CN1103354C - Multi-component copolymerized fluoric paint containing triflurochloroethene as main component and its preparing process - Google Patents
Multi-component copolymerized fluoric paint containing triflurochloroethene as main component and its preparing process Download PDFInfo
- Publication number
- CN1103354C CN1103354C CN99112990A CN99112990A CN1103354C CN 1103354 C CN1103354 C CN 1103354C CN 99112990 A CN99112990 A CN 99112990A CN 99112990 A CN99112990 A CN 99112990A CN 1103354 C CN1103354 C CN 1103354C
- Authority
- CN
- China
- Prior art keywords
- monomer
- monomers
- mol ratio
- paint
- ketone
- 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.)
- Expired - Fee Related
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention relates to multi-component copolymerized fluoric paint with chlorotrifluoroethylene as a main component. The paint is composed of four monomers of A. chlorotrifluoroethylene, B. fatty acid olefine ester or/and isoalkene, C. fatty acid olefine alcohol, hydroxyalkyl ester or/and alkenyl enediol ether, D. aliphatic olefinic acid and solvent (aliphatic ketone, acetate, etc.) which are copolymerized under the condition that an initiator (azo compound or organic peroxide) exists. Compared with the prior art, the paint has the characteristics that a copolymer has high solid content (60 to 72%) and low viscosity (the coating viscosity of four cups is from 45 to 80s), and the paint can be well wet with pigment and has high dispersion. Paint defects of loose colors, etc. can be prevented. A made paint film has good physical performance and has the advantages of high hardness, softness, good luster, strong adhesive force, salt and fog resistance, chemicals resistance and high weatherability.
Description
The present invention relates to the fluorinated copolymer paint field, particularly with trifluorochloroethylene and a plurality of unsaturated fatty acids compounds of group copolymerization coating and method for making thereof.
The ionic dissociation energy of the carbon-fluorine bond of fluoropolymer is more much bigger than hydrocarbon key, and the bond distance of carbon-fluorine bond is also than hydrocarbon key much shorter, so fluoropolymer has favorable mechanical performance and excellent chemicals-resistant, weathering resistance.Because fluoropolymer has higher degree of crystallinity, be not soluble in the solvent, then need could form paint film as coating by sintering, this construction difficult problem has influenced fluorinated copolymer in the application of scope and different field widely.If introduce the monomer copolymerization with it of relevant functional group in fluorochemical monomer, then the solubility property of multipolymer is improved, and can carry out coating decoration with the traditional paint constructional method.Add linking agent during construction or use up, the electron rays irradiation makes its film-forming.
Du pont company was developed based on vinylidene fluoride in the seventies, with tetrafluoroethylene, vinyl butyrate copolymerization and random copolymers.It dissolves in methylethylketone, and the irradiation of available light or electron rays is carried out crosslinked.Its shortcoming be the irradiation of construction time or electron rays less than local crosslinked insufficient, influence coating quality.The terpolymer fluorine coating with trifluorochloroethylene, alkane vinyl ether, hydroxy butyl vinyl ether of Japan AGC Co., Ltd. exploitation at the end of the eighties to the beginning of the nineties (as the clear 61-57609 of Ri Tekai etc.), application property goes a step further than E.I.Du Pont Company, but the post-treatment when making lacquer is poor, be that the colo(u)rant dispersion wettability is poor, easily produce lacquer diseases such as loose colour.Contemporaneously, Daikin company developed the fluorine coating based on tetrafluoroethylene, and the same with Asahi Glass company product all is to form paint film by chemically crosslinked.Chinese patent CN1145386A provides the quarternary copolymerized introducing carboxyl functional group based on trifluorochloroethylene, not only make its energy acid-and base-resisting and toluene, and solved fluorine coating and made colo(u)rant dispersion wettability difference and the easy shortcomings such as coating with lacquer disease that produces when coating with lacquer, but produce the deficiency of anti-lower alcohol (methyl alcohol, ethanol etc.) and acetone equal solvent poor performance.France Atochem (FR) Cedex 22, 94091 Paris La Defense, France is at CN1046912A, CN1046911, CN1060850A, patents such as CN1060849A are all emphasized: the fluorochemical monomer segment is by vinylidene chloride and tetrafluoroethylene, trifluorochloroethylene, select another kind of fluorochemical monomer in conjunction with obtaining in R 1216 or the three kinds of monomers at least two kinds the mixture, rather than adopt single fluorochemical monomer, the molten Jie's property that does not promptly still have the solution of fine solution multipolymer, that is to say the degree of crystallinity of the multipolymer of failing to reduce better, make it to be dissolved in easily in the solution, and the solids content of multipolymer low (15～45%), difference of hardness, gloss is bad.The feature of another French Patent (FP2569703) is that trifluorochloroethylene combines with vinyl ester, and functional group is provided by the allyl deriv of monohydroxy.The same with the clear 61-57609 of Ri Tekai, the multipolymer good solubility needs the quantity of vinyl ester generally more, up to 60～70%, and performance such as so the fluorochemical monomer amount is few and influence its chemicals-resistant, and is weather-proof.
