CN102363640A - Acrylic ester powdered resin having self-cleaning property and synthesizing method thereof - Google Patents
Acrylic ester powdered resin having self-cleaning property and synthesizing method thereof Download PDFInfo
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- CN102363640A CN102363640A CN 201110183187 CN201110183187A CN102363640A CN 102363640 A CN102363640 A CN 102363640A CN 201110183187 CN201110183187 CN 201110183187 CN 201110183187 A CN201110183187 A CN 201110183187A CN 102363640 A CN102363640 A CN 102363640A
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Abstract
The invention relates to an acrylic ester powdered resin having a self-cleaning property and a synthesizing method thereof. The acrylic ester powdered resin comprises the following components in part by weight: 8-15 parts of polymeric carboxylic acids, 40-60 parts of methyl methacrylates, 10-25 parts of butyl acrylates, 10-30 parts of butyl methacrylates, 5-20 parts of fluorinated monomers, 10-20 parts of methyl isobornyl thiocyanoacetates and 1.5-3.5 parts of initiating agents. Several conventional acrylate monomers, isobornyl acrylate monomers and fluorinated acrylate monomers are copolymerized, degassed, crushed and like, thereby acquiring the powdered acrylic resin having an excellent property. Compared with the prior art, the resin synthesized according to the synthesizing method has excellent ageing resistance and scraping resistance as well as self-cleaning property, contains no VOC (Volatile Organic Compounds) and has water solubility.
Description
Technical field
The present invention relates to a kind of powdex and compound method thereof, especially relate to a kind of propenoate powder resin and compound method thereof with self-cleaning performance.
Background technology
Along with the day by day concern of countries in the world to environmental protection, and the increasingly stringent of relevant prevention and cure of pollution rules, revolutionary change has taken place in resin manufacture industry in the past few years, and just the solvent type resin with original high pollution is transformed into oligosaprobic resin.Environment-friendly resin can comprise that 100% is solid resinous, water-base resin and powder solid resin.100% solid resinous viscosity is excessive, present stage domestic equipment do not catch up with, construction is difficulty; Water-base resin generally needs the outer small-molecular emulsifier that adds, and there is certain influence in the later stage film properties; Though also there is certain defective in powdex, batch stability is better, and does not contain volatile matter, can play good environment protecting.
The powdex preparation roughly divides three types: mass polymerization, letex polymerization and solution polymerization.The bulk polymerization heat is difficult to timely release, has the danger of blast; The residual certain emulsifying agent of meeting affects to resin property in the letex polymerization resin.Solution polymerization, suitable operation, cost is practiced thrift in the recyclable utilization of solvent.What adopt when the present invention is synthetic is the environment-friendly type etoh solvent.Initiator adopts azobisisobutyronitrile, azo diisoamyl eyeball and the azo two eyeball tool in different heptan can.
Conventional powder solid resin is in friction resistant, and all there is certain defective in aspect performances such as high-low temperature resistant and automatically cleaning.The powder solid resin that the present invention makes is introduced the low surface energy fluorochemical monomer and is participated in copolymerization, is that the resin that makes has certain fluoro-resin characteristic; Exactly remedied the performance deficiency of conventional propenoate; And have water-solublely, do not contain emulsifying agent, the performance deficiency that does not exist the emulsifying agent migration to bring.
Summary of the invention
The object of the invention is exactly for the defective that overcomes above-mentioned prior art existence a kind of excellent weather resistance that has to be provided; Anti-aging; The anti-performance of wiping is good, and the propenoate powder resin and the compound method thereof with self-cleaning performance of excellent protectiveness can be provided various base materials.
The object of the invention can be realized through following technical scheme:
A kind of propenoate powder resin with self-cleaning performance is characterized in that this powdex is prepared by following component and weight part content:
Polymerizable carboxylic acid 8～15;
TEB 3K 40～60;
Bing Xisuandingzhi 10～25;
NSC 20956 10～30;
Fluorochemical monomer 5～20;
Methyl isobornyl thiocyanoacetate 10～20;
Initiator 1.5～3.5.
