CN102585108A - Polyester-modified organic fluorine-silicon acrylic resin and preparation method thereof as well as paint using resin - Google Patents
Polyester-modified organic fluorine-silicon acrylic resin and preparation method thereof as well as paint using resin Download PDFInfo
- Publication number
- CN102585108A CN102585108A CN201210013155XA CN201210013155A CN102585108A CN 102585108 A CN102585108 A CN 102585108A CN 201210013155X A CN201210013155X A CN 201210013155XA CN 201210013155 A CN201210013155 A CN 201210013155A CN 102585108 A CN102585108 A CN 102585108A
- Authority
- CN
- China
- Prior art keywords
- polyester
- fluorine
- organic silicon
- vinyl resin
- polyester modification
- 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.)
- Pending
Links
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses polyester-modified organic fluorine-silicon acrylic resin and a preparation method thereof as well as paint using the resin. The polyester-modified organic fluorine-silicon acrylic resin is prepared by polymerizing a polyester precursor, a mixed monomer and an initiator in a mixed solvent, wherein the mixed monomer used in reaction comprises the following components: ethyl acrylate, methacrylic acid, isobornyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, butyl acrylate, glycidyl tertcarbonate, fluorine-containing methacrylate monomer and organic silicon intermediate. The paint comprises the following components: the polyester-modified organic fluorine-silicon acrylic resin, titanium white, a dispersing agent, a flatting agent, an ultraviolet-resistant absorber, dimethylbenzene, isophorone and propylene glycol methyl ether acetate. According to the invention, the polyester-modified organic fluorine-silicon acrylic resin is obtained by polymerizing the polyester precursor with an acrylic acid monomer solution, and is prepared into the paint; the resin has good property and is superior to fluorine-acrylic resin in the aspects of distinctness of image, hardness, acid-alkali resistance, high-low temperature resistance and the like.
Description
Technical field
The present invention relates to polyester modification organic silicon-fluorine vinyl resin preparation field, is meant that especially lower run machine skin material is with polyester modification organic silicon-fluorine vinyl resin of coating and preparation method thereof.
Background technologyOrganosilicon material is because silica bond energy (460 kJ/mol) is higher than carbon-oxygen bond (351 kJ/mol) and carbon-carbon bond (347 kJ/mol), and the coating that therefore contains organosilicon material has characteristics such as high-weatherability, excellent anti-stain characteristic, strong antiacid rain property.Fluorin modified crylic acid resin is then having advantageous characteristic aspect non-corrosibility, contamination resistance, chemical-resistant and the outdoor overlength weathering resistance.Fluorin modified crylic acid resin has certain report, but is used for patent of invention that coating makes seldom, and Chinese disclosure of the Invention number is used for the manufacturing of helicopter skining paint for CN1923868A has reported a kind of fluorin modified crylic acid resin, has obtained good result.Along with the raising that coating is required; When satisfying characteristics such as weathering resistance, anti-stain characteristic, antiacid rain property, chemical-resistant; Be necessary to continue to promote the overall quality of resin at aspects such as clarity, hardness and high-low temperature resistants; Therefore can polyester and fluorin modified crylic acid be contained the resin-bonded of silicone intermediate, obtained performance is the resin material of excellence more.At present, organic-silicon-modified resin is a lot, studies also comparatively fully, but to the research of polyester modification perfluoroalkyl acrylate resin seldom, and the perfluoroalkyl acrylate resin that will contain silicone intermediate carries out polyester modification, and report is not arranged so far.
Summary of the invention
The present invention has three targets; First target is to overcome some shortcoming and defect that prior art exists; Provide a kind of resin property good, especially at the polyester modification organic silicon-fluorine vinyl resin of aspect superior performances such as clarity, hardness, resistance to acids and bases, high-low temperature resistant.Second target of the present invention provides the preparation method of above-mentioned polyester modification organic silicon-fluorine vinyl resin.The 3rd target of the present invention provides a kind of above-mentioned polyester modification organic silicon-fluorine vinyl resin coatings formulated of utilizing.