At the defective that above-mentioned prior art exists, the present invention aims to provide the fluorinated copolymer coating of a kind of low viscosity, high solids content, good solubility property, and this coating has good salt spray resistance, performances such as chemicals-resistant, weathering resistance.
It is principal monomer that the present invention adopts trifluorochloroethylene, and the monomer that contains vinyl that is equipped with function carries out quarternary copolymerized reaction, uses following four kinds of raw materials: (1) uses following four kinds of monomer: CF
2=CFC1 A
B
1R
3-C=CH
2B R
4B
2CH
2=CH-R
5-OH C
1C
C
2CH
2=CH-R
7-O-R
8-OH C
3 D is R wherein
1=C
1～C
5Normal chain alkyl;
R
2＝(CH
2)nCH，n＝0～2；
R
3, R
4=C
1～C
2Normal chain alkyl;
R
5＝(CH
2)m
1，m
1＝1～4；
R
6＝(CH
2)m
2，m
2＝2～3；
R
7＝(CH
2)m
3，m
3＝0～2；
R
8＝(CH
2)m
4，m
4＝4～6；
R
9=(CH
2) m
5, m
5=0～8; The molar percentage of four kinds of lists when participating in reaction is:
A：50.0～60.0％
B：30.0～40.0％
C：6.0～9.5％
D：0.5～4.0％
When using monomers B, B
1, B
2Can use separately, also can be simultaneously and usefulness, and the time spent therebetween mol ratio be B
1: B
2=1.00: 0.5～1.00.Combined effect is better than single.When using monomer C, C
1, C
2, C
3All can use separately, also optional wherein both and usefulness, or the three is with using.Both combined effects are better, and mol ratio therebetween is: C
1: C
3=1.00: 1.00～2.00; C
1: C
2=1.00: 1.00～2.00; C
2: C
3==1.00: 1.00～1.10; The three is C with its mol ratio of time spent
1: C
2: C
3=1.00: 1.00～2.00: 1.00～2.00.The present invention is mated with C monomers B in when research and has been carried out a large amount of experiments and surveyed its performance, all gets single monomer as B and C and particularly uses B in the monomers B separately
1The time, only use C among the monomer C
2Or C
3In a kind of monomer, use monomers B separately
2The time, can use the C among the monomer C
1, C
2, C
3In a kind of; All get two kinds of monomers and usefulness among monomers B, the C; Get among the B two monomers in the single monomer and C and with or B in two monomers and C in single monomer and usefulness; Getting among the B in the single monomer and C three monomers uses with; Getting among the B in two monomers and C three monomers uses with etc.Experimental results show that net effect has all had progress than prior art.Particularly among the B among two monomers and the C two monomer combined effects more outstanding.
