CN108822757A - A kind of low viscous PET protection film of foam material - Google Patents

A kind of low viscous PET protection film of foam material Download PDF

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Publication number
CN108822757A
CN108822757A CN201810536596.5A CN201810536596A CN108822757A CN 108822757 A CN108822757 A CN 108822757A CN 201810536596 A CN201810536596 A CN 201810536596A CN 108822757 A CN108822757 A CN 108822757A
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low viscous
protection film
foam material
low
pet protection
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CN108822757B (en
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吴卓慧
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Ningbo Kelaien New Material Technology Co Ltd
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Ningbo Kelaien New Material Technology Co Ltd
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22Plastics; Metallised plastics
    • C09J7/25Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255Polyesters
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/0804Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/38Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3842Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
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    • C08G18/00Polymeric products of isocyanates or isothiocyanates
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    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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    • C08G18/00Polymeric products of isocyanates or isothiocyanates
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    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44Polycarbonates
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    • C08G18/48Polyethers
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    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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    • C08G18/00Polymeric products of isocyanates or isothiocyanates
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    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
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    • C08G18/00Polymeric products of isocyanates or isothiocyanates
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    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
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    • C09J2301/30Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
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    • C09J2301/40Additional features of adhesives in the form of films or foils characterized by the presence of essential components
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    • C09J2467/00Presence of polyester
    • C09J2467/006Presence of polyester in the substrate
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    • C09J2475/00Presence of polyurethane

Abstract

The present invention provides a kind of foam material low viscous PET protection film, is made of PET base material layer, low viscous middle layer and protective layer, preparation process is simple, easy to operate, is suitable for industrialized production.First, for the chain extender of the low viscose glue of high-performance at acidity, acidic materials can inhibit the generation of biuret to react, and then inhibit cross-linking reaction, and viscosity reduces;Second, catalyst is mild acidic ion liquid, its catalytic activity is lower, it restrained effectively its nucleophilic attack to isocyanates, to reduce the activity that isocyanates is reacted with macromolecule dihydric alcohol hydroxyl, there is preferable synergistic effect with emulsifier, reduce the viscosity of product, improves the low viscose glue storage stability energy of high-performance.Therefore, PET protection film provided by the invention have the characteristics that it is low it is viscous, easily tear take, residue glue, stickiness be not good, heat-resisting quantity is good and excellent in mechanical performance.

Description

A kind of low viscous PET protection film of foam material
Technical field
The present invention relates to protection technical field of membrane, and in particular to a kind of low viscous PET protection film of foam material.
Background technique
Protective film has infiltrated through all trades and professions, such as instrument, instrument, electronics, machinery, building, automobile manufacture and label etc. Industry, the application of protective film not only improve the presentation quality of product, facilitate material processing, while also improving material Utilization rate reduces the production cost of product.
Foam material refers to based on the polymer such as plastics, rubber, elastomer, natural macromolecular material and inside it Poromerics with numerous bubbles can also be considered as the composite material using gas as filler.Foam material has sound insulation, protects Temperature is cut operating costs and the advantages such as energy conservation and environmental protection, and sports goods, electronics, precision instrument, household electrical appliances, automobile etc. are widely used in Field.With the development of society and the promotion of people's demand, demand of the foam material to protective film is incrementally increased, however market On protective film in the prevalence of some non-refractories, be not easy to tear take, residue glue is remaining, stickiness difference and viscosity are unstable etc. Problem.
Therefore, prepare it is low it is viscous, easily tear take, residue glue, stickiness be not good, heat-resisting quantity is good and the foaming body of excellent in mechanical performance Material is of great significance for protective film industry with low viscous PET protection film.
Summary of the invention
The main purpose of the present invention is to provide a kind of low viscous PET protection film of foam material, have it is low it is viscous, easily tear It takes, the characteristics of residue glue, stickiness be not good, heat-resisting quantity is good, excellent in mechanical performance.
