standard |
TABLE 2
And D, carrying out a degradation test on the used improved degradable BOPP adhesive tape prepared in the step D, wherein the degradation test comprises the following steps: cutting the improved degradable BOPP adhesive tape into 25mm multiplied by 25mm, counting 100 pieces, and weighing; burying the 100 improved degradable BOPP adhesive tapes and household garbage into fertile soil, keeping the temperature between 20 and 30 ℃, and well ventilating; and observing the residual condition of the improved degradable BOPP adhesive tape after 6 months.
The basic performance of the improved degradable BOPP adhesive tape prepared in the embodiment 2 meets the use requirement of the adhesive tape; the observations after 6 months were: the 100 improved degradable BOPP adhesive tapes are reduced by more than 80% or basically disappear, and have good degradation performance in a simulated natural environment.
Example 3
A. Preparation of modified polycaprolactone xylene solution:
A1. adding 1.4kg of triisopropoxyaluminum (catalyst) into 24kg of dimethylbenzene, stirring, standing for 60-80 min, filtering, and adjusting the concentration to obtain 25kg of a 5% triisopropoxyaluminum dimethylbenzene solution;
A2. mixing 47.1kg of dimethylbenzene, 70kg of epsilon-CL (caprolactone) and 4.25kg of hydroxyethyl acrylate (first initiator) under the condition of introducing nitrogen, heating to 140-150 ℃, and refluxing for 30-50 min;
A3. under the condition of introducing nitrogen, dropwise adding all the triisopropoxyaluminum xylene solutions prepared in the step A1 into the mixed solution in the step A2 for 20-30 min, and refluxing at 135-145 ℃ for 5-6 h to prepare about 180kg of modified acrylic acid hydroxy polycaprolactone xylene solution;
B. synthesizing the improved degradable pressure-sensitive adhesive:
B1. adding 0.2kg of AIBN (second initiator) into 7kg of ethyl acetate (organic solvent), stirring, standing for 60-80 min, and removing water and impurities separated out after the solution is layered, clarified and transparent to obtain a first initiator solution; adding 0.72kg of AIBN (second initiator) into 20kg of ethyl acetate (organic solvent), stirring, standing for 60-80 min, and removing impurities separated by layering after the solution is layered, clarified and transparent to obtain a second initiator solution; adding 0.3kg of AIBN (second initiator) into 10kg of ethyl acetate (organic solvent), stirring, standing for 60-80 min, and removing impurities separated by layering after the solution is layered, clarified and transparent to obtain a third initiator solution;
B2. mixing 60kg of methyl acrylate, 60kg of ethyl acrylate, 75kg of butyl acrylate, 15kg of acrylic acid (acrylic acid and ester monomers thereof) and all the acrylic acid hydroxy polycaprolactone xylene solution prepared in the step A3 to obtain 390kg of monomer mixed solution;
B3. adding 100kg of ethyl acetate (organic solution) and all the second initiator solution prepared in the step B1 into 312kg of monomer mixed solution, and stirring for 5-10 min to prepare monomer dropping liquid;
B4. mixing the residual monomer mixed solution used in the step B3 with an organic solvent under the condition of introducing nitrogen, heating to 78-82 ℃, and refluxing for 10-20 min; dropwise adding all the first initiator solution prepared in the step B1 for 10-15 min; refluxing for 30-50 min; dropwise adding all the monomer dropwise added liquid prepared in the step B3 for 180-200 min; preserving the heat for 60-80 min; dropwise adding all the third initiator solution prepared in the step B1 for 10-15 min; refluxing for 120-160 min at 80-88 ℃; adding 20kg of ethyl acetate (organic solvent), and dripping for 5-10 min; cooling to 35-40 ℃ to obtain a pre-adhesive;
B5. filtering all the pre-adhesives obtained in the step B4, and hermetically storing to obtain an improved degradable pressure-sensitive adhesive with the solid content of 35%;
C. preparing an improved degradable pressure-sensitive adhesive coating liquid:
C1. mixing 0.5kg of methyl aziridine (curing agent) and 10kg of ethyl acetate (organic solvent), and stirring to obtain a crosslinking agent diluent;
C2. adding 50kg of the improved degradable pressure-sensitive adhesive obtained in the step B5 into 25kg of (organic solvent), and stirring for 30-50 min to obtain a glue diluent;
C3. adding all the cross-linking agent diluent obtained in the step C1 into the glue diluent obtained in the step C2, adding 0.57kg of tributyl citrate, and stirring for 30-50 min to obtain an improved degradable pressure-sensitive adhesive coating liquid;
D. coating the improved degradable pressure-sensitive adhesive coating liquid:
and D, coating the improved degradable pressure-sensitive adhesive coating liquid prepared in the step C3 on the surface of the degradable textured paper substrate with the corona value not lower than 40mN/m, wherein the coating thickness is about 30 micrometers, drying for 1 minute by using an oven at the temperature of 130 ℃ to obtain a degradable pressure-sensitive adhesive coating, attaching degradable glassine release paper on the surface of the coating, and performing postcuring treatment at the temperature of 50 ℃ for not lower than 48 hours to obtain the improved degradable paper-based adhesive tape.