For realizing first target of the present invention; Its technical scheme is to be made by polyester presoma, mix monomer (containing silicone intermediate and fluorine-containing methacrylate monomer) and initiator polyreaction in mixed solvent, the reaction used each raw material amount by percentage to the quality:
The amount of polyester presoma accounts for the 13-16% of total charging capacity;
The amount of mixed solvent accounts for the 28-32% of total charging capacity;
The amount of initiator accounts for total charging capacity (1.8-2.2%);
The amount of mix monomer accounts for the 51-55% of total charging capacity,
This mix monomer comprises following component, accounts for the mass percent meter of mix monomer:
Ethyl propenoate 4-8%; Methylacrylic acid 6%-8%; Isobornyl methacrylate 16-20%; NSC 20956 11%-15%; Rocryl 400 15%-19%; Bing Xisuandingzhi 16%-20%; Tertiary carbonic acid glycidyl ester 6-8%; Fluorine-containing methacrylate monomer 11%-15%; Silicone intermediate 2-4%.
Above-mentioned described polyester presoma is prepared by following mode: with TriMethylolPropane(TMP) (12-15%), and NSC 6366 (28-34%), phthalic anhydride (21-25%); M-phthalic acid (27-32%), toluene (5-7%), Dibutyltin oxide (0.20-0.30%); Anti--168 (0.35-0.65%) drop into and have in the flask of water trap, and fully logical nitrogen heats up then gradually; Basically dissolve to material; Start to stir and also to continue to heat up,, keep reflux dewatering and control the water trap head temperature being controlled at 160-180 ° of C at 100 ° below the C, the temperature of reaction of flask to refluxing; When dehydrating amount reach theoretical water 90% the time, the temperature in the flask can raise gradually, but is controlled at 210 ° below the C; When dehydrating amount during near theoretical value, get material and measure acid number, when acid number is 8 mgKOH/g, be reaction end; Stop heating, cool to about 80 ° of C naturally, add YLENE and N-BUTYL ACETATE solvent (weight ratio 1:1) latting drown then; Consumption is about 33% of total charging capacity, stirs, and filters.Described theoretical dehydrating amount is about 12% of above-mentioned total charging capacity.
Above-mentioned described fluorine-containing methacrylate monomer is a trifluoroethyl methacrylate, vinylformic acid hexafluoro butyl ester and methylacrylic acid hexafluoro butyl ester.
Above-mentioned described silicone intermediate is prepared from following mode: eight vinyl cyclotetrasiloxanes and octamethylcyclotetrasiloxane carry out polymerization and obtain (eight vinyl cyclotetrasiloxanes and octamethylcyclotetrasiloxane mass percent are 65-73:35-27) under alkali metal hydroxide catalysis.Catalyzer can be a sodium hydroxide, Pottasium Hydroxide, volatile caustic; Butyl alcohol-tert potassium, consumption (mass percent) is 0.5-2%, temperature of reaction 80-140 ° of C; Reaction times 5-7 hour, gained organosilicon intermediate product water white transparency, purity 100%; Viscosity (being coated with-4 glasss) is 160-210 second, and molecular weight is 650-970 (gel chromatography).
Above-mentioned described initiator is two t-amyl peroxy things.
Above-mentioned described mixed solvent is YLENE and N-BUTYL ACETATE, and proportioning (mass ratio) is 1:1.
For realizing second target of the present invention, technical scheme of the present invention may further comprise the steps:
(1) raw material is equipped with: this step comprises following each operation, and each operation of this step in no particular order
A) preparation mix monomer, the amount of mix monomer accounts for the 51-55% of total charging capacity, and this mix monomer comprises following component, accounts for the mass percent meter of mix monomer:
Ethyl propenoate 4-8%; Methylacrylic acid 6%-8%; Isobornyl methacrylate 16-20%; NSC 20956 11%-15%; Rocryl 400 15%-19%; Bing Xisuandingzhi 16%-20%; Tertiary carbonic acid glycidyl ester 6-8%; Fluorine-containing methacrylate monomer 11%-15%; Silicone intermediate 2-4%.