To achieve the above objectives, the technical solution adopted by the present invention is:
The low viscous PET protection film of a kind of foam material, by the PET base material layer, low viscous middle layer and guarantor stacked gradually Sheath composition, the low viscous middle layer are formed by the low viscose glue of high-performance, and the low viscose glue of high-performance is polynary by 20-80 parts by weight macromolecular Alcohol, 3-10 parts by weight isocyanates, 2-5 parts by weight chain extender, 0.5-2 parts by weight salt forming agent, 4-10 part by weight of catalyst, 10- 30 weight parts organic solvents and 100-150 parts by weight of deionized water composition, the chain extender are carboxylic acid type ionic liquid 1- second Imidazole acid cation dihydromethyl propionic acid anion salt, the catalyst are ionic liquid 1- methyl -3- ethyl imidazol(e) bromide.
Preferably, the PET base material layer is with a thickness of 50-200 μm.
Preferably, the protective layer is PET film, with a thickness of 20-100 μm.
Preferably, the low viscose glue of the high-performance is prepared as follows:Macromolecular polyol is true at 100-120 DEG C Sky dehydration 1-5h, is cooled to 60-80 DEG C;Then isocyanates, organic solvent and catalyst is added, in 500-1500r/min Under the conditions of isothermal reaction 2-6h;Chain extender chain extending reaction 1-5h is added, is cooled to 30-50 DEG C;
Then salt forming agent and deionized water is added, high speed shear disperses 0.5-2h under the conditions of 1000-3000r/min, obtains To the low viscose glue of high-performance.
Preferably, the macromolecular polyol is polyester polyol, one in the pure and mild polycarbonate polyol of polyether polyols Kind is several.
Preferably, the isocyanates is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate and 4,4 '-diphenyl One or more of methane diisocyanate.
Preferably, the chain extender is prepared as follows:Imidazol-1-acetic acid and ethyl acetate are hybridly prepared into matter The solution that score is 30-50% is measured, then addition and the equimolar bromoethane of imidazol-1-acetic acid, in 450-750r/min condition Lower agitating and heating reacts 6-18h after being warming up to 50-80 DEG C, obtains intermediate;Addition and imidazol-1-acetic acid into the intermediate Equimolar dihydromethyl propionic acid, agitating and heating reacts 8-24h after being warming up to 60-90 DEG C under the conditions of 300-500r/min, from The heart washs to obtain chain extender.
Preferably, the salt forming agent is one or more of triethylamine, NaOH, KOH and ammonium hydroxide.
Preferably, the organic solvent is one in acetone, butanone, N-Methyl pyrrolidone and n,N-Dimethylformamide Kind is several.
Preferably, the catalyst is prepared as follows:It is 1 by molar ratio:1 methylimidazole and bromoethane exists 6-18h is reacted after agitating and heating is warming up to 50-80 DEG C under the conditions of 450-750r/min, is washed repeatedly, is urged with ethyl acetate Agent.
The present invention provides a kind of foam material low viscous PET protection film, by PET base material layer, low viscous middle layer and guarantor Sheath composition, preparation process is simple, easy to operate, is suitable for industrialized production.First, the chain extender of the low viscose glue of high-performance is at acid Property, acidic materials can inhibit the generation of biuret to react, and then inhibit cross-linking reaction, so that the degree of cross linking be made to reduce, viscosity is reduced; Second, the catalyst of the low viscose glue of high-performance is mild acidic ion liquid, and catalytic activity is lower, and it is right to restrained effectively its The nucleophilic attack of isocyanates has to reduce the activity that isocyanates is reacted with macromolecule dihydric alcohol hydroxyl with emulsifier Preferable synergistic effect reduces the viscosity of product;The viscosity for controlling reaction system simultaneously is avoided generating implode or gel, be mentioned The high low viscose glue storage stability energy of high-performance.Therefore, there is PET protection film provided by the invention low viscous, easy tear to take, is not residual The characteristics of glue, stickiness are good, heat-resisting quantity is good and excellent in mechanical performance, at the same PET film also have it is excellent heat-resisting, cold-resistant Property, good chemical resistance and oil resistivity.
