CN101602905B - Preparation method of solvent-free polyacrylate flow smoothing agent - Google Patents
Preparation method of solvent-free polyacrylate flow smoothing agent Download PDFInfo
- Publication number
- CN101602905B CN101602905B CN2008100388011A CN200810038801A CN101602905B CN 101602905 B CN101602905 B CN 101602905B CN 2008100388011 A CN2008100388011 A CN 2008100388011A CN 200810038801 A CN200810038801 A CN 200810038801A CN 101602905 B CN101602905 B CN 101602905B
- Authority
- CN
- China
- Prior art keywords
- solvent
- preparation
- smoothing agent
- flow smoothing
- polyacrylate flow
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention relates to a preparation method of a solvent-free polyacrylate flow smoothing agent. The preparation method comprises the following steps: 10-30wt% of polyacrylic acid flow smoothing agent which does not contain a solvent is used as prepreg, then 70-90wt% of mixed monomer which can be polymerized is dropped in, and the solvent-free polyacrylate flow smoothing agent is obtained by carrying out a free radical polymerization reaction at 100-170 DEG C. Compared with the prior art, the invention has the characteristics of low temperature, normal pressure, no solvent, waste reduction, and the like and conforms to the trend of environmental protection, and the manufactured polyacrylate flow smoothing agent can be applied to the flow smoothing and shrinkproof holes of systems with solvents or without solvents and powder bodies.
Description
Technical field
The present invention relates to the preparation method of polyacrylate flow agent, relate in particular to a kind of preparation method of solvent-free polyacrylate flow smoothing agent.
Background technology
Coating is the organism of a kind of flow state or pulverulence, can evenly cover on the body surface, and securely attached to body surface, be referred to as coating.Coating assorted the one coating process that don't work all has one to flow and the process of drying and forming-film after the construction, form gradually then one smooth, smooth, film uniformly.Coating can not only play protection, decoration function, also can design specific functions such as having insulation, conduction, anti-electrostatic, temperature indicating, mildew-resistant or sterilization concurrently simultaneously.Solvent based coating is in the exsiccant process, and along with the evaporation of solvent, the surface tension on the top layer of filming improves, viscosity increases, temperature descends; Cause the difference of top layer and bottom surface tension force, viscosity and temperature, coating is moved toward the top layer from bottom, and the top layer of coating sinks because of action of gravity; Form convection current, this convection current forms erose lines in film coated surface, is referred to as uncle and receives born of the same parents; These lines still can't be eliminated behind dried coating film, promptly form the orange peel phenomenon of general normal theory.And solvent-free or powder coating is in the process of film sclerosis or fusion levelling; Formed surface tension gradient in the local area, i.e. shrinkage cavity partly is the low surface tension material, because the low surface tension material always presents the expansion trend that stretches; Make it therefrom spread around the mind-set; And the tight all around high surface tension part of closely touching mutually is tendencies toward shrinkage, under the two-way interaction, just forms permanent shrinkage cavity.In addition, the dealing with improperly or pollute of ground, and in the coating process, the pollution of air as coating cloud, dust, aqueous vapor etc. are arranged in the air, all possibly cause the defective of filming.
As everyone knows, the major function of coating is to decorate and protection, if film unfairness and irregular shrinkage cavity or defective occur, does not only have decorative effect, and can reduce or damage its defencive function.The effective ways that overcome these disadvantages add shrinkproof hole flow agent exactly.Flow agent is a kind of coatings additive(s), and surface tension itself is lower, and compatible limited with coating resin, can move to coatingsurface at short notice and form unimolecular layer, reduces surface tension gradient, avoids uncle to receive eddy effect, prevents depression, the enhancement levelling.
Polyacrylate flow agent is exactly often to be used for solving film depression, shrinkage cavity, promotes a kind of flow agent of levelling, and its stable in properties is facile hydrolysis not; Have excellent anti-opticity and the resistance to deterioration of revolving; And non-volatile, can improve the snappiness and the shock-resistance of filming, do not influence recoat.The method of manufacture of polyacrylate flow agent is not to adopt solution polymerization at present; Directly use, like publication number CN1571822A, CN1345900A, US5047259, or with removal of solvents; Be applied to solvent-free or powder coating, like publication number CN1277231A, US5397844.Above method of manufacture all need be used solvent, if will be applied to solvent-free or powder coating, then needs vacuum to remove solvent, and the source of both having consumed energy is time-consuming again, and the problem of solvent waste liquid is arranged.
