CN112831308A - Single-component solvent-free hot melt adhesive and preparation method and use method thereof - Google Patents
Single-component solvent-free hot melt adhesive and preparation method and use method thereof Download PDFInfo
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- CN112831308A CN112831308A CN202110116091.5A CN202110116091A CN112831308A CN 112831308 A CN112831308 A CN 112831308A CN 202110116091 A CN202110116091 A CN 202110116091A CN 112831308 A CN112831308 A CN 112831308A
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
Abstract
The invention discloses a single-component solvent-free hot melt adhesive, a preparation method and a use method thereof, wherein the hot melt adhesive is prepared from the following raw materials in parts by weight: 30-50 parts of isocyanate, 60-90 parts of polyester polyol, 10-30 parts of polyether polyol, 0.1-5 parts of chain extender, 0.1-2 parts of curing agent, 0.1-3 parts of polycarbodiimide, 0.1-2 parts of adhesion promoter, 0.1-0.5 part of catalyst and 0.1-0.3 part of antioxidant. According to the invention, an organic solvent and a double part of A-type substance are not required to be added, the VOC discharge amount can be greatly reduced, the pollution of the hot melt adhesive to the environment is effectively improved, the viscosity of the hot melt adhesive is 5000mpa.s, the NOC% is 8.5% measured according to the weight ratio, and the hot melt adhesive has good boiling resistance, high-temperature boiling resistance, eight-five experiment resistance, salt mist resistance, hydrochloric acid resistance, electrolysis resistance and deep punching resistance.
Description
Technical Field
The invention relates to a single-component solvent-free hot melt adhesive, a preparation method and a use method thereof, and belongs to the technical field of hot melt adhesives.
Background
In industrial production, materials and compounding are often realized by means of adhesives, common compound adhesives are divided into solvent adhesives and solvent-free adhesives, the solvent adhesives and the solvent-free adhesives can be realized in a single-component or double-component mode, and the solvent adhesives and the solvent-free adhesives are used in a heating mode or a non-heating mode according to formula components.
In typical coating fields, for example, metal coating, and metal plate coating, which are processing techniques for bonding a plastic film to a metal plate by hot pressing the plastic film and the metal plate at a high temperature, have been produced in japan in 1977, and are first used for can making, instead of internal coating and external coating, and have been developed into various fields such as building material interiors, home appliance housings, and ship interiors.
At present, the processing of metal plate coating is mainly to coat a bi-component solvent adhesive on the surface of a metal plate, to bake the metal plate at a high temperature through a long-distance drying tunnel, to volatilize the solvent, to adhere a film on the surface of the metal plate at a high temperature by means of the adhesive in a molten state, and to form firm bonding after cooling. When the Laminated sheet is applied to a Laminated sheet in the can manufacturing industry, the Laminated sheet is commonly called Laminated Steel (Laminated Steel), and the Laminated sheet is formed by laminating a PET, PC, PE or PP film and a metal sheet (a galvanized sheet, a cold-rolled sheet, an aluminum sheet, a stainless Steel sheet, an alloy sheet and the like) by adopting the process. In the process, a large amount of organic solvent is volatilized to influence the environment, and the solvent used in the process can leave harmful substances in the final product. These harmful substances have a harmful effect on the human body when they permeate into foods, cosmetics, and the like. Therefore, the inner wall of a metal packaging can, particularly a food can and a cosmetic can, is not coated by adopting the process at present, and the outer wall of the can body is only coated by adopting the process.
However, the inner wall of the metal packaging can must be coated to meet the relevant industrial standards, and for this requirement, the existing treatment method is to coat the inner wall of the can with resin. However, since the paint used in this coating process contains a bisphenol a (Bis-phenol a) substance, which is an internationally recognized environmental hormone, as a harmful substance of the environmental hormone, elution occurs. Once bisphenol A is dissolved out excessively and enters the packaged object, the adverse effect on the human body can be generated.
Also for example, in the solar back sheet manufacturing industry, there is a need to compound various high-tech high-performance thin films, such as PET film, polyvinyl fluoride PVF film, polyvinylidene fluoride PVDF film, polyethylene-tetrafluoroethylene copolymer ETFE film or polyethylene PE film, or 3-layer or 2-layer composite structure of PVDF/PET/PVDF, PVDF/PE high-performance thin film, on the solar back sheet. These films themselves possess good weatherability, excellent mechanical, electrical or chemical properties, hydrolysis resistance: the alloy is subjected to a double 85 test without delamination for 2000-3000 hours at 85 ℃ and 85% RH. Based on the technical requirements of film covering of the solar back panel, the glue used by the composite film is a two-component solvent type adhesive so as to support the performance of the laminated structure after compounding not to be reduced. When the bicomponent solvent adhesive is coated, the solid content is about 25-30 percent, and 70-75 percent is organic solvent.