Specific embodiment
It is described below for disclosing the present invention so that those skilled in the art can be realized the present invention.It is excellent in being described below Embodiment is selected to be only used as illustrating, it may occur to persons skilled in the art that other obvious modifications.
The present invention provides a kind of foam material low viscous PET protection film, by stack gradually PET base material layer, it is low it is viscous in Interbed and protective layer composition, the low viscous middle layer are formed by the low viscose glue of high-performance, and the low viscose glue of high-performance is by 20-80 parts by weight Macromolecular polyol, 3-10 parts by weight isocyanates, 2-5 parts by weight chain extender, 0.5-2 parts by weight salt forming agent, 4-10 parts by weight Catalyst, 10-30 weight parts organic solvent and 100-150 parts by weight of deionized water composition, the chain extender be carboxylic acid type from Sub- liquid 1- acetic acid glyoxaline cation dihydromethyl propionic acid anion salt, the catalyst are ionic liquid 1- methyl -3- ethyl Imidazoles bromide.
Preferably, the PET base material layer is with a thickness of 50-200 μm;The protective layer is PET film, with a thickness of 20-100μm。
Preferably, the low viscose glue of the high-performance is prepared as follows:By macromolecular polyol in 100-120 Vacuum dehydration 1-5h at DEG C, is cooled to 60-80 DEG C;Then isocyanates, organic solvent and catalyst is added, in 500- Isothermal reaction 2-6h under the conditions of 1500r/min;Chain extender chain extending reaction 1-5h is added, is cooled to 30-50 DEG C;Then salt is added into Agent and deionized water, high speed shear disperses 0.5-2h under the conditions of 1000-3000r/min, obtains the low viscose glue of high-performance.
Preferably, the macromolecular polyol is polyester polyol, the pure and mild polycarbonate polyol of polyether polyols One or more of.The isocyanates is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate and 4,4 '-diphenyl One or more of methane diisocyanate.
Preferably, the chain extender is prepared as follows:Imidazol-1-acetic acid is mixed with ethyl acetate and is matched The solution that mass fraction is 30-50% is made, then addition and the equimolar bromoethane of imidazol-1-acetic acid, in 450-750r/ 6-18h is reacted after agitating and heating is warming up to 50-80 DEG C under the conditions of min, obtains intermediate;Addition and miaow into the intermediate The equimolar dihydromethyl propionic acid of azoles -1- acetic acid, agitating and heating is reacted after being warming up to 60-90 DEG C under the conditions of 300-500r/min 8-24h, centrifuge washing obtain chain extender.
Chain extender has played important function to the preparation to the low viscose glue of high-performance, and chain extender can inhibit at acidity, acidic materials The generation of biuret is reacted, and then inhibits cross-linking reaction, so that the degree of cross linking be made to reduce, viscosity is reduced.
Preferably, the salt forming agent is preferably one or more of triethylamine, NaOH, KOH and ammonium hydroxide.It is described Organic solvent is preferably one or more of acetone, butanone, N-Methyl pyrrolidone and N,N-dimethylformamide.
Preferably, the catalyst is prepared as follows:It is 1 by molar ratio:1 methylimidazole and bromine second Alkane reacts 6-18h after agitating and heating is warming up to 50-80 DEG C under the conditions of 450-750r/min, is washed repeatedly, is obtained with ethyl acetate To catalyst.
Catalyst has played facilitation to the preparation to the low viscose glue of high-performance, and catalyst is mild acidic ion liquid, Its catalytic activity is lower, restrained effectively its nucleophilic attack to isocyanates, to reduce isocyanates and macromolecular The activity of binary alcoholic extract hydroxyl group reaction, reduces the viscosity of product;The viscosity for controlling reaction system simultaneously avoids generating implode or solidifying Glue improves the low viscose glue storage stability energy of high-performance.