Summary of the invention
The object of the invention is exactly for the weak point that overcomes above-mentioned prior art existence preparation method and the application thereof that a kind of method is simple, cost is low, environmental protection subtracts useless solvent-free polyacrylate flow smoothing agent to be provided.
The object of the invention can be realized through following technical scheme: a kind of preparation method of solvent-free polyacrylate flow smoothing agent; It is characterized in that; With not solvent-laden ROHM flow agent 10～30wt% as preparatory pan feeding; Splash into polymerisable mix monomer 70～90wt% again, under 100 ℃～170 ℃, carry out Raolical polymerizable and get.
Described not solvent-laden ROHM flow agent is commercially available modest Levelol 892 of moral or Levelol896.
Described mix monomer is mixed by propenoate and methacrylate monomers 50～98wt%, chain-transfer agent 1～3wt%, initiator 1～5wt% and other copolymerizable monomer 0～10wt%.
Described propenoate and methacrylate monomers unit comprise the alkyl acrylate and the alkyl methacrylate of straight chain, branching or cyclic fatty alcohol with 0～22 carbon atom; Acrylamide and methacrylic vinegar amine with straight chain, branching or cyclic aliphatic amine of 1～22 carbon atom; Have the acrylic acid hydroxy alkyl ester and the hydroxyalkyl methacrylate of straight chain, branching or the cyclic aliphatic diol of 2～36 carbon atoms, have the perfluoroalkyl acrylate or the perfluoroalkyl methacrylate of 6-20 carbon atom.
Described chain regulator may command molecule amount is big or small, comprises the alkyl sulfhydryl, 2 of C10～C15,4-phenylbenzene-4-methylpentene.
Described other copolymerizable monomer comprises vinyl ester with 3～20 carbon atoms and in the verivate one or more thereof.
The initiator that described radical polymerization uses is selected from one or more in organo-peroxide, the azo-type initiator.
Described initiator comprises Diisopropyl azodicarboxylate (AIBN), diphenyl peroxide first vinegar (BPO), t-butyl-oxybenzoate, peroxide-2-ethyl hexanoic acid tert-butyl, ditertiary butyl peroxide.
The preferable temperature of reaction of described Raolical polymerizable is 110 ℃～150 ℃.
Described mix monomer is preferably mixed by propenoate and methacrylate monomers 82～98wt%, chain-transfer agent 1～3wt%, initiator 1～5wt% and other copolymerizable monomer 0～10wt%.
Compared with prior art, the preparation method of polyacrylate flow agent of the present invention does not use solvent; Not only manufacturing step is simple, and production cost reduces, and meets environmental protection and subtract useless; It can directly use solvent, the solvent-free and powder coating system of being added on, or and inorganic matter carrier, like silicon-dioxide, aluminum oxide or zeyssatite etc.; After manufacturing the powder flow agent, be added into powder coating again, can make the purpose that coating reaches levelling, ground is wetting and prevent shrinkage cavity.
Embodiment
Below be embodiment and the comparative example of doing according to technical scheme of the present invention, in order to further explanation the present invention.
Embodiment 1
Use a 1000ml four neck glass reaction bottles configuration whisking appliance, temperature controller, prolong.In reaction flask, load the not solvent-laden ROHM flow agent Levelol 892 of 120g; As preparatory pan feeding; Splash into polymerisable mixed monomer solution 880g again; After this mixed monomer solution is mixed by n-butyl acrylate 12.5wt%, TEB 3K 3.98wt%, ethyl acrylate 79.55wt%, lauryl mercaptan 2.27wt% and peroxide-2-ethyl hexanoic acid tert-butyl 1.7wt%; In 4 hours, add gradually in the reaction flask, system keeps 120 ℃ again and continues 3 hours, carries out Raolical polymerizable and gets.