Also for example, flexible packaging, which typically includes food, pesticide, pharmaceutical packaging, often includes film/film and film/aluminum foil structures, is multi-layer laminated. These composite articles are typically formed by compounding one or more of the following materials, such as aluminum foil, pretreated PE and PP (CPP, OPP), polyester, polyamide (nylon), and/or unplasticized PVC, etc., which require the composite article to be retort resistant, deep-draw resistant. The existing glue for compounding the flexible package is also a two-component solvent type, and the solid content is about 30-40% and 60-70% is an organic solvent in general coating.
For example, the lithium battery, the power battery diaphragm and the soft package lithium battery are compounded by an aluminum plastic film, the back electrolyte of the lithium battery diaphragm is fully impregnated between the anode and the cathode, and the anode and the cathode active substances are separated; and in the electrochemical reaction, a channel through which ions move is formed. At present, the constituent structures of separator materials are various, but high-quality separator materials must have extremely high barrier properties, good deep drawing resistance, puncture resistance, electrolyte corrosion resistance, and insulation properties. Taking the aluminum-plastic film material of the soft package lithium battery as an example, the functional structure is generally 3 layers, including an outer nylon layer, a middle aluminum foil layer, and an inner heat-sealing layer. The outer nylon layer protects the aluminum foil layer from being scratched, and the outer layer material is required to be puncture-resistant and impact-resistant; the aluminum foil layer plays a role in blocking, prevents moisture from invading and blocks oxygen to protect the battery contents; the inner layer is an electrolytic-resistant layer, so that leaked electrolyte is prevented from corroding the aluminum foil layer, and the composite strength between the inner layer and the aluminum foil layer is required to be high. The layers are pressed and bonded through an adhesive, and the key for producing the aluminum plastic film is to uniformly and firmly bond the three layers of functional materials. It is also currently the case in this field that two-part solvent-based adhesives are relied upon for bonding.
Similarly, in the electronic and electric film industry, the water filtration industry, the building material and decoration material industry, the special textile composite industry, and the solvent-based two-component adhesives have wide applications, such as the composite technology of functional films such as water treatment films, gas separation films, special separation films, ion exchange films, and the like, and the two-layer, three-layer or multi-layer composite technology between materials such as high-performance carbon fibers, silicon carbide fibers, ultra-high molecular weight polyethylene fibers, high-performance aramid fibers, high-performance fibers/resins, aluminum foils (AI), non-woven fabrics, high-performance fibers, textiles, and the like, and film materials such as PP, PE, PET, TPU, PVDF, BOPP, CPP, Nylon, aluminized films, and the like. Depending on the actual application, some films are compounded with films, and some films are compounded with other materials. However, without exception, as long as the high requirements on the performances of boiling resistance, high-temperature boiling resistance, hydrochloric acid resistance, chemical resistance and the like exist, a two-component solvent-based adhesive is adopted, and some manufacturers in the industry adopt the two-component solvent-free adhesive for compounding, but the performance is inevitably reduced.
In the prior art, a solvent is used as a carrier in a two-component solvent-based adhesive, and common solvents comprise ethyl acetate, butanone, acetone, xylene, toluene, dichloromethane and the like. The molecular weight of the adhesive can be reacted to be large enough in the synthesis process, and the viscosity is kept at a proper level under the regulation of the solvent; in addition, the solubility of the solvent is utilized to more conveniently and easily add effective hydrolysis resistance agent and other functional materials, and the performance requirements such as boiling resistance, high-temperature boiling resistance, double-eight-five experiment resistance, salt mist resistance, hydrochloric acid resistance, electrolyte resistance, deep drawing resistance and the like can be more easily met. Therefore, the traditional bi-component solvent adhesive becomes a representative of thin material composite high-performance adhesive, and is suitable for a plurality of film material composite processing occasions with higher requirements on the performance.
