CN101659726A - Benzene-free acrylic resin and preparation method thereof - Google Patents
Benzene-free acrylic resin and preparation method thereof Download PDFInfo
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- CN101659726A CN101659726A CN200910093629A CN200910093629A CN101659726A CN 101659726 A CN101659726 A CN 101659726A CN 200910093629 A CN200910093629 A CN 200910093629A CN 200910093629 A CN200910093629 A CN 200910093629A CN 101659726 A CN101659726 A CN 101659726A
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Abstract
The invention relates to a benzene-free acrylic resin and a preparation method thereof and adopts benzene-free solvent to completely substitute for dimethylbenzene as reflux solvent and diluting solvent. Through matching of all components, the reflux temperature of the resin properly meets requirement, the technical difficulty of 'reflux temperature' of resin is thoroughly solved and the participation of benzene series solvent is fundamentally eliminated, thus producing true benzene-free acrylic resin, greatly reducing the pollution to the environment in production and construction and ensuring the health of human body.
Description
Technical field
The present invention relates to paint field, particularly a kind of benzene-free acrylic resin and preparation method thereof.
Background technology
At present, environment-friendly type coating has had application very widely in the decorations field.Along with the development of society, the continuous enhancing of people's environmental consciousness, the theory deep day by day, healthy, environmental protection of international trade contact also is incorporated in the industrial coating field gradually, and this also has higher requirement to industrial coating.
Acrylic coating is with the mechanical property of its splendid guarantor's look gloss retention, brilliance, and excellent anti-marquis's performance is widely used in the application of industrial circle, as vehicle body, various hardware, instrument shell or the like.Acrylic coating is feedstock production with the acrylic resin, acrylic coating at present commonly used can be divided into two kinds of solvent-borne type and water-baseds according to the difference of the solvent that adopts, because acrylic resin is to be formed by esters of acrylic acid and other vinyl monomer copolymerization, temperature of reaction is generally 120 ℃～140 ℃, just in the boiling range of dimethylbenzene, so when the synthesizing propylene acid resin, all adopt dimethylbenzene as reflux solvent and diluting solvent, the resin of therefore traditional solvent-type acrylic lacquer and system lacquer usefulness, all be to adopt toluene, hazardous solvents such as dimethylbenzene, as diluting solvent or reflux solvent, can't satisfy environmental requirement.
Water soluble acrylic acid coating is compared with solvent-type acrylic coating from product performance, construction technology or the like aspect, all there is very big gap, can only under the situation of minority conditions permit, realize substituting, so present solvent-type acrylic product is still in occupation of the very big market share.
In order to reach environmental requirement, each production of resins producer has attempted a lot of methods, come the consumption of the benzene kind solvent in the instead of resins production, but eventually because of the particular restriction of reactive acrylic resin temperature, dimethylbenzene can't be substituted fully, the content of benzene series thing can only be reduced, therefore as reflux solvent, " environmental protection " acrylic resin on the market all because the resin of system lacquer usefulness can't accomplish really do not have benzene, all can't be accomplished real " no benzene " environmental protection.
Therefore, be necessary to propose a kind of acrylic resin of real no benzene.
Summary of the invention
The purpose of this invention is to provide a kind of acrylic resin that does not have benzene fully and preparation method thereof.
Benzene-free acrylic resin of the present invention adopts non-toluene solvent to replace dimethylbenzene as reflux solvent and diluting solvent, and wherein non-toluene solvent is to be selected from acetates solvent and the aromatic solvent one or more; The cooperation of preferred acetates solvent and aromatic solvent.
Wherein, described acetates solvent is one or more in vinyl acetic monomer, the N-BUTYL ACETATE; Described aromatic solvent is one or more in S-100A aromatic solvent, the S-150 aromatic solvent.
Benzene-free acrylic resin of the present invention comprises that following components in weight percentage is a raw material:
Acrylic ester monomer: 15～50%;
Benzene alkene: 19～31%;
Alkenoic acid: 0～5%;
Initiator: 0.6～2%;
Non-toluene solvent: 30～50%;
At 130 ℃～140 ℃, adopt non-toluene solvent as reflux solvent and diluting solvent, under action of evocating,, comprise acrylic ester monomer, benzene alkene, alkenoic acid with above-mentioned monomer, carry out building-up reactions and make.
In the raw material, can comprise 5～25% hydroxy acrylate monomer in the described acrylic ester monomer.