Following component of the raw material of this powdex and weight part content prepare:
Polymerizable carboxylic acid 8～10;
TEB 3K 42～50;
Bing Xisuandingzhi 15～20;
NSC 20956 12～18;
Fluorochemical monomer 8～12;
Methyl isobornyl thiocyanoacetate 12～15;
Initiator 1.5～3.5.
Described polymerizable carboxylic acid is one or both in vinylformic acid or the methylene-succinic acid.
Described fluorochemical monomer is one or both in propylene hexafluoro butyl ester, methylacrylic acid hexafluoro butyl ester or the methylacrylic acid ten difluoro heptyl esters.
Described initiator is a kind of in azobisisobutyronitrile, azo diisoamyl eyeball or azo two eyeball in different heptan.
A kind of compound method with propenoate powder resin of self-cleaning performance is characterized in that this method may further comprise the steps:
(1) get the raw materials ready according to following component and weight part content:
Polymerizable carboxylic acid 8～15,
TEB 3K 40～60,
Bing Xisuandingzhi 10～25,
NSC 20956 10～30,
Fluorochemical monomer 5～20,
Methyl isobornyl thiocyanoacetate 10～20,
Initiator 1.5～3.5;
(2) be that 100～120 solvent is put in the reactor drum that has condensing reflux with weight part content; The monomer that will constitute except that other component of initiator mixes the monomer solution that obtains and adds Dropping feeder, and it is to join in another Dropping feeder after 20～30 the dissolution with solvents that initiator is used weight part content, and the solvent in the reactor drum is heated to 60～72 ℃; Feed nitrogen; In reactor drum, drip monomer solution and initiator solution then, dominant discharge, monomer solution is controlled at 3～3.5h and drips; Initiator solution is controlled at 4～4.5h and drips; The controlling reactor temperature is 60～75 ℃ of insulation reaction 1h again, and the resin solution that makes is reclaimed solvent through vacuum outgas, pulverizes the propenoate powder resin that obtains having self-cleaning performance through overcooling then.
Described solvent is an ethanol.
Described propenoate powder resin with self-cleaning performance has water-soluble, zero VOC.
Compared with prior art, the powder fluorine-containing powdex that the present invention makes has excellent friction resistant performance, and high widely low temperature applicable performance does not contain small-molecular emulsifier, and has water-soluble and self-cleaning performance, and zero VOC.So the coating that uses resin of the present invention to access has excellent weather resistance, and is anti-aging, the anti-performance of wiping is good, and self-cleaning performance is excellent, can excellent protectiveness be provided to various base materials, and VOC free, environmental protection.
Embodiment
Below in conjunction with specific embodiment the present invention is elaborated.
Embodiment 1
Get the raw materials ready by weight:
100 parts of ethanol are put into have in the reactor drum that condensation returns, monomer is mixed the adding Dropping feeder, 1.8 parts initiator joins in the Dropping feeder with 20 parts alcohol solvent.Ethanol in the reactor drum is heated to 72 ℃, feeds nitrogen, begin to drip monomer solution and initiator solution, dominant discharge, monomer solution is controlled at 3～3.5h and drips, and initiator solution is controlled at 4～4.5h and drips, 75 ℃ of insulation reaction one hour.Solvent is reclaimed in the resin solution vacuum outgas that makes, pulverize, both got powdex through cooling.
Embodiment 2
Get the raw materials ready by weight:
120 parts of ethanol are put into have in the reactor drum that condensation returns, monomer is mixed the adding Dropping feeder, 1.6 parts initiator joins in the Dropping feeder with 30 parts alcohol solvent.Ethanol in the reactor drum is heated to 60～65 ℃, feeds nitrogen, begin to drip monomer solution and initiator solution, dominant discharge, monomer solution is controlled at 3～3.5h and drips, and initiator solution is controlled at 4～4.5h and drips, 62 ℃ of insulation reaction one hour.Solvent is reclaimed in the resin solution vacuum outgas that makes, pulverize, both got powdex through cooling.