B) preparation polyester presoma, this polyester presoma consumption is the 13-16% of total charging capacity;
C) preparation mixed solvent, this mixed solvent accounts for the 28-32% of total charging capacity;
Polyreaction: get the bottoming of polyester presoma, logical nitrogen heats up; Stir, be raised to about 125 ° of C, the formula ratio that adds mixed solvent down of refluxing 65% in the flask that has water-and-oil separator; Heat to reflux temperature, the mix monomer with 100% is placed in the tap funnel, with the initiator of 10% dissolution with solvents dilution 75% and be placed in another tap funnel; Simultaneously evenly be added to reactive system with 3～4 hours liquid with two tap funnels and carry out polyreaction, after dropwising, insulation is 2～3 hours under reflux temperature; Then with remaining solvent and initiator; At the uniform velocity added with 1～2 hour and to deepen polymerization in the reactive system, continue reaction 3～5 hours up to the acid number of resin less than set quota, obtain polyester modification perfluoroalkyl acrylate resin material.
For realizing the 3rd target of the present invention, its technical scheme is to comprise following component, in mass fraction, and polyester modification organic silicon-fluorine vinyl resin, 48 parts; White titanium pigment, 28 parts; Dispersion agent, 2 parts; Flow agent, 1 part; Ultraviolet-resistant absorbent, 2 parts; YLENE, 9 parts; Different fluorine that ketone, 5 parts; 1-Methoxy-2-propyl acetate, 4 parts.
For this reason; The present invention utilizes polyester presoma and silicone intermediate, Acrylic Acid Monomer solution polymerization to obtain polyester modification organic silicon-fluorine vinyl resin and be mixed with skin material to carry out application with coating; The application result shows that resin property is excellent, obviously is superior to being used for the skining paint of perfluoroalkyl acrylate resins at aspects such as clarity, hardness, resistance to acids and bases, high-low temperature resistants.
Technique effect
The polyester modification organic silicon-fluorine vinyl resin that the present invention makes has following technical indicator: as clear as crystal liquid, solids constituent 64-66%; Viscosity (Ge Shi pipe, 25 ° of C) 9-13s; Acid number < 11 mgKOH/>g.The actual use properties of resin is investigated through the application that skin material coats that is used for of preparation; Test-results shows: coating performance is good; For example obviously be superior to often being coated with the S04 coating property, especially at aspect excellent performances such as clarity, hardness, resistance to acids and bases, high-low temperature resistants.
Embodiment
Through embodiment the present invention is carried out concrete description below; Only be used for the present invention is further specified; Can not be interpreted as the qualification to protection domain of the present invention, the technician in this field can make some nonessential improvement and adjustment to the present invention according to the content of foregoing invention.
Embodiment 1
The preparation of organosilicon intermediate: with eight vinyl cyclotetrasiloxanes, 227 grams, octamethylcyclotetrasiloxane 74 grams join in the four-hole boiling flask of 500mL, stir; Add each 3 gram of volatile caustic and butyl alcohol-tert potassium again, heat up, maintain the temperature at 135-145 ° of C and reacted 5.5 hours down; Stopped reaction, cooling obtains silicone intermediate; The product water white transparency, viscosity (being coated with-4 glasss) is 195 seconds, molecular weight 913 (gel chromatography).
Embodiment 2
The preparation of polyester presoma.With 259 gram NSC 6366s, 81 gram TriMethylolPropane(TMP)s, 179 gram phthalic anhydrides, 201 gram m-phthalic acids; 36 gram toluene, 1.7 gram Dibutyltin oxides, 3.9 grams anti--168 are put in the four-hole boiling flask that has water trap, logical nitrogen; Heat up, when material dissolves basically, start stirring.Continue to heat up, reflux dewatering, the preceding control water trap head temperature of 90% [theoretical water is 73 grams] that does not reach theoretical value in dehydration is no more than 100 ° of C, and the temperature of reaction of flask is controlled at 160-180 ° of C; When dehydrating amount reach theoretical water 90% the time, the temperature in the flask raises gradually, but is no more than 210 ° of C.When dehydrating amount during near theoretical value, the survey acid number of drawing materials when acid number is 8 mgKOH/g, is reaction end, cools to 80 ° of C, adds YLENE and N-BUTYL ACETATE solvent 238 gram (weight ratio 1:1) latting drowns, stirs filtration.Testing index is: solids constituent 69.2%, acid number are 6.6 mgKOH/g, and viscosity (25 ° of C, Ge Shi pipe) is 24s.
