CN106977657A - A kind of aqueous peelable resin and its preparation method and application - Google Patents

A kind of aqueous peelable resin and its preparation method and application Download PDF

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Publication number
CN106977657A
CN106977657A CN201610035116.8A CN201610035116A CN106977657A CN 106977657 A CN106977657 A CN 106977657A CN 201610035116 A CN201610035116 A CN 201610035116A CN 106977657 A CN106977657 A CN 106977657A
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parts
weight
aqueous peelable
peelable resin
diisocyanate
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Inventor
钱涛
郎伟敏
邓庆芝
刘海龙
李希
徐凯
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Hangzhou Jihua Polymer Materials Co Ltd
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Hangzhou Jihua Polymer Materials Co Ltd
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Publication of CN106977657A publication Critical patent/CN106977657A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • CCHEMISTRY; METALLURGY
    • 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
    • C08G18/10Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • CCHEMISTRY; METALLURGY
    • 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
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67Unsaturated compounds having active hydrogen
    • C08G18/671Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/20Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses aqueous peelable resin of one kind and its preparation method and application, the aqueous peelable resin is prepared from by the component of following parts by weight:Polyether Glycols or 10-20 parts of polyester diol, 5-10 parts of diisocyanate, 1-2 parts of small molecule chain extender, 1-2 parts of hydrophilic chain extender, 0.5-1.5 parts of double bond end-capping reagent, 0.01-0.05 parts of catalyst, 0.6-2 parts of nertralizer, 5-10 parts of acrylic monomer, 0.1-0.5 parts of initiator, 40-60 parts of water.Both aqueous peelable the resin-bonded polyacrylate and polyurethane that the present invention is prepared performances, can meet appropriate adhesive force and good rippability.

Description

A kind of aqueous peelable resin and its preparation method and application
Technical field
It is aqueous peelable more specifically to one kind the present invention relates to polymeric material field Resin and its preparation method and application.
Background technology
Metal surface, which is frequently encountered, needs the occasion of provisional protection, and transportation is the most normal See, such as aluminium alloy, surface protection when plastic-steel door and window dispatches from the factory, to prevent surface tear etc., Avoid influence refined, reduce product specification.Except transportation, in the intermediate treatment of processing factory Process there is also the occasion for needing to use provisional protection, such as metal hardware stamping, wire drawing aluminium sheet, The temporary obscuration protection to substrate metal surface is needed in the process such as sputter template, to ensure The final mass and aesthetic of product are not interfered with process.It is general to be protected using interim The mode of film, is protected temporarily to metal surface, after the completion of protection, is removed by peeling off Diaphragm.
And for non-stick pan field, it is often necessary to the inside of aluminum pot is carried out not gluing processing, that is, sprayed Coating tetrafluoroethylene coating or ceramic coating;And for the outside of aluminum pot, it would be desirable that aluminium can be kept The outward appearance of itself, in order to strengthen corrosion-resistant and heat resistance, it is necessary to be handled by anodic oxidation; Current technique is first internally to spray polytetrafluorethylecoatings coatings or ceramic coating, then external again Portion carries out anodized, but is due to that anode oxidation process will carry out pickling to aluminium pot surface Oxide layer and pollutant are removed with alkali cleaning, inevitably internal coating surface is caused brokenly It is bad, therefore needed in anode oxidation process to the progress temporary obscuration protection of aluminum pot coated inside.
At present using it is more be cover plate protection by the way of, but this mode complex operation is time-consuming Arduously;And by spraying one layer of peelable protective film again in coating surface, simple and convenient, protection Effect is good.This layer of peelable protective film has the requirement of the following aspects:1 and non-sticking lining There is certain adhesive force, will not peel off in process;2nd, barriering effect is good, can protect Non-sticking lining is not contaminated, is not contacted by acid, alkali;3rd, it is easily peelable, it will can just be protected with hand Whole of film is torn, and is not hindered coating, is left no trace.