Polymerization is to adopt the quarternary copolymerized technology of solution method.Solvent is the mixture of aliphatic ketone of aromatic benzene class (toluene, dimethylbenzene etc.) (methylethylketone, methyl iso-butyl ketone (MIBK) etc.) and acetates (vinyl acetic monomer, N-BUTYL ACETATE etc.), and its weight percent proportioning is: benzene class: ketone: ester class=10: 50～60: 30～40.Also can adopt ketone and ester class mixed solvent, wherein ketone accounts for 50～70%.The consumption of solvent is 20～30% of a reaction-ure mixture.Initiator is azo-compound or organo-peroxide commonly used, and as azobisisobutyronitrile, benzoyl peroxide etc., consumption is 1～3% of a monomer total amount.
Operation steps is during polymerization; Add solvent, the three kinds of monomers in addition except that trifluorochloroethylene in autoclave according to the order of sequence, initiator is closed autoclave, connect vacuum, Open valve adds the trifluorochloroethylene monomer under the negative pressure, valve-off after adding specified amount, open and stir, heat up, be controlled at 65～75 ℃.Pressure is about 0.80～0.85MPa when reacting initial, and reaction at the end is about 0.55MPa, and the reaction times is 18～20h.Reaction finishes, and the cooling blowing obtains faint yellow transparent viscous liquid, and its solid content reaches 60～72%, and hydroxyl value is 45～75mgKOH/g, and acid number is 10～30mgKOH/g, and proportion is 1.10～1.20, and being coated with-4 glasss of viscosity is 45～80s.
(comprise B with above four kinds of monomers
1, B
2, C
1, C
2, C
3) its chain-like structure synoptic diagram of polymkeric substance of obtaining of copolymerization is:
Owing to adopt vinyl ester can reduce the degree of crystallinity of fluoropolymer, make it to be dissolved in the solvent better.Yet vinyl ester chain facile hydrolysis, for overcoming this defective, the present invention adopts vinyl ester and vinyl compound and uses, particularly with isomerized vinyl compound and usefulness, be more conducive to improve its second-order transition temperature, increase hardness of paint film, to improve water-fast erosion.Introduce multiple hydroxy-containing compounds such as enol, olefin(e) acid hydroxy ester, diols alkenyl ether, except that cross-linking set is provided, also directly influence some other physical and chemical performance of paint film such as its sticking power.Compete poly-power difference owing to each is monomeric, the present invention introduces these hydroxy-containing compounds combinations, coupling, makes its coordination, evenly enters polymer segment, its hydroxyl homogeneous distribution, thus make product innovation performance homogeneous.The introducing of these compositions not only obtains the multipolymer of high fluorine content with combination rightly, and has unprecedented premium properties.
Compared with prior art, the advantage that the present invention has is: (40～80s) meet the requirement of present environmental protection to coating to (1) high solids content (60～72%) low viscosity, and prior art is unapproachable.Fluorine coating solid content as Japan AGC Co., Ltd. is the highest by 48～50%.(2) can be well wetting with pigment, disperse can prevent the sick generations of lacquer such as loose colour easily.(3) paint film that obtains has excellent rerum natura: 1. pendulum-rocker hardness reaches 0.75～0.88, than day Asahi Glass product 0.7 height; 2. flexibility reaches below the 2mm, and the paint film model is through folding, even base material fracture and paint film does not chap, do not come off; 3. gloss reaches as high as 92%, also is higher than day index of the rising sun product 85%, and French atropic company product index only is 69%; 4. sticking power (method of drawing a circle) is 1 grade, and shock-resistant is 50cm, is quite advanced index.(3) salt fog resistance is strong, and 2000h is 1 grade, is better than CN1145386A product (576h just is 1 grade), with day the Asahi Glass product suitable.(4) chemical-resistant is strong, and 1. the paint film sample is at 10%HCl, 10%H
2SO
4, soak two all no changes among the 10%NaOH, be better than method atropic company product, suitable with the Asahi Glass product; 2. anti-acetone is cleaned＞100 times with acetone, is better than the CN1145386A product index.(5) good weatherability, artificial accelerated aging 2000h loss of gloss rate 5～11% is better than a day Asahi Glass product (26%), French atropic company's product (30%) and CN1145386A product (1500h, loss of gloss rate 24%).
