CN106543348A - A kind of acrylic resin with environment-friendlyplasticizer plasticizer with excellent compatibility - Google Patents

A kind of acrylic resin with environment-friendlyplasticizer plasticizer with excellent compatibility Download PDF

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Publication number
CN106543348A
CN106543348A CN201611031235.2A CN201611031235A CN106543348A CN 106543348 A CN106543348 A CN 106543348A CN 201611031235 A CN201611031235 A CN 201611031235A CN 106543348 A CN106543348 A CN 106543348A
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acrylic resin
environment
initiator
plasticizer
resin according
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CN106543348B (en
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刘倩
李翔
吴建军
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Boli'er Chemical (yangzhou) Co Ltd
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Boli'er Chemical (yangzhou) Co Ltd
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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
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/14Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F2/00Processes of polymerisation
    • C08F2/12Polymerisation in non-solvents
    • C08F2/16Aqueous medium
    • C08F2/20Aqueous medium with the aid of macromolecular dispersing agents
    • 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
    • C08F2/00Processes of polymerisation
    • C08F2/38Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/16Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/10Esters; Ether-esters
    • C08K5/101Esters; Ether-esters of monocarboxylic acids
    • C08K5/103Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/10Esters; Ether-esters
    • C08K5/12Esters; Ether-esters of cyclic polycarboxylic acids
    • 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
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/16Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/16Applications used for films

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of acrylic resin with environment-friendlyplasticizer plasticizer with excellent compatibility, described acrylic resin is obtained by the polymerization of following mass percent by following monomer:Methyl methacrylate 40.0~50.0%, butyl methacrylate 30.0~50.0%, isobutyl methacrylate 0~10.0%, acrylic acid methyl ester. 3.0~15.0%, methacrylic acid 0.2~2.0%, ethyl methacrylate 0~10.0%, hydroxyethyl methylacrylate 0.2~2.0%, the mass percent sum of above-mentioned monomer is 100%.The acrylic resin that the present invention is provided has the excellent compatibility with non-phthalic acid ester class environment-friendlyplasticizer plasticizer, can dissolve each other completely to form clear solution and film forming with environment-friendlyplasticizer plasticizer, and film toughness reaches 0T levels, there is good stability, environmental protection, safety non-toxic, alternative PVC is used.

