CN116239985A - Adhesive for B-grade insulating paper composite material and preparation method thereof - Google Patents

Adhesive for B-grade insulating paper composite material and preparation method thereof Download PDF

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Publication number
CN116239985A
CN116239985A CN202310314558.6A CN202310314558A CN116239985A CN 116239985 A CN116239985 A CN 116239985A CN 202310314558 A CN202310314558 A CN 202310314558A CN 116239985 A CN116239985 A CN 116239985A
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parts
curing agent
adhesive
main agent
methyl acetate
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王含含
杜海
隋学斌
赫长生
曹学
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Nantong Comens New Materials Co ltd
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Nantong Comens New Materials Co ltd
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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
    • C09J175/06—Polyurethanes from polyesters
    • 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
    • C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
    • 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
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
    • C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether groups
    • 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
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08G18/58—Epoxy resins
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention discloses an adhesive for a B-class insulating paper composite material and a preparation method thereof, wherein the adhesive comprises a main agent and a curing agent, and the weight ratio of the main agent to the curing agent is 10:1, a step of; the main agent is methyl acetate solution containing high molecular polyester polyol and bisphenol A epoxy resin, the rotational viscosity of the main agent is 100-500 mPa.s at 25 ℃ and the solid content is 28-32%; the curing agent is methyl acetate solution containing polycaprolactone isocyanate prepolymer, the rotational viscosity of the curing agent is 500-1000 mPa.s at 25 ℃, the solid content is 48-52%, and the-NCO content is 6-8%. The invention has excellent bonding performance, can meet the composite requirement of the B-class insulating paper composite material, ensures that the B-class insulating composite material has excellent mechanical property, high temperature resistance and hydrolysis resistance, has excellent initial bonding force and final bonding strength between non-woven fabrics/PET sheets/non-woven fabrics films, and has excellent flexibility.

Description

Adhesive for B-grade insulating paper composite material and preparation method thereof
Technical Field
The invention relates to the field of chemical adhesives, in particular to an adhesive for a B-class insulating paper composite material and a preparation method thereof.
Background
The rapid rise in socioeconomic levels has prompted the rapid development of various motors, transformers and other electronic equipment, and has placed higher demands on their carrying capacity. Electronic devices are subject to static charge by rubbing during storage, transportation and use. If static charges which cannot be transferred or released in time accumulate, and flammable substances contained in the air are added, the electronic equipment can explode and even fire disaster occurs in the using process, so that the insulating material is a vital component part in the electronic equipment.
In general, the insulating material in an electric machine is mainly insulating paper, insulating film, and a multi-layer flexible composite of two products. The non-woven fabric is made of polyester fibers and polyester fibers through a needling process, has the characteristics of moisture resistance, flexibility, flame retardance, low price, recycling and the like, and is widely popularized in the heat insulation and electric heating sheet industry. The heat resistant grade of the insulation is classified into grade A (limit allowable working temperature is 105 ℃, such as phenolic Paper board), grade E (limit allowable working temperature is 120 ℃, such as heat modified cellulose insulation Paper TUK Paper developed by American West House electric company first)
Figure BDA0004149826990000011
) Class B (limit allowable working temperature 130 ℃, such as novel high temperature resistant insulating paper developed by DuPont company of America using mixed papermaking process)>
Figure BDA0004149826990000012
T910), etc.
The B-class insulating paper composite material with high temperature resistance and humidity and heat aging resistance has higher performance requirements on the composite adhesive, and the existing polyurethane adhesive can hardly meet the requirements. The high-end polyurethane product has excellent performance, but the raw materials are expensive, the finished glue has high selling price, and the glue is not easy to popularize and sell in the market.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide an adhesive for a B-stage insulating paper composite material and a preparation method thereof, so as to improve the bonding performance, high temperature resistance, oil resistance and wet heat resistance of the B-stage insulating paper composite material, meet the composite requirement of the B-stage insulating paper composite material, have excellent initial bonding force and final bonding strength between non-woven fabrics/PET (polyethylene terephthalate) sheets/non-woven fabrics films, and well solve the defects and shortcomings of the prior art.
The invention aims at realizing the following technical scheme:
an adhesive for a B-stage insulation paper composite, comprising: the curing agent comprises a main agent and a curing agent, wherein the weight ratio of the main agent to the curing agent is 10:1, a step of;
the main agent is methyl acetate solution containing high molecular weight polyester polyol and bisphenol A epoxy resin, the rotational viscosity of the main agent is 100-500 mPa.s at 25 ℃, and the solid content is 28-32%;
the curing agent is methyl acetate solution of polycaprolactone isocyanate prepolymer, the rotational viscosity of the curing agent at 25 ℃ is 500-1000 mPa.s, the solid content is 48-52%, and the-NCO content is 6-8%.