Patent CN102863888B provides a kind of peelable heat-resisting corrosion protection coating, should Coating is to be consolidated by the linear polyester resins or acrylic resin of hydroxyl with isocyanate polymer Obtained by change, the coating is free of solvent, with enhanced water resistance, oil resistivity, temperature tolerance, wear-resisting Property and removability;But the coating is by the way of bi-component solidification, and preparation process is more, and There is security risk in the isocyanate polymer used.Patent CN103360931A discloses one Plant using aqueous polyurethane and styrene-acrylic emulsion as the aqueous Stripable paint of main component, its film forming is resistance to Aqueous, salt tolerance and Corrosion Protection are excellent;But the coating needs spraying 3-4 roads, and need to do Dry 7 days could progressive can test, thickness of dry film is 80-90 μm, complex process, time-consuming Effort, and thickness is still larger, it is more using coating content.
The content of the invention
The technical problem to be solved in the present invention is, for prior art drawbacks described above there is provided A kind of aqueous peelable resin protected suitable for non-sticking lining surface temporary obscuration and its preparation Method.The innovative point of the present invention is, by carrying out Molecular Design to the resin, to pass through letter Single convenient process conditions, are realized when thickness of dry film is only 20-40 μm, so that it may to not gluing Coating plays excellent insulation blocking effect;The protection film of resin formation is acidproof, alkaline-resisting, Complete protection after, with hand can readily whole peel off, do not hinder coating, leave no trace;Should Resin is as a kind of water-base resin, and VOC (VOC) content is low, prepare and It is environmentally safe during use, and preparation method is simple and easy to apply, raw material is conveniently easy to get, single Usage amount in plane product is small.
Realizing first purpose of the present invention can be reached by adopting the following technical scheme that:
A kind of aqueous peelable resin, is prepared from by the component of following parts by weight:
Aqueous peelable resin of the present invention, wherein, by the component of following parts by weight It is prepared from:
Aqueous peelable resin of the present invention, wherein, the polyether Glycols or polyester The molecular weight of dihydric alcohol is 1000-3000;The polyether Glycols are selected from polypropylene glycol or poly- four Hydrogen furans glycol;The polyester diol be selected from polyethylene glycol adipate, polyadipate oneself One kind in diol ester, poly adipate succinic acid ester.
Aqueous peelable resin of the present invention, wherein, the diisocyanate is selected from first Phenylene diisocyanate, methyl diphenylene diisocyanate, IPDI, six Methylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, the isocyanic acid of xyxylene two One kind in ester, tetramethylxylylene diisocyanate.
Aqueous peelable resin of the present invention, wherein, the small molecule chain extender is small Molecule dihydric alcohol or small molecule diamine;The small molecule dihydric alcohol is selected from ethylene glycol, 1,2- One kind in propane diols, 1,4- butanediols, diglycol, 1,6-HD;It is described Small molecule diamine in ethylenediamine, 1,4- cyclohexane diamines, IPD one Kind;The hydrophilic chain extender is selected from dihydromethyl propionic acid or dimethylolpropionic acid.
Aqueous peelable resin of the present invention, wherein, the double bond end-capping reagent is selected from first Base hydroxy-ethyl acrylate, hydroxy-ethyl acrylate, hydroxy propyl methacrylate, acrylic acid hydroxypropyl One kind in ester;The catalyst is selected from stannous octoate, dibutyltin diacetate, two bays One kind in sour dibutyl tin;The nertralizer is in sodium hydroxide, ammoniacal liquor, triethylamine One kind;
Aqueous peelable resin of the present invention, wherein, the acrylic monomer is selected from Methyl methacrylate, n-butyl acrylate, methyl acrylate, n-BMA In one kind;The initiator is selected from azodiisobutyronitrile or potassium peroxydisulfate;The water is pure Water purification or deionized water.