Concrete synthesis technique is with reference to embodiment 1, and different is that temperature of reaction will drop to 60～65 ℃, because of azo two eyeball kick off temperature in different heptan lower than azo diisoamyl eyeball.
Embodiment 3
Get the raw materials ready by weight:
110 parts of ethanol are put into have in the reactor drum that condensation returns, 1.6 parts initiators and monomer mixed solvent are evenly added Dropping feeder, the ethanol in the reactor drum is heated to 72 ℃; Feed nitrogen, begin to drip monomer solution and initiator solution, dominant discharge; Monomer solution is controlled at 3～3.5h and drips; Add 0.4 part of initiator and 30 parts of alcoholic acid solution, be controlled at 1～1.5h and drip off, 75 ℃ of insulation reaction are one hour then.Solvent is reclaimed in the resin solution vacuum outgas that makes, pulverize, both got powdex through cooling.
Different with embodiment 1,2 is that azobisisobutyronitrile solubleness in ethanol is little, therefore adopts a part to be dissolved in the monomer, and then adds a part of azobisisobutyronitrile ethanolic soln.
Embodiment 4
A kind of compound method with propenoate powder resin of self-cleaning performance may further comprise the steps:
(1) gets the raw materials ready according to following component and content: polymerizable carboxylic acid 8kg, TEB 3K 40kg, Bing Xisuandingzhi 10kg, NSC 20956 10kg, fluorochemical monomer 5kg, methyl isobornyl thiocyanoacetate 10kg, initiator 1.5kg; Wherein, Polymerizable carboxylic acid is a vinylformic acid; Fluorochemical monomer is a propylene hexafluoro butyl ester, and initiator is an azobisisobutyronitrile;
(2) ethanol of 100kg is put in the reactor drum that has condensing reflux, the monomer that will constitute except that other component of initiator mixes the monomer solution that obtains and adds Dropping feeder, with joining in another Dropping feeder behind the dissolve with ethanol of initiator with 20kg; Solvent in the reactor drum is heated to 60 ℃, feeds nitrogen, in reactor drum, drip monomer solution and initiator solution then; Dominant discharge; Monomer solution is controlled at 3h and drips, and initiator solution is controlled at 4h and drips, and the controlling reactor temperature is 60 ℃ of insulation reaction 1h again; The resin solution that makes is reclaimed solvent through vacuum outgas; Pulverize the propenoate powder resin that obtains having self-cleaning performance through overcooling then, this resin has water-soluble, zero VOC.
Embodiment 5
A kind of compound method with propenoate powder resin of self-cleaning performance may further comprise the steps:
(1) gets the raw materials ready according to following component and content: polymerizable carboxylic acid 9kg, TEB 3K 42kg, Bing Xisuandingzhi 15kg, NSC 20956 12kg, fluorochemical monomer 8kg, methyl isobornyl thiocyanoacetate 12kg, initiator 2kg; Wherein, Polymerizable carboxylic acid is a methylene-succinic acid; Fluorochemical monomer is the mixture of methylacrylic acid hexafluoro butyl ester and methylacrylic acid ten difluoro heptyl esters, and initiator is an azo diisoamyl eyeball;
(2) ethanol of 110kg is put in the reactor drum that has condensing reflux, the monomer that will constitute except that other component of initiator mixes the monomer solution that obtains and adds Dropping feeder, with joining in another Dropping feeder behind the dissolve with ethanol of initiator with 25kg; Solvent in the reactor drum is heated to 65 ℃, feeds nitrogen, in reactor drum, drip monomer solution and initiator solution then; Dominant discharge; Monomer solution is controlled at 3.5h and drips, and initiator solution is controlled at 4.5h and drips, and the controlling reactor temperature is 70 ℃ of insulation reaction 1h again; The resin solution that makes is reclaimed solvent through vacuum outgas; Pulverize the propenoate powder resin that obtains having self-cleaning performance through overcooling then, this resin has water-soluble, zero VOC.