Embodiment 3
Polyester modification organic silicon-fluorine vinyl resin.Get polyester presoma 180 grams, put into the four-hole boiling flask of water-and-oil separator, heat up, stir, be raised to about 125 ° of C.Add 65% (234 gram) (by YLENE, N-BUTYL ACETATE 1:1 preparation, total amount is 360 grams) of solvent formula amount, heat to reflux temperature.[amount of mix monomer is 636 grams with 100% mix monomer; Ethyl propenoate (4%), isobornyl methacrylate (18%), NSC 20956 (16%), Rocryl 400 (14%), Bing Xisuandingzhi (19%), methylacrylic acid (12%) and fluorine-containing methacrylate monomer (15%; Trifluoroethyl methacrylate: methylacrylic acid hexafluoro butyl ester: the weight ratio of methylacrylic acid hexafluoro isopropyl ester is 1:2:2), silicone intermediate (2%) is put into tap funnel; With two t-amyl peroxy thing initiators of 15% dissolution with solvents dilution 80% (containing initiator 19 grams) and be injected in another tap funnel, the liquid in two tap funnels evenly is added drop-wise in the reactive system again with 4 hours.After dropwising, insulation is 1.5 hours under reflux temperature, with remaining solvent and initiator (total amount 20%), in 1.5 hours, at the uniform velocity is added drop-wise in the reaction kettle then.Continue reaction 4 hours up to the acid number of resin less than set quota, promptly get polyester modification perfluoroalkyl acrylate resin.The index of measuring is: solids constituent, 64.8%; Viscosity (Ge Shi pipe, 25 ° of C), 12 s; Acid number, 9.7 mgKOH/g.
Embodiment 4
The varnish preparation.With the above-mentioned synthetic polyester modification organic silicon-fluorine vinyl resin preparation coating that obtains, basic recipe is following: polyester modification organic silicon-fluorine vinyl resin, 48 parts (mass percent); White titanium pigment, 28 parts; Dispersion agent, 2 parts; Flow agent, 1 part; Ultraviolet-resistant absorbent, 2 parts; YLENE, 9 parts; Different fluorine that ketone, 5 parts; 1-Methoxy-2-propyl acetate, 4 parts.Solidifying agent adopts DESMODUR N-3390 HDI trimer curing agent.The ratio of white paint and solidifying agent is 100: 27.Coat-thickness is about 25 μ m.Join coating try to be coated with at low flyer with skin material, the performance that records is following:
Claims (8)
1. polyester modification organic silicon-fluorine vinyl resin, it is characterized in that: it is made by polyester presoma, mix monomer and initiator polyreaction in mixed solvent, the amount of used each raw material of reaction by percentage to the quality:
The amount of polyester presoma accounts for the 13-16% of total charging capacity;
The amount of mixed solvent accounts for the 28-32% of total charging capacity;
The amount of initiator accounts for the 1.8-2.2% of total charging capacity;
The amount of mix monomer accounts for the 51-55% of total charging capacity, and said mix monomer comprises following component, accounts for the mass percent meter of mix monomer:
Ethyl propenoate 4-8%; Methylacrylic acid 6%-8%; Isobornyl methacrylate 16-20%; NSC 20956 11%-15%; Rocryl 400 15%-19%; Bing Xisuandingzhi 16%-20%; Tertiary carbonic acid glycidyl ester 6-8%; Fluorine-containing methacrylate monomer 11%-15%; Silicone intermediate 2-4%.
2. a kind of polyester modification organic silicon-fluorine vinyl resin according to claim 1; It is characterized in that: described polyester presoma prepares in the following manner: by mass percent TriMethylolPropane(TMP) 12-15%, NSC 6366 28-34%, phthalic anhydride 21-25%, m-phthalic acid 27-32%, toluene 5-7%, Dibutyltin oxide 0.20-0.30% and anti--168 0.35-0.65% input are had in the flask of water trap; Fully logical nitrogen; Heat up gradually then; Basically dissolve to material, start to stir and continue and heat up, to refluxing; Keep reflux dewatering and control the water trap head temperature at 100 ° below the C, the temperature of reaction of flask is controlled at 160-180 ° of C; When dehydrating amount reach theoretical water 90% the time, the temperature in the flask can raise gradually, but is controlled at 210 ° below the C; When dehydrating amount during near theoretical value; Getting material and measure acid number, is reaction end when acid number is 8 mgKOH/g, stops heating; Naturally cool to 80 ° of C; Add YLENE and N-BUTYL ACETATE solvent latting drown that the mass percent weight ratio is 1:1 then, its consumption is 33% of total charging capacity, stirs at last, filters.