Realize that second object of the present invention can reach by adopting the following technical scheme that:
A kind of preparation method of aqueous peelable resin as described above, comprises the following steps:
(1) polyaminoester emulsion/acrylic monomer mixture is prepared:By polyether Glycols or poly- Ester dihydric alcohol is put into reactor, is warming up to 100-120 DEG C, vacuum dehydration 0.5-2h, so Be cooled to afterwards after 50-60 DEG C stop vacuumize, sequentially added under stirring diisocyanate, Small molecule chain extender, hydrophilic chain extender and catalyst, simultaneously controlling reaction temperature exists for slow heating 70-90 DEG C, 2-4h is reacted, the content of NCO in performed polymer is surveyed with di-n-butylamine method, NCO is treated Stable content is cooled to 60-70 DEG C after 1-3%, adds double bond end-capping reagent, reacts 1-2h, 40-50 DEG C is cooled to, nertralizer is added, neutralized after 15-30min, half weight is added Acrylic monomer, add water emulsification 15-30min under 1000-1500rpm stirrings, is gathered Urethane emulsion/acrylic monomer mixture;
(2) polyacrylate-polyurethane copolymer emulsion is prepared:By gathering that step (1) is obtained Urethane emulsion/acrylic monomer mixture is added in reactor, adds initiator, heating To 60-80 DEG C, 0.5h is incubated, the acrylic monomer of second half weight is added drop-wise to reactor In, rate of addition is 1-2 drops/s, continues to react 3-6h, cooling discharge, poly- third obtained Olefin(e) acid ester-polyurethane copolymerization emulsion is aqueous peelable resin.
Realize that third object of the present invention can reach by adopting the following technical scheme that:This hair The application of aqueous peelable tree described in first bright purpose, it is used to be used as metal surface Temporary protective material.
The invention has the advantages that:
(1) aqueous peelable the resin-bonded polyacrylate and poly- ammonia that the present invention is prepared Both esters performance, can meet appropriate adhesive force and good rippability;
(2) after aqueous peelable resin film forming of the invention, when thickness of dry film is 20-40 μm, Can acid and alkali-resistance corrosion, soda acid immersion after, still can with whole stripping, and it is shielded not Snearing layer surface remains to keep original outward appearance and performance;
(3) preparation method of the invention is simple and easy to apply, and raw material is conveniently easy to get, and prepares Resin is as a kind of water-base resin, and VOC content is low, to environment without dirt during preparation and use Dye;
(4) aqueous peelable resin of the invention can be by conventional coating application mode, such as Spraying, showering, dip-coating etc., are coated on the non-sticking lining that need to be protected, and the resin compactness Well, harmful effect of the external environment condition to coating surface can effectively be completely cut off.
Embodiment
Below, with reference to embodiment, the present invention is described further:
Embodiment 1
A kind of aqueous peelable resin, is made by following preparation method:
(1) 10 parts by weight, molecular weight are put into reactor for 2000 polypropylene glycol In, 100 DEG C are warming up to, then vacuum dehydration 0.5h is cooled to after 50 DEG C and stops taking out 5 parts by weight of toluene diisocyanate, 1 parts by weight Isosorbide-5-Nitrae-fourth two are sequentially added under vacuum, stirring Alcohol, 1.2 parts by weight dihydromethyl propionic acids and 0.01 parts by weight of octanoic acid stannous, treat temperature stabilization Afterwards, simultaneously controlling reaction temperature, at 70 DEG C, reacts 2h for slow heating, is surveyed with di-n-butylamine method NCO content in performed polymer, it is stable after 1.5-2.5% after NCO content, it is cooled to 60 DEG C, 0.5 weight parts of methacrylic acid hydroxyl ethyl ester is added, 1h is reacted, is cooled to 40 DEG C, 1 parts by weight triethylamine is added, is neutralized after 15min, 1.5 weight parts of methacrylic acid first are added Ester, 1 weight parts of methacrylic acid N-butyl, add water emulsification under 1000rpm stirrings 15min, obtains polyaminoester emulsion/acrylic monomer mixture;
(2) polyaminoester emulsion for obtaining step (1)/acrylic monomer mixture is added Into reactor, 0.1 parts by weight azodiisobutyronitrile is added, 60 DEG C, insulation are warming up to 0.5h, 1.5 parts by weight of methylmethacrylate, 1 weight parts of methacrylic acid N-butyl are dripped It is added in reactor, rate of addition is 1-2 drops/s, continues to react 3h, cooling discharge is obtained To polyacrylate-polyurethane copolymer emulsion be the peelable resin of institute's water requiremen.