Preferably, the raw material of described benzene-free acrylic resin comprises following components in weight percentage:
Acrylic ester monomer: 20～35%;
Benzene alkene: 19～31%;
Alkenoic acid: 0～5%;
Initiator: 1～2%;
Non-toluene solvent: 35～45%;
Wherein, comprise 5～15% hydroxy acrylate monomer in the described acrylic ester monomer.
Wherein, described acrylic ester monomer is one or more in butyl acrylate, methyl methacrylate, ethyl propenoate, the Jia Jibingxisuanyizhi;
Described hydroxyl acrylic monomer is one or both of Hydroxyethyl acrylate, Propylene glycol monoacrylate.
Described benzene alkene is vinylbenzene;
Described alkenoic acid is one or more in vinylformic acid, the methacrylic acid;
Described initiator is benzoyl peroxide or dicumyl peroxide.
The present invention also provides the preparation method of above-mentioned benzene-free acrylic resin, and described preparation method comprises:
(1) non-toluene solvent is mixed, get wherein part adding reactor, be used for rebasing solvent;
(2) with various monomers, comprise acrylic ester monomer, benzene alkene and alkenoic acid, and the initiator of 50-80% formula ratio mixes;
(3) the reactor stirring is warming up to 130 ℃～140 ℃, drips the mixture of step (2);
(4) dropwise, be incubated 1-3 hour, drip the residue initiator;
(5) dropwise after, be incubated 2-4 hour, add the residue non-toluene solvent;
(6) cooling is filtered, packing.
Wherein, the amount of rebasing solvent can be according to the common practise decision of this area, and the 10-70% that generally gets non-toluene solvent adds reactor, is used as rebasing solvent.
The present invention has overcome the difficult point on the prior art, adopt non-toluene solvent to substitute dimethylbenzene fully and make reflux solvent and diluting solvent, and each component carried out suitable proportioning, the resin reflux temperature is just met the demands, solved fully " reflux temperature " technical barrier, fundamentally stopped the adding of benzene series solvent, thereby produced real benzene-free acrylic resin, significantly reduce the environmental pollution in production and the construction, ensured HUMAN HEALTH.
Embodiment
Following examples are used to illustrate the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
Benzene-free acrylic resin composition and proportioning are as shown in table 1:
Table 1 benzene-free acrylic resin is formed and proportioning
| Form | Charging capacity (kilogram) |
| N-BUTYL ACETATE | ??114 |
| S-100A aromatic solvent (1) | ??250 |
| Propylene glycol monoacrylate | ??58 |
| Ethyl propenoate | ??103 |
| Methyl methacrylate | ??121 |
| Vinylbenzene | ??256 |
| Dicumyl peroxide (1) | ??8 |
| Dicumyl peroxide (2) | ??2.9 |
| S-100A aromatic solvent (2) | ??87.1 |
| Add up to | ??1000 |
No benzene environment-friendly type acrylic resin preparation process concrete steps are as follows among the present invention:
(1) with N-BUTYL ACETATE 114KG, and S-100A aromatic solvent (1) 250KG, accurately reactor is gone in weighing reserve,
(2) with various monomers: Propylene glycol monoacrylate 58KG, ethyl propenoate 103KG, methyl methacrylate 121KG, after the accurate weighing of vinylbenzene 200KG, be equipped with successively into the monomer dropping jar, in addition with residue 56KG vinylbenzene dissolving dicumyl peroxide 8KG, stirs dissolved fully in 10 minutes after, continue to be equipped with into the monomer dropping jar
(3) stir at the uniform velocity and heat up, temperature to 135～140 ℃ begin to reflux, and drip the monomer mixture of step (2), about 2 hours of dropping process,
(4) after monomer dropping finishes, be incubated 2 hours, during will fill a prescription in remaining dicumyl peroxide (2) 2.9KG be dissolved in the S-100A aromatic solvent of 30KG, stir 10 minutes fully the dissolving after, be equipped with into the monomer dropping jar standby again;
(5) drip the initiator solution that step (4) prepares, be incubated 3 hours again after finishing, adjust viscosity with residue S-100A aromatic solvent, to acceptability limit; Consumption is 57.1KG,
(6) resin is cooled to 90 ℃, filters, detect, pack.
The no phenyl ring that makes is protected the resin index: viscosity 12S (form pipe), amount of solid content 56%.
After joining lacquer in order to last resin, the detection data of the environmental type acrylic paint that obtains are as shown in table 2:
The performance of the acrylic paint of table 2 benzene-free acrylic resin preparation
| Interventions Requested | Detected result | The method of inspection |
| Paint film color and outward appearance | Meet model color, smooth smooth | Range estimation |
| Viscosity (being coated with-4) s | ??52 | ??GB/T1723 |
| Fineness μ m | ??20 | ??GB/T1724 |
| Time of drying, the h surface drying was done solid work oven dry | ??1 ??48 ??90℃/30min | ??GB/T1728 |
| Hardness | ??0.65 | ??GB/T1730 |
| Shock strength, cm | ??50 | ??GB/T1732 |
| Sticking power, level | ??1 | ??GB/T1720 |
| Snappiness, mm | ??1 | ??GB/T1731 |
| Gloss, (60 °) | ??94 | ??GB/T9754 |
| Water tolerance (24h) | Non-foaming | ??GB/T9274 |
| Petrol-resistance 120# (24h) | Non-foaming, wrinkle resistant | ??GB/T9274 |
| Artificial ageing resistance (800h) loss of gloss, efflorescence/level variable color/level | ??≤2 ??≤1 | ??GB/T1865 |
| Benzene content mg/kg | Do not detect | ??GB?18581 |
| Toluene and dimethylbenzene mg/kg | Do not detect | ??GB18581 |
| Lead content mg/kg | Do not detect | ??ROHS |
| Cadmium content mg/kg | Do not detect | ??ROHS |
| Mercury content mg/kg | Do not detect | ??ROHS |
| Content of 6-valence Cr ions mg/kg | Do not detect | ??ROHS |
Embodiment 2
Benzene-free acrylic resin composition and proportioning are as shown in table 3:
Table 3 benzene-free acrylic resin is formed and proportioning
| Form | Charging capacity (kilogram) |
| N-BUTYL ACETATE | ??130 |
| S-100A aromatic solvent (1) | ??190 |
| Propylene glycol monoacrylate | ??113 |
| Ethyl propenoate | ??118 |
| Methyl methacrylate | ??168 |
| Methacrylic acid | ??3 |
| Vinylbenzene | ??193 |
| Dicumyl peroxide (1) | ??11 |
| Dicumyl peroxide (2) | ??4 |
| S-100A aromatic solvent (2) | ??60 |
| Add up to | ??1000 |
No benzene environment-friendly type acrylic resin preparation process concrete steps are as follows among the present invention:
(1) with N-BUTYL ACETATE, and S-100A aromatic solvent (1), accurately reactor is gone in weighing reserve,
(2) with various monomers: Propylene glycol monoacrylate, ethyl propenoate, methyl methacrylate, methacrylic acid, part vinylbenzene, accurately after the weighing, be equipped with successively, dissolve dicumyl peroxide with residual styrene in addition into the monomer dropping jar, stir 10 minutes fully the dissolving after, continue to be equipped with into the monomer dropping jar;
(3) stir at the uniform velocity and heat up, temperature to 135～140 ℃ begin to reflux, and drip the monomer mixture of step (2), about 2 hours of dropping process,
(4) after monomer dropping finishes, be incubated 2 hours, during will fill a prescription in the S-100A aromatic solvent that is dissolved in of remaining dicumyl peroxide (2), stir 10 minutes fully after the dissolving, be equipped with into the monomer dropping jar standby again;
(5) drip the initiator solution that step (4) prepares, be incubated 3 hours again after finishing, adjust viscosity with residue S-100A aromatic solvent, to acceptability limit; Consumption is 57.1KG,
(6) resin is cooled to 90 ℃, filters, detect, pack.
The no phenyl ring that makes is protected the resin index: viscosity 11S (form pipe), solid part 60%.
Embodiment 3
Benzene-free acrylic resin composition and proportioning are as shown in table 4:
Table 4 benzene-free acrylic resin is formed and proportioning
| Form | Charging capacity (kilogram) |
| N-BUTYL ACETATE | ??130 |
| S-100A aromatic solvent (1) | ??200 |
| Propylene glycol monoacrylate | ??82 |
| Ethyl propenoate | ??88 |
| Methyl methacrylate | ??71 |
| Vinylformic acid | ??41 |
| Vinylbenzene | ??291 |
| Dicumyl peroxide (1) | ??12 |
| Dicumyl peroxide (2) | ??4 |
| S-100A aromatic solvent (2) | ??81 |
| Add up to | ??1000 |
No benzene environment-friendly type acrylic resin preparation process concrete steps are as follows among the present invention:
(1) with N-BUTYL ACETATE, and S-100A aromatic solvent (1), accurately reactor is gone in weighing reserve,
(2) with various monomers: Propylene glycol monoacrylate, ethyl propenoate, methyl methacrylate, vinylformic acid, part vinylbenzene accurately after the weighing, is equipped with into the monomer dropping jar successively, dissolve dicumyl peroxide with residual styrene in addition, stir 10 minutes fully the dissolving after, continue to be equipped with into the monomer dropping jar;
(3) stir at the uniform velocity and heat up, temperature to 135～140 ℃ begin to reflux, and drip the monomer mixture of step (2), about 2 hours of dropping process,
(4) after monomer dropping finishes, be incubated 2 hours, during will fill a prescription in the S-100A aromatic solvent that is dissolved in of remaining dicumyl peroxide (2), stir 10 minutes fully after the dissolving, be equipped with into the monomer dropping jar standby again;
(5) drip the initiator solution that step (4) prepares, be incubated 3 hours again after finishing, adjust viscosity with residue S-100A aromatic solvent, to acceptability limit; Consumption is 57.1KG,
(6) resin is cooled to 90 ℃, filters, detect, pack.
The no phenyl ring that makes is protected the resin index: viscosity 10S (form pipe), solid part 59%.
Claims (10)
1, a kind of benzene-free acrylic resin is characterized in that, adopting non-toluene solvent, described non-toluene solvent is to be selected from acetates solvent and the aromatic solvent one or more.
2, benzene-free acrylic resin as claimed in claim 1 is characterized in that, described non-toluene solvent is the cooperation of acetates solvent and aromatic solvent.
As the arbitrary described benzene-free acrylic resin of claim 1-2, it is characterized in that 3, described acetates solvent is one or more in vinyl acetic monomer, the N-BUTYL ACETATE; Described aromatic solvent is one or more in S-100A aromatic solvent, the S-150 aromatic solvent.
As the arbitrary described benzene-free acrylic resin of claim 1-3, it is characterized in that 4, described benzene-free acrylic resin comprises that following components in weight percentage is a raw material:
Acrylic ester monomer: 15～50%;
Benzene alkene: 19～31%;
Alkenoic acid: 0～5%;
Initiator: 0.6～2%;
Non-toluene solvent: 30～50%;
At 130 ℃～140 ℃, adopt non-toluene solvent as reflux solvent and diluting solvent, under action of evocating, above-mentioned monomer is carried out building-up reactions make.
5, benzene-free acrylic resin as claimed in claim 4 is characterized in that, comprises 5～25% hydroxy acrylate monomer in the described acrylic ester monomer.
As claim 4 or 5 described benzene-free acrylic resins, it is characterized in that 6, described benzene-free acrylic resin comprises that following components in weight percentage is a raw material:
Acrylic ester monomer: 20～35%;
Benzene alkene: 19～31%;
Alkenoic acid: 0～5%;
Initiator: 1～2%;
Non-toluene solvent: 35～45%;
Wherein, comprise 5～15% hydroxy acrylate monomer in the described acrylic ester monomer.
As the arbitrary described benzene-free acrylic resin of claim 4-6, it is characterized in that 7, described acrylic ester monomer is one or more in butyl acrylate, methyl methacrylate, ethyl propenoate, the Jia Jibingxisuanyizhi; Described hydroxyl acrylic monomer is one or both of Hydroxyethyl acrylate, Propylene glycol monoacrylate.
8,, it is characterized in that described benzene alkene is vinylbenzene as the arbitrary described benzene-free acrylic resin of claim 4-6; Described alkenoic acid is one or more in vinylformic acid, the methacrylic acid.
As the arbitrary described benzene-free acrylic resin of claim 4-6, it is characterized in that 9, described initiator is benzoyl peroxide or dicumyl peroxide.
10, a kind of preparation method as the arbitrary described benzene-free acrylic resin of claim 5-9 comprises:
(1) non-toluene solvent is mixed, get wherein part adding reactor, be used for rebasing solvent;
(2) various monomers and 50-80% formula ratio initiator are mixed;
(3) the reactor stirring is warming up to 130 ℃～140 ℃, drips the mixture of step (2);
(4) dropwise, be incubated 1-3 hour, drip the residue initiator;
(5) dropwise after, be incubated 2-4 hour, add the residue non-toluene solvent;
(6) cooling is filtered, packing.