Embodiment 6
A kind of compound method with propenoate powder resin of self-cleaning performance may further comprise the steps:
(1) gets the raw materials ready according to following component and content: polymerizable carboxylic acid 10kg, TEB 3K 50kg, Bing Xisuandingzhi 20kg, NSC 20956 18kg, fluorochemical monomer 12kg, methyl isobornyl thiocyanoacetate 15kg, initiator 3kg; Polymerizable carboxylic acid is the mixture of vinylformic acid and methylene-succinic acid; Fluorochemical monomer is the mixture of propylene hexafluoro butyl ester and methylacrylic acid hexafluoro butyl ester, and initiator is azo two eyeball in different heptan;
(2) ethanol of 110kg is put in the reactor drum that has condensing reflux, the monomer that will constitute except that other component of initiator mixes the monomer solution that obtains and adds Dropping feeder, with joining in another Dropping feeder behind the dissolve with ethanol of initiator with 25kg; Solvent in the reactor drum is heated to 65 ℃, feeds nitrogen, in reactor drum, drip monomer solution and initiator solution then; Dominant discharge; Monomer solution is controlled at 3.5h and drips, and initiator solution is controlled at 4.5h and drips, and the controlling reactor temperature is 70 ℃ of insulation reaction 1h again; The resin solution that makes is reclaimed solvent through vacuum outgas; Pulverize the propenoate powder resin that obtains having self-cleaning performance through overcooling then, this resin has water-soluble, zero VOC.
Embodiment 7
A kind of compound method with propenoate powder resin of self-cleaning performance may further comprise the steps:
(1) gets the raw materials ready according to following component and content: polymerizable carboxylic acid 15kg, TEB 3K 60kg, Bing Xisuandingzhi 25kg, NSC 20956 30kg, fluorochemical monomer 20kg, methyl isobornyl thiocyanoacetate 20kg, initiator 3.5kg; Polymerizable carboxylic acid is a methylene-succinic acid; Fluorochemical monomer is the mixture of propylene hexafluoro butyl ester and methylacrylic acid hexafluoro butyl ester, and initiator is azo two eyeball in different heptan;
(2) ethanol of 120kg is put in the reactor drum that has condensing reflux, the monomer that will constitute except that other component of initiator mixes the monomer solution that obtains and adds Dropping feeder, with joining in another Dropping feeder behind the dissolve with ethanol of initiator with 30kg; Solvent in the reactor drum is heated to 72 ℃, feeds nitrogen, in reactor drum, drip monomer solution and initiator solution then; Dominant discharge; Monomer solution is controlled at 3.5h and drips, and initiator solution is controlled at 4.5h and drips, and the controlling reactor temperature is 75 ℃ of insulation reaction 1h again; The resin solution that makes is reclaimed solvent through vacuum outgas; Pulverize the propenoate powder resin that obtains having self-cleaning performance through overcooling then, this resin has water-soluble, zero VOC.
Claims (8)
1. propenoate powder resin with self-cleaning performance is characterized in that this powdex is obtained by the feedstock production of following component and weight part content:
Polymerizable carboxylic acid 8～15;
TEB 3K 40～60;
Bing Xisuandingzhi 10～25;
NSC 20956 10～30;
Fluorochemical monomer 5～20;
Methyl isobornyl thiocyanoacetate 10～20;
Initiator 1.5～3.5.
2. a kind of propenoate powder resin with self-cleaning performance according to claim 1 is characterized in that following component of the raw material of this powdex and weight part content prepare:
Polymerizable carboxylic acid 8～10;
TEB 3K 42～50;
Bing Xisuandingzhi 15～20;
NSC 20956 12～18;
Fluorochemical monomer 8～12;
Methyl isobornyl thiocyanoacetate 12～15;
Initiator 1.5～3.5.
3. a kind of propenoate powder resin with self-cleaning performance according to claim 1 is characterized in that described polymerizable carboxylic acid is one or both in vinylformic acid or the methylene-succinic acid.
4. a kind of propenoate powder resin with self-cleaning performance according to claim 1 is characterized in that, described fluorochemical monomer is one or both in propylene hexafluoro butyl ester, methylacrylic acid hexafluoro butyl ester or the methylacrylic acid ten difluoro heptyl esters.