Comparative example 1
Use a 1000ml four neck glass reaction bottles configuration whisking appliance, temperature controller, prolong.In reaction flask, load the YLENE of 200g, be heated to 120 ℃.After 100g n-butyl acrylate, 30g TEB 3K, 660g ethyl acrylate and 10g peroxide-2-ethyl hexanoic acid tert-butyl mix, in 4 hours, add gradually in the reaction flask, system keeps 120 ℃ again and continues 3 hours.Be warming up to 150 ℃ at last, vacuumize and remove 200g YLENE, can obtain the vinylformic acid levelling agent of solid content＞98%.
Embodiment 2
Use a 1000ml four neck glass reaction bottles configuration whisking appliance, temperature controller, prolong.The not solvent-laden ROHM flow agent Levelol 896 that in reaction flask, loads 100g is as preparatory pan feeding; Splash into polymerisable mixed monomer solution 900g again, this mixed monomer solution is by Bing Xisuandingzhi 79wt% and methacrylate monomers 5wt%, chain-transfer agent 2; 4-phenylbenzene-4-methylpentene 1wt%; Vinyl acetate 10wt% after ditertiary butyl peroxide 5wt% mixes, added in the reaction flask in 3 hours gradually; 170 ℃ of system held continue 4 hours, carry out Raolical polymerizable and get.
Embodiment 3
Use a 1000ml four neck glass reaction bottles configuration whisking appliance, temperature controller, prolong.The not solvent-laden ROHM flow agent Levelol 896 that in reaction flask, loads 300g is as preparatory pan feeding; Splash into polymerisable mix monomer 700g again, this mixed monomer solution is by Bing Xisuandingzhi 89.5wt% and methylacrylic acid perfluoro capryl ethyl ester 5wt%, lauryl mercaptan 2wt%; After Diisopropyl azodicarboxylate (AIBN) 3.5wt% mixes; In 4 hours, add gradually in the reaction flask, 100 ℃ of system held continue 3 hours, carry out Raolical polymerizable and get.
Embodiment 4
Use a 1000ml four neck glass reaction bottles configuration whisking appliance, temperature controller, prolong.The not solvent-laden ROHM flow agent Levelol 892 that in reaction flask, loads 200g splashes into polymerisable mix monomer 800g again as preparatory pan feeding, and this mixed monomer solution is by ethyl acrylate 86wt% and vinylformic acid N; N-dimethylamino-propyl ester 10wt%; Lauryl mercaptan 3wt% after peroxide-2-ethyl hexanoic acid tert-butyl 1wt% mixes, added in the reaction flask in 3 hours gradually; 110 ℃ of system held continue 4 hours, carry out Raolical polymerizable and get.
Table one. the synthesizing formula (representing) of embodiment 1～4 and comparative example 1 with weight percent
| The name of an article | Embodiment 1 | Comparative example 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Levelol?892 | 13 | - | 20 | ||
| Levelol?896 | - | 10 | 30 | ||
| YLENE | 20 | ||||
| N-butyl acrylate | 10.6 | 10 | 71.1 | 62.7 | |
| TEB 3K | 3.2 | 3 | 4.5 | ||
| Ethyl acrylate | 69.7 | 66 | 68.8 | ||
| The methylacrylic acid perfluor is hot | 3.5 |
| The base ethyl ester | |||||
| Vinylformic acid N, N-dimethylamino-propyl ester | 8 | ||||
| Vinyl acetate | 9 | ||||
| Lauryl mercaptan | 2 | 1.4 | 2.4 | ||
| 2,4-phenylbenzene-4-methylpentene | 0.9 | ||||
| Peroxide-2-ethyl hexanoic acid tert-butyl | 1.5 | 1 | 0.8 | ||
| Ditertiary butyl peroxide | 4.5 | ||||
| Diisopropyl azodicarboxylate (AIBN) | 2.5 |
Realize the flow agent of gained via embodiment 1～4 and comparative example 1, can prepare through the prescription of table two and obtain the epoxy polyester powder coating.
Table diepoxy polyester powder coating prescription
Annotate: the 663U mixture of 10% flow agent A or B is to be mixed with kibbler with the 663U of 90 weight % and got by the flow agent A of 10 weight % or B.