However, two-part solvent-based adhesives also suffer from a number of drawbacks. In the process of producing the bi-component solvent-based adhesive, because a large amount of organic solvent is used, the VOC emission is large, and a large amount of environmental protection facilities and environmental protection disposal cost are required to be invested for preventing environmental pollution. In addition, when the bi-component solvent-based adhesive is subjected to composite production, the organic solvent is dried by means of high-temperature baking in a long-distance baking channel, and the general defects of complex process, high energy consumption, large equipment occupation area, high comprehensive cost and the like exist. In addition, in the use process of a composite structure product formed by bonding the two-component solvent-based adhesive, because a large amount of solvent is used, the potential safety hazard of enterprises is high, the solvent remained in the colloid is slowly precipitated, and certain potential safety hazard exists on human bodies and the environment, so that the solvent-based adhesive also has a plurality of use limitations.
However, the existing single-component solvent-free hot melt adhesive or two-component solvent-free adhesive is synthesized by using conventional polyester polyether, the production process is environment-friendly and has little pollution, and solvent toxicity residue is avoided, but when the molecular weight is synthesized to be large enough, the viscosity is overlarge, the leveling, the spreading and the coating performances are poor, and the single-component solvent-free hot melt adhesive or the two-component solvent-free adhesive cannot be suitable for plastic-aluminum and other composite processes; the molecular weight synthesis is small, and the performances of boiling resistance, high-temperature boiling resistance, double-eighty-five experiment resistance, salt mist resistance, hydrochloric acid resistance, electrolyte resistance, deep drawing resistance and the like can not meet the requirements.
Therefore, how to overcome the defects of synthesis and performance of the solvent-free hot flux, and meet the requirements of a film coating process and product performance while eliminating the influence of the solvent in the solvent-based adhesive on the environment and the human body becomes a difficult problem for technicians in the field to overcome.
Disclosure of Invention
The invention aims to provide a single-component solvent-free hot melt adhesive, a preparation method and a use method thereof, and the hot melt adhesive solves the problems that a solvent type hot melt adhesive solvent in the prior art has great environmental pollution and potential safety hazard to a human body, and also solves the problems that the performance of the solvent-free hot melt adhesive in the prior art is difficult to meet the requirement of a film covering process and the performance of a product after film covering is ensured.
In order to achieve the purpose, the invention adopts the technical scheme that: the single-component solvent-free hot melt adhesive is prepared from the following raw materials in parts by weight: 30-50 parts of isocyanate, 60-90 parts of polyester polyol, 10-30 parts of polyether polyol, 0.1-5 parts of chain extender, 0.1-2 parts of curing agent, 0.1-3 parts of polycarbodiimide, 0.1-2 parts of adhesion promoter, 0.1-0.5 part of catalyst and 0.1-0.3 part of antioxidant.
The further improved scheme in the technical scheme is as follows:
1. in the above embodiment, the isocyanate is one or a mixture of more of polyphenyl polymethylene polyisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate.
2. In the above scheme, the polyester polyol includes one or more of epoxy acrylic modified saturated polyester, aliphatic polyol, aromatic polyol, polycaprolactone polyol and polycarbonate diol.
3. In the above scheme, the average molecular weight of the polyester polyol is 500-4000.
4. In the above scheme, the polyether polyol is one or a mixture of more of polyoxypropylene diol, polyoxypropylene triol, polytetrahydrofuran diol, tetrahydrofuran-oxypropylene copolyol, graft polyether polyol and heterocycle modified polyether polyol.
5. In the scheme, the polyether polyol has the average molecular weight of 400-4000.
6. In the above scheme, the chain extender is one or a mixture of more of 1, 4-butanediol, 1, 6-hexanediol, glycerol, trimethylolpropane, diethylene glycol, triethylene glycol, neopentyl glycol, sorbitol, diethylaminoethanol, 3 '-dichloro-4, 4' -diaminodiphenylmethane, ethylenediamine, N-dihydroxy (diisopropyl) aniline, and hydroquinone-bis (β -hydroxyethyl) ether.
7. In the above scheme, the curing agent comprises one or two of aliphatic amine curing agent and imidazole curing agent;
the aliphatic amine curing agent is one or a mixture of more of ethylenediamine, hexamethylenediamine, diethylenetriamine and triethylene tetramine;
the imidazole curing agent is a closed product prepared by reacting various imidazoles with Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI) and diphenylmethane diisocyanate (MDI).