3. a kind of polyester modification organic silicon-fluorine vinyl resin according to claim 1 is characterized in that: described initiator is two t-amyl peroxy things.
4. a kind of polyester modification organic silicon-fluorine vinyl resin according to claim 1, it is characterized in that: mixed solvent is YLENE and N-BUTYL ACETATE, proportioning is 1:1.
5. a kind of polyester modification organic silicon-fluorine vinyl resin according to claim 1 is characterized in that: described methyl fluoride acrylate monomer is any one or a few in trifluoroethyl methacrylate, methylacrylic acid hexafluoro butyl ester, the methylacrylic acid hexafluoro isopropyl ester.
6. a kind of polyester modification organic silicon-fluorine vinyl resin according to claim 1; It is characterized in that: described silicone intermediate is prepared from following mode: with mass percent is that eight vinyl cyclotetrasiloxanes and the octamethylcyclotetrasiloxane of 65-73:35-27 carries out polymerization and obtain under alkali metal hydroxide catalysis; Said basic metal catalytic materials is a kind of in sodium hydroxide, Pottasium Hydroxide, volatile caustic, the butyl alcohol-tert potassium; Its consumption is 0.5-2%, temperature of reaction 80-140 ° of C, reaction times 5-7 hour; Gained silicone intermediate product water white transparency, its purity are 100%, viscosity is 160-210 second, molecular weight is 650-970.
7. the preparation method of a kind of polyester modification organic silicon-fluorine vinyl resin according to claim 1 is characterized in that: described polyester modification organic silicon-fluorine vinyl resin is prepared from following polyreaction: get the bottoming of polyester presoma, logical nitrogen; Heat up, stir, be raised to 125 ° of C; Reflux the formula ratio that adds mixed solvent down 65% in the flask that has water-and-oil separator, heat to reflux temperature, the mix monomer with 100% is placed in the tap funnel; With the initiator of 10% dissolution with solvents dilution 75% and be placed in another tap funnel; Simultaneously evenly be added to reactive system with 3～4 hours liquid with two tap funnels and carry out polyreaction, after dropwising, insulation is 2～3 hours under reflux temperature; Then with remaining solvent and initiator; At the uniform velocity added with 1～2 hour and to deepen polymerization in the reactive system, continue reaction 3～5 hours up to the acid number of resin less than set quota, obtain polyester modification perfluoroalkyl acrylate resin material.
8. one kind is utilized the described polyester modification organic silicon-fluorine of claim 1 vinyl resin institute coatings formulated, and it is characterized in that: it comprises following component, in parts by weight:
Polyester modification organic silicon-fluorine vinyl resin: 48 parts; White titanium pigment: 28 parts; Dispersion agent: 2 parts; Flow agent: 1 part; Ultraviolet-resistant absorbent: 2 parts; YLENE: 9 parts; Different fluorine that ketone: 5 parts; 1-Methoxy-2-propyl acetate: 4 parts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210013155XA CN102585108A (en) | 2012-01-17 | 2012-01-17 | Polyester-modified organic fluorine-silicon acrylic resin and preparation method thereof as well as paint using resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210013155XA CN102585108A (en) | 2012-01-17 | 2012-01-17 | Polyester-modified organic fluorine-silicon acrylic resin and preparation method thereof as well as paint using resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102585108A true CN102585108A (en) | 2012-07-18 |
Family
ID=46474406
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210013155XA Pending CN102585108A (en) | 2012-01-17 | 2012-01-17 | Polyester-modified organic fluorine-silicon acrylic resin and preparation method thereof as well as paint using resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102585108A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214632A (en) * | 2013-04-15 | 2013-07-24 | 湖北大学 | Water-soluble fluoroacrylic acid-polyester transparent insulating resin and preparation method thereof |
| CN103275330A (en) * | 2013-06-07 | 2013-09-04 | 苏州兴业材料科技股份有限公司 | Fluorine-containing organosilicone dual-modified acrylic resin material for aircraft skin coating |
| CN103666165A (en) * | 2013-09-11 | 2014-03-26 | 东莞上海大学纳米技术研究院 | Preparation method of organic fluorine-silicon bionic anti-fouling resin and product |
| CN104002061A (en) * | 2014-05-21 | 2014-08-27 | 广州柏仕达新材料有限公司 | High-performance high-stability nanometer soldering paste and preparation method thereof |
| CN105400254A (en) * | 2015-11-27 | 2016-03-16 | 宁波双人新材料有限公司 | Weather-proof polyester powder coating and preparation method thereof |
| CN109734884A (en) * | 2019-01-14 | 2019-05-10 | 浙江天女集团制漆有限公司 | A kind of resistance to deep-draw water-borne acrylic acid modified polyester resin and preparation method thereof |
| CN110684186A (en) * | 2019-10-12 | 2020-01-14 | 杭州金质丽科技有限公司 | Organosilicon modified fluorine-containing powder resin, preparation method and super-lubricating powder coating |
| CN111363130A (en) * | 2020-04-29 | 2020-07-03 | 广东邦弗特新材料有限公司 | Epoxy acrylic fluorine-containing resin modified saturated polyester resin and preparation method thereof |
| CN114437301A (en) * | 2021-11-18 | 2022-05-06 | 江苏沃莱新材料有限公司 | Polyester modified hydroxyl acrylic resin and preparation method thereof, high-durability hydroxyl acrylic resin coating and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1178819A (en) * | 1997-10-15 | 1998-04-15 | 上海市建筑科学研究院 | Silicon propyl resin for paint and its producing method |
| CN101113192A (en) * | 2007-07-07 | 2008-01-30 | 中国化工建设总公司常州涂料化工研究院 | Cross-linking type fluorine-containing acrylic resin |
| CN102190759A (en) * | 2011-03-22 | 2011-09-21 | 温州大学 | Polyester modified fluoro acrylic resin, and preparation method and coating thereof |
-
2012
- 2012-01-17 CN CN201210013155XA patent/CN102585108A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1178819A (en) * | 1997-10-15 | 1998-04-15 | 上海市建筑科学研究院 | Silicon propyl resin for paint and its producing method |
| CN101113192A (en) * | 2007-07-07 | 2008-01-30 | 中国化工建设总公司常州涂料化工研究院 | Cross-linking type fluorine-containing acrylic resin |
| CN102190759A (en) * | 2011-03-22 | 2011-09-21 | 温州大学 | Polyester modified fluoro acrylic resin, and preparation method and coating thereof |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214632A (en) * | 2013-04-15 | 2013-07-24 | 湖北大学 | Water-soluble fluoroacrylic acid-polyester transparent insulating resin and preparation method thereof |
| CN103214632B (en) * | 2013-04-15 | 2015-06-24 | 湖北大学 | Water-soluble fluoroacrylic acid-polyester transparent insulating resin and preparation method thereof |
| CN103275330A (en) * | 2013-06-07 | 2013-09-04 | 苏州兴业材料科技股份有限公司 | Fluorine-containing organosilicone dual-modified acrylic resin material for aircraft skin coating |
| CN103666165B (en) * | 2013-09-11 | 2015-12-09 | 东莞上海大学纳米技术研究院 | The bionical antifouling resin preparation method of organic fluorinated silicone and goods |
| CN103666165A (en) * | 2013-09-11 | 2014-03-26 | 东莞上海大学纳米技术研究院 | Preparation method of organic fluorine-silicon bionic anti-fouling resin and product |
| CN104002061A (en) * | 2014-05-21 | 2014-08-27 | 广州柏仕达新材料有限公司 | High-performance high-stability nanometer soldering paste and preparation method thereof |
| CN104002061B (en) * | 2014-05-21 | 2015-12-02 | 广州柏仕达新材料有限公司 | A kind of high-performance high stable nanometer solder(ing) paste and preparation method thereof |
| CN105400254A (en) * | 2015-11-27 | 2016-03-16 | 宁波双人新材料有限公司 | Weather-proof polyester powder coating and preparation method thereof |
| CN105400254B (en) * | 2015-11-27 | 2017-08-18 | 宁波双人新材料有限公司 | A kind of weatherable polyether powder coating and preparation method thereof |