The preparation method of the adhesive for preparing the B-stage insulating paper composite material comprises the following steps: preparing a main agent and a curing agent respectively;
the preparation method of the main agent comprises the following steps: adding high molecular weight polyester polyol, bisphenol A epoxy resin and methyl acetate into a reaction kettle, heating to 70-85 ℃, stirring for 2-4 hours, uniformly mixing, cooling to 25 ℃, and preparing a methyl acetate solution with the solid content of 28-32% and the rotational viscosity of 100-500 mPas at 25 ℃ as a main agent;
the preparation of the curing agent comprises the following steps: adding polycaprolactone dihydric alcohol, methyl acetate and carbodiimide modified MDI into another reaction kettle, heating to 70-85 ℃, cooling to 60 ℃ after reacting for 2-4 hours, adding polycaprolactone triol, heating to 80-90 ℃, reacting for 2-4 hours, after detecting that the hydroxyl value is 0mgKOH/g, cooling to room temperature, and preparing a methyl acetate solution with the solid content of 48-52%, the NCO content of 6-8% and the rotational viscosity of 500-1000 mPas at 25 ℃ as a curing agent;
mixing the main agent and the curing agent according to the following weight ratio of 10: and mixing the materials according to the weight ratio of 1 to obtain the adhesive for the B-class insulating paper composite material.
Compared with the prior art, the adhesive for the B-stage insulating paper composite material and the preparation method thereof provided by the invention have the beneficial effects that:
the main agent adopts high molecular weight polyester polyol with a main component of a specific structural design, and has excellent initial adhesion and final adhesion strength between non-woven fabrics/PET sheets/non-woven fabrics after the high molecular weight polyester polyol reacts with a curing agent; the adhesive force of the adhesive to the PET sheet is enhanced by adding bisphenol A epoxy resin, and the heat resistance of the adhesive layer at high temperature is improved; the curing agent adopts the polycaprolactone resin modified isocyanate prepolymer with excellent high temperature resistance and corrosion resistance, and has excellent bonding strength to non-woven fabrics after being crosslinked and cured with the main agent, and also has excellent high temperature resistance, oil resistance, acid and alkali corrosion resistance and other performances; the composite adhesive formed by the main agent and the curing agent can be used for composite adhesion between B-class insulating paper composite materials, and can meet the requirements of the composite insulating materials on performances such as adhesion strength, high-humidity temperature resistance, chemical resistance and the like; the use of lower cost methyl acetate instead of ethyl acetate in both the main and curing agents minimizes binder costs and, in addition, the alcohol component starting material for the high molecular weight polyester polyol is derived from the distilled alcohol component of the recycled polyester polycondensation process. The distilled alcohol component is reused after being collected and purified, thus reducing the cost of the glue product.
Detailed Description
The technical scheme in the embodiment of the invention is clearly and completely described below in combination with the specific content of the invention; it will be apparent that the described embodiments are only some embodiments of the invention, but not all embodiments, which do not constitute limitations of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The terms that may be used herein will first be described as follows:
the term "and/or" is intended to mean that either or both may be implemented, e.g., X and/or Y are intended to include both the cases of "X" or "Y" and the cases of "X and Y".
The terms "comprises," "comprising," "includes," "including," "has," "having" or other similar referents are to be construed to cover a non-exclusive inclusion. For example: including a particular feature (e.g., a starting material, component, ingredient, carrier, formulation, material, dimension, part, means, mechanism, apparatus, step, procedure, method, reaction condition, processing condition, parameter, algorithm, signal, data, product or article of manufacture, etc.), should be construed as including not only a particular feature but also other features known in the art that are not explicitly recited.
The term "consisting of … …" is meant to exclude any technical feature element not explicitly listed. If such term is used in a claim, the term will cause the claim to be closed, such that it does not include technical features other than those specifically listed, except for conventional impurities associated therewith. If the term is intended to appear in only a clause of a claim, it is intended to limit only the elements explicitly recited in that clause, and the elements recited in other clauses are not excluded from the overall claim.
The term "parts by mass" means a mass ratio relationship between a plurality of components, for example: if the X component is described as X parts by mass and the Y component is described as Y parts by mass, the mass ratio of the X component to the Y component is expressed as x:y;1 part by mass may represent any mass, for example: 1 part by mass may be expressed as 1kg or 3.1415926 kg. The sum of the mass parts of all the components is not necessarily 100 parts, and may be more than 100 parts, less than 100 parts, or 100 parts or equal. The parts, proportions and percentages described herein are by mass unless otherwise indicated.
When concentrations, temperatures, pressures, dimensions, or other parameters are expressed as a range of values, the range is to be understood as specifically disclosing all ranges formed from any pair of upper and lower values within the range of values, regardless of whether ranges are explicitly recited; for example, if a numerical range of "2 to 8" is recited, that numerical range should be interpreted to include the ranges of "2 to 7", "2 to 6", "5 to 7", "3 to 4 and 6 to 7", "3 to 5 and 7", "2 and 5 to 7", and the like. Unless otherwise indicated, numerical ranges recited herein include both their endpoints and all integers and fractions within the numerical range.
The adhesive for the B-stage insulation paper composite material and the preparation method thereof provided by the invention are described in detail below. What is not described in detail in the embodiments of the present invention belongs to the prior art known to those skilled in the art. The specific conditions are not noted in the examples of the present invention and are carried out according to the conditions conventional in the art or suggested by the manufacturer. The reagents or apparatus used in the examples of the present invention were conventional products commercially available without the manufacturer's knowledge.
The embodiment of the invention provides an adhesive for a B-class insulating paper composite material, which comprises the following components: the weight ratio of the main agent to the curing agent is 10:1, a step of;
wherein the main agent is methyl acetate solution containing high molecular weight polyester polyol and bisphenol A epoxy resin, the main agent has a rotational viscosity of 100-500 mPa.s at 25 ℃ and a solid content of 28-32%;
the curing agent is methyl acetate solution containing polycaprolactone isocyanate prepolymer, the rotational viscosity of the curing agent is 500-1000 mPa.s at 25 ℃, the solid content is 48-52%, and the-NCO content is 6-8%.
Specifically, the adhesive for a B-stage insulation paper composite includes the following embodiments:
(1) The main agent comprises the following raw materials in parts by weight: 30-35 parts of high molecular weight polyester polyol, 8-12 parts of bisphenol A type epoxy resin and 58-62 parts of methyl acetate.
(2) The curing agent comprises the following raw materials in parts by weight: 31-35 parts of carbodiimide modified MDI (methylene diphenyl diisocyanate), 3-10 parts of polycaprolactone diol, 3-12 parts of polycaprolactone triol and 48-52 parts of methyl acetate.
(3) In the main agent, the relative molecular weight of the high molecular weight polyester polyol is 20000-35000 g/mol, the acid value is less than 1mgKOH/g, the hydroxyl value is 3-6 mgKOH/g, and the glass transition temperature is-10-5 ℃. The high molecular weight polyester polyol is prepared by taking adipic acid, isophthalic acid, phthalic anhydride, ethylene glycol, glycerol and diethylene glycol as raw materials, and carrying out esterification and polycondensation reaction on the raw materials and a catalyst; wherein the catalyst is selected from one or two of stannous octoate, antimonous oxide, dibutyl tin dilaurate, antimony acetate or tetra-n-butyl titanate. The high molecular weight polyester polyol comprises the following raw materials in parts by weight: 6 to 12 parts of isophthalic acid, 5 to 10 parts of phthalic anhydride, 26 to 31 parts of adipic acid, 18 to 30 parts of ethylene glycol, 5 to 8 parts of glycerol, 15 to 25 parts of diethylene glycol and 0.001 to 0.002 part of catalyst.
(4) Among the main agents, bisphenol a type epoxy resins having an epoxy value of 0.2 to 0.52 are preferably used, and any one of bisphenol a type epoxy resins E51, E44, E32, E20 and the like is preferably used.
(5) Among the curing agents, the polycaprolactone diol preferably adopts any one of the Capa series polycaprolactone diol products Capa 2043, capa 2201 and Capa 2701 of Pasteur.
(6) Among the curing agents, the polycaprolactone triol preferably adopts any one of the Capa series polycaprolactone triol products Capa 3035, capa 3050 and Capa 3201 of Pasteur.
The embodiment of the invention also provides a preparation method of the adhesive for the B-stage insulating paper composite material, which is used for preparing the adhesive for the B-stage insulating paper composite material and comprises the following steps: preparing a main agent and a curing agent respectively; wherein, the liquid crystal display device comprises a liquid crystal display device,
the preparation method of the main agent comprises the following steps: weighing the following raw materials in parts by weight: 30-35 parts of high molecular weight polyester polyol, 8-12 parts of bisphenol A type epoxy resin and 58-62 parts of methyl acetate; adding high molecular weight polyester polyol, bisphenol A epoxy resin and methyl acetate into a reaction kettle, heating to 70-85 ℃, stirring for 2-4 hours, uniformly mixing, cooling to 25 ℃, and preparing a methyl acetate solution with the solid content of 28-32% and the rotational viscosity of 100-500 mPas at 25 ℃ into the main agent.
The preparation of the curing agent comprises the following steps: weighing the following raw materials in parts by weight: 31-35 parts of carbodiimide modified MDI (methylene diphenyl diisocyanate), 3-10 parts of polycaprolactone diol, 3-12 parts of polycaprolactone triol and 48-52 parts of methyl acetate; adding polycaprolactone dihydric alcohol, methyl acetate and carbodiimide modified MDI into another reaction kettle, heating to 70-85 ℃, cooling to 60 ℃ after reacting for 2-4 hours, adding polycaprolactone triol, heating to 80-90 ℃, reacting for 2-4 hours, after detecting that the hydroxyl value is 0mgKOH/g, cooling to room temperature, and preparing a methyl acetate solution with the solid content of 48-52%, the NCO content of 6-8 and the rotational viscosity of 500-1000 mPas at 25 ℃ as a curing agent.
The main agent and the curing agent prepared by the method are mixed according to the following weight ratio of 10: and mixing the materials according to the weight ratio of 1 to obtain the adhesive for the B-class insulating paper composite material.
Specifically, the preparation method of the adhesive for the B-class insulating paper composite material comprises the following embodiments:
(1) Among the main agents, bisphenol a type epoxy resins having an epoxy value of 0.2 to 0.52 are preferably used, and any one of bisphenol a type epoxy resins E51, E44, E32, E20 and the like is preferably used.
(2) Among the curing agents, the polycaprolactone diol preferably adopts any one of the Capa series polycaprolactone diol products Capa 2043, capa 2201 and Capa 2701 of Pasteur.
(3) Among the curing agents, the polycaprolactone triol preferably adopts any one of the Capa series polycaprolactone triol products Capa 3035, capa 3050 and Capa 3201 of Pasteur.
(4) In the main agent, the preparation method of the high molecular weight polyester polyol comprises the following steps:
weighing the following raw materials in parts by weight: 6-12 parts of isophthalic acid, 5-10 parts of phthalic anhydride, 26-31 parts of adipic acid, 18-30 parts of ethylene glycol, 5-8 parts of glycerol, 15-25 parts of diethylene glycol and 0.001-0.002 part of catalyst;
esterification reaction: adding adipic acid, isophthalic acid, phthalic anhydride, ethylene glycol, glycerol, diethylene glycol and a catalyst into a polyester synthesis kettle, heating to 120 ℃, preserving heat for 1 hour, gradually heating the kettle to 210-230 ℃ at a heating rate of 10 ℃/30min after solid raw materials are completely dissolved, controlling a water outlet speed, and reacting for 6-10 hours at a fractionation column temperature of not higher than 110 ℃ to complete esterification reaction; the water yield is 10-22% of the total weight of the raw materials, and the acid value of the esterified product is less than or equal to 15mgKOH/g;
polycondensation reaction: after the esterification reaction is finished, vacuumizing the polyester synthesis kettle, pre-vacuumizing for 40 minutes according to the sequence of-0.02 MPa, -0.04MPa, -0.06MPa and-0.08 MPa, controlling the kettle temperature of the polyester synthesis kettle to 245-255 ℃, then performing long vacuumizing operation, wherein the vacuum degree reaches-0.1 MPa, the long vacuumizing time is 6-8 hours, the distilled alcohol of the polyester synthesis kettle after the long vacuumizing accounts for 5-12% of the total weight of the raw materials, the material is discharged to obtain the final product with the hydroxyl value of 3-6 mgKOH/g, the acid value is less than or equal to 1mgKOH/g, the glass transition temperature is-10-5 ℃, and the relative molecular weight is 20000-35000 g/mol, and the final product is the high molecular weight polyester polyol.
The adhesive for the B-stage insulating paper composite material can be used for compounding the B-stage insulating composite material, and a non-woven fabric/PET sheet/non-woven fabric insulating paper structure prepared from the product after compounding and curing is excellent in peel strength and high temperature resistance, so that the B-stage insulating composite material has excellent mechanical properties and high temperature resistance, and meets the use requirements of the B-stage insulating composite material.
In conclusion, compared with the prior art, the adhesive provided by the embodiment of the invention has the advantages that the bisphenol A type epoxy resin with high proportion is added into the main agent, so that the heat resistance and the oil resistance of the adhesive layer under the damp and hot condition are improved; hydroxyl in the high molecular weight polyester polyol and-NCO in the curing agent are subjected to crosslinking reaction to improve the crosslinking density of the adhesive layer, so that the adhesive strength and heat resistance of the adhesive layer are improved. The curing agent adopts the polycaprolactone resin modified isocyanate prepolymer with excellent high temperature resistance and corrosion resistance, and has excellent bonding strength to non-woven fabrics after being crosslinked and cured with the main agent, and also has excellent high temperature resistance, oil resistance, acid and alkali corrosion resistance and other performances. The composite adhesive formed by the main agent and the curing agent can be used for composite adhesion between B-class insulating paper composite materials, and can meet the requirements of the composite insulating materials on performances such as adhesion strength, high-humidity temperature resistance, chemical resistance and the like.
In order to more clearly show the technical scheme and the technical effects provided by the invention, the adhesive for the B-stage insulation paper composite material and the preparation method thereof provided by the embodiment of the invention are described in detail in the following by using specific embodiments.