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| CN200910093629A CN101659726B (en) | 2009-09-25 | 2009-09-25 | Benzene-free acrylic resin and preparation method thereof |
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| CN101659726B CN101659726B (en) | 2012-10-03 |
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| CN101787097A (en) * | 2010-03-12 | 2010-07-28 | 北京化工大学 | Preparation method of water-soluble solid styrene-acrylic resin |
| CN105001368A (en) * | 2015-07-18 | 2015-10-28 | 山东路美交通设施有限公司 | Thermoplastic benzene-free acrylic resin |
| CN107573456A (en) * | 2017-08-23 | 2018-01-12 | 广东彤德新材料有限公司 | A kind of high adhesion force without benzene Hydroxylated acrylic resin and preparation method thereof |
| CN108976337A (en) * | 2018-05-28 | 2018-12-11 | 莱阳红安化工有限公司 | A kind of environmental protection thermosetting acrylic resin and preparation method thereof |
| CN109679016A (en) * | 2018-12-13 | 2019-04-26 | 清远市浩宇化工科技有限公司 | A kind of preparation method and applications of the environmental protection without the automobile-used acrylic resin of benzene |
| CN111349189A (en) * | 2020-04-26 | 2020-06-30 | 杨光云 | Flame-retardant nitrogen-phosphorus synergistic carbon nanotube modified acrylic resin material and preparation method thereof |
| CN114395070A (en) * | 2021-12-16 | 2022-04-26 | 广东贝壳新材料科技有限公司 | Preparation method of benzene-free hydroxy acrylic resin |
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| CN1049023A (en) * | 1989-07-27 | 1991-02-06 | 广州科技开发总公司棠溪有机化工厂 | The diluent for paint of no benzene |
| CN1048873A (en) * | 1990-06-05 | 1991-01-30 | 张展洪 | The production method of non-bezene acrylic acid resin baking finish and self-drying paint |
| JP3870682B2 (en) * | 2000-09-25 | 2007-01-24 | 東洋インキ製造株式会社 | Paint composition |
| DE10339137A1 (en) * | 2003-08-22 | 2005-03-10 | Basf Ag | Composition especially for coating textiles or leather contains a (co)polymer obtained using a photoinitiator, a plasticizer and a branched compound with terminal double bonds |
| CN1970652A (en) * | 2005-11-23 | 2007-05-30 | 黄永平 | Environment-friendly health type paint thinner |
| CN101168629A (en) * | 2006-10-26 | 2008-04-30 | 陈广康 | Multifunctional safety dope diluent |
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2009
- 2009-09-25 CN CN200910093629A patent/CN101659726B/en not_active Expired - Fee Related
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| CN101787097A (en) * | 2010-03-12 | 2010-07-28 | 北京化工大学 | Preparation method of water-soluble solid styrene-acrylic resin |
| CN105001368A (en) * | 2015-07-18 | 2015-10-28 | 山东路美交通设施有限公司 | Thermoplastic benzene-free acrylic resin |
| CN107573456A (en) * | 2017-08-23 | 2018-01-12 | 广东彤德新材料有限公司 | A kind of high adhesion force without benzene Hydroxylated acrylic resin and preparation method thereof |
| CN107573456B (en) * | 2017-08-23 | 2020-06-02 | 广东彤德新材料有限公司 | High-adhesion benzene-free hydroxyl acrylic resin and preparation method thereof |
| CN108976337A (en) * | 2018-05-28 | 2018-12-11 | 莱阳红安化工有限公司 | A kind of environmental protection thermosetting acrylic resin and preparation method thereof |
| CN108976337B (en) * | 2018-05-28 | 2019-07-19 | 莱阳红安化工有限公司 | A kind of environmental protection thermosetting acrylic resin and preparation method thereof |
| CN109679016A (en) * | 2018-12-13 | 2019-04-26 | 清远市浩宇化工科技有限公司 | A kind of preparation method and applications of the environmental protection without the automobile-used acrylic resin of benzene |
| CN111349189A (en) * | 2020-04-26 | 2020-06-30 | 杨光云 | Flame-retardant nitrogen-phosphorus synergistic carbon nanotube modified acrylic resin material and preparation method thereof |
| CN114395070A (en) * | 2021-12-16 | 2022-04-26 | 广东贝壳新材料科技有限公司 | Preparation method of benzene-free hydroxy acrylic resin |
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