CN112195009A - Adhesive for solvent-free composite membrane and production method thereof - Google Patents
Adhesive for solvent-free composite membrane and production method thereof Download PDFInfo
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- CN112195009A CN112195009A CN202011047843.9A CN202011047843A CN112195009A CN 112195009 A CN112195009 A CN 112195009A CN 202011047843 A CN202011047843 A CN 202011047843A CN 112195009 A CN112195009 A CN 112195009A
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C—CHEMISTRY; METALLURGY
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
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- C—CHEMISTRY; METALLURGY
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C—CHEMISTRY; METALLURGY
- 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
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
Abstract
The invention provides an adhesive for a solvent-free composite membrane and a production method thereof, wherein the production method comprises the following steps: reacting diphenylmethane diisocyanate and polypropylene glycol 3000 serving as raw materials for 2.5-3.5 hours at the temperature of 80-85 ℃ by taking triethanolamine as a catalyst to prepare a polyurethane adhesive prepolymer; taking adipic acid, phthalic anhydride, 1, 6-hexanediol and neopentyl glycol as raw materials, taking methane sulfonic acid as a catalyst, and carrying out esterification reaction for 6-8 h at the temperature of 220-240 ℃ to prepare an esterification product; then carrying out polycondensation reaction to prepare compound polyester polyol with the acid value lower than 1 mgKOH/g; the adhesive for the solvent-free composite film is prepared by taking a polyurethane adhesive prepolymer and a compound polyester polyol as raw materials under the conditions that the curing temperature is 60-80 ℃ and the curing time is 2-3 d. The solvent-free two-component polyurethane adhesive prepared by the invention is suitable for packaging medicinal materials, and has the advantages of high peel strength and strong high temperature resistance.
Description
Technical Field
The invention relates to the technical field of packaging materials, in particular to an adhesive for a solvent-free composite film and a production method thereof.
Background
The solvent-free composite film is formed by coating an adhesive on a substrate and then adhering materials to be combined, and is one of the current common medicine packaging materials. And the binder is an important component in the solvent-free composite film.
In the prior art, the adhesive used in the solvent-free composite film is mainly solvent-based Polyurethane adhesive, Polyurethane is fully called Polyurethane (Polyurethane), and is a high polymer with more characteristic units of carbamate groups (-NHCOO-) on a main chain, and the conventional solvent-based Polyurethane adhesive has the problems of low peel strength and poor high temperature resistance.
Disclosure of Invention
In view of the above situation, the invention provides an adhesive for a solvent-free composite film and a production method thereof, so as to prepare a solvent-free two-component polyurethane adhesive suitable for packaging medicinal materials, and the adhesive has the advantages of high peel strength and strong high temperature resistance.
The technical scheme of the invention is as follows:
a method for producing an adhesive for a solvent-free composite film, comprising:
reacting diphenylmethane diisocyanate and polypropylene glycol 3000 serving as raw materials for 2.5-3.5 hours at the temperature of 80-85 ℃ by taking triethanolamine as a catalyst to prepare a polyurethane adhesive prepolymer;
taking adipic acid, phthalic anhydride, 1, 6-hexanediol and neopentyl glycol as raw materials, taking methane sulfonic acid as a catalyst, and carrying out esterification reaction for 6-8 h at the temperature of 220-240 ℃ to prepare an esterification product; then carrying out polycondensation reaction to prepare compound polyester polyol with the acid value lower than 1 mgKOH/g;
the adhesive for the solvent-free composite film is prepared by taking a polyurethane adhesive prepolymer and a compound polyester polyol as raw materials under the conditions that the curing temperature is 60-80 ℃ and the curing time is 2-3 d.
According to the production method of the adhesive for the solvent-free composite film, provided by the invention, the symmetrical and regular molecular structure in diphenylmethane diisocyanate and the special structure of polypropylene glycol 3000 containing side groups are utilized, so that the prepared polyurethane adhesive prepolymer has excellent mechanical property, flexibility and hydrolysis resistance, then, the isocyanate group in the polyurethane adhesive prepolymer is utilized to react with the hydroxyl group in the self-made compound polyester polyol, two oligomer molecules are further converted into a polymer with higher molecular weight through the interaction between groups, the flow form is converted into a solid state, the actual measurement shows that the peeling strength of the adhesive reaches not less than 2.8N/mm, the peeling strength is high, the adhesive starts to generate heat loss when reaching 500 ℃, and the high temperature resistance is strong.
In addition, the production method of the adhesive for the solvent-free composite membrane provided by the invention also has the following technical characteristics:
further, in the step of preparing the polyurethane adhesive prepolymer by using diphenylmethane diisocyanate and polypropylene glycol 3000 as raw materials and triethanolamine as a catalyst and reacting for 2 hours at the temperature of 75 ℃, the material ratio of the diphenylmethane diisocyanate to the polypropylene glycol 3000 is (4-6): 1.
furthermore, in the step of preparing the polyurethane adhesive prepolymer, the amount of triethanolamine added is 0.1% of the total amount of the raw materials by taking diphenylmethane diisocyanate and polypropylene glycol 3000 as raw materials and triethanolamine as a catalyst and reacting for 2 hours at the temperature of 75 ℃.
Further, the conditions of the polycondensation reaction are as follows:
the polycondensation reaction temperature is 250-270 ℃, the polycondensation reaction time is 6-8 h, antimony trioxide is used as a catalyst, the maximum vacuum degree is 0.1MPa, and the ratio of alkyd raw materials is 1.2.
Further, the addition amount of antimony trioxide is 0.1% of the total amount of the raw materials.
Further, in the step of preparing the adhesive for the solvent-free composite film by using the polyurethane adhesive prepolymer and the compound polyester polyol as raw materials under the conditions that the curing temperature is 60-80 ℃ and the curing time is 2-3 d, the material ratio of the polyurethane adhesive prepolymer to the compound polyester polyol is (1.2-1.6): 1.
further, the hydroxyl value of the compound polyester polyol prepared by the polycondensation reaction is 56-60.
Detailed Description
The present invention will now be described more fully hereinafter with reference to various embodiments for the purpose of facilitating an understanding of the invention, but the invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Example 1:
a method for producing an adhesive for a solvent-free composite film, comprising:
step 1, reacting diphenylmethane diisocyanate and polypropylene glycol 3000 serving as raw materials for 3 hours at 85 ℃ by using triethanolamine as a catalyst to prepare a polyurethane adhesive prepolymer, wherein the material ratio of the diphenylmethane diisocyanate to the polypropylene glycol 3000 is 4: 1, the adding amount of triethanolamine is 0.1 percent of the total amount of the raw materials in the step 1;
step 2, carrying out esterification reaction for 7 hours at the temperature of 220 ℃ by using adipic acid, phthalic anhydride, 1, 6-hexanediol and neopentyl glycol as raw materials and methane sulfonic acid as a catalyst to prepare an esterification product; then, carrying out polycondensation reaction at the polycondensation reaction temperature of 260 ℃ for 8h, using antimony trioxide as a catalyst, wherein the maximum vacuum degree is 0.1MPa, the alkyd raw material ratio is 1.2, the addition amount of the antimony trioxide is 0.1% of the total amount of the raw materials in the step 2, preparing the compound polyester polyol with the acid value lower than 1mgKOH/g, and the hydroxyl value of the prepared compound polyester polyol is 60;
step 3, taking the polyurethane adhesive prepolymer and the compound polyester polyol as raw materials, wherein the material ratio of the polyurethane adhesive prepolymer to the compound polyester polyol is 1.4: 1, preparing the adhesive for the solvent-free composite membrane under the conditions that the curing temperature is 80 ℃ and the curing time is 3 d.
Peel Strength test
The peel strength of the adhesive prepared in this example to a BOPET (biaxially oriented polypropylene film)/PE (polyethylene film) composite material was tested using the national standard GB/T2791-1995. The test results are: the peel strength of the adhesive prepared in this example to a BOPET/PE composite film was 2.9N/mm.
Thermogravimetric experiments
The adhesive prepared in the embodiment is weighed to be 20mg, the flow of the inert gas is controlled to be 50 mL/min-55 mL/min in a high-purity inert atmosphere, the heating rate is controlled to be 10 ℃/min, and the thermogravimetric analysis degree range is 0-800 ℃. The test results show that the adhesive prepared in this example begins to lose heat at temperatures greater than 510 ℃.