The present invention compared with the existing technology, has the following advantages and beneficial effect:
(1) foam material of the invention is with low viscous PET protection film by PET base material layer, low viscous middle layer and protective layer Composition, preparation process is simple, easy to operate, is suitable for industrialized production;
(2) the low viscous PET protection film of foam material of the invention have it is low it is viscous, easily tear take, not residue glue, stickiness it is good, The characteristics of heat-resisting quantity is good and excellent in mechanical performance, while PET film also has excellent heat-resisting, cold resistance, good resistance toization Learn drug and oil resistivity;
(3) for the chain extender of the low viscose glue of high-performance at acidity, acidic materials can inhibit the generation of biuret to react, and then inhibit Cross-linking reaction, so that the degree of cross linking be made to reduce, viscosity is reduced;
(4) catalyst of the low viscose glue of high-performance is mild acidic ion liquid, and catalytic activity is lower, effectively inhibits Its nucleophilic attack to isocyanates, so that the activity that isocyanates is reacted with macromolecule dihydric alcohol hydroxyl is reduced, with cream Agent has preferable synergistic effect, reduces the viscosity of product;The viscosity for controlling reaction system simultaneously avoids generating implode or solidifying Glue improves the low viscose glue storage stability energy of high-performance.
For a further understanding of the present invention, technical solution provided by the invention is carried out specifically below with reference to embodiment Bright, protection scope of the present invention is not limited by the following examples.
Chemical reagent used in the embodiment of the present invention is commercially available:Macromolecular polyol is limited purchased from the auspicious promise chemical industry in Qingdao Company;Isocyanates is purchased from nine Chemical Co., Ltd. of nation of Shanghai;Salt forming agent and organic solvent are purchased from Changzhou inspiration chemical industry Co., Ltd;PET film is purchased from ZheJiang NanYang Science Co., Ltd.
Embodiment 1:
Foam material of the invention with low viscous PET protection film by 50 μm of PET base material layer, 5 μm of low viscous middle layer with And 20 μm of protective layer forms.
Low viscous middle layer is formed by the low viscose glue of high-performance, and the low viscose glue of high-performance is more by 20 parts by weight macromolecular polyol polyethers First alcohol, 3 parts by weight isocyanates toluene di-isocyanate(TDI)s, 2 parts by weight chain extenders, 0.5 parts by weight salt forming agent triethylamine, 4 weight Part catalyst, 10 weight parts organic solvent acetone and 100 parts by weight of deionized water composition, specific preparation method are as follows:
(1) by macromolecular polyol at 100 DEG C vacuum dehydration 5h, be cooled to 60 DEG C;
(2) isocyanates, organic solvent and catalyst, isothermal reaction 6h under the conditions of 500r/min is added;
(3) chain extender chain extending reaction 1h is added, above-mentioned reaction product is cooled to 30 DEG C or so;
(4) salt forming agent and deionized water is added, high speed shear disperses 2h under the conditions of 1000r/min, and it is low to obtain high-performance Viscose glue, it is spare.
Chain extender carboxylic acid type ionic liquid 1- acetic acid glyoxaline cation dihydromethyl propionic acid anion salt, specific preparation method It is as follows:
(1) it after imidazol-1-acetic acid and ethyl acetate being hybridly prepared into the solution that mass fraction is 30%, adds and miaow The equimolar bromoethane of azoles -1- acetic acid, agitating and heating reacts 18h after being warming up to 50 DEG C under the conditions of 450r/min, obtains centre Body;
(2) it adds with the equimolar dihydromethyl propionic acid of imidazol-1-acetic acid, agitating and heating liter under the conditions of 300r/min For temperature to reacting for 24 hours after 60 DEG C, centrifuge washing obtains chain extender, spare.
The catalyst is ionic liquid 1- methyl -3- ethyl imidazol(e) bromide, and specific preparation method is as follows:
By equimolar methylimidazole and bromoethane, agitating and heating is reacted after being warming up to 50 DEG C under the conditions of 450r/min 18h is washed repeatedly with ethyl acetate, obtains catalyst, spare.