Embodiment 1
Emphasize B=B
1, C=C
1+ C
3
2L has and adds 80g vinegar ester butyl ester, 170g methyl iso-butyl ketone (MIBK), 180g vinyl acetate in the autoclave of induction stirring, 29g butyleneglycol vinyl ether, 11.6g vinyl carbinol (mol ratio, vinyl carbinol: butyleneglycol vinyl ether=1.0～1.25), the 8g+-olefin(e) acid, the 8g Diisopropyl azodicarboxylate.After vacuumizing, fills by autoclave nitrogen, vacuumize once more, the back joins feed valve and trifluorochloroethylene storage bottle under vacuum for several times repeatedly, and regulated valve makes trifluorochloroethylene (purity 99%) add 380g in the autoclave, valve-off, open and stir, heat up, temperature in the kettle is controlled at 68 ± 2 ℃, and the still internal pressure is up to 0.8MPa, pressure is 0.6MPa behind the 18h, reaction terminating.The cooling blowing.The solid content that obtains multipolymer is 66%, and being coated with-4 glasss of viscosity is 48s, and hydroxyl value 58mgkOH/g, acid number are 15mgKOH/g, and proportion is 1.18.
Test: use N-BUTYL ACETATE: it is 50% solution 750g that the mixed solvent of dimethylbenzene=2: 1 is mixed with solid content with multipolymer, add 250g titanium dioxide (JR701), stirring the back is below the 25 μ m being ground to fineness in the QZM-conoidal mill, by 10: 2 adding linking agent (being 2 parts) HDI, become various models and coupon to carry out performance test by the GB spray, the result is as follows:
The physicals of table 1 paint film
| Sticking power (method of drawing a circle) level | Shock-resistant cm | Hardness (fork method) | Gloss (60 ° of angles) | Pliability test mm |
| 1 | 50 | 0.85 | 92 | 1 |
Table 2 paint film chemical resistance
Salt spray resistance 2000h, paint film no change are 1 grade; The 2000h of anti-the artificial accelerated aging, paint film loss of gloss rate 7%, paint film does not have other catabiosis such as efflorescence, be full of cracks.
Embodiment 2
Emphasize B=B
1, C=C
1+ C
2
Operation steps and reaction conditions are with example 1.Feeding quantity is: 170g methyl iso-butyl ketone (MIBK), 80g N-BUTYL ACETATE, 180g vinyl acetate, the 29g Hydroxyethyl acrylate, 11.6g vinyl carbinol, (mol ratio, vinyl carbinol: 8g+-olefin(e) acid Hydroxyethyl acrylate=1: 1.25), 8g Diisopropyl azodicarboxylate, 390g trifluorochloroethylene.Reaction ends to such an extent that the solid content of multipolymer is 69%, and being coated with-4 glasss of viscosity is 60s, and proportion is 1.16.
Test: make model and coupon by the method that example is, being coated with gloss after tested is 88%, artificial accelerated aging 2000h loss of gloss rate is 11%, pliability test be 2mm, hardness be 0.80 outer other with example 1.
Embodiment 3
Emphasize C=C
3, B=B
1+ B
2
Operation steps and reaction conditions are with embodiment 1.Feeding quantity is the 80g N-BUTYL ACETATE, 210g methyl iso-butyl ketone (MIBK), 178g pineapple aldehyde, the 56g iso-butylene (mol ratio, pineapple aldehyde: iso-butylene=1.14: 1.00), 40.8g ethylene glycol propenyl ether, the 4g butenoic acid, 8g initiator Diisopropyl azodicarboxylate, trifluorochloroethylene 380g.The reaction end multipolymer solid content 62%, be coated with-4 glasss of viscosity 80s, proportion 1.10.
Test: make model and coupon by embodiment 1 method, removing gloss after tested is 75%, artificial accelerated aging 2000h, paint film loss of gloss rate be 10% outer other with embodiment 1.