Evaluation condition:
1, by prescription that various raw materials hand mix in plastic tape is even
2, open the condensation water circulation system, open the ice water circulation system, open tabletting machine
The inlet end temperature of 3, opening and regulating the powder forcing machine is 95 ℃, and the temperature of exit end is 100 ℃, and equitemperature arrives back adjusting screw(rod) rotating speed to appropriate speed and begin to extrude
4, pour the powder coating that mixes into opening for feed and make its automatic feed and extrude, process sheet through the tabletting machine cooling press then
5, pass through the pulverizing of kibbler requirements at the higher level after the pulverizing compressed tablet just earlier again, at last through 200 purpose screen filtration finished product powder coating
6, last on tinplate tin or aluminium sheet electrostatic spraying thickness be the rete that is coated with of 50-70um, be positioned in 200 ℃ of baking ovens and toast 10min, the powder coating layer is heating and curing
7, last test physicals
Experimental result shows, the flow agent that embodiment 1～4 and comparative example 1 are prepared all can obtain the appearance of film that leveling characteristics is good, tangerine line degree is slight, clarity is good at the epoxy polyester powder coating.Test result is shown in table three.
Table three. the application performance assessment result
Claims (9)
1. the preparation method of a solvent-free polyacrylate flow smoothing agent; It is characterized in that, not solvent-laden ROHM flow agent 10～30wt% as preparatory pan feeding, is splashed into polymerisable mix monomer 70～90wt% again; Under 100 ℃～170 ℃, carry out Raolical polymerizable and get.
2. the preparation method of a kind of solvent-free polyacrylate flow smoothing agent according to claim 1 is characterized in that, described not solvent-laden ROHM flow agent is commercially available modest Levelol 892 of moral or Levelol896.
3. the preparation method of a kind of solvent-free polyacrylate flow smoothing agent according to claim 1; It is characterized in that described mix monomer is mixed by propenoate and methacrylate monomers 82～98wt%, chain-transfer agent 1～3wt%, initiator 1～5wt% and other copolymerizable monomer 0～10wt%.
4. the preparation method of a kind of solvent-free polyacrylate flow smoothing agent according to claim 3; It is characterized in that; Described propenoate and methacrylate monomers unit comprise the alkyl acrylate and the alkyl methacrylate of straight chain, branching or cyclic fatty alcohol with 0～22 carbon atom; Have the acrylic acid hydroxy alkyl ester and the hydroxyalkyl methacrylate of straight chain, branching or the cyclic aliphatic diol of 2～36 carbon atoms, have the perfluoroalkyl acrylate or the perfluoroalkyl methacrylate of 6-20 carbon atom.
5. the preparation method of a kind of solvent-free polyacrylate flow smoothing agent according to claim 3 is characterized in that, described chain-transfer agent may command molecule amount is big or small, comprises the alkyl sulfhydryl, 2 of C10～C15,4-phenylbenzene-4-methylpentene.
6. the preparation method of a kind of solvent-free polyacrylate flow smoothing agent according to claim 3 is characterized in that, described other copolymerizable monomer comprises vinyl ester with 3～20 carbon atoms and in the verivate one or more thereof.
7. the preparation method of a kind of solvent-free polyacrylate flow smoothing agent according to claim 1 is characterized in that, the initiator that described radical polymerization uses is selected from one or more in organo-peroxide, the azo-type initiator.
8. the preparation method of a kind of solvent-free polyacrylate flow smoothing agent according to claim 7; It is characterized in that described initiator comprises Diisopropyl azodicarboxylate (AIBN), BPO (BPO), t-butyl-oxybenzoate, peroxide-2-ethyl hexanoic acid tert-butyl, ditertiary butyl peroxide.