Example 2:
a method for producing an adhesive for a solvent-free composite film, comprising:
step 1, reacting diphenylmethane diisocyanate and polypropylene glycol 3000 serving as raw materials for 3.5 hours at 83 ℃ by using triethanolamine as a catalyst to prepare a polyurethane adhesive prepolymer, wherein the material ratio of the diphenylmethane diisocyanate to the polypropylene glycol 3000 is 4: 1, the adding amount of triethanolamine is 0.1 percent of the total amount of the raw materials in the step 1;
step 2, taking adipic acid, phthalic anhydride, 1, 6-hexanediol and neopentyl glycol as raw materials, taking methane sulfonic acid as a catalyst, and carrying out esterification reaction for 8 hours at the temperature of 240 ℃ to prepare an esterification product; then, carrying out polycondensation reaction at the polycondensation reaction temperature of 260 ℃ for 7h, using antimony trioxide as a catalyst, wherein the maximum vacuum degree is 0.1MPa, the alkyd raw material ratio is 1.2, the addition amount of the antimony trioxide is 0.1% of the total amount of the raw materials in the step 2, preparing the compound polyester polyol with the acid value lower than 1mgKOH/g, and the hydroxyl value of the prepared compound polyester polyol is 58;
step 3, taking the polyurethane adhesive prepolymer and the compound polyester polyol as raw materials, wherein the material ratio of the polyurethane adhesive prepolymer to the compound polyester polyol is 1.5: 1, preparing the adhesive for the solvent-free composite membrane under the conditions that the curing temperature is 80 ℃ and the curing time is 2.5 d.
Peel Strength test
The peel strength of the adhesive prepared in this example to a BOPET (biaxially oriented polypropylene film)/PE (polyethylene film) composite material was tested using the national standard GB/T2791-1995. The test results are: the peel strength of the adhesive prepared in this example to a BOPET/PE composite film was 2.9N/mm.
Thermogravimetric experiments
The adhesive prepared in the embodiment is weighed to be 20mg, the flow of the inert gas is controlled to be 50 mL/min-55 mL/min in a high-purity inert atmosphere, the heating rate is controlled to be 10 ℃/min, and the thermogravimetric analysis degree range is 0-800 ℃. The test results show that the adhesive prepared in this example begins to lose heat at temperatures greater than 530 ℃.
Example 3
A method for producing an adhesive for a solvent-free composite film, comprising:
step 1, reacting diphenylmethane diisocyanate and polypropylene glycol 3000 serving as raw materials for 2.5 hours at the temperature of 80 ℃ by using triethanolamine as a catalyst to prepare a polyurethane adhesive prepolymer, wherein the material ratio of the diphenylmethane diisocyanate to the polypropylene glycol 3000 is 6: 1, the adding amount of triethanolamine is 0.1 percent of the total amount of the raw materials in the step 1;
step 2, taking adipic acid, phthalic anhydride, 1, 6-hexanediol and neopentyl glycol as raw materials, taking methane sulfonic acid as a catalyst, and carrying out esterification reaction for 8 hours at the temperature of 240 ℃ to prepare an esterification product; then, carrying out polycondensation reaction at the polycondensation reaction temperature of 270 ℃ for 7h, using antimony trioxide as a catalyst, wherein the maximum vacuum degree is 0.1MPa, the alkyd raw material ratio is 1.2, the addition amount of the antimony trioxide is 0.1% of the total amount of the raw materials in the step 2, preparing the compound polyester polyol with the acid value lower than 1mgKOH/g, and the hydroxyl value of the prepared compound polyester polyol is 56;
step 3, taking the polyurethane adhesive prepolymer and the compound polyester polyol as raw materials, wherein the material ratio of the polyurethane adhesive prepolymer to the compound polyester polyol is 1.5: 1, preparing the adhesive for the solvent-free composite membrane under the conditions that the curing temperature is 70 ℃ and the curing time is 2 d.
Peel Strength test
The peel strength of the adhesive prepared in this example to a BOPET (biaxially oriented polypropylene film)/PE (polyethylene film) composite material was tested using the national standard GB/T2791-1995. The test results are: the peel strength of the adhesive prepared in this example to a BOPET/PE composite film was 2.8N/mm.
Thermogravimetric experiments
The adhesive prepared in the embodiment is weighed to be 20mg, the flow of the inert gas is controlled to be 50 mL/min-55 mL/min in a high-purity inert atmosphere, the heating rate is controlled to be 10 ℃/min, and the thermogravimetric analysis degree range is 0-800 ℃. The test results show that the adhesive prepared in this example begins to lose heat at temperatures greater than 500 ℃.
Example 4
A method for producing an adhesive for a solvent-free composite film, comprising:
step 1, reacting diphenylmethane diisocyanate and polypropylene glycol 3000 serving as raw materials for 3 hours at 85 ℃ by using triethanolamine as a catalyst to prepare a polyurethane adhesive prepolymer, wherein the material ratio of the diphenylmethane diisocyanate to the polypropylene glycol 3000 is 5: 1, the adding amount of triethanolamine is 0.1 percent of the total amount of the raw materials in the step 1;
step 2, taking adipic acid, phthalic anhydride, 1, 6-hexanediol and neopentyl glycol as raw materials, taking methane sulfonic acid as a catalyst, and carrying out esterification reaction for 6 hours at the temperature of 220 ℃ to prepare an esterification product; then, carrying out polycondensation reaction at the temperature of 250 ℃ for 6h, using antimony trioxide as a catalyst, wherein the maximum vacuum degree is 0.1MPa, the alkyd raw material ratio is 1.2, the addition amount of the antimony trioxide is 0.1% of the total amount of the raw materials in the step 2, preparing the compound polyester polyol with the acid value lower than 1mgKOH/g, and the hydroxyl value of the prepared compound polyester polyol is 60;
step 3, taking the polyurethane adhesive prepolymer and the compound polyester polyol as raw materials, wherein the material ratio of the polyurethane adhesive prepolymer to the compound polyester polyol is 1.2: 1, preparing the adhesive for the solvent-free composite membrane under the conditions that the curing temperature is 70 ℃ and the curing time is 2 d.
Peel Strength test
The peel strength of the adhesive prepared in this example to a BOPET (biaxially oriented polypropylene film)/PE (polyethylene film) composite material was tested using the national standard GB/T2791-1995. The test results are: the peel strength of the adhesive prepared in the embodiment to the BOPET/PE composite film is 3.0N/mm.
Thermogravimetric experiments
The adhesive prepared in the embodiment is weighed to be 20mg, the flow of the inert gas is controlled to be 50 mL/min-55 mL/min in a high-purity inert atmosphere, the heating rate is controlled to be 10 ℃/min, and the thermogravimetric analysis degree range is 0-800 ℃. The test results show that the adhesive prepared in this example begins to lose heat at temperatures greater than 510 ℃.
Example 5
A method for producing an adhesive for a solvent-free composite film, comprising:
step 1, reacting diphenylmethane diisocyanate and polypropylene glycol 3000 serving as raw materials for 2.5 hours at 85 ℃ by using triethanolamine as a catalyst to prepare a polyurethane adhesive prepolymer, wherein the material ratio of the diphenylmethane diisocyanate to the polypropylene glycol 3000 is 5: 1, the adding amount of triethanolamine is 0.1 percent of the total amount of the raw materials in the step 1;
step 2, carrying out esterification reaction for 7 hours at the temperature of 230 ℃ by using adipic acid, phthalic anhydride, 1, 6-hexanediol and neopentyl glycol as raw materials and methane sulfonic acid as a catalyst to prepare an esterification product; then, carrying out polycondensation reaction at the temperature of 250 ℃ for 8h, using antimony trioxide as a catalyst, wherein the maximum vacuum degree is 0.1MPa, the alkyd raw material ratio is 1.2, the addition amount of the antimony trioxide is 0.1% of the total amount of the raw materials in the step 2, preparing the compound polyester polyol with the acid value lower than 1mgKOH/g, and the hydroxyl value of the prepared compound polyester polyol is 58;
step 3, taking the polyurethane adhesive prepolymer and the compound polyester polyol as raw materials, wherein the material ratio of the polyurethane adhesive prepolymer to the compound polyester polyol is 1.6: 1, preparing the adhesive for the solvent-free composite membrane under the conditions that the curing temperature is 60 ℃ and the curing time is 2.5 d.
Peel Strength test
The peel strength of the adhesive prepared in this example to a BOPET (biaxially oriented polypropylene film)/PE (polyethylene film) composite material was tested using the national standard GB/T2791-1995. The test results are: the peel strength of the adhesive prepared in this example to a BOPET/PE composite film was 2.8N/mm.
Thermogravimetric experiments
The adhesive prepared in the embodiment is weighed to be 20mg, the flow of the inert gas is controlled to be 50 mL/min-55 mL/min in a high-purity inert atmosphere, the heating rate is controlled to be 10 ℃/min, and the thermogravimetric analysis degree range is 0-800 ℃. The test results show that the adhesive prepared in this example begins to lose heat at temperatures greater than 510 ℃.