| CN109734884A (en) * | 2019-01-14 | 2019-05-10 | 浙江天女集团制漆有限公司 | A kind of resistance to deep-draw water-borne acrylic acid modified polyester resin and preparation method thereof |
| CN109734884B (en) * | 2019-01-14 | 2021-04-09 | 浙江天女集团制漆有限公司 | Deep drawing resistant waterborne acrylic modified polyester resin and preparation method thereof |
| CN110684186A (en) * | 2019-10-12 | 2020-01-14 | 杭州金质丽科技有限公司 | Organosilicon modified fluorine-containing powder resin, preparation method and super-lubricating powder coating |
| CN111363130A (en) * | 2020-04-29 | 2020-07-03 | 广东邦弗特新材料有限公司 | Epoxy acrylic fluorine-containing resin modified saturated polyester resin and preparation method thereof |
| CN114437301A (en) * | 2021-11-18 | 2022-05-06 | 江苏沃莱新材料有限公司 | Polyester modified hydroxyl acrylic resin and preparation method thereof, high-durability hydroxyl acrylic resin coating and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102585108A (en) | Polyester-modified organic fluorine-silicon acrylic resin and preparation method thereof as well as paint using resin | |
| CN102190759B (en) | Polyester modified fluoro acrylic resin, and preparation method and coating thereof | |
| CN107075341B (en) | Stripping film is with re-releasing additive and stripping film organopolysiloxane composition and stripping film | |
| CN105061700B (en) | Nano silicon/polyacrylate organic inorganic hybridization water-dispersed resin and preparation method thereof | |
| CN106749856B (en) | Silica solution and preparation method thereof, acrylic resin, acrylic acid double-component polyurethane coating | |
| CN102134296B (en) | Fluosilicic modification water-soluble acrylic resin dispersion and uses thereof | |
| CN101705048B (en) | Highly transparent unsaturated polyester primer and preparation method as well as use method thereof | |
| CN101108946A (en) | Nano transparent insulating paint and its preparing process | |
| CN101560278B (en) | Methyl methacrylate-styrene copolymer containing fluoro-acrylate and preparation method thereof | |
| CN108864359A (en) | A kind of preparation method of high performance water-soluble high solid low viscosity acrylic resin | |
| CN103131354B (en) | Styrene modified polyvinyl acetate emulsion and preparation method | |
| CN105246980B (en) | Color compositions, cured film, colored filter, layered product and pigment dispersing agent | |
| CN104559727A (en) | Double-component polyurethane white glass finishing varnish and preparation method thereof | |
| CN102533185B (en) | Waterborne acrylate adhesive | |
| CN103193917A (en) | Method for preparing pure acrylate copolymer coating emulsion for building external wall elastic coating | |
| CN106700047A (en) | Modified high-solid low-viscous polyester resin, preparation method of modified high-solid low-viscous polyester resin, and application of modified high-solid low-viscous polyester resin in coating | |
| CN106243272A (en) | A kind of high adhesion force aqueous thermosetting acrylic resin and preparation method and application | |
| CN109666111A (en) | A kind of Nano-meter SiO_22/ organosilicon-modified acrylate emulsion | |
| CN103937357A (en) | Preparation method of water-repellent hybrid fluorine-containing resin coating | |
| CN113336886A (en) | Acrylic emulsion for weather-resistant cross-linked soft porcelain and preparation method thereof | |
| CN105732909B (en) | A kind of preparation method of acrylic polysiloxane water-based emulsion | |
| CN105315871B (en) | Device and method for producing super-amphiphobic paint with modification of modified particles | |
| CN110294825A (en) | A kind of hud typed tertiary carbon redispersable latex powder and preparation method thereof | |
| CN108929628A (en) | A kind of high performance corrosion-proof water-proof elastic dope | |
| CN105219311A (en) | A kind of preparation of water soluble acrylic acid ester pressure-sensitive and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120718 |