Embodiment 2
A kind of aqueous peelable resin, is made by following preparation method:
(1) 10 parts by weight, molecular weight are put into for 3000 polyethylene glycol adipate In reactor, 100 DEG C or so are warming up to, then vacuum dehydration 1h is cooled to 60 DEG C Stop vacuumizing afterwards, 8 parts by weight IPDIs, 2 weights are sequentially added under stirring Measure part diglycol, 1.4 parts by weight dimethylolpropionic acids and the bay of 0.02 parts by weight two Sour dibutyl tin, treats after temperature stabilization, slowly heats up and controlling reaction temperature is at 80 DEG C, 3h is reacted, the content of NCO in performed polymer is surveyed with di-n-butylamine method, NCO stable content is treated After 1.5-2.5%, 60 DEG C are cooled to, 1.0 parts by weight of acrylic acid hydroxyl ethyl esters, reaction are added 2h, is cooled to 50 DEG C, adds 1 parts by weight triethylamine, neutralizes after 20min, adds 2 weights Part methyl methacrylate, 1 parts by weight of acrylic acid N-butyl are measured, is added under 1500rpm stirrings Water emulsification 30min, obtains polyaminoester emulsion/acrylic monomer mixture;
(2) polyaminoester emulsion for obtaining step (1)/acrylic monomer mixture is added Into reactor, 0.1 parts by weight potassium peroxydisulfate is added, 80 DEG C are warming up to, 0.5h is incubated, 2 parts by weight of methylmethacrylate, 1 parts by weight of acrylic acid N-butyl are added drop-wise to reactor In, rate of addition is 1-2 drops/s, continues to react 3h, cooling discharge, obtained polypropylene Acid esters-polyurethane copolymerization emulsion is the peelable resin of institute's water requiremen.
Embodiment 3
A kind of aqueous peelable resin, is made by following preparation method:
(1) 10 parts by weight, molecular weight are put into instead for 2000 polytetrahydrofuran diol Answer in device, be warming up to 120 DEG C or so, then vacuum dehydration 1h is cooled to after 60 DEG C Stopping is vacuumized, and 10 parts by weight hexamethylene diisocyanates, 2 weights are sequentially added under stirring Measure part ethylenediamine, 2 parts by weight dihydromethyl propionic acids and the acetic acid dibutyl of 0.05 parts by weight two Tin, is treated after temperature stabilization, simultaneously controlling reaction temperature, at 90 DEG C, reacts 2h for slow heating, The content of NCO in performed polymer is surveyed with di-n-butylamine method, treats NCO stable content in 1.5-2.5% Afterwards, 70 DEG C are cooled to, 1.5 parts by weight of acrylic acid hydroxypropyl acrylates are added, 2h is reacted, is cooled to 50 DEG C, 0.6 parts by weight of sodium hydroxide is added, is neutralized after 30min, 3 parts by weight methyl are added Methyl acrylate, 1 parts by weight of acrylic acid N-butyl, 1 parts by weight of acrylic acid methyl esters, Add water emulsification 30min under 1500rpm stirrings, obtains polyaminoester emulsion/acrylic monomer and mixes Compound;
(2) polyaminoester emulsion for obtaining step (1)/acrylic monomer mixture is added Into reactor, 0.5 parts by weight potassium peroxydisulfate is added, 80 DEG C are warming up to, 0.5h is incubated, By 3 parts by weight of methylmethacrylate, 1 parts by weight of acrylic acid N-butyl, 1 parts by weight propylene Sour methyl esters is added drop-wise in reactor, and rate of addition is 1-2 drops/s, continues to react 6h, cooling Discharging, obtained polyacrylate-polyurethane copolymer emulsion is the peelable tree of institute's water requiremen Fat.
Embodiment 4
A kind of aqueous peelable resin, is made by following preparation method:
(1) 10 parts by weight molecular weight are put into instead for 1000 poly adipate succinic acid ester Answer in device, be warming up to 100 DEG C or so, then vacuum dehydration 0.5h is cooled to 50 DEG C Stop vacuumizing afterwards, the isocyanic acid of 10 parts by weight dicyclohexyl methyl hydride two is sequentially added under stirring Ester, 1.5 parts by weight IPDs, 2 parts by weight dihydromethyl propionic acids and 0.01 parts by weight Dibutyl tin laurate, is treated after temperature stabilization, simultaneously controlling reaction temperature exists for slow heating 70 DEG C, 4h is reacted, the content of NCO in performed polymer is surveyed with di-n-butylamine method, NCO content is treated It is stable to be cooled to 60 DEG C after 1.5-2.5%, add 1 weight parts of methacrylic acid hydroxypropyl Ester, reacts 2h, is cooled to 50 DEG C, adds 0.6 parts by weight ammoniacal liquor, neutralizes after 15min, 3 parts by weight of methylmethacrylate, 1 parts by weight of acrylic acid N-butyl are added, in 1000rpm Add water emulsification 15min under stirring, obtains polyaminoester emulsion/acrylic monomer mixture;
(2) polyaminoester emulsion for obtaining step (1)/acrylic monomer mixture is added Into reactor, 0.2 parts by weight azodiisobutyronitrile is added, 60 DEG C, insulation are warming up to 0.5h, 3 parts by weight of methylmethacrylate, 1 parts by weight of acrylic acid N-butyl are added drop-wise to instead Answer in device, rate of addition is 1-2 drops/s, continue to react 3h, cooling discharge, what is obtained is poly- Acrylate-polyurethane copolymer emulsion is the peelable resin of institute's water requiremen.
Below, the aqueous peelable resin prepared to embodiment 1-4 carries out performance test, table 1 For the basic performance method of testing of film, wherein resistance to acids and bases is to carry out anode according to aluminium sheet The maximum conditions that can be born during oxidation processes.Table 2 is film basic performance test result.
The test condition of the performance of aqueous peelable resin obtained by the embodiment of the present invention of table 1
Test event Test condition
Solid content 10min is heated at 120 DEG C
Thickness Film thickness gauge
Peelable degree Range estimation
Acid resistance 200g/L sulfuric acid solutions, 30min, 20-25 DEG C
Alkali resistance 200g/L sodium hydroxide solutions, 30min, 55-60 DEG C
Water resistance Drop 1 is dripped on hanging peelable film, observes 1h
Oil resistivity Drop 1 drips dimethicone on hanging peelable film, observes 1h
The results of property of aqueous peelable resin obtained by the embodiment of the present invention of table 2
Note:In table 2+for stripping process it is slightly imperfect, it is necessary to could peel off twice completely, ++ for can quick completely stripping once.
The resin that this method is prepared is computed, and its theoretical coated weight is 6-8m2/kg。
From above-mentioned Biao Ke get, designing the peelable film prepared by the formula of the present invention can be effective Prevent metal surface by acid and alkali corrosion.The resin can be molten in 55-60 DEG C of 200g/L NaOH 30 minutes are soaked in liquid without no foaming that comes off, film is complete, and simultaneously can be at 20-25 DEG C 200g/L H2SO4Kept for 30 minutes in solution, can simply complete stripping after washing. And the film stripped down can distinguish Waterproofing/oilproofing 1h and will not permeate.
The design principle of the aqueous peelable resin formula of the present invention is as follows:Aqueous polyurethane be with Highly polar carbamate groups are the polymer of primary structure, with excellent flexible Property, wearability, chemical-resistant, strong adhesive force, and with water substitute organic solvent make For decentralized medium, with nontoxic, nonflammable, free from environmental pollution, energy-conservation, safe and reliable The advantages of, but due to introducing hydrophilic radical in molecular structure, aqueous polyurethane it is water-fast Some performances such as property, resistance to acids and bases are also less desirable;Polyacrylate dispersion has excellent Hardness, glossiness, water resistance, stain resistance, resistance to acids and bases and good weatherability, Mutual supplement with each other's advantages can be realized by being combined with aqueous polyurethane.
The present invention is sealed by using double bond containing end-capping reagent to aqueous polyurethane strand End, and then can carry out emulsion copolymerization with acrylic monomer, has obtained a kind of polyurethane-poly- The copolymer emulsion of acrylate, is compared with existing PUA emulsions, can be more effective With reference to the excellent properties of both polyurethane and polyacrylate, its peelable film prepared is met The adhesive force appropriate to non-viscous paint and good rippability, and in smaller thickness Good acid-fast alkali-proof and water and oil-resistant can be played, excellent interim protection can be played and made With.
It will be apparent to those skilled in the art that technical scheme and structure that can be as described above Think, make other various corresponding changes and deformation, and all these change and deformation It should all belong within the protection domain of the claims in the present invention.

Claims (9)

1. a kind of aqueous peelable resin, it is characterised in that be prepared from by the component of following parts by weight:
2. aqueous peelable resin according to claim 1, it is characterised in that be prepared from by the component of following parts by weight:
3. aqueous peelable resin according to claim 1 or 2, it is characterised in that the polyether Glycols or the molecular weight of polyester diol are 1000-3000;The polyether Glycols are selected from polypropylene glycol or polytetrahydrofuran diol;The one kind of the polyester diol in polyethylene glycol adipate, polyadipate hexylene glycol ester, poly adipate succinic acid ester.
4. aqueous peelable resin according to claim 1 or 2, characterized in that, the one kind of the diisocyanate in toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, IPDI, hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate.
5. aqueous peelable resin according to claim 1 or 2, it is characterised in that the small molecule chain extender is small molecule dihydric alcohol or small molecule diamine;The one kind of the small molecule dihydric alcohol in ethylene glycol, 1,2- propane diols, 1,4- butanediols, diglycol, 1,6-HD;The one kind of the small molecule diamine in ethylenediamine, 1,4- cyclohexane diamines, IPD;The hydrophilic chain extender is selected from dihydromethyl propionic acid or dimethylolpropionic acid.
6. aqueous peelable resin according to claim 1 or 2, it is characterised in that the one kind of the double bond end-capping reagent in hydroxyethyl methacrylate, hydroxy-ethyl acrylate, hydroxy propyl methacrylate, hydroxypropyl acrylate;The one kind of the catalyst in stannous octoate, dibutyltin diacetate, dibutyl tin laurate;The one kind of the nertralizer in sodium hydroxide, ammoniacal liquor, triethylamine.
7. aqueous peelable resin according to claim 1 or 2, it is characterised in that the one kind of the acrylic monomer in methyl methacrylate, n-butyl acrylate, methyl acrylate, n-BMA;The initiator is selected from azodiisobutyronitrile or potassium peroxydisulfate;The water is pure water or deionized water.
8. a kind of preparation method of aqueous peelable resin as claimed in claim 1 or 2, it is characterised in that comprise the following steps:
(1) polyaminoester emulsion/acrylic monomer mixture is prepared:Polyether Glycols or polyester diol are put into reactor, it is warming up to 100-120 DEG C, vacuum dehydration 0.5-2h, then it is cooled to after 50-60 DEG C and stops vacuumizing, diisocyanate is sequentially added under stirring, small molecule chain extender, hydrophilic chain extender and catalyst, slowly heat up and controlling reaction temperature is at 70-90 DEG C, react 2-4h, it is cooled to 60-70 DEG C, add double bond end-capping reagent, react 1-2h, it is cooled to 40-50 DEG C, add nertralizer, neutralize after 15-30min, add the acrylic monomer of half weight, add water emulsification 15-30min under 1000-1500rpm stirrings, obtain polyaminoester emulsion/acrylic monomer mixture;
(2) polyacrylate-polyurethane copolymer emulsion is prepared:The polyaminoester emulsion that step (1) is obtained/acrylic monomer mixture is added in reactor, add initiator, it is warming up to 60-80 DEG C, it is incubated 0.5h, the acrylic monomer of second half weight is added drop-wise in reactor, rate of addition is 1-2 drops/s, continues to react 3-6h, cooling discharge, obtained polyacrylate-polyurethane copolymer emulsion is aqueous peelable resin.