In order to achieve the above purpose, the invention also provides a technical scheme that: a preparation method of the single-component solvent-free hot melt adhesive comprises the following steps:
s1: taking 60-90 parts of polyester polyol and 10-30 parts of polyether polyol, fully and uniformly mixing, and dehydrating for 2-4 hours in a vacuum environment at the dehydration temperature of 100-160 ℃;
s2: cooling the mixture obtained by dehydration in the step S1 to 50-90 ℃, adding 0.1-3 parts of polycarbodiimide, 0.1-2 parts of curing agent and 0.1-2 parts of adhesion promoter, and stirring for 5-10 minutes;
s3: adding 30-50 parts of isocyanate, 0.1-0.5 part of catalyst and 0.1-0.3 part of antioxidant into the stirring container in the step S2, preserving heat at 50-90 ℃, and reacting for 20-60 minutes;
s4: and adding 0.1-5 parts of chain extender, and continuously stirring for 10-40 minutes to obtain a hot melt adhesive finished product.
In order to achieve the purpose, the invention also provides another technical scheme that: a using method of a single-component solvent-free hot melt adhesive comprises the steps of applying the hot melt adhesive between a base layer and a laminating material to form an intermediate layer; wherein the environmental temperature is 20-30 ℃, the humidity is 40-80%, and the surface temperature of the composite material is 20-30 ℃.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. according to the single-component solvent-free hot melt adhesive, the preparation method and the use method thereof, organic solvent and double A-component substances are not required to be added, VOC (volatile organic compound) emission can be greatly reduced, the pollution of the hot melt adhesive to the environment is effectively improved, and the solvent is not required to be stored, used and discharged, so that the investment of environmental protection facilities of enterprises is reduced, the cost of environmental protection disposal is reduced, and the potential safety hazard brought to the enterprises by solvent storage is avoided.
2. The invention relates to a single-component solvent-free hot melt adhesive and a preparation method and a using method thereof, wherein the viscosity of the hot melt adhesive prepared from 30-50 parts of isocyanate, 60-90 parts of polyester polyol, 10-30 parts of polyether polyol, 0.1-5 parts of chain extender, 0.1-2 parts of curing agent, 0.1-3 parts of polycarbodiimide, 0.1-2 parts of adhesion promoter, 0.1-0.5 part of catalyst and 0.1-0.3 part of antioxidant at 80 ℃ is 5000mpa.s, the NOC% is 8.5% measured according to the weight ratio, and the hot melt adhesive has good boiling resistance, high-temperature boiling resistance, eighty five experiment resistance, salt mist resistance, hydrochloric acid resistance, electrolysis resistance and deep punching resistance.
Detailed Description
Example 1: the single-component solvent-free hot melt adhesive is prepared from the following raw materials in parts by weight: 30 parts of isocyanate, 60 parts of polyester polyol, 20 parts of polyether polyol, 0.2 part of chain extender, 0.8 part of curing agent, 2 parts of polycarbodiimide, 1.5 parts of adhesion promoter, 0.1 part of catalyst and 0.2 part of antioxidant.
The isocyanate is one or a mixture of more of polyphenyl polymethylene polyisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate.
The polyester polyol comprises epoxy acrylic acid modified saturated polyester, one or more of aliphatic polyol, aromatic polyol, polycaprolactone polyol and polycarbonate diol; the average molecular weight of the polyester polyol is 500-4000.
The polyether polyol is one or a mixture of more of polyoxypropylene diol, polyoxypropylene triol, polytetrahydrofuran diol, tetrahydrofuran-propylene oxide copolymerized diol, graft polyether polyol and heterocycle modified polyether polyol; the polyether polyol has an average molecular weight of 400-4000.
The chain extender is one or a mixture of more of 1, 4-butanediol, 1, 6-hexanediol, glycerol, trimethylolpropane, diethylene glycol, triethylene glycol, neopentyl glycol, sorbitol, diethylaminoethanol, 3 '-dichloro-4, 4' -diaminodiphenylmethane, ethylenediamine, N-dihydroxy (diisopropyl) aniline and hydroquinone-di (beta-hydroxyethyl) ether.
The curing agent comprises one or two of aliphatic amine curing agent and imidazole curing agent; the aliphatic amine curing agent is one or a mixture of more of ethylenediamine, hexamethylenediamine, diethylenetriamine and triethylene tetramine; the imidazole curing agent is a closed product prepared by reacting various imidazoles with Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI) and diphenylmethane diisocyanate (MDI).