Description

A kind of acrylic resin with environment-friendlyplasticizer plasticizer with excellent compatibility
Technical field
The present invention is to be related to a kind of acrylic resin, specifically, is to be related to one kind to have good phase with environment-friendlyplasticizer plasticizer The acrylic resin of capacitive, belongs to acrylic materials technical field.
Background technology
PVC (polrvinyl chloride) is a kind of application general-purpose plastics widely, is mainly used in tubing, sheet material, undulation degree The fields such as material, membrane material, plastisol.Wherein, pvc plastisol is the main seal glue of automobile, about China's automobile adhesive 1/3.In recent years, the pay attention to day by day with people to Environmental Health, some problems that PVC brings also increasingly are closed by people Note, for example:Residual monomer vinyl chloride in PVC, migrates out product surface with the time, and larger shadow can be caused to health Ring;The combustion product bioxin meeting serious environment pollution of PVC, has strong carcinogenecity, and can cause deformity, can be to human body Immunologic function and reproductive function cause to damage.In addition, the heat stability of PVC product, weatherability are poor, in heat, oxygen, light Under effect, PVC can remove HCl formed conjugated bonds and make resin discoloration, product become fragile, degradation.
Acrylic resin be by esters of acrylic acid and methyl acrylic ester and other resins made by olefinic type monomers copolymerization, With excellent light resistance and anti-outdoor aging performance, and biodegradable in the environment and chemical degradation, combustion product Predominantly carbohydrate, environmental sound.Therefore, gradually adopt acrylic resin to substitute PVC at present to use.
In order that plastics have good toughness, film property, it will usually the plasticizer for adding property compatible good wherein, Domestic main plasticizer is phthalate material at present, such as:DOP (dinoctyl phthalate), DEHP neighbour's benzene Dioctyl phthalate two (2- Octyl Nitrites).But, this kind of plasticizer has heavy damage to the healthy reproduction of the mankind, especially child, together When also can to environment, therefore, many countries have begun to disable phthalate material, the substitute is Novel environment-friendlyplasticizer plasticizer, such as Yi Siman TXIB, DOTP of successful commercialization etc..The environment-friendly type plasticising such as TXIB, DOTP at present Agent is primarily adapted for use in PVC plastic, for example:A kind of Chinese patent " the disposable handss of environmental protection polyvinyl chlorides of CN201110318486.X- In the preparation method of set " using DOTP as PVC plastic product plasticizer, product is nontoxic, excellent performance;Chinese patent With DOTP as plasticizer system in " a kind of preparation methoies of environmental protection polyvinyl chloride aqueouss artificial leather of CN201510146563.6- " Standby dermatine, meets the environmentally friendly high request both at home and abroad to synthetic leather;A kind of Chinese patent " systems of CN201110428652.1- The method of the standby pvc plastisol for including NBR " is using TXIB as plastisol plasticizer.
Acrylic resin will replace PVC, it is also desirable to possess and PVC identicals film property and toughness, therefore, it is also desirable to add The good plasticizer of property compatible, but, the environment-friendlyplasticizer plasticizer compatibility such as current acrylic resin and TXIB, DOTP is not It is good, there is presently no with regard to the environment-friendlyplasticizer plasticizers such as TXIB, DOTP are added in acrylic resins with improve its toughness, The relevant report of film property.
The content of the invention
For prior art exist the problems referred to above, it is an object of the invention to provide one kind have with environment-friendlyplasticizer plasticizer it is good The acrylic resin of the good compatibility, to meet environmental requirement.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of acrylic resin with environment-friendlyplasticizer plasticizer with excellent compatibility, is by following quality hundred by following monomer Divide and obtain than polymerization:
The mass percent sum of above-mentioned monomer is 100%.
Preferably, the acrylic resin is obtained by the polymerization of following mass percent by following monomer:
The mass percent sum of above-mentioned monomer is 100%.
Preferably, the acrylic resin is to carry out suspension polymerisation by above-mentioned monomer to obtain.
Used as further preferred scheme, the formula of suspension polymerization system is as follows:In terms of 100 mass parts, monomer total amount is accounted for 30.0~45.0 mass parts, initiator account for 0.1~2.0 mass parts, and dispersant accounts for 0.1~2.0 mass parts, and surfactant is accounted for 0.05~0.1 mass parts, molecular weight regulator account for 0.2~1.0 mass parts, and remaining is deionized water.
Used as further preferred scheme, the initiator is azo-initiator or organic peroxy class initiator, the idol At least one of the nitrogen class initiator in azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), the organic peroxy class initiator are selected from At least one in dibenzoyl peroxide, dilauroyl peroxide, di-t-butyl peroxide.
Used as further preferred scheme, the dispersant is selected from polyvinyl alcohol, polyacrylic acid, cellulose, magnesium carbonate, carbonic acid At least one in calcium.
As further preferred scheme, the surfactant selected from sodium lauryl sulphate, dodecylbenzene sodium sulfonate, At least one in polyether surfactant.
As further preferred scheme, the molecular weight regulator selected from n-dodecyl mercaptan, secondary lauryl mercaptan, At least one in tert-dodecylmercaotan, mercaptoethanol, TGA.
Heretofore described environment-friendlyplasticizer plasticizer refers to 2,2,4- TMPD isobutyl esters (TXIB), terephthaldehyde The non-phthalic ester plasticizers such as the different monooctyl ester (DOTP) of acid, epoxidation oils and fatss.
Compared with prior art, the present invention has following significance beneficial effect:
Experiment is proved:Acrylic resin and 2,2,4- TMPD isobutyl esters (TXIB) that the present invention is provided, to benzene The non-phthalic acid ester class environment-friendlyplasticizer plasticizer such as the different monooctyl ester of dioctyl phthalate (DOTP), epoxidation oils and fatss has the excellent compatibility, Can dissolve each other completely at a certain temperature to form clear solution and film forming with environment-friendlyplasticizer plasticizer by a certain percentage, and film toughness reaches To 0T levels, there is no plasticizer exudation within one week in 60 DEG C of standings, there is good stability, environmental protection, safety non-toxic, it is alternative PVC is used;In addition, the acrylic resin that the present invention is provided can be prepared using process for suspension polymerization, with preparation technology letter It is single, it is with low cost, without the need for special installation and harsh conditions, it is easy to accomplish the advantages of large-scale production, with extremely strong practical valency Value.
Description of the drawings
Test schematic diagrams of the Fig. 1 for membrane material toughness.
Specific embodiment