Example 1
The embodiment of the invention provides an adhesive for a B-stage insulating paper composite material, and the preparation method comprises the following steps:
(11) Preparation of high molecular weight polyester polyols
Esterification reaction: 29 parts by weight of adipic acid, 8 parts by weight of isophthalic acid, 6 parts by weight of phthalic anhydride, 30 parts by weight of ethylene glycol, 5 parts by weight of glycerol, 22 parts by weight of diethylene glycol and 0.002 parts by weight of antimony trioxide are added into a polyester synthesis kettle, the temperature is raised to 120 ℃ and kept for 1 hour, after the solid raw materials are completely dissolved, the kettle temperature is gradually raised to 210-230 ℃ at a heating rate of 10 ℃/30min, the water outlet speed is controlled, the temperature of a fractionating column is not higher than 110 ℃, and the esterification reaction is completed for 7 hours; 10 parts by weight of total water yield, and the acid value of the esterified product is 11mgKOH/g;
polycondensation reaction: after the esterification reaction is finished, vacuumizing the polyester synthesis kettle, pre-vacuumizing for 40 minutes according to the sequence of-0.02 MPa, -0.04MPa, -0.06MPa and-0.08 MPa, controlling the kettle temperature of the polyester synthesis kettle to 245-255 ℃, then performing long vacuumizing operation, wherein the vacuum degree reaches-0.1 MPa, the long vacuumizing time is 6 hours, and discharging the distilled alcohol of the polyester synthesis kettle after the long vacuumizing is 5 parts by weight, so that the hydroxyl value is 5mgKOH/g, the acid value is 0.01mgKOH/g, the glass transition temperature is-8 ℃, and the final product with the relative molecular mass of 22440g/mol is the high molecular weight polyester polyol.
(12) Preparation of the Main agent
31 parts by weight of the prepared high molecular weight polyester polyol, 20 parts by weight of bisphenol A epoxy resin E and 57 parts by weight of methyl acetate are added into a reaction kettle, the temperature is raised to 70-85 ℃ and the mixture is stirred for 4 hours, the temperature is reduced to 25 ℃ after the uniform mixing, and the methyl acetate solution with 31% of solid content and 400 mPas of rotational viscosity at 25 ℃ is prepared as the main agent.
(13) Preparation of curing agent
Adding 2043 parts by weight of polycaprolactone dihydric alcohol Capa (TM) 2043, 51 parts by weight of methyl acetate and 32 parts by weight of carbodiimide modified MDI into another reaction kettle, heating to 70-85 ℃, cooling to 60 ℃ after reacting for 4 hours, adding 3035 11 parts by weight of polycaprolactone trihydric alcohol Capa (TM) to 70-85 ℃, reacting for 3 hours, detecting that the hydroxyl value is 0mgKOH/g, cooling to room temperature, and preparing a methyl acetate solution with the solid content of 48%, the NCO content of 7% and the rotational viscosity of 900 mPa.s at 25 ℃ into a curing agent.
(14) Mixing the main agent and the curing agent in proportion
The main agent and the curing agent are mixed according to the following ratio of 10: and (3) uniformly mixing the materials according to the weight ratio to obtain the adhesive for the B-class insulating paper composite material.
Specifically, the adhesive for the B-class insulating paper composite material in the embodiment 1 is used for compounding non-woven fabrics/PET (sheet material)/non-woven fabrics insulating paper, and after curing for 72 hours at 60 ℃, the non-woven fabrics of the composite material layer are torn or can not be peeled; and (3) placing the composite film in a 180 ℃ oven for baking for 5min to detect the high temperature resistance of the composite film, wherein no bubbling layering phenomenon exists. The mechanical property and the high temperature resistance of the composite film meet the use requirement of the B-class insulating paper composite material.
Example 2
The embodiment of the invention provides an adhesive for a B-stage insulating paper composite material, and the preparation method comprises the following steps:
(21) Preparation of high molecular weight polyester polyols
Esterification reaction: adding 26 parts by weight of adipic acid, 9 parts by weight of isophthalic acid, 7 parts by weight of phthalic anhydride, 28 parts by weight of ethylene glycol, 6 parts by weight of glycerin, 24 parts by weight of diethylene glycol and 0.002 parts by weight of dibutyltin dilaurate into a polyester synthesis kettle, heating to 120 ℃ and preserving heat for 1 hour, gradually heating the kettle to 210-230 ℃ at a heating rate of 10 ℃/30min after solid raw materials are completely dissolved, controlling the water outlet speed, and reacting for 6 hours at a fractionating column temperature of not higher than 110 ℃ to complete esterification reaction; 11 parts by weight of total water yield, and the acid value of the esterified product is 13mgKOH/g;
polycondensation reaction: after the esterification reaction is finished, vacuumizing the polyester synthesis kettle, pre-vacuumizing for 40 minutes according to the sequence of-0.02 MPa, -0.04MPa, -0.06MPa and-0.08 MPa, controlling the kettle temperature of the polyester synthesis kettle to 245-255 ℃, then performing long vacuumizing operation, wherein the vacuum degree reaches-0.1 MPa, the long vacuumizing time is 7 hours, and discharging the distilled alcohol of the polyester synthesis kettle after the long vacuumizing is 6 parts by weight, so that the hydroxyl value is 4mgKOH/g, the acid value is 0.03mgKOH/g, the glass transition temperature is-5 ℃, and the final product with the relative molecular mass of 28050g/mol is the high molecular weight polyester polyol.
(22) Preparation of the Main agent
Adding 32 parts by weight of the prepared high molecular weight polyester polyol, 13 parts by weight of bisphenol A epoxy resin E44 and 55 parts by weight of methyl acetate into a reaction kettle, heating to 70-85 ℃, stirring for 4 hours, uniformly mixing, cooling to 25 ℃, and preparing a methyl acetate solution with the solid content of 32% and the rotational viscosity of 500 mPas at 25 ℃ into a main agent.
(23) Preparation of curing agent
Adding 2043 parts by weight of polycaprolactone dihydric alcohol Capa (TM) 2043, 48 parts by weight of methyl acetate and 33 parts by weight of carbodiimide modified MDI into another reaction kettle, heating to 70-85 ℃, cooling to 60 ℃ after reacting for 4 hours, adding 3050 11 parts by weight of polycaprolactone trihydric alcohol Capa (TM) to 70-85 ℃, reacting for 3 hours, detecting that the hydroxyl value is 0mgKOH/g, cooling to room temperature, and preparing a methyl acetate solution with the solid content of 50%, the NCO content of 8% and the rotational viscosity of 950 mPa.s at 25 ℃ into a curing agent.
(24) Mixing the main agent and the curing agent in proportion
The main agent and the curing agent are mixed according to the following ratio of 10: and mixing the materials according to the weight ratio of 1 to obtain the adhesive for the B-class insulating paper composite material.
Specifically, the adhesive for the B-class insulating paper composite material in the embodiment 2 is used for compounding a non-woven fabric/PET (sheet)/non-woven fabric insulating paper structure, and after curing for 72 hours at 60 ℃, the non-woven fabric of the composite material layer is torn or can not be peeled; and (3) placing the composite film in a 180 ℃ oven for baking for 5min to detect the high temperature resistance of the composite film, wherein no bubbling layering phenomenon exists. The mechanical property and the high temperature resistance of the composite film meet the use requirement of the B-class insulating paper composite material.
Example 3
The embodiment of the invention provides an adhesive for a B-stage insulating paper composite material, and the preparation method comprises the following steps:
(31) Preparation of high molecular weight polyester polyols
Esterification reaction: 31 parts by weight of adipic acid, 8 parts by weight of isophthalic acid, 6 parts by weight of phthalic anhydride, 26 parts by weight of ethylene glycol, 8 parts by weight of glycerin, 21 parts by weight of diethylene glycol and 0.002 parts by weight of tetra-n-butyl titanate are added into a polyester synthesis kettle, the temperature is raised to 120 ℃ and kept for 1 hour, after the solid raw materials are completely dissolved, the kettle temperature is gradually raised to 210-230 ℃ at a heating rate of 10 ℃/30min, the water outlet speed is controlled, the temperature of a fractionating column is not higher than 110 ℃, and the esterification reaction is completed after the reaction is completed for 6 hours; 9 parts by weight of total water yield, and the acid value of the esterified product is 10mgKOH/g;
polycondensation reaction: after the esterification reaction is finished, vacuumizing the polyester synthesis kettle, pre-vacuumizing for 40 minutes according to the sequence of-0.02 MPa, -0.04MPa, -0.06MPa and-0.08 MPa, controlling the kettle temperature of the polyester synthesis kettle to 245-255 ℃, then performing long vacuumizing operation, wherein the vacuum degree reaches-0.1 MPa, the long vacuumizing time is 8 hours, the distilled alcohol of the polyester synthesis kettle after the long vacuumizing is 9 parts by weight, discharging to obtain a hydroxyl value of 3.5mgKOH/g, an acid value of 0.02mgKOH/g, a glass transition temperature of 2 ℃, and a final product with a relative molecular mass of 32057g/mol, namely the high molecular weight polyester polyol.
(32) Preparation of the Main agent
Adding 35 parts by weight of the prepared high molecular weight polyester polyol, 12 parts by weight of bisphenol A epoxy resin E51 and 53 parts by weight of methyl acetate into a reaction kettle, heating to 80-90 ℃, stirring for 4 hours, uniformly mixing, cooling to room temperature, and preparing a methyl acetate solution with the solid content of 52% and the rotational viscosity of 1000 mPas at 25 ℃ as a main agent.
(33) Preparation of curing agent
Adding 2201 weight part of polycaprolactone dihydric alcohol Capa (TM), 51 weight part of methyl acetate and 33 weight parts of carbodiimide modified MDI into another reaction kettle, heating to 80-90 ℃, cooling to 60 ℃ after reacting for 4 hours, adding 3201 12 weight parts of polycaprolactone trihydric alcohol Capa (TM), heating to 80-90 ℃, reacting for 3 hours, detecting that the hydroxyl value is 0mgKOH/g, cooling to room temperature, and preparing a methyl acetate solution with the solid content of 62%, the NCO content of 7% and the rotational viscosity of 800 mPa.s at 25 ℃ into a curing agent.
(34) Mixing the main agent and the curing agent in proportion
The main agent and the curing agent are mixed according to the following ratio of 10: and mixing the materials according to the weight ratio of 1 to obtain the adhesive for the B-class insulating paper composite material.
Specifically, the adhesive for the B-class insulating paper composite material in the embodiment 2 is used for compounding a non-woven fabric/PET (sheet)/non-woven fabric insulating paper structure, and after curing for 72 hours at 60 ℃, the non-woven fabric of the composite material layer is torn or can not be peeled; and (3) placing the composite film in a 180 ℃ oven for baking for 5min to detect the high temperature resistance of the composite film, wherein no bubbling layering phenomenon exists. The mechanical property and the high temperature resistance of the composite film meet the use requirement of the B-class insulating paper composite material.
(4) Performance detection
The adhesives for B-stage insulation paper composites prepared in example 1, example 2 and example 3 according to the present invention and commercially available adhesives for B-stage insulation paper composites were subjected to the following parallel comparative property test under the same conditions:
according to the proportion of the main agent and the curing agent in the adhesives prepared in the invention examples 1, 2 and 3, the main agent and the curing agent of each adhesive are mixed uniformly in proportion, methyl acetate is added to dilute the concentration of the working solution to 35wt%, a 5# glue spreading rod is used for gluing two sides of a PET sheet, then the PET sheet is placed in a 60 ℃ oven for drying the solvent, non-woven fabrics are attached to two sides of the PET sheet, and finally a rubber roller with the dead weight of 2kg is used for laminating the composite film, so that the non-woven fabrics/PET (sheet)/non-woven fabrics of the composite film with the insulation structure corresponding to the embodiment are obtained.
(41) Primary adhesion detection: the nonwoven fabric/PET (sheet)/nonwoven fabric corresponding to the above example was left at room temperature for 5 to 10 minutes, and then the T-peel strength was measured.
(42) Peel strength after curing: after the nonwoven fabric/PET (sheet)/nonwoven fabric corresponding to the above example was placed in an oven at 60 ℃ for curing for 72 hours, the interlayer T-peel strength of the nonwoven fabric/PET (sheet)/nonwoven fabric was measured.
(43) High temperature resistance detection: the nonwoven fabric/PET (sheet)/nonwoven fabric corresponding to the above example was baked in an oven at 180℃for 5 to 10 minutes, and whether or not the nonwoven fabric/PET (sheet)/nonwoven fabric had the adverse phenomena of foaming, delamination, etc. was observed.
The above performance tests were carried out using the adhesives for B-stage insulation paper composites of examples 1, 2 and 3 of the present invention, and the results are shown in Table 1 below:
TABLE 1
Figure BDA0004149826990000101
As can be seen from table 1 above: compared with the comparative example, the adhesive provided by the embodiment of the invention has excellent bonding performance and high temperature resistance, can meet the bonding and use requirements of the B-stage insulating paper composite material, and can be used for compounding a B-stage insulating paper composite material non-woven fabric/PET (sheet)/non-woven fabric structure.
In summary, the adhesive disclosed by the embodiment of the invention has excellent bonding performance, can be used for compounding a B-class insulating paper composite material structure, has excellent initial bonding force and final bonding strength between the compounded non-woven fabrics/PET (polyethylene terephthalate) sheets/non-woven fabrics, and has excellent flexibility, so that the composite requirement of the B-class insulating paper composite material can be met, and the B-class insulating composite material has excellent mechanical property, high temperature resistance and hydrolysis resistance.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the scope of the present invention should be included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims. The information disclosed in the background section herein is only for enhancement of understanding of the general background of the invention and is not to be taken as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.

Claims (8)

1. An adhesive for a B-stage insulating paper composite material, comprising: the curing agent comprises a main agent and a curing agent, wherein the weight ratio of the main agent to the curing agent is 10:1, a step of;
the main agent is methyl acetate solution containing high molecular weight polyester polyol and bisphenol A epoxy resin, the rotational viscosity of the main agent is 100-500 mPa.s at 25 ℃, and the solid content is 28-32%;
the curing agent is methyl acetate solution of polycaprolactone isocyanate prepolymer, the rotational viscosity of the curing agent at 25 ℃ is 500-1000 mPa.s, the solid content is 48-52%, and the-NCO content is 6-8%.
2. The adhesive for the B-stage insulation paper composite material according to claim 1, wherein the main agent comprises the following raw materials in parts by weight: 30-35 parts of high molecular weight polyester polyol, 8-12 parts of bisphenol A type epoxy resin and 58-62 parts of methyl acetate;
the curing agent comprises the following raw materials in parts by weight: 31-35 parts of carbodiimide modified MDI (methylene diphenyl diisocyanate), 3-10 parts of polycaprolactone diol, 3-12 parts of polycaprolactone triol and 48-52 parts of methyl acetate.
3. The adhesive for B-stage insulating paper composite according to claim 1 or 2, wherein the relative molecular weight of the high molecular weight polyester polyol in the main agent is 20000 to 35000g/mol, the acid value is less than 2mgKOH/g, the hydroxyl value is 8 to 10mgKOH/g, and the glass transition temperature is-10 to 5 ℃.
4. The adhesive for a B-stage insulation paper composite according to claim 1 or 2, wherein the high molecular weight polyester polyol in the main agent is a high molecular weight polyester polyol prepared by esterifying and polycondensing isophthalic acid, phthalic anhydride, adipic acid, ethylene glycol, glycerin and diethylene glycol as raw materials with a catalyst; wherein the catalyst adopts one or two of stannous octoate, antimonous oxide, dibutyl tin dilaurate, antimony acetate and tetra-n-butyl titanate.
5. The adhesive for a B-stage insulation paper composite according to claim 4, wherein the high molecular weight polyester polyol comprises the following raw materials in parts by weight: 6 to 12 parts of isophthalic acid, 5 to 10 parts of phthalic anhydride, 26 to 31 parts of adipic acid, 18 to 30 parts of ethylene glycol, 5 to 8 parts of glycerol, 15 to 25 parts of diethylene glycol and 0.001 to 0.002 part of catalyst.
6. A method for preparing the adhesive for a B-stage insulation paper composite according to any one of claims 1 to 5, comprising: preparing a main agent and a curing agent respectively;
the preparation method of the main agent comprises the following steps: adding high molecular weight polyester polyol, bisphenol A epoxy resin and methyl acetate into a reaction kettle, heating to 70-85 ℃, stirring for 2-4 hours, uniformly mixing, cooling to 25 ℃, and preparing a methyl acetate solution with the solid content of 28-32% and the rotational viscosity of 100-500 mPas at 25 ℃ as a main agent;
the preparation of the curing agent comprises the following steps: adding polycaprolactone dihydric alcohol, methyl acetate and carbodiimide modified MDI into another reaction kettle, heating to 70-85 ℃, cooling to 60 ℃ after reacting for 2-4 hours, adding polycaprolactone triol, heating to 80-90 ℃, reacting for 2-4 hours, after detecting that the hydroxyl value is 0mgKOH/g, cooling to room temperature, and preparing a methyl acetate solution with the solid content of 48-52%, the NCO content of 6-8% and the rotational viscosity of 500-1000 mPas at 25 ℃ as a curing agent;
mixing the main agent and the curing agent according to the following weight ratio of 10: and mixing the materials according to the weight ratio of 1 to obtain the adhesive for the B-class insulating paper composite material.
7. The method for preparing the adhesive for the B-stage insulating paper composite material according to claim 6, wherein in the preparation of the main agent, the raw materials are used in parts by weight: 30-35 parts of high molecular weight polyester polyol, 8-12 parts of bisphenol A type epoxy resin and 58-62 parts of methyl acetate;
in the preparation of the curing agent, the raw materials are used in parts by weight: 31-35 parts of carbodiimide modified MDI (methylene diphenyl diisocyanate), 3-10 parts of polycaprolactone diol, 3-12 parts of polycaprolactone triol and 48-52 parts of methyl acetate.
8. The method for preparing the adhesive for a B-stage insulation paper composite according to claim 6 or 7, wherein the high molecular weight polyester polyol used in the preparation of the main agent is prepared by the following means:
weighing the following raw materials in parts by weight: 6-12 parts of isophthalic acid, 5-10 parts of phthalic anhydride, 26-31 parts of adipic acid, 18-30 parts of ethylene glycol, 5-8 parts of glycerol, 15-25 parts of diethylene glycol and 0.001-0.002 part of catalyst;
esterification reaction: adding adipic acid, isophthalic acid, phthalic anhydride, ethylene glycol, glycerol, diethylene glycol and a catalyst into a polyester synthesis kettle, heating to 120 ℃, preserving heat for 1 hour, gradually heating the kettle to 210-230 ℃ at a heating rate of 10 ℃/30min after solid raw materials are completely dissolved, controlling a water outlet speed, and reacting for 6-10 hours at a fractionation column temperature of not higher than 110 ℃ to complete esterification reaction; the water yield is 10-22% of the total weight of the raw materials, and the acid value of the esterified product is less than or equal to 15mgKOH/g;
polycondensation reaction: after the esterification reaction is finished, vacuumizing the polyester synthesis kettle, pre-vacuumizing for 40 minutes according to the sequence of-0.02 MPa, -0.04MPa, -0.06MPa and-0.08 MPa, controlling the kettle temperature of the polyester synthesis kettle to 245-255 ℃, then performing long vacuumizing operation, wherein the vacuum degree reaches-0.1 MPa, the long vacuumizing time is 6-8 hours, the distilled alcohol of the polyester synthesis kettle after the long vacuumizing accounts for 5-12% of the total weight of the raw materials, the material is discharged to obtain the final product with the hydroxyl value of 3-6 mgKOH/g, the acid value is less than or equal to 1mgKOH/g, the glass transition temperature is-10-5 ℃, and the relative molecular weight is 20000-35000 g/mol, and the final product is the high molecular weight polyester polyol.
CN202310314558.6A 2023-03-28 2023-03-28 Adhesive for B-grade insulating paper composite material and preparation method thereof Pending CN116239985A (en)

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