A preparation method of the single-component solvent-free hot melt adhesive comprises the following steps:
s1: taking 60 parts of polyester polyol and 20 parts of polyether polyol, fully and uniformly mixing, and dehydrating for 3 hours in a vacuum environment at the dehydration temperature of 130 ℃;
s2: cooling the mixture obtained by dehydration in the step S1 to 65 ℃, adding 2 parts of polycarbodiimide, 0.8 part of curing agent and 1.5 parts of adhesion promoter, and stirring for 15 minutes;
s3: adding 30 parts of isocyanate, 0.1 part of catalyst and 0.2 part of antioxidant into the stirring container in the step S2, preserving heat at 70 ℃, and reacting for 45 minutes;
s4: and adding 0.2 part of chain extender, continuously stirring for 25 minutes, discharging, and filling into a sealed container with an aluminum foil inner bag to obtain a hot melt adhesive finished product.
Wherein the polyester polyol is epoxy acrylic acid modified saturated polyester, is a polymer containing two hydroxyl groups and is formed by condensation polymerization of adipic acid, isophthalic acid, hexanediol and neopentyl glycol, and has an average molecular weight of 2000.
Wherein the polyether polyol is tetrahydrofuran-propylene oxide copolymer glycol, graft polyether polyol or heterocycle modified polyether polyol, and has molecular weight of 1000.
Wherein the antioxidant is irganox 1010.
Wherein the catalyst is organic bismuth.
Wherein the hydrolysis resistant agent refers to polycarbodiimide Stabaxol P200.
Wherein the latent curing agent refers to ketoxime blocked isocyanate curing agent.
Wherein the chain extender is a dimethylolbutyric acid modifier.
Wherein the adhesion promoter is Degussa LTW (an ester compound).
A using method of a single-component solvent-free hot melt adhesive comprises the steps of applying the hot melt adhesive between a base layer and a laminating material to form an intermediate layer; wherein the environmental temperature is 20-30 ℃, the humidity is 40-80%, and the surface temperature of the composite material is 20-30 ℃.
Performance evaluation:
the viscosity of the one-component solvent-free hot-melt adhesive of this example was measured using an SNB-AI viscometer, spindle # 27. The single-component solvent-free hot melt adhesive of the embodiment is heated and stirred in an SNB-AI viscometer for 30 minutes, the displayed value is read, and the displayed value of the viscosity is kept unchanged for 20 minutes, namely the measured viscosity of the hot melt adhesive is obtained. The one-component, solvent-free hot melt adhesive of this example had a viscosity of 4000mpa.s at 80 ℃.
Secondly, measuring the content (NCO%) of isocyanate groups: the single-component solvent-free hot-melt adhesive of this example was reacted for 20 minutes with an excess of di-N-butylamine in N-methylpyrrolidone, and then the NCO% was determined by titration with hydrochloric acid, and the NCO% by weight was determined to be 9.5%.
Example 2: the single-component solvent-free hot melt adhesive is prepared from the following raw materials in parts by weight: 30 parts of isocyanate, 80 parts of polyester polyol, 15 parts of polyether polyol, 0.5 part of chain extender, 1 part of curing agent, 1.5 parts of polycarbodiimide, 1 part of adhesion promoter, 0.2 part of catalyst and 0.1 part of antioxidant.
The isocyanate is one or a mixture of more of polyphenyl polymethylene polyisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate.
The polyester polyol comprises epoxy acrylic acid modified saturated polyester, one or more of aliphatic polyol, aromatic polyol, polycaprolactone polyol and polycarbonate diol; the average molecular weight of the polyester polyol is 500-4000.
The polyether polyol is one or a mixture of more of polyoxypropylene diol, polyoxypropylene triol, polytetrahydrofuran diol, tetrahydrofuran-propylene oxide copolymerized diol, graft polyether polyol and heterocycle modified polyether polyol; the polyether polyol has an average molecular weight of 400-4000.
The chain extender is one or a mixture of more of 1, 4-butanediol, 1, 6-hexanediol, glycerol, trimethylolpropane, diethylene glycol, triethylene glycol, neopentyl glycol, sorbitol, diethylaminoethanol, 3 '-dichloro-4, 4' -diaminodiphenylmethane, ethylenediamine, N-dihydroxy (diisopropyl) aniline and hydroquinone-di (beta-hydroxyethyl) ether.
The curing agent comprises one or two of aliphatic amine curing agent and imidazole curing agent; the aliphatic amine curing agent is one or a mixture of more of ethylenediamine, hexamethylenediamine, diethylenetriamine and triethylene tetramine; the imidazole curing agent is a closed product prepared by reacting various imidazoles with Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI) and diphenylmethane diisocyanate (MDI).
A preparation method of the single-component solvent-free hot melt adhesive comprises the following steps:
s1: taking 80 parts of polyester polyol and 15 parts of polyether polyol, fully and uniformly mixing, and dehydrating for 3 hours in a vacuum environment at the dehydration temperature of 160 ℃;
s2: cooling the mixture obtained by dehydration in the step S1 to 90 ℃, adding 1.5 parts of polycarbodiimide, 1 part of curing agent and 1 part of adhesion promoter, and stirring for 30 minutes;
s3: adding 30 parts of isocyanate, 0.2 part of catalyst and 0.1 part of antioxidant into the stirring container in the step S2, preserving heat at 90 ℃ and reacting for 60 minutes;
s4: adding 0.5 part of chain extender, continuously stirring for 40 minutes, then discharging, and filling into a sealed container with an aluminum foil inner bag to obtain a hot melt adhesive finished product.
Wherein the polyester polyol is epoxy acrylic acid modified saturated polyester, is a polymer containing two hydroxyl groups and is formed by condensation polymerization of adipic acid, isophthalic acid, hexanediol and neopentyl glycol, and has an average molecular weight of 2000.
Wherein the polyether polyol is tetrahydrofuran-propylene oxide copolymer glycol, graft polyether polyol or heterocycle modified polyether polyol, and has molecular weight of 1000.
Wherein the antioxidant is irganox 1010.
Wherein the catalyst is organic bismuth.
Wherein the hydrolysis resistant agent refers to polycarbodiimide Stabaxol P200.
Wherein the latent curing agent refers to ketoxime blocked isocyanate curing agent.
Wherein the chain extender is a dimethylolbutyric acid modifier.
Wherein the adhesion promoter is Degussa LTW (an ester compound).
A using method of a single-component solvent-free hot melt adhesive comprises the steps of applying the hot melt adhesive between a base layer and a laminating material to form an intermediate layer; wherein the environmental temperature is 20-30 ℃, the humidity is 40-80%, and the surface temperature of the composite material is 20-30 ℃.
Performance evaluation:
the viscosity of the one-component solvent-free hot-melt adhesive of this example was measured using an SNB-AI viscometer, spindle # 27. The single-component solvent-free hot melt adhesive of the embodiment is heated and stirred in an SNB-AI viscometer for 30 minutes, the displayed value is read, and the displayed value of the viscosity is kept unchanged for 20 minutes, namely the measured viscosity of the hot melt adhesive is obtained. The one-component, solvent-free hot melt adhesive of this example had a viscosity of 3000mpa.s at 80 ℃.
Secondly, measuring the content (NCO%) of isocyanate groups: the single-component solvent-free hot-melt adhesive of this example was reacted for 20 minutes with an excess of di-N-butylamine in N-methylpyrrolidone, and then the NCO% was determined by titration with hydrochloric acid, and the NCO% by weight was determined to be 10.8%.
Example 3: the single-component solvent-free hot melt adhesive is prepared from the following raw materials in parts by weight: 30 parts of isocyanate, 50 parts of polyester polyol, 50 parts of polyether polyol, 1 part of chain extender, 1.5 parts of curing agent, 3 parts of polycarbodiimide, 2 parts of adhesion promoter, 0.5 part of catalyst and 0.3 part of antioxidant.
The isocyanate is one or a mixture of more of polyphenyl polymethylene polyisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate.
The polyester polyol comprises epoxy acrylic acid modified saturated polyester, one or more of aliphatic polyol, aromatic polyol, polycaprolactone polyol and polycarbonate diol; the average molecular weight of the polyester polyol is 500-4000.
The polyether polyol is one or a mixture of more of polyoxypropylene diol, polyoxypropylene triol, polytetrahydrofuran diol, tetrahydrofuran-propylene oxide copolymerized diol, graft polyether polyol and heterocycle modified polyether polyol; the polyether polyol has an average molecular weight of 400-4000.
The chain extender is one or a mixture of more of 1, 4-butanediol, 1, 6-hexanediol, glycerol, trimethylolpropane, diethylene glycol, triethylene glycol, neopentyl glycol, sorbitol, diethylaminoethanol, 3 '-dichloro-4, 4' -diaminodiphenylmethane, ethylenediamine, N-dihydroxy (diisopropyl) aniline and hydroquinone-di (beta-hydroxyethyl) ether.
The curing agent comprises one or two of aliphatic amine curing agent and imidazole curing agent; the aliphatic amine curing agent is one or a mixture of more of ethylenediamine, hexamethylenediamine, diethylenetriamine and triethylene tetramine; the imidazole curing agent is a closed product prepared by reacting various imidazoles with Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI) and diphenylmethane diisocyanate (MDI).
A preparation method of the single-component solvent-free hot melt adhesive comprises the following steps:
s1: taking 50 parts of polyester polyol and 50 parts of polyether polyol, fully and uniformly mixing, and dehydrating for 3 hours in a vacuum environment at the dehydration temperature of 100 ℃;
s2: cooling the mixture obtained by dehydration in the step S1 to 5 ℃, adding 3 parts of polycarbodiimide, 1.5 parts of curing agent and 2 parts of adhesion promoter, and stirring for 5 minutes;
s3: adding 30 parts of isocyanate, 0.5 part of catalyst and 0.3 part of antioxidant into the stirring container in the step S2, preserving heat at 50 ℃, and reacting for 20 minutes;
s4: adding 1 part of chain extender, continuously stirring for 10 minutes, then discharging, and filling into a sealed container with an aluminum foil inner bag to obtain a hot melt adhesive finished product.
Wherein the polyester polyol is epoxy acrylic acid modified saturated polyester, is a polymer containing two hydroxyl groups and is formed by condensation polymerization of adipic acid, isophthalic acid, hexanediol and neopentyl glycol, and has an average molecular weight of 2000.
Wherein the polyether polyol is tetrahydrofuran-propylene oxide copolymer glycol, graft polyether polyol or heterocycle modified polyether polyol, and has molecular weight of 1000.
Wherein the antioxidant is irganox 1010.
Wherein the catalyst is organic bismuth.
Wherein the hydrolysis resistant agent refers to polycarbodiimide Stabaxol P200.
Wherein the latent curing agent refers to ketoxime blocked isocyanate curing agent.
Wherein the chain extender is a dimethylolbutyric acid modifier.
Wherein the adhesion promoter is Degussa LTW (an ester compound).
A using method of a single-component solvent-free hot melt adhesive comprises the steps of applying the hot melt adhesive between a base layer and a laminating material to form an intermediate layer; wherein the environmental temperature is 20-30 ℃, the humidity is 40-80%, and the surface temperature of the composite material is 20-30 ℃.
Performance evaluation:
the viscosity of the one-component solvent-free hot-melt adhesive of this example was measured using an SNB-AI viscometer, spindle # 27. The single-component solvent-free hot melt adhesive of the embodiment is heated and stirred in an SNB-AI viscometer for 30 minutes, the displayed value is read, and the displayed value of the viscosity is kept unchanged for 20 minutes, namely the measured viscosity of the hot melt adhesive is obtained. The one-component, solvent-free hot melt adhesive of this example had a viscosity of 5000mpa.s at 80 ℃.
Secondly, measuring the content (NCO%) of isocyanate groups: the single-component solvent-free hot-melt adhesive of this example was reacted for 20 minutes with an excess of di-N-butylamine in N-methylpyrrolidone, and then the NCO% was determined by titration with hydrochloric acid, and the NCO% by weight was determined to be 8.5%.
The working principle is as follows: heating the single-component solvent-free hot melt adhesive to 40-120 ℃ in a melt adhesive machine, beating the melted hot melt adhesive between coating unit rollers of a three-roller or five-roller compound machine through the hot melt adhesive machine, transferring the molten hot melt adhesive to the surface of a base material or a membrane material through a coating roller of the three-roller or five-roller coating compound machine, or coating the molten hot melt adhesive on the surface of the base material or the membrane material through a traceless scraping gun coating machine with a heating device, compounding different materials by about 1-30g of square coating weight, uniformly coating the surfaces of the base material or the membrane material, adding a humidifier at the unwinding position of the membrane material if necessary, and humidifying the membrane material during compounding. Preferably, the gluing roller of the three-roller or five-roller compound machine or the coater with the traceless scraping gun is provided with a heating device which is preheated to 40-120 ℃. And then, covering the surface of the hot melt adhesive layer with a film material or a base material by rolling, and fully contacting and bonding the base material and the film material to obtain the film-coated material. The film-covered material is placed in a natural environment, and the hot melt adhesive absorbs moisture and is cured. Curing time is generally 2-7 days under optimum ambient temperature and humidity conditions.
By adopting the scheme, organic solvent and double A-class substances are not required to be added, VOC discharge amount can be greatly reduced, pollution of the hot melt adhesive to the environment is effectively improved, and investment of enterprise environment-friendly facilities is reduced, environment-friendly disposal cost is reduced, and potential safety hazard brought to enterprises by solvent storage is avoided.
In addition, the viscosity of the hot melt adhesive prepared from 30-50 parts of isocyanate, 60-90 parts of polyester polyol, 10-30 parts of polyether polyol, 0.1-5 parts of chain extender, 0.1-2 parts of curing agent, 0.1-3 parts of polycarbodiimide, 0.1-2 parts of adhesion promoter, 0.1-0.5 part of catalyst and 0.1-0.3 part of antioxidant at 80 ℃ is 5000mpa.s, and the NOC% is 8.5% measured according to the weight ratio.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. The single-component solvent-free hot melt adhesive is characterized by comprising the following raw materials in parts by weight: 30-50 parts of isocyanate, 60-90 parts of polyester polyol, 10-30 parts of polyether polyol, 0.1-5 parts of chain extender, 0.1-2 parts of curing agent, 0.1-3 parts of polycarbodiimide, 0.1-2 parts of adhesion promoter, 0.1-0.5 part of catalyst and 0.1-0.3 part of antioxidant.
2. The one-component solvent-free hot melt adhesive of claim 1, wherein the isocyanate is one or more of polyphenyl polymethylene polyisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate.
3. The one-component solvent-free hot melt adhesive of claim 1, wherein the polyester polyol comprises one or more of epoxy acrylic modified saturated polyester, aliphatic polyol, aromatic polyol, polycaprolactone polyol, and polycarbonate diol.
4. The single-component solvent-free hot melt adhesive for coated iron according to claim 3, wherein the polyester polyol has an average molecular weight of 500-4000.
5. The single-component solvent-free hot melt adhesive of claim 1, wherein the polyether polyol is one or more of polyoxypropylene diol, polyoxypropylene triol, polytetrahydrofuran diol, tetrahydrofuran-oxypropylene copolyol, graft polyether polyol and heterocycle modified polyether polyol.
6. The one-component solvent-free hot melt adhesive as claimed in claim 5, wherein the polyether polyol has an average molecular weight of 400-4000.
7. The one-component solvent-free hot melt adhesive of claim 1, wherein the chain extender is one or more of 1, 4-butanediol, 1, 6-hexanediol, glycerol, trimethylolpropane, diethylene glycol, triethylene glycol, neopentyl glycol, sorbitol, diethylaminoethanol, 3 '-dichloro-4, 4' -diaminodiphenylmethane, ethylenediamine, N-dihydroxy (diisopropyl) aniline, hydroquinone-bis (β -hydroxyethyl) ether.
8. The single-component solvent-free hot melt adhesive as claimed in claim 1, wherein the curing agent comprises one or two of an aliphatic amine curing agent and an imidazole curing agent;
the aliphatic amine curing agent is one or a mixture of more of ethylenediamine, hexamethylenediamine, diethylenetriamine and triethylene tetramine;
the imidazole curing agent is a closed product prepared by reacting various imidazoles with Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI) and diphenylmethane diisocyanate (MDI).
9. The preparation method of the single-component solvent-free hot melt adhesive as claimed in claims 1 to 8, wherein the preparation method comprises the following steps:
s1: taking 60-90 parts of polyester polyol and 10-30 parts of polyether polyol, fully and uniformly mixing, and dehydrating for 2-4 hours in a vacuum environment at the dehydration temperature of 100-160 ℃;
s2: cooling the mixture obtained by dehydration in the step S1 to 50-90 ℃, adding 0.1-3 parts of polycarbodiimide, 0.1-2 parts of curing agent and 0.1-2 parts of adhesion promoter, and stirring for 5-10 minutes;
s3: adding 30-50 parts of isocyanate, 0.1-0.5 part of catalyst and 0.1-0.3 part of antioxidant into the stirring container in the step S2, preserving heat at 50-90 ℃, and reacting for 20-60 minutes;
s4: and adding 0.1-5 parts of chain extender, and continuously stirring for 10-40 minutes to obtain a hot melt adhesive finished product.
10. The use method of the single-component solvent-free hot melt adhesive as claimed in claims 1 to 8, wherein the hot melt adhesive is applied between the base layer and the bonding material to form an intermediate layer; wherein the environmental temperature is 20-30 ℃, the humidity is 40-80%, and the surface temperature of the composite material is 20-30 ℃.
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