Embodiment 4
Emphasize C=C
1+ C
3, B=B
1+ B
2
Operation steps and reaction conditions are with embodiment 1.Feeding quantity is the 80g N-BUTYL ACETATE, the 170g methyl iso-butyl ketone (MIBK), the 120g vinyl acetate, 56g iso-butylene (mol ratio, vinyl acetate: iso-butylene=1.4: 1.0), 29g butyleneglycol vinyl ether, 11.6g vinyl carbinol (mol ratio, vinyl carbinol: butyleneglycol vinyl ether=1.00: 1.25), the 8g undecylenic acid, initiator 8g Diisopropyl azodicarboxylate, trifluorochloroethylene are 400g.Reaction ends, and the solids content of polymkeric substance is 70%, and being coated with-4 glasss of viscosity is 56s, proportion 1.15.
Test 1: be mixed with compound colored paint with primary colors red, orchid, green color and multipolymer, all do not produce and grow dim and lacquer such as loose colour disease.
Embodiment 5
Emphasize that the monomer in B, the C component can use separately.
Operation steps and reaction conditions be with example 1, feeding quantity dimethylbenzene 50g, 50g N-BUTYL ACETATE, the 180g methyl iso-butyl ketone (MIBK), the 193g vinyl acetate, 45g butyleneglycol vinyl ether, 10g undecylenic acid, 6.5g Diisopropyl azodicarboxylate, the 375g trifluorochloroethylene, reaction ends, and the solid content of multipolymer is 63%, being coated with-4 glasss of viscosity is 78s, proportion 1.10.
Test: press embodiment 1 method and sample, after tested: except that gloss is 72%, hardness is 0.75, artificial accelerated aging 2000h loss of gloss rate is 11%, other are with example 1.
Claims (9)
1, a kind of fluoro-containing coating is the multiple copolymer based on trifluorochloroethylene, and the chain-like structure synoptic diagram that it is characterized by multipolymer is:
R wherein
1=C
1～C
5Normal chain alkyl;
R
2＝(CH
2)
nCH，n＝0～2；
R
3, R
4=C
1～C
2Normal chain alkyl;
R
5＝(CH
2)m
1，m
1＝1～4；
R
6＝(CH
2)m
2，m
2＝2～3；
R
7＝(CH
2)m
3，m
3＝0～2；
R
8＝(CH
2)m
4，m
4＝4～6；
R
9＝(CH
2)m
5，m
5＝0～8；
A, B, the shared molar percentage of C, D are:
A：50.0～60.0％，
B：30.0～40.0％，
C：6.0～9.5％，
D:0.5～4.0%, wherein B=B
1+ B
2, its mol ratio is B
1: B
2=1.00: 0.50～1.00;
C=C
1+ C
2+ C
3, its mol ratio is
C
1: C
2: C
3=1.00: 1.00～2.00: 1.00～2.00; Polymkeric substance is a light yellow viscous liquid, and its solid content is 60～72%, and being coated with-4 glasss of viscosity is 45～80s, and hydroxyl value is 45～75mgkOH/g, and acid number is 10～30mgKOH/g, and proportion is 1.10～1.20.
2, fluoro-containing coating according to claim 1 is characterized by in chain-like structure B=B
1+ B
2The time, the structure of C is C
1, C
2, C
3In two kinds of structures, its mol ratio is: C
1: C
3=1.00: 1.00～2.00, C
1: C
2=1.00: 1.00～2.00, C
2: C
3=1.00: 1.00～1.10;
3, fluoro-containing coating as claimed in claim 1 is characterized by in chain-like structure, and the structure of B has only B
1Or B
2In a kind of structure.
4, fluoro-containing coating as claimed in claim 1 is characterized by in chain-like structure, and the structure of C has only C
1, C
2, C
3In a kind of structure.
5, fluoro-containing coating as claimed in claim 1 is characterized by in chain-like structure, if the B structure has only B
1During structure, its C-structure has C
2Or C
3A kind of structure; If the B structure has only B
2During structure, C-structure has C
1, C
2, C
3In a kind of structure.
6, a kind of manufacture method of the fluoro-containing coating based on trifluorochloroethylene is characterized by and adopts the quarternary copolymerized method of liquid, and used raw material is: (1) uses following four kinds of monomer: CF
2=CFC1 A
B
1B
B
2CH
2=CH-R
5-OH C
1 
C
2CCH
2=CH-R
7-O-R
8-OH C
3 D is R wherein
1=C
1～C
5Normal chain alkyl;
R
2＝(CH
2)nCH，n＝0～2；
R
3, R
4=C
1～C
2Normal chain alkyl;
R
5＝(CH
2)m
1，m
1＝1～4；
R
6＝(CH
2)m
2，m
2＝2～3；
R
7＝(CH
2)m
3，m
3＝0～2；
R
8＝(CH
2)m
4，m
4＝4～6；
R
9=(CH
2) m
5, m
5=0～8; Molar percentage was when four kinds of monomers were participated in reaction:
A： 50.0～60.0％
B： 30.0～40.0％
C： 6.0～9.5％
D： 0.5～4.0％
When wherein using monomers B, B=B
1+ B
2, its mol ratio is B
1: B
2=1.00: 0.50～1.00 when using monomer C, 1. C=C
1+ C
2+ C
3, its mol ratio is
C
1∶C
2∶C
3＝1.00∶1.00～2.00∶1.00～2.00；
2. C=C
1+ C
3, its mol ratio is: C
1: C
3=1.00: 1.00～2.00,
C=C
1+ C
2, its mol ratio is: C
1: C
2=1.00: 1.00～2.00
C=C
2+ C
3, its mol ratio is: C
2: C
3=1.00: 1.00～1.10
(2) solvent is the mixture of benzene class, ketone and ester class, and its weight percent proportioning is 10%: 50～60%: 30～40%; The mixture of also available ketone and ester class, its ketone accounts for 50～70% of total amount; Described ketone is methyl ethyl ketone, methyl iso-butyl ketone (MIBK), and the benzene class is toluene, dimethylbenzene; The ester class is vinyl acetic monomer, N-BUTYL ACETATE; Solvent load is 20～30% of a reaction-ure mixture;
(3) initiator is azo-compound or organo-peroxide, and consumption is 1～3% of a monomer total amount;
Polymerization procedure is: add solvent, three kinds of monomers except that trifluorochloroethylene, initiator in the autoclave according to the order of sequence, decompression adds trifluorochloroethylene down, stirs, intensification also is controlled at 65～75 ℃, the reaction initial pressure is 0.80～0.85MPa, reaction 18～20h, cooling blowing.
7, the manufacture method of fluorine coating as claimed in claim 5 is characterized by when using monomers B, only uses B
1Or B
2In a kind of monomer.
8, the manufacture method of fluorine coating as claimed in claim 5 is characterized by when using monomer C, only uses C
1, C
2, C
3, in a kind of monomer.