And D, performing performance test on the improved degradable paper-based adhesive tape prepared in the step D according to the standard in the table 3.
| Item | Unit of | Reference value | Test standard |
| Appearance of the product | --- | Smooth surface, no spot, impurity, dirt, scratch, and no adhesive migration | Visualization |
| Total thickness of | μm | 175±10 | GB/T 7125-2014 |
| Thickness of the substrate | μm | 65±5 | GB/T 7125-2014 |
| Thickness of release film | μm | 80±10 | GB/T 7125-2014 |
| 180 degree peel force | gf/25mm | 1000±200 | GB/T 2792-2014 |
| Viscosity-holding property | Hour(s) | ≥120 | GB/T 4851-2014 |
| Temperature resistance | 130℃/30min | No crack, no residual glue, no falling off and no cracking | Enterprise standard |
TABLE 3
And D, performing a degradation test on the used improved degradable paper-based adhesive tape prepared in the step D, wherein the degradation test comprises the following steps: cutting the improved degradable paper-based adhesive tape into 25mm multiplied by 25mm, counting 100 pieces, and weighing; burying the 100 improved degradable paper-based adhesive tapes and domestic garbage into fertile soil, keeping the temperature between 20 and 30 ℃, and ventilating well; and observing the residual condition of the improved degradable paper-based adhesive tape after 6 months.
The basic performance of the improved degradable paper-based adhesive tape prepared in the embodiment 3 meets the use requirement of the adhesive tape; the observations after 6 months were: the 100 pieces of improved degradable paper-based adhesive tapes lose more than 90% of weight or basically disappear, and have good degradation performance in a simulated natural environment.
The invention has the beneficial effects that: 1. the preparation method is simple and easy to implement; 2. the prepared degradable pressure-sensitive adhesive and adhesive tape have good degradation performance under natural conditions; 3. compared with the traditional adhesive tape preparation process, the adhesive tape has good bearing performance.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (7)
1. The preparation method of the improved degradable adhesive tape is characterized by comprising the following steps:
A. preparation of modified polycaprolactone xylene solution:
A1. adding a catalyst into xylene, stirring, standing for 60-80 min, filtering, and adjusting the concentration to obtain a 5% catalyst and xylene mixed solution;
A2. mixing xylene, caprolactone and a first initiator, heating to 140-150 ℃, and refluxing for 30-50 min;
A3. dropwise adding all the mixed solution of the catalyst and the xylene prepared in the step A1 into the mixed solution in the step A2 for 20-30 min, and refluxing for 5-6 h at 135-145 ℃ to prepare a modified polycaprolactone xylene solution;
B. synthesizing the improved degradable pressure-sensitive adhesive:
B1. adding a second initiator into an organic solvent, stirring, standing for 60-80 min, and removing water and impurities separated from the solution after the solution is layered, clarified and transparent to obtain a first initiator solution; adding a second initiator into an organic solvent, stirring, standing for 60-80 min, and removing water and impurities separated by layering after the solution is layered, clarified and transparent to obtain a second initiator solution; adding the second initiator into an organic solvent, stirring, standing for 60-80 min, and removing water and impurities separated by layering after the solution is layered, clarified and transparent to obtain a third initiator solution;
B2. mixing acrylic acid and ester monomers thereof with the all modified polycaprolactone xylene solution prepared in the step A3 to obtain a monomer mixed solution;
B3. adding the organic solution and all the second initiator solutions prepared in the step B1 into 75-80% of the total weight of the monomer mixed solution prepared in the step B2, and stirring for 5-10 min to prepare monomer dropping liquid;
B4. mixing the residual monomer mixed solution used in the step B3 with an organic solvent, heating to 78-82 ℃, and refluxing for 10-20 min; dropwise adding all the first initiator solution prepared in the step B1 for 10-15 min; refluxing for 30-50 min; dropwise adding all the monomer dropwise added liquid prepared in the step B3 for 180-200 min; preserving the heat for 60-80 min; dropwise adding all the third initiator solution prepared in the step B1 for 10-15 min; refluxing for 120-160 min at 80-88 ℃; adding an organic solvent, and dropwise adding for 5-10 min; cooling to 35-40 ℃ to obtain a pre-adhesive;
B5. filtering all the pre-adhesives obtained in the step B4, and hermetically storing to obtain an improved degradable pressure-sensitive adhesive with the solid content of 35%;
C. preparing an improved degradable pressure-sensitive adhesive coating liquid:
C1. mixing and stirring a curing agent and an organic solvent to obtain a cross-linking agent diluent;
C2. adding the improved degradable pressure-sensitive adhesive obtained in the step B5 into an organic solvent, and stirring for 30-50 min to obtain an adhesive diluent;
C3. adding all the cross-linking agent diluent obtained in the step C1 into the glue diluent obtained in the step C2, and stirring for 30-50 min to obtain an improved degradable pressure-sensitive adhesive coating liquid;
D. coating the improved degradable pressure-sensitive adhesive coating liquid:
and D, coating the improved degradable pressure-sensitive adhesive coating liquid prepared in the step C3 on the surface of the degradable base material, drying to obtain an improved degradable pressure-sensitive adhesive coating, attaching a degradable release film to the surface of the coating, and performing post-curing treatment to obtain an improved degradable adhesive tape.