5. a kind of propenoate powder resin with self-cleaning performance according to claim 1 is characterized in that, described initiator is a kind of in azobisisobutyronitrile, azo diisoamyl eyeball or azo two eyeball in different heptan.
6. compound method with propenoate powder resin of self-cleaning performance as claimed in claim 1 is characterized in that this method may further comprise the steps:
(1) get the raw materials ready according to following component and weight part content:
Polymerizable carboxylic acid 8～15,
TEB 3K 40～60,
Bing Xisuandingzhi 10～25,
NSC 20956 10～30,
Fluorochemical monomer 5～20,
Methyl isobornyl thiocyanoacetate 10～20,
Initiator 1.5～3.5;
(2) be that 100～120 solvent is put in the reactor drum that has condensing reflux with weight part content; The monomer that will constitute except that other component of initiator mixes the monomer solution that obtains and adds Dropping feeder, and it is to join in another Dropping feeder after 20～30 the dissolution with solvents that initiator is used weight part content, and the solvent in the reactor drum is heated to 60～72 ℃; Feed nitrogen; In reactor drum, drip monomer solution and initiator solution then, dominant discharge, monomer solution is controlled at 3～3.5h and drips; Initiator solution is controlled at 4～4.5h and drips; The controlling reactor temperature is 60～75 ℃ of insulation reaction 1h again, and the resin solution that makes is reclaimed solvent through vacuum outgas, pulverizes the propenoate powder resin that obtains having self-cleaning performance through overcooling then.
7. a kind of compound method with propenoate powder resin of self-cleaning performance according to claim 6 is characterized in that described solvent is an ethanol.
8. a kind of compound method with propenoate powder resin of self-cleaning performance according to claim 6 is characterized in that described propenoate powder resin with self-cleaning performance has water-soluble, zero VOC.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201110183187 CN102363640A (en) | 2011-06-30 | 2011-06-30 | Acrylic ester powdered resin having self-cleaning property and synthesizing method thereof |
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| CN 201110183187 CN102363640A (en) | 2011-06-30 | 2011-06-30 | Acrylic ester powdered resin having self-cleaning property and synthesizing method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107537590A (en) * | 2016-06-28 | 2018-01-05 | 中国石油化工股份有限公司 | The low pure hydrogen reduction method of hydrocarbon steam conversion catalyst |
| CN107641468A (en) * | 2017-10-26 | 2018-01-30 | 浙江华彩新材料有限公司 | A kind of water proof fire retardant powdery paints and preparation method thereof |
| CN110343208A (en) * | 2019-06-11 | 2019-10-18 | 中山华明泰科技股份有限公司 | A kind of powder acrylic resin preparation method and application |
| CN115109488A (en) * | 2022-07-29 | 2022-09-27 | 安徽美佳新材料股份有限公司 | Self-cleaning powder coating based on fluorine modified acrylate polymer and preparation method thereof |
-
2011
- 2011-06-30 CN CN 201110183187 patent/CN102363640A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107537590A (en) * | 2016-06-28 | 2018-01-05 | 中国石油化工股份有限公司 | The low pure hydrogen reduction method of hydrocarbon steam conversion catalyst |
| CN107537590B (en) * | 2016-06-28 | 2020-07-10 | 中国石油化工股份有限公司 | Low-purity hydrogen reduction method for hydrocarbon steam conversion catalyst |
| CN107641468A (en) * | 2017-10-26 | 2018-01-30 | 浙江华彩新材料有限公司 | A kind of water proof fire retardant powdery paints and preparation method thereof |
| CN110343208A (en) * | 2019-06-11 | 2019-10-18 | 中山华明泰科技股份有限公司 | A kind of powder acrylic resin preparation method and application |
| CN115109488A (en) * | 2022-07-29 | 2022-09-27 | 安徽美佳新材料股份有限公司 | Self-cleaning powder coating based on fluorine modified acrylate polymer and preparation method thereof |
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Application publication date: 20120229 |