9. a kind of application of aqueous peelable tree according to claim 1 or 2, it is characterised in that:It is used for the temporary protective material as metal surface.
CN201610035116.8A 2016-01-19 2016-01-19 A kind of aqueous peelable resin and its preparation method and application Pending CN106977657A (en)

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CN107722687A (en) * 2017-09-19 2018-02-23 河北晨阳工贸集团有限公司 Water-based peelable resin and preparation method thereof
CN109403091A (en) * 2018-10-30 2019-03-01 浙江蓝宇数码科技股份有限公司 A kind of environment-friendly digital weaving inking printing pigment ink and preparation method
CN109486402A (en) * 2018-11-19 2019-03-19 山东天庆科技发展有限公司 Aqueous peelable resin of one kind and preparation method thereof
CN111808561A (en) * 2020-06-16 2020-10-23 惠州市亨迪树脂制品有限公司 Modified polyurethane adhesive for TPR sole treatment-free and preparation method thereof
JP2021006638A (en) * 2020-09-24 2021-01-21 藤森工業株式会社 Anti-static surface protective film
CN112726273A (en) * 2021-01-30 2021-04-30 汕头市鑫源化工科技有限公司 Water-based high-gloss paint and preparation method thereof
CN112759718A (en) * 2020-12-30 2021-05-07 上海宝庆通用电工有限公司 Strippable resin and preparation method thereof
CN113683936A (en) * 2021-08-27 2021-11-23 浙江高成绿能科技有限公司 Water-based strippable nuclear biochemical protective film spraying liquid and preparation and use methods thereof

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CN107722687A (en) * 2017-09-19 2018-02-23 河北晨阳工贸集团有限公司 Water-based peelable resin and preparation method thereof
CN107722687B (en) * 2017-09-19 2020-02-07 河北晨阳工贸集团有限公司 Water-based peelable resin and preparation method thereof
CN109403091A (en) * 2018-10-30 2019-03-01 浙江蓝宇数码科技股份有限公司 A kind of environment-friendly digital weaving inking printing pigment ink and preparation method
CN109486402A (en) * 2018-11-19 2019-03-19 山东天庆科技发展有限公司 Aqueous peelable resin of one kind and preparation method thereof
CN111808561A (en) * 2020-06-16 2020-10-23 惠州市亨迪树脂制品有限公司 Modified polyurethane adhesive for TPR sole treatment-free and preparation method thereof
JP2021006638A (en) * 2020-09-24 2021-01-21 藤森工業株式会社 Anti-static surface protective film
JP7007440B2 (en) 2020-09-24 2022-01-24 藤森工業株式会社 Antistatic surface protective film
CN112759718A (en) * 2020-12-30 2021-05-07 上海宝庆通用电工有限公司 Strippable resin and preparation method thereof
CN112726273A (en) * 2021-01-30 2021-04-30 汕头市鑫源化工科技有限公司 Water-based high-gloss paint and preparation method thereof
CN112726273B (en) * 2021-01-30 2023-08-22 汕头市鑫源化工科技有限公司 Water-based high-gloss paint and preparation method thereof
CN113683936A (en) * 2021-08-27 2021-11-23 浙江高成绿能科技有限公司 Water-based strippable nuclear biochemical protective film spraying liquid and preparation and use methods thereof

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