Embodiment 2:
Foam material of the invention is with low viscous PET protection film by 100 μm of PET base material layer, 10 μm of low viscous middle layer And 50 μm of protective layer forms.
Low viscous middle layer is formed by the low viscose glue of high-performance, and the low viscose glue of high-performance is more by 80 parts by weight macromolecular polyol polyester First alcohol, 5 4,4 '-methyl diphenylene diisocyanates of parts by weight isocyanates, 3 parts by weight chain extenders, 0.5-2 parts by weight salt forming agent Ammonium hydroxide, 4-10 part by weight of catalyst, 10 weight parts organic solvent N-Methyl pyrrolidones and 100 parts by weight of deionized water groups At specific preparation method is as follows:
(1) by macromolecular polyol at 120 DEG C vacuum dehydration 2h, be cooled to 80 DEG C;
(2) isocyanates, organic solvent and catalyst, isothermal reaction 2h under the conditions of 1500r/min is added;
(3) chain extender chain extending reaction 2h is added, above-mentioned reaction product is cooled to 50 DEG C or so;
(4) salt forming agent and deionized water is added, high speed shear disperses 0.5h under the conditions of 3000r/min, obtains high-performance Low viscose glue, it is spare.
Chain extender carboxylic acid type ionic liquid 1- acetic acid glyoxaline cation dihydromethyl propionic acid anion salt, specific preparation method It is as follows:
(1) it after imidazol-1-acetic acid and ethyl acetate being hybridly prepared into the solution that mass fraction is 50%, adds and miaow The equimolar bromoethane of azoles -1- acetic acid, agitating and heating reacts 6h after being warming up to 80 DEG C under the conditions of 750r/min, obtains centre Body;
(2) it adds with the equimolar dihydromethyl propionic acid of imidazol-1-acetic acid, agitating and heating liter under the conditions of 500r/min For temperature to 8h is reacted after 90 DEG C, centrifuge washing obtains chain extender, spare.
The catalyst is ionic liquid 1- methyl -3- ethyl imidazol(e) bromide, and specific preparation method is as follows:
By equimolar methylimidazole and bromoethane, agitating and heating is reacted after being warming up to 80 DEG C under the conditions of 750r/min 6h is washed repeatedly with ethyl acetate, obtains catalyst, spare.
Embodiment 3:
Foam material of the invention is with low viscous PET protection film by 200 μm of PET base material layer, 20 μm of low viscous middle layer And 50 μm of protective layer forms.
Low viscous middle layer is formed by the low viscose glue of high-performance, and the low viscose glue of high-performance is by the 80 poly- carbonic acid of parts by weight macromolecular polyol Ester polyol, 10 parts by weight methyl diphenylene diisocyanates, 5 parts by weight chain extenders, 2 parts by weight salt forming agent KOH, 10 parts by weight Catalyst, 30 weight parts organic solvent n,N-Dimethylformamide and 150 parts by weight of deionized water composition, specific preparation method It is as follows:
(1) by macromolecular polyol at 120 DEG C vacuum dehydration 1h, be cooled to 80 DEG C;
(2) isocyanates, organic solvent and catalyst, isothermal reaction 2h under the conditions of 1500r/min is added;
(3) chain extender chain extending reaction 5h is added, above-mentioned reaction product is cooled to 50 DEG C or so;
(4) salt forming agent and deionized water is added, high speed shear disperses 0.5h under the conditions of 3000r/min, obtains high-performance Low viscose glue, it is spare.
Chain extender carboxylic acid type ionic liquid 1- acetic acid glyoxaline cation dihydromethyl propionic acid anion salt, specific preparation method It is as follows:
(1) it after imidazol-1-acetic acid and ethyl acetate being hybridly prepared into the solution that mass fraction is 50%, adds and miaow The equimolar bromoethane of azoles -1- acetic acid, agitating and heating reacts 18h after being warming up to 50 DEG C under the conditions of 750r/min, obtains centre Body;
(2) it adds with the equimolar dihydromethyl propionic acid of imidazol-1-acetic acid, agitating and heating liter under the conditions of 500r/min For temperature to 8h is reacted after 90 DEG C, centrifuge washing obtains chain extender, spare.
The catalyst is ionic liquid 1- methyl -3- ethyl imidazol(e) bromide, and specific preparation method is as follows:
By equimolar methylimidazole and bromoethane, agitating and heating is reacted after being warming up to 80 DEG C under the conditions of 750r/min 6h is washed repeatedly with ethyl acetate, obtains catalyst, spare.
Embodiment 4:
Foam material, with embodiment 2, only uses commercially available low viscose glue with low viscous PET protection film preparation method.
Embodiment 5:
Foam material, with embodiment 2, only uses commercially available chain extender and catalysis with low viscous PET protection film preparation method Agent.
Embodiment 6:
Foam material, with embodiment 2, only uses commercially available chain extender with low viscous PET protection film preparation method.
Embodiment 7:
Foam material, with embodiment 2, only uses commercially available catalyst with low viscous PET protection film preparation method.
The adhesive property test of the low viscous PET protection film of foam material is referring to standard GB/T/T 2792-1995;It is resistance to High-temperature behavior is that sample is pasted on to 304SUS plate, 120 DEG C of holding 60min;Mechanics Performance Testing reference standard GB/T/ T3398.2-2008。
The foam material of preparation of the embodiment of the present invention is as shown in table 1 with the performance test results of low viscous PET protection film.
The low viscous PET protection film main performance index of foam material of 1 embodiment 1-6 of table preparation
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and what is described in the above embodiment and the description is only the present invention Principle, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these variation and Improvement is both fallen in the range of claimed invention.The present invention claims protection scope by appended claims and its Equivalent defines.

Claims (10)

1. a kind of low viscous PET protection film of foam material, which is characterized in that by stack gradually PET base material layer, low viscous centre Layer and protective layer composition, the low viscous middle layer are formed by the low viscose glue of high-performance, and the low viscose glue of high-performance is divided greatly by 20-80 parts by weight Sub- polyalcohol, 3-10 parts by weight isocyanates, 2-5 parts by weight chain extender, 0.5-2 parts by weight salt forming agent, the catalysis of 4-10 parts by weight Agent, 10-30 weight parts organic solvent and 100-150 parts by weight of deionized water composition,
The chain extender is carboxylic acid type ionic liquid 1- acetic acid glyoxaline cation dihydromethyl propionic acid anion salt,
The catalyst is ionic liquid 1- methyl -3- ethyl imidazol(e) bromide.
2. the low viscous PET protection film of foam material according to claim 1, which is characterized in that the PET base material thickness Degree is 50-200 μm.
3. the low viscous PET protection film of foam material according to claim 1, which is characterized in that the protective layer is PET Film, with a thickness of 20-100 μm.
4. the low viscous PET protection film of foam material according to claim 1, which is characterized in that the high-performance is low viscous Glue is prepared as follows:
By macromolecular polyol at 100-120 DEG C vacuum dehydration 1-5h, be cooled to 60-80 DEG C;
Then isocyanates, organic solvent and catalyst, isothermal reaction 2-6h under the conditions of 500-1500r/min is added;
Chain extender chain extending reaction 1-5h is added, is cooled to 30-50 DEG C;
Then salt forming agent and deionized water is added, high speed shear disperses 0.5-2h under the conditions of 1000-3000r/min, obtains height The low viscose glue of performance.
5. the low viscous PET protection film of foam material according to claim 1, which is characterized in that the macromolecular is polynary Alcohol is one or more of polyester polyol, the pure and mild polycarbonate polyol of polyether polyols.
6. the low viscous PET protection film of foam material according to claim 1, which is characterized in that the isocyanates is One or more of toluene di-isocyanate(TDI), methyl diphenylene diisocyanate and 4,4 '-methyl diphenylene diisocyanates.