9, the manufacture method of fluorine coating as claimed in claim 5 is characterized by the B in the independent use monomers B
1The time, use the C among the monomer C
2Or C
3A kind of monomer; Use the B in the monomers B separately
2The time, can use the C among the monomer C
1, C
2Or C
3A kind of monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99112990A CN1103354C (en) | 1999-06-04 | 1999-06-04 | Multi-component copolymerized fluoric paint containing triflurochloroethene as main component and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99112990A CN1103354C (en) | 1999-06-04 | 1999-06-04 | Multi-component copolymerized fluoric paint containing triflurochloroethene as main component and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1276399A CN1276399A (en) | 2000-12-13 |
| CN1103354C true CN1103354C (en) | 2003-03-19 |
Family
ID=5276229
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99112990A Expired - Fee Related CN1103354C (en) | 1999-06-04 | 1999-06-04 | Multi-component copolymerized fluoric paint containing triflurochloroethene as main component and its preparing process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1103354C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100586968C (en) * | 2005-09-05 | 2010-02-03 | 同济大学 | Water-based fluoropolymer emulsion, preparation method and application thereof |
| CN101125979B (en) * | 2006-08-18 | 2010-05-12 | 无锡市雅丽涂料有限公司 | Thermosetting fluorine-carbon resin for metal coiled material and coating thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1046911A (en) * | 1989-04-28 | 1990-11-14 | 阿托化学公司 | Hardenable fluorinated copolymer, its method for making and the application in paint and coating |
-
1999
- 1999-06-04 CN CN99112990A patent/CN1103354C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1046911A (en) * | 1989-04-28 | 1990-11-14 | 阿托化学公司 | Hardenable fluorinated copolymer, its method for making and the application in paint and coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1276399A (en) | 2000-12-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1144822C (en) | Preparation of fluorated polymer | |
| CN101585899B (en) | Cationic modified epoxy resin emulsion and preparation method and application thereof | |
| CN100586979C (en) | Preparation method of acrylic acid-epoxy resin modified aqueous polyurethane | |
| CN100451042C (en) | Fluoride core-shell acrylic-resin emulsion, its production and use | |
| CN101560278B (en) | Methyl methacrylate-styrene copolymer containing fluoro-acrylate and preparation method thereof | |
| CN102358815A (en) | One-component self-drying acrylic acid grafted epoxy ester aqueous dispersion coating and its preparation method | |
| CN110511388A (en) | A kind of modified hydroxyl acrylic emulsion and preparation method thereof for aqueous coatings for tin plate printing | |
| CN102911540A (en) | Hydrophobic MMA (Methl Methacrylate) resin floor coating and preparation method thereof | |
| FR2601374A1 (en) | SEQUENTIALLY PRODUCED POLYMER PARTICLES, AQUEOUS DISPERSIONS OF SEQUENTIALLY PRODUCED POLYMER PARTICLES, PROCESSES FOR THE PREPARATION OF SEQUENTIALLY PRODUCED POLYMER PARTICLES, AND USES OF SEQUENTIALLY PRODUCED POLYMER PARTICLES | |
| CN103965393A (en) | Water-based acrylic resin | |
| CN101747464B (en) | Fluoro olefin copolymerization fluororesin with fluoric lateral group or fluoric branched chain | |
| KR0185669B1 (en) | Copolymer latex from esters of (meth)acrylic acid and vinyl esters of branched chain carboxylic acids | |
| CN1103354C (en) | Multi-component copolymerized fluoric paint containing triflurochloroethene as main component and its preparing process | |
| CN1229406C (en) | Aqueous fluoric resin and its prepn and application | |
| CN112851882B (en) | Preparation method of epoxy resin modified styrene-acrylic emulsion for plastic ink | |
| CN102964513A (en) | Preparation method of fluorine-containing water-based self-crosslinking acrylic resin emulsion | |
| CN1046912A (en) | Its method for making of hardenable fluorinated copolymer and the application in paint and coating | |
| FR2889196A1 (en) | AQUEOUS DISPERSION OF STRUCTURED POLYMER, PROCESS FOR PRODUCING THE SAME, AND APPLICATIONS THEREOF IN FORMULATIONS FOR PAINTS | |
| EP0614919A1 (en) | A latex composition containing polymer particles having core/shell structure | |
| CN1111571C (en) | Fluoric copolymer paint and method for making thereof based on tetrafluoroethylene | |
| CN1278285A (en) | Fluoropolymer dispersion coatings from modified thermoplastic vinylidene fluoride based resins | |
| KR0185668B1 (en) | Copolymer latex from esters of(meth)acrylic acid and vinyl esters of branched chain carboxylic acids and preparation thereof | |
| CN112979862A (en) | Styrene-acrylic emulsion and preparation method thereof | |
| JP3146842B2 (en) | Water-based paints composed of fluorinated copolymers | |
| JP2893766B2 (en) | Method for producing fluorovinyl nonaqueous polymer dispersion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |