CN101659726B - Benzene-free acrylic resin and preparation method thereof - Google Patents
Benzene-free acrylic resin and preparation method thereof Download PDFInfo
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- CN101659726B CN101659726B CN200910093629A CN200910093629A CN101659726B CN 101659726 B CN101659726 B CN 101659726B CN 200910093629 A CN200910093629 A CN 200910093629A CN 200910093629 A CN200910093629 A CN 200910093629A CN 101659726 B CN101659726 B CN 101659726B
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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, like vehicle body, various hardware, instrument shell or the like.Acrylic coating is feedstock production with the vinyl resin, and acrylic coating at present commonly used can be divided into solvent-borne type and two kinds of water-baseds according to the difference of the solvent that adopts, owing to vinyl 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 YLENE, so when the synthesizing propylene acid resin, all adopt YLENE as reflux solvent and diluting solvent; The resin of therefore traditional solvent-type acrylic lacquer and system lacquer usefulness; All be to adopt hazardous solvents such as toluene, YLENE,, can't satisfy environmental requirement as diluting solvent or reflux solvent.
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, comes 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; YLENE can't be substituted fully, the content of benzene series thing can only be reduced, therefore as reflux solvent; " environmental protection " vinyl 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 vinyl resin of real no benzene.
Summary of the invention
The purpose of this invention is to provide a kind of vinyl 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 YLENE 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, said acetates solvent is one or more in vinyl acetic monomer, the N-BUTYL ACETATE; Said 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 said acrylic ester monomer.
Preferably, the raw material of said 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 said acrylic ester monomer.
Wherein, said acrylic ester monomer is one or more in Bing Xisuandingzhi, TEB 3K, ethyl propenoate, the Jia Jibingxisuanyizhi;
Said hydroxyl acrylic monomer is one or both of Hydroxyethyl acrylate, Propylene glycol monoacrylate.
Said benzene alkene is vinylbenzene;
Said alkenoic acid is one or more in vinylformic acid, the methylacrylic acid;
Said initiator is Lucidol or Di Cumyl Peroxide 99.
The present invention also provides the preparation method of above-mentioned benzene-free acrylic resin, and said preparation method comprises:
(1) non-toluene solvent is mixed, get wherein part adding reaction kettle, 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 reaction kettle 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 reaction kettle, is used as rebasing solvent.
The present invention has overcome the difficult point on the prior art, adopts non-toluene solvent to substitute YLENE fully and makes reflux solvent and diluting solvent, and each component is 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 explain the present invention, but are not used for limiting scope of the present 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 |
| TEB 3K | 121 |
| Vinylbenzene | 256 |
| Di Cumyl Peroxide 99 (1) | 8 |
| Di Cumyl Peroxide 99 (2) | 2.9 |
| S-100A aromatic solvent (2) | 87.1 |
| Add up to | 1000 |
To prepare the process concrete steps following for no benzene environment-friendly type vinyl resin among the present invention:
(1) with N-BUTYL ACETATE 114KG, and S-100A aromatic solvent (1) 250KG, accurately reaction kettle is gone in weighing reserve,
(2) with various monomers: Propylene glycol monoacrylate 58KG, ethyl propenoate 103KG, TEB 3K 121KG; After the accurate weighing of vinylbenzene 200KG; Be equipped with successively into the monomer dropping jar, in addition with residue 56KG vinylbenzene dissolving Di Cumyl Peroxide 99 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 Di Cumyl Peroxide 99 (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 subsequent use again;
(5) drip the initiator solution that step (4) prepares, be incubated 3 hours again after finishing, with residue S-100A aromatic solvent adjustment viscosity, 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 YLENE 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 |
| TEB 3K | 168 |
| Methylacrylic acid | 3 |
| Vinylbenzene | 193 |
| Di Cumyl Peroxide 99 (1) | 11 |
| Di Cumyl Peroxide 99 (2) | 4 |
| S-100A aromatic solvent (2) | 60 |
| Add up to | 1000 |
To prepare the process concrete steps following for no benzene environment-friendly type vinyl resin among the present invention:
(1) with N-BUTYL ACETATE, and S-100A aromatic solvent (1), accurately reaction kettle is gone in weighing reserve,
(2) with various monomers: Propylene glycol monoacrylate, ethyl propenoate, TEB 3K; Methylacrylic acid, part vinylbenzene; Accurately after the weighing, be equipped with successively, dissolve Di Cumyl Peroxide 99 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 Di Cumyl Peroxide 99 (2), stir 10 minutes fully after the dissolving, be equipped with into the monomer dropping jar subsequent use again;
(5) drip the initiator solution that step (4) prepares, be incubated 3 hours again after finishing, with residue S-100A aromatic solvent adjustment viscosity, 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 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 |
| TEB 3K | 71 |
| Vinylformic acid | 41 |
| Vinylbenzene | 291 |
| Di Cumyl Peroxide 99 (1) | 12 |
| Di Cumyl Peroxide 99 (2) | 4 |
| S-100A aromatic solvent (2) | 81 |
| Add up to | 1000 |
To prepare the process concrete steps following for no benzene environment-friendly type vinyl resin among the present invention:
(1) with N-BUTYL ACETATE, and S-100A aromatic solvent (1), accurately reaction kettle is gone in weighing reserve,
(2) with various monomers: Propylene glycol monoacrylate, ethyl propenoate, TEB 3K, vinylformic acid; Part vinylbenzene accurately after the weighing, is equipped with into the monomer dropping jar successively; Dissolve Di Cumyl Peroxide 99 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 Di Cumyl Peroxide 99 (2), stir 10 minutes fully after the dissolving, be equipped with into the monomer dropping jar subsequent use again;
(5) drip the initiator solution that step (4) prepares, be incubated 3 hours again after finishing, with residue S-100A aromatic solvent adjustment viscosity, 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 59%.
Claims (6)
1. a benzene-free acrylic resin is characterized in that, adopts non-toluene solvent, and said non-toluene solvent is the cooperation of acetates solvent and aromatic solvent;
Said acetates solvent is one or more in vinyl acetic monomer, the N-BUTYL ACETATE; Said aromatic solvent is one or more in S-100A aromatic solvent, the S-150 aromatic solvent;
Said 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;
Said acrylic ester monomer is one or more in Bing Xisuandingzhi, TEB 3K, ethyl propenoate, the Jia Jibingxisuanyizhi; Said benzene alkene is vinylbenzene; Said alkenoic acid is one or more in vinylformic acid, the methylacrylic acid.
2. benzene-free acrylic resin as claimed in claim 1 is characterized in that, said initiator is Lucidol or Di Cumyl Peroxide 99.
3. benzene-free acrylic resin as claimed in claim 1 is characterized in that, comprises 5～25% hydroxy acrylate monomer in the said acrylic ester monomer.
4. benzene-free acrylic resin as claimed in claim 3 is characterized in that, said 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 said acrylic ester monomer;
Said acrylic ester monomer is one or more in Bing Xisuandingzhi, TEB 3K, ethyl propenoate, the Jia Jibingxisuanyizhi; Said benzene alkene is vinylbenzene; Said alkenoic acid is one or more in vinylformic acid, the methylacrylic acid; Said hydroxy acrylate monomer is one or both of Hydroxyethyl acrylate, Propylene glycol monoacrylate.
5. like claim 3 or 4 described benzene-free acrylic resins, it is characterized in that said initiator is Lucidol or Di Cumyl Peroxide 99.
6. preparation method like the arbitrary described benzene-free acrylic resin of claim 1-5 comprises:
(1) non-toluene solvent is mixed, get wherein part adding reaction kettle, be used for rebasing solvent;
(2) various monomers and 50-80% formula ratio initiator are mixed;
(3) the reaction kettle 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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| CN101787097B (en) * | 2010-03-12 | 2011-11-09 | 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 |
| 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 |
| 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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| 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 |
| JP2002097405A (en) * | 2000-09-25 | 2002-04-02 | Toyo Ink Mfg Co Ltd | Coating material 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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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP2002097405A (en) * | 2000-09-25 | 2002-04-02 | Toyo Ink Mfg Co Ltd | Coating material 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 |
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| CN101168629A (en) * | 2006-10-26 | 2008-04-30 | 陈广康 | Multifunctional safety dope diluent |
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Effective date of registration: 20161012 Address after: 101111, 7, five street, 17 light street, Beijing, Tongzhou District Patentee after: Beijing Red Lion Technology Development Co. Ltd. Address before: 101111, No. five, seventeen street, Tongzhou District, Beijing Patentee before: Beijing Hongshi Paint Co., Ltd. |
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