7. the low viscous PET protection film of foam material according to claim 1, which is characterized in that the chain extender according to Following method preparation:
Imidazol-1-acetic acid and ethyl acetate are hybridly prepared into the solution that mass fraction is 30-50%, are then added and imidazoles- The equimolar bromoethane of 1- acetic acid, agitating and heating reacts 6-18h after being warming up to 50-80 DEG C under the conditions of 450-750r/min, obtains To intermediate;
Addition and the equimolar dihydromethyl propionic acid of imidazol-1-acetic acid into the intermediate, under the conditions of 300-500r/min Agitating and heating reacts 8-24h after being warming up to 60-90 DEG C, centrifuge washing obtains chain extender.
8. the low viscous PET protection film of foam material according to claim 1, which is characterized in that the salt forming agent is three One or more of ethamine, NaOH, KOH and ammonium hydroxide.
9. the low viscous PET protection film of foam material according to claim 1, which is characterized in that the organic solvent is One or more of acetone, butanone, N-Methyl pyrrolidone and N,N-dimethylformamide.
10. the low viscous PET protection film of foam material according to claim 1, which is characterized in that the catalyst according to Following method preparation:
It is 1 by molar ratio:1 methylimidazole and bromoethane agitating and heating under the conditions of 450-750r/min is warming up to 50-80 DEG C After react 6-18h, washed repeatedly with ethyl acetate, obtain catalyst.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110591590A (en) * 2019-07-26 2019-12-20 四川羽玺新材料股份有限公司 Preparation process of low-viscosity high-temperature-resistant protective film

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1424309A (en) * 2002-12-19 2003-06-18 中国科学院兰州化学物理研究所 Production of carbaminate by amine reacted with dimethyl ester carbonate
CN101092399A (en) * 2007-04-11 2007-12-26 东华大学 Method for preparing ionic liquid with anion being as ion in halogen family
CN101891876A (en) * 2010-07-23 2010-11-24 浙江大学 Imidazole salt type cationic polyurethane and preparation method thereof
CN102351796A (en) * 2011-08-23 2012-02-15 林州市科能材料科技有限公司 Production process of imidazole ionic liquid
EP2500376A1 (en) * 2011-03-17 2012-09-19 Basf Se Antistatic or electrically conductive polyurethanes
CN103589385A (en) * 2013-10-17 2014-02-19 昆山韩保胶带科技有限公司 Protective film pressure sensitive adhesive tape
JP2017075289A (en) * 2015-10-16 2017-04-20 日東電工株式会社 Adhesive sheet joint separating method

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1424309A (en) * 2002-12-19 2003-06-18 中国科学院兰州化学物理研究所 Production of carbaminate by amine reacted with dimethyl ester carbonate
CN101092399A (en) * 2007-04-11 2007-12-26 东华大学 Method for preparing ionic liquid with anion being as ion in halogen family
CN101891876A (en) * 2010-07-23 2010-11-24 浙江大学 Imidazole salt type cationic polyurethane and preparation method thereof
EP2500376A1 (en) * 2011-03-17 2012-09-19 Basf Se Antistatic or electrically conductive polyurethanes
CN102351796A (en) * 2011-08-23 2012-02-15 林州市科能材料科技有限公司 Production process of imidazole ionic liquid
CN103589385A (en) * 2013-10-17 2014-02-19 昆山韩保胶带科技有限公司 Protective film pressure sensitive adhesive tape
JP2017075289A (en) * 2015-10-16 2017-04-20 日東電工株式会社 Adhesive sheet joint separating method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
OAKI,Y 等: "Nanosegregated composites of an imidazolium salt and a layered inorganic compound: Organization of both anions and cations in interlayer space", 《NANOSCALE》 *
沈玉龙 等: "《绿色化学》", 30 April 2016, 中国环境出版社 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110591590A (en) * 2019-07-26 2019-12-20 四川羽玺新材料股份有限公司 Preparation process of low-viscosity high-temperature-resistant protective film
CN110591590B (en) * 2019-07-26 2021-10-01 四川羽玺新材料股份有限公司 Preparation process of low-viscosity high-temperature-resistant protective film

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