2. The method for preparing the improved degradable adhesive tape according to claim 1, wherein the method comprises the following steps: the steps A2, A3 and B4 are all carried out under the condition of introducing nitrogen; the operation of step B2 was performed in a stainless steel vessel; in the step B3, the organic solution and the second initiator solution are added into the monomer mixed solution in an amount which is 75-80% of the total weight of the monomer mixed solution, and the part of the monomer mixed solution is stirred; step C2, adding the improved degradable pressure-sensitive adhesive into the organic solvent and simultaneously stirring the organic solvent; c3, adding the cross-linking agent diluent into the glue diluent and stirring the glue diluent; in the step B4, the organic solvent added in the previous step is cooled, and before the organic solvent is added, the dropwise adding device is washed by the organic solvent; and D, rectifying and purifying the polycaprolactone, the first initiator and all xylene used in the preparation process in the step A2 before use.
3. The method for preparing the improved degradable adhesive tape according to claim 1, wherein the method comprises the following steps: in the step D, the surface of the degradable base material is subjected to corona treatment, and the corona value is not lower than 40 mN/m; the post-curing treatment temperature is not lower than 50 ℃ and the time is not lower than 48 hours.
4. The method for preparing the improved degradable adhesive tape according to claim 1, wherein the method comprises the following steps: the mass ratio of the organic solvent mixed with the second initiator and the second initiator in the step B1 is at least 10: 1; the amount of the catalyst used in the step A1 is 1/500-1/50 of the mole number of the caprolactone used in the step A2; the mass of the first initiator in the step A2 is 20-50% of the mole number of the caprolactone.
5. The method for preparing the improved degradable adhesive tape according to claim 1, wherein the method comprises the following steps: the catalyst in the step A1 is an alkoxy metal compound or Lewis acid; in the step A2, the first initiator is hydroxyethyl acrylate; the caprolactone in the step A2 is epsilon-CL; the second initiator in step B1 is AIBN; the organic solvent used in the preparation method of the improved degradable adhesive tape is ethyl acetate.
6. The method for preparing the improved degradable adhesive tape according to claim 1, wherein the method comprises the following steps: the improved degradable pressure-sensitive adhesive comprises 60-90% of polyacrylate polymers polymerized by alpha-position methyl-free acrylic acid with ester group carbon atom number not more than 4 and ester monomers thereof and 10-40% of polyhydroxyl polycaprolactone polymers; the acrylic polymer includes: 15-30% of ethyl acrylate, 30-50% of methyl acrylate, less than or equal to 30% of butyl acrylate and 15-50% of mixture of acrylic acid and hydroxyethyl acrylate.
7. An adhesive tape, characterized in that: the adhesive tape is produced by the production method according to any one of claims 1 to 6.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106833449A (en) * | 2017-02-13 | 2017-06-13 | 深圳市壹零壹工业设计有限公司 | A kind of biodegradable polydactyl acid adhesive tape and preparation method thereof |
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| CN108250368A (en) * | 2018-01-18 | 2018-07-06 | 中国科学院长春应用化学研究所 | A kind of biodegradable pressure-sensitive adhesive agent and preparation method thereof |
| CN111621241A (en) * | 2020-06-08 | 2020-09-04 | 苏州世华新材料科技股份有限公司 | Preparation method of degradable bio-based acrylate pressure-sensitive adhesive protective film |
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| CN106833449A (en) * | 2017-02-13 | 2017-06-13 | 深圳市壹零壹工业设计有限公司 | A kind of biodegradable polydactyl acid adhesive tape and preparation method thereof |
| CN107556936A (en) * | 2017-09-08 | 2018-01-09 | 安徽明讯新材料科技股份有限公司 | A kind of environmentally friendly diaphragm for touch-control glass screen and preparation method thereof |
| CN108250368A (en) * | 2018-01-18 | 2018-07-06 | 中国科学院长春应用化学研究所 | A kind of biodegradable pressure-sensitive adhesive agent and preparation method thereof |
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