Technical solution of the present invention is described in further detail and completely with reference to embodiment and comparative example.
Embodiment
0.1 mass parts dispersant (polyvinyl alcohol) and 64.4 mass parts deionized waters are uniformly mixed at room temperature, Then heat to 65 DEG C;Add the monomer of composition, 0.55 mass parts initiator (two isobutyl of azo shown in 34.67 mass parts tables 1 Nitrile), 0.07 mass of surface activating agent (sodium lauryl sulphate), 0.21 mass parts molecular weight regulator (dodecyl sulfur Alcohol), insulated and stirred is reacted 8 hours, and mixing speed is 450rpm, obtains final product acrylic resin of the present invention.
1 monomer composition formula of table (wt%, mass percent)
Numbering MMA BMA IBMA MA MAA EMA HEMA
1 42.0 42.0 0 12.6 1.7 0 1.7
2 47.2 47.2 0 4.8 0.4 0 0.4
3 45.9 36.7 0 13.8 1.8 0 1.8
4 45.9 36.7 9.2 4.6 1.8 0 1.8
5 45.9 36.7 0 4.6 1.8 9.2 1.8
6 44.6 35.7 4.5 8.9 0.9 4.5 0.9
Note:English abbreviations of the MMA for methyl methacrylate (CAS#80-62-6), BMA is n-BMA (CAS#97-88-1) english abbreviation, english abbreviations of the IBMA for isobutyl methacrylate (CAS#97-86-9), MA is third The english abbreviation of e pioic acid methyl ester (CAS#96-33-3), english abbreviations of the MAA for methacrylic acid (CAS#79-41-4), EMA is The english abbreviation of ethyl methacrylate (CAS#97-63-2), HEMA are hydroxyethyl methylacrylate (CAS#868-77-9) English abbreviation.
The compatibility and stability test:
Obtained acrylic resin in embodiment is pressed into quality shown in table 2 respectively with environment-friendlyplasticizer plasticizer TXIB, DOTP Than being blended at different temperatures, to investigate the compatibility between acrylic resin of the present invention and environment-friendlyplasticizer plasticizer, Then gained mixture is stood at room temperature to investigate the stability of mixture.Detailed Experimental is the results are shown in Table shown in 2.
2 compatibility of table and stability experiment result
Note:N represents insoluble, and P represents partial miscibility, and A represents whole dissolvings, and TL represents transparency liquid, and TS represents transparent solid Body.
From 2 experimental result of table:The acrylic resin that the present invention is provided is had with environment-friendlyplasticizer plasticizer TXIB and DOTP There is the good compatibility, and the mixture formed after mixing has good stability.
The test of film property and film toughness and plasticizer exudation situation:
Obtained acrylic resin in embodiment is heated to the mixture of environment-friendlyplasticizer plasticizer TXIB or DOTP respectively Liquid, carries out film after forming clear solution, then gained resin film is placed in 60 DEG C of baking ovens and stands one week, so by thickness 0.5mm After test film toughness, concrete method of testing is as follows:By panel clamp on bending instrument, then to film outside direction doubling, after release Again by 180 ° of doublings of model, clamped with bending instrument and be allowed to be substantially parallel, the explanation if film does not split is 0T, if it find that opening Split, then carried out to curved on this basis, if not having breakage, deflection meter is 1T, the like 2T, 3T is obtained, numerical value is less, Represent that the bending radius of film is less, the stress being subject to is bigger, and corresponding toughness is also better, conversely, numerical value is bigger, represent bending Radius is bigger, toughness poorer (shown in Figure 1).Meanwhile, resin film is stood into one week in 60 DEG C, to investigate plasticising in resin Situation is oozed out in agent.Detailed Experimental is the results are shown in Table shown in 3.
The experimental result of 3 film toughness of table and plasticizer exudation situation
Note:NS is represented does not have plasticizer exudation;T represents that film is transparent.
From 3 experimental result of table:The acrylic resin that the present invention is provided is formed with environment-friendlyplasticizer plasticizer TXIB and DOTP Transparent mixed solution be respectively provided with good film property, and film toughness can reach 0T levels and with good stability, 60 There is no plasticizer exudation situation within one week in DEG C standing.
Comparative example
0.1 mass parts dispersant (polyvinyl alcohol) and 64.4 mass parts deionized waters are uniformly mixed at room temperature, Then heat to 65 DEG C;Add the contrast monomer of composition shown in 34.67 mass parts tables 4, (azo two is different for 0.55 mass parts initiator Butyronitrile), 0.07 mass of surface activating agent (sodium lauryl sulphate), 0.21 mass parts molecular weight regulator (dodecyl Mercaptan), insulated and stirred is reacted 8 hours, and mixing speed is 450rpm, obtains contrasting acrylic resin.
Table 4 contrasts the compositing formula (wt%, mass percent) of monomer
Numbering MMA BMA IBMA MA MAA EMA HEMA
7 66.7 0 0 0 0 33.3 0
8 55.6 0 0 0 0 44.4 0
9 66.7 0 0 33.3 0 0 0
10 55.6 0 0 44.4 0 0 0
11 0 66.7 0 33.3 0 0 0
12 0 55.6 0 44.4 0 0 0
13 0 0 66.7 33.3 0 0 0
14 0 0 55.6 44.4 0 0 0
Using with embodiment identical method of testing, investigate contrast acrylic resin and environment-friendlyplasticizer plasticizer TXIB and DOTP The compatibility, stability, film property, film toughness and plasticizer exudation situation.
The compatibility and the experiment of stability of acrylic resin and environment-friendlyplasticizer plasticizer TXIB and DOTP are contrasted with regard to gained The results are shown in Table shown in 5.
5 compatibility of table and stability experiment result
Note:N represents insoluble, and P represents partial miscibility, and A represents whole dissolvings, and IL represents opaque liquid, and L/S represents solid-liquid Layering, IS represent opaque solid.
Contrast table 2 and table 5 are visible:Under identical preparation technology, the propylene prepared using the monomer of composition of the present invention Acid resin compared to other constitute contrast monomers prepare contrast acrylic resin for, with environment-friendlyplasticizer plasticizer TXIB With the more preferable compatibility of DOTP, the mixed solution for being formed has more preferable stability.
The film toughness and increasing of acrylic resin and environment-friendlyplasticizer plasticizer TXIB and the mixed solution of DOTP are contrasted with regard to gained Modeling agent is oozed out the specific experiment of situation and be the results are shown in Table shown in 6.
The experimental result of 6 film toughness of table and plasticizer exudation situation
Note:YS indicates plasticizer exudation;I represents that film is opaque.
Contrast table 3 and table 6 are visible:Using composition of the present invention monomer prepare acrylic resin compared to other groups Into contrast monomer prepare contrast acrylic resin for, it is molten with the mixing for being formed of environment-friendlyplasticizer plasticizer TXIB and DOTP Liquid has more preferable film property and film toughness and stability.
Finally need it is pointed out here that be:The above is only the part preferred embodiment of the present invention, it is impossible to be interpreted as to this The restriction of bright protection domain, those skilled in the art's the above of the invention make some it is nonessential improvement and Adjustment belongs to protection scope of the present invention.

Claims (8)

1. a kind of and environment-friendlyplasticizer plasticizer has the acrylic resin of excellent compatibility, it is characterised in that described acrylic acid tree Fat is obtained by the polymerization of following mass percent by following monomer:
The mass percent sum of above-mentioned monomer is 100%.
2. acrylic resin according to claim 1, it is characterised in that:The acrylic resin is carried out by the monomer Suspension polymerisation is obtained.
3. acrylic resin according to claim 2, it is characterised in that the formula of suspension polymerization system is as follows:With 100 matter Amount part meter, monomer total amount account for 30.0~45.0 mass parts, and initiator accounts for 0.1~2.0 mass parts, and dispersant accounts for 0.1~2.0 mass Part, surfactant accounts for 0.05~0.1 mass parts, and molecular weight regulator accounts for 0.2~1.0 mass parts, and remaining is deionized water.
4. acrylic resin according to claim 3, it is characterised in that:The initiator is azo-initiator or organic Peroxide initiator, at least one of the azo-initiator in azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile) are described to have At least one of the machine peroxide initiator in dibenzoyl peroxide, dilauroyl peroxide, di-t-butyl peroxide.
5. acrylic resin according to claim 3, it is characterised in that:The dispersant is selected from polyvinyl alcohol, polypropylene Acid, cellulose, magnesium carbonate, at least one in Calcium Carbonate.
6. acrylic resin according to claim 3, it is characterised in that:The surfactant is selected from lauryl sulphate acid At least one in sodium, dodecylbenzene sodium sulfonate, polyether surfactant.
7. acrylic resin according to claim 3, it is characterised in that:The molecular weight regulator is selected from dodecyl At least one in mercaptan, secondary lauryl mercaptan, tert-dodecylmercaotan, mercaptoethanol, TGA.
8. acrylic resin according to claim 1, it is characterised in that:Described environment-friendlyplasticizer plasticizer is non-O-phthalic Acid ester type plasticizer.
CN201611031235.2A 2016-11-22 2016-11-22 A kind of acrylic resin with environment-friendlyplasticizer plasticizer with excellent compatibility Active CN106543348B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108948254A (en) * 2018-07-06 2018-12-07 莱阳红安化工有限公司 A kind of feature of environmental protection acrylic resin and preparation method thereof

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CN102585072A (en) * 2012-01-11 2012-07-18 南京瑞固聚合物有限公司 Room temperature self-crosslinking acrylic ester emulsion
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CN103756602A (en) * 2014-01-10 2014-04-30 佛山市奥雅图胶粘实业有限公司 Acrylate pressure-sensitive adhesive for protective film and preparation method thereof
CN105884965A (en) * 2016-06-12 2016-08-24 上海未泉新材料科技有限公司 Flexible acrylic resin

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108948254A (en) * 2018-07-06 2018-12-07 莱阳红安化工有限公司 A kind of feature of environmental protection acrylic resin and preparation method thereof
CN108948254B (en) * 2018-07-06 2019-06-04 莱阳红安化工有限公司 A kind of feature of environmental protection acrylic resin and preparation method thereof

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