Table 1 compares the performance of the adhesive in each of the above examples with that of the prior art, and the peel strength test is the same as the experimental conditions of the thermogravimetric experiment.
TABLE 1 comparison of results table
As can be seen from Table 1, the adhesive prepared by the embodiments of the present invention has significantly better peel strength and heat resistance than the prior art.
In conclusion, according to the production method of the adhesive for the solvent-free composite film, provided by the invention, the symmetrical and regular molecular structure in the diphenylmethane diisocyanate and the special structure of the polypropylene glycol 3000 containing the side group are utilized, so that the prepared polyurethane adhesive prepolymer has excellent mechanical property, flexibility and hydrolysis resistance, then the isocyanate group in the polyurethane adhesive prepolymer is utilized to react with the hydroxyl group in the self-made complex polyester polyol, two oligomer molecules are further converted into a polymer with higher molecular weight through interaction between groups, the flow form is converted into a solid state, the actual measurement shows that the peeling strength of the adhesive reaches not less than 2.8N/mm, the peeling strength is high, the adhesive starts to generate heat loss when reaching 500 ℃ during thermogravimetric analysis, and the high temperature resistance is strong.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. A method for producing an adhesive for a solvent-free composite film, comprising:
reacting diphenylmethane diisocyanate and polypropylene glycol 3000 serving as raw materials for 2.5-3.5 hours at the temperature of 80-85 ℃ by taking triethanolamine as a catalyst to prepare a polyurethane adhesive prepolymer;
taking adipic acid, phthalic anhydride, 1, 6-hexanediol and neopentyl glycol as raw materials, taking methane sulfonic acid as a catalyst, and carrying out esterification reaction for 6-8 h at the temperature of 220-240 ℃ to prepare an esterification product; then carrying out polycondensation reaction to prepare compound polyester polyol with the acid value lower than 1 mgKOH/g;
the adhesive for the solvent-free composite film is prepared by taking a polyurethane adhesive prepolymer and a compound polyester polyol as raw materials under the conditions that the curing temperature is 60-80 ℃ and the curing time is 2-3 d.
2. The production method of the adhesive for the solvent-free composite film according to claim 1, wherein in the step of preparing the polyurethane adhesive prepolymer, the material ratio of the diphenylmethane diisocyanate to the polypropylene glycol 3000 is (4-6): 1.
3. the method for producing the adhesive for the solvent-free composite film according to claim 2, wherein in the step of preparing the polyurethane adhesive prepolymer, the triethanolamine is added in an amount of 0.1% of the total amount of the raw materials, wherein the raw materials are diphenylmethane diisocyanate and polypropylene glycol 3000, and the triethanolamine is used as a catalyst, and the reaction is carried out at a temperature of 75 ℃ for 2 hours.
4. The method for producing an adhesive for a solvent-free composite film according to claim 1, wherein the conditions of the polycondensation reaction are:
the polycondensation reaction temperature is 250-270 ℃, the polycondensation reaction time is 6-8 h, antimony trioxide is used as a catalyst, the maximum vacuum degree is 0.1MPa, and the ratio of alkyd raw materials is 1.2.
5. The method for producing an adhesive for a solvent-free composite film according to claim 4, wherein the antimony trioxide is added in an amount of 0.1% of the total amount of the raw materials.
6. The method for producing the adhesive for the solvent-free composite film according to claim 1, wherein in the step of preparing the adhesive for the solvent-free composite film by using the polyurethane adhesive prepolymer and the complex polyester polyol as raw materials under the conditions that the curing temperature is 60-80 ℃ and the curing time is 2-3 d, the material ratio of the polyurethane adhesive prepolymer to the complex polyester polyol is (1.2-1.6): 1.
7. the production method of the adhesive for the solvent-free composite film according to claim 1, wherein the hydroxyl value of the compound polyester polyol prepared by the polycondensation is 56-60.
8. An adhesive for a solvent-free composite film, which is produced by the method for producing an adhesive for a solvent-free composite film according to any one of claims 1 to 7.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597470A (en) * | 2008-06-03 | 2009-12-09 | 北京高盟燕山科技有限公司 | A kind of solvent free bi-component polyurethane adhesive and preparation method thereof |
| CN108559440A (en) * | 2018-04-27 | 2018-09-21 | 上海回天新材料有限公司 | A kind of no-solvent type polyurethane laminating adhesive and its preparation method and application of high speed compound, rapid aging |
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2020
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