9. the preparation method of a kind of solvent-free polyacrylate flow smoothing agent according to claim 1 is characterized in that, the preferable temperature of reaction of described Raolical polymerizable is 110 ℃～150 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100388011A CN101602905B (en) | 2008-06-11 | 2008-06-11 | Preparation method of solvent-free polyacrylate flow smoothing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100388011A CN101602905B (en) | 2008-06-11 | 2008-06-11 | Preparation method of solvent-free polyacrylate flow smoothing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101602905A CN101602905A (en) | 2009-12-16 |
| CN101602905B true CN101602905B (en) | 2012-01-25 |
Family
ID=41468807
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100388011A Active CN101602905B (en) | 2008-06-11 | 2008-06-11 | Preparation method of solvent-free polyacrylate flow smoothing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101602905B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153902B (en) * | 2011-03-11 | 2013-05-29 | 安徽嘉智信诺化工有限公司 | Fluorocarbon anti-shrinkage flatting agent for coating ink |
| CN102786626B (en) * | 2012-07-16 | 2016-03-02 | 六安科瑞达新型材料有限公司 | A kind of preparation method of polyacrylate(s) flow agent actives used for powder coating |
| CN102807806A (en) * | 2012-07-26 | 2012-12-05 | 惠州市至上化工有限公司 | Nano silica-modified recoatable rubber paint used on plastic and processing technology for paint |
| CN103102446B (en) * | 2013-03-01 | 2017-10-20 | 湖北乾兴化工有限公司 | A kind of car refinishing paint Hydroxylated acrylic resin and preparation method thereof |
| CN104448080A (en) * | 2014-11-15 | 2015-03-25 | 安徽景成化工科技有限公司 | Preparation method for poly(n-butyl acrylate) leveling agent |
| CN105131175B (en) * | 2015-08-20 | 2018-06-26 | 黄山华惠科技有限公司 | A kind of Silicone modified acryl's ester levelling agent and preparation method |
| CN105754028B (en) * | 2016-03-08 | 2018-08-14 | 东莞建晖纸业有限公司 | A kind of rheological agent synthetic method of papermaking paint |
| CN109575733B (en) * | 2018-12-06 | 2021-02-05 | 山东中佳生活服务有限公司 | Safe and environment-friendly anti-skid composition and application thereof in vehicles |
-
2008
- 2008-06-11 CN CN2008100388011A patent/CN101602905B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN101602905A (en) | 2009-12-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101602905B (en) | Preparation method of solvent-free polyacrylate flow smoothing agent | |
| CN102199377B (en) | Ultraviolet curing processing agent | |
| CN103866607B (en) | A kind of high-strength direct is aluminized aqueous basecoat and its preparation method and application | |
| CN102533063B (en) | Ultraviolet ray-curable low-gloss flow-coating paint and preparation method thereof | |
| CN103540240B (en) | UV-composite laser coating composition | |
| WO2019223026A1 (en) | Coil coating based on eb-curing | |
| CN103304719A (en) | Acrylic emulsion and preparation method and application in waterborne polyvinyl chloride (PVC) wallpaper ink thereof | |
| CN107141425A (en) | A kind of baking vanish aqueous epoxy resins and preparation method and application | |
| CN107266625B (en) | A kind of PVC furniture film water inkwood rouge and preparation method thereof | |
| CN106833295A (en) | A kind of electrostatic spraying high abrasion UV white primers | |
| TWI616494B (en) | Topcoat composition, method of coating substrates with the same, and substrate | |
| CN104592843A (en) | High-flatness water transfer film coating and preparation method thereof | |
| CN105949859B (en) | A kind of powdery paints optical brightener and preparation method and application | |
| CN103289456A (en) | UV film-pressed yellowing-resistant topcoat gloss paint | |
| TWI630108B (en) | Low-gloss sheet and its molded product | |
| KR101169203B1 (en) | ECO friendly and recyclable water soluble coating materials for paper coating and manufacturing method thereof | |
| CN1612921A (en) | Pressure sensitive adhesive film for overlamination | |
| CN106752606B (en) | A kind of aqueous fluorine silica acrylic acid coating and preparation method thereof | |
| JP6481565B2 (en) | Hard coating agent for decorative film, cured film, plastic film, and molded product | |
| JP2008169345A (en) | Resin composition for plastic coating material and plastic coating material using the same | |
| CN105038479A (en) | Modified acrylic resin energy-saving and environment-friendly coating for microwave oven shell | |
| CN105037778A (en) | Preparing method for environment-friendly composite material for sanitary product | |
| CN104356841A (en) | Self-cleaning acrylic coating | |
| CN106905842B (en) | Wear-resisting super-hydrophobic self-cleaning coating and preparation method thereof | |
| CN108624240A (en) | Room temperature ketone hydrazine self-crosslinking acrylic resin aqueous dispersion and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |