CN101544732B - Preparation method of fluorine-containing multipolymer - Google Patents
Preparation method of fluorine-containing multipolymer Download PDFInfo
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- CN101544732B CN101544732B CN2009100312695A CN200910031269A CN101544732B CN 101544732 B CN101544732 B CN 101544732B CN 2009100312695 A CN2009100312695 A CN 2009100312695A CN 200910031269 A CN200910031269 A CN 200910031269A CN 101544732 B CN101544732 B CN 101544732B
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Abstract
The invention relates to a preparation method of fluorine-containing multipolymer which can be used for producing dope with excellent combination property, good stability and low cost. The preparation method of fluorine-containing multipolymer is as follows: 15-25 portions of metacrylic acid ester which is monomer, 5-10 portions of acrylic ester and 5-10 portions of functional monomer are performed with graft copolymerization reaction in solution of 10-20 portions of fluorocarbon resin which is soluble under normal temperature, and the structural formulas of the metacrylic acid ester, the acrylic ester and the functional monomer are respectively shown as (1), (2) and (3), wherein R1 and R2 which are mutually independent are alkyl with 1-4 carbon atoms, R3 is H, hydroxyethyl group or hydroxypropyl, and R4 is H or cymene. The invention has excellent combination property, can stably exist for a long time without being added with dispersion stabilizer and does not delaminate, thereby effectively lowers the cost of product.
Description
Technical field
The present invention relates to a kind of preparation method of fluorinated copolymer, belong to paint field.
Background technology
Fluorocarbon resin is the resin that a class has excellent properties such as excellent weathering resistance, contamination resistance, Waterproofing/oilproofing, erosion resistance, but because the fluorocarbon resin processing difficulties needs ability film forming more than 300 ℃, can not construct at normal temperatures.Nineteen eighty-two, Japan utilized molecular chain designing technique and membrane technique, took the lead in developing the normal temperature solidified fluorocarbon coating of FEVE, had expanded the range of application of fluorocarbon coating greatly, and fluorocarbon coating is used in daily life becomes possibility.But fluorocarbon coating costs an arm and a leg, and this has limited applying of fluorocarbon coating greatly.
Pure acrylic acid coating is the another kind of building coating of supplying in the market, and over-all properties is better, and glossiness is good, and cost is lower, but performances such as its contamination resistance, Waterproofing/oilproofing, weathering resistance, erosion resistance still remain to be improved.
WO 03/02660 discloses a kind of coating composition that contains the perfluoroalkyl acrylate emulsion, it is the aqueous fluorine-containing multipolymer that obtains by with fluoride monomers, vinyl ether monomers and acrylic monomer copolymerization, to reduce product cost, but, for weathering resistance, contamination resistance, Waterproofing/oilproofing, the erosion resistance that guarantees product, must guarantee that obtaining molecular chain structure replaces uniform multipolymer, so the processing requirement height, product cost is still higher simultaneously.
CN95106651.X discloses a kind of stable aqueous dispersion that contains the hydroxylation fluorinated copolymer, by hydroxylation fluorinated copolymer and acrylic polymers blend are formed, but must add emulsifying agent and could keep the stable of water dispersion, thereby increase the cost of product.
Up to the present, still lack in the prior art and have excellent comprehensive performance and coating with low cost.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of fluorinated copolymer, the gained fluorinated copolymer can be used for producing excellent comprehensive performance, good stability and coating with low cost.
The preparation method of described fluorinated copolymer, for in the solution of the soluble fluorocarbon resin of normal temperature, making monomer methacrylic ester, acrylate, functional monomer carry out graft copolymerization, the consumption of fluorocarbon resin, methacrylic ester, acrylate, functional monomer is respectively 10～20 parts, 15～25 parts, 5～10 parts, 5～10 parts, described umber is a weight part, the structural formula of methacrylic ester, acrylate, functional monomer is respectively shown in (1), (2), (3)
CH
2＝CH-COO-R
2
(2)
Wherein, R
1, R
2Independently be the alkyl of 1-4 separately for carbonatoms, R
3Be H, hydroxyethyl or hydroxypropyl, R
4Be H or methyl.
As preferred version, the hydroxyl value of described fluorocarbon resin is 30～70, and acid value is 2～6mgKOH/g.The fluorine content of fluorocarbon resin is preferably 24%～40%.
As preferred version, methacrylic ester is the mixture of the arbitrary proportion of methyl methacrylate and Jia Jibingxisuanyizhi or butyl methacrylate.
As preferred version, acrylate is ethyl propenoate or butyl acrylate.
As preferred version, functional monomer is the mixture of methacrylic acid and Hydroxyethyl acrylate or Propylene glycol monoacrylate, and wherein the consumption of methacrylic acid is 0.1～1 weight part.
The molecular weight of described fluorocarbon resin is preferably 5000～30000.
Generally speaking, the soluble fluorocarbon resin of normal temperature all obtains by vinyl fluoride and vinyl ether or vinyl ester modification by copolymerization, and vinyl ether or vinyl ester can be provided at the solvability in the organic solvent, and fluorocarbon resin can be dissolved in the usual vehicle at normal temperatures.For solvent of the present invention is the good solvent of fluorocarbon resin.According to the similar compatibility principle, the solubility parameter of the solvent of use should be as far as possible be close with the solubility parameter of fluorocarbon resin, and the solubility parameter of aforementioned fluorocarbon resin is 7.5～9.5.As preferred version, described solvent is the mixture of dimethylbenzene, N-BUTYL ACETATE, 1-Methoxy-2-propyl acetate and pimelinketone, the consumption of dimethylbenzene, N-BUTYL ACETATE, 1-Methoxy-2-propyl acetate and pimelinketone is respectively 5～12 parts, 12～20 parts, 5～10 parts, 1～5 part, and described umber is a weight part.
Described graft copolymerization is a Raolical polymerizable, and the solids content of gained fluorinated copolymer is 50 ± 2%.
The preparation method of described fluorinated copolymer comprises the steps:
A. fluorocarbon resin is dissolved in the organic solvent, obtains fluorocarbon resin solution;
B. fluorocarbon resin solution is warming up to 100～110 ℃;
C. drip the mixture of monomer and part initiator in 3～4h, be incubated 1～1.5h then, wherein said part initiator accounts for 4/5～7/8 of initiator total amount;
D. add remaining initiator, be incubated 1.5～2h then.
Initiator select common practise for use for this area, as preferably, described graft copolymerization is initiator with the benzoyl peroxide, initiator amount is 0.2～1 weight part.
The above weight part number average adopts same benchmark.
The present invention selects specific fluorocarbon resin for use, in its solution, make acrylic monomer graft copolymerization, the gained fluorinated copolymer not only has performances such as the weathering resistance, contamination resistance, Waterproofing/oilproofing, erosion resistance of fluorocarbon resin excellence, the glossiness that also has acrylic coating, the product high comprehensive performance need not to add dispersion stabilizer, promptly can steady in a long-termly exist, not stratified, effectively reduce product cost.
Embodiment
Below the present invention is elaborated, wherein fluorocarbon resin is selected the KF300 fluorocarbon resin product of the safe chemical Group Co.,Ltd in Jiangsu and the RFS-2000 fluorocarbon resin of auspicious fluorine chemical Science and Technology Ltd. for use, its solid content is 〉=50%, and the performance index of the fluorocarbon resin that wherein contains are as shown in table 1.Described umber is weight part, and each embodiment adopts same benchmark.
The performance index of table 1 fluorocarbon resin
| Index | KF300? | RFS-2000? |
| Fluorine content, % (calculating of 100% solid) | 25±1? | 35±1? |
| Molecular weight | 20000～30000? | 6000～25000? |
| Hydroxyl value | 47～53? | 30～50? |
| Acid value, mgKOH/g | 3±1? | 3～6? |
| Color and luster (Fe-Co colorimetric) | ≤3? | ≤2? |
Embodiment 1
1. 40 parts of KF300 are dissolved in the mixed solvent of forming by 8 parts of dimethylbenzene, 15 parts of N-BUTYL ACETATEs, 5 parts of 1-Methoxy-2-propyl acetates and 2 parts of pimelinketone, obtain fluorocarbon resin solution, be warming up to 100-110 ℃ then.
2. 8.5 parts of methyl methacrylates, 8.5 parts of butyl methacrylate, 6.5 parts of butyl acrylates, 0.5 part of methacrylic acid, 6.0 parts of Hydroxyethyl acrylates and 0.35 part of benzoyl peroxide are mixed; in 3.5h, splash in the fluorocarbon resin solution, be incubated 1.5h then.
3. add 0.05 part of benzoyl peroxide again, be incubated 2h then, obtain solids content and be 50% fluorinated copolymer.
Embodiment 2
1. 20 parts of RFS-2000 are dissolved in the mixed solvent of forming by 10 parts of dimethylbenzene, 18 parts of N-BUTYL ACETATEs, 8 parts of 1-Methoxy-2-propyl acetates and 4 parts of pimelinketone, obtain fluorocarbon resin solution, be warming up to 100-110 ℃ then.
2. 12.5 parts of methyl methacrylates, 11.5 parts of Jia Jibingxisuanyizhis, 8.5 parts of ethyl propenoates, 0.5 part of methacrylic acid, 7.0 parts of Hydroxyethyl acrylates and 0.6 part of benzoyl peroxide are mixed; in 4h, splash in the fluorocarbon resin solution, be incubated 1h then.
3. add 0.15 part of benzoyl peroxide again, be incubated 1.5h then, obtain solids content and be 50% fluorinated copolymer.
Comparative examples
Pure acrylic acid hydroxy resin (solid content 50%, hydroxyl value 80) mixes with the mass ratio of KF300 resin by 6: 4, obtains hybrid resin.
Embodiment 1,2 gained fluorinated copolymers and comparative examples gained hybrid resin are deposited in 50 ℃ baking oven, and its outward appearance of routine observation the results are shown in Table 2.
Table 2 package stability
| ? | Embodiment 1 | Embodiment 2 | Contrast |
| 0 day | Transparent | Transparent | Little muddy |
| 30 days | No abnormal | No abnormal | Muddy |
| 60 days | No abnormal | No abnormal | Layering |
| 180 days | No abnormal | No abnormal | Gel |
Application Example 1
Become whitewash 1 with embodiment 1 gained fluorinated copolymer by formulation in the table 3, adopt the former R-930 titanium dioxide of Japanese stone, resin-pigment ratio is 1/1.5, and solidifying agent adopts the N-75 product (solid content 75%) of Bayer AG ,-OH/-NCO=1: 1.
Table 3 white paint preparation prescription
| Material name | Whitewash 1 | Whitewash 2 | Whitewash 3 | Whitewash 4 |
| Embodiment 1 resin | 60? | /? | /? | /? |
| Embodiment 2 resins | /? | 57.8? | /? | /? |
| Embodiment 3 resins | /? | /? | 57.2? | /? |
| Embodiment 4 resins | /? | /? | /? | 64? |
| Titanium dioxide R-930 | 25? | 25? | 25? | 25? |
| Solidifying agent | 10? | 11.6? | 11.9? | 7.3? |
| Mixed solvent * | 30? | 30.6? | 30.9? | 28.7? |
| Add up to | 125? | 125? | 125? | 125? |
| Solids coatings | 50％? | 50％? | 50％? | 50％? |
*Mixed solvent is formed: dimethylbenzene 45%, N-BUTYL ACETATE 45%, 1-Methoxy-2-propyl acetate 6%, pimelinketone 4%, above-mentioned per-cent are mass percent.
Application Example 2
Become whitewash 2 with embodiment 2 gained fluorinated copolymers by formulation in the table 3, adopt the former R-930 titanium dioxide of Japanese stone, resin-pigment ratio is 1/1.5, and solidifying agent adopts the N-75 product (solid content 75%) of Bayer AG ,-OH/-NCO=1: 1.
Application Example 3
With pure acrylic acid hydroxy resin (solid content 50%, hydroxyl value 80) become whitewash 3 by formulation in the table 3, adopt the former R-930 titanium dioxide of Japanese stone, resin-pigment ratio is 1/1.5, solidifying agent adopts the N-75 product (solid content 75%) of Bayer AG ,-OH/-NCO=1: 1.
Application Example 4
Become whitewash 4 with outsourcing fluorocarbon resin (the KF300 fluorocarbon resin product of the safe chemical Group Co.,Ltd in Jiangsu) by formulation in the table 3, adopt the former R-930 titanium dioxide of Japanese stone, resin-pigment ratio is 1/1.5, solidifying agent adopts the N-75 product (solid content 75%) of Bayer AG ,-OH/-NCO=1: 1.
With reference to industry standard HG/T 3792-2005 " cross-linking type fluorine resin coating ", implement tree 1-4 gained whitewash to using, carry out the detection of physical and chemical performance, the results are shown in Table 4.
Table 4
Claims (10)
1. the preparation method of a fluorinated copolymer, it is characterized in that the soluble fluorocarbon resin of normal temperature is dissolved in the organic solvent, obtain fluorocarbon resin solution, make the monomer methacrylic ester then, acrylate, functional monomer carries out graft copolymerization and obtains fluorinated copolymer in fluorocarbon resin solution, fluorocarbon resin, methacrylic ester, acrylate, the consumption of functional monomer is respectively 10～20 parts, 15～25 parts, 5～10 parts, 5～10 parts, described umber is a weight part, methacrylic ester, acrylate, the structural formula of functional monomer is respectively as (1), (2), (3) shown in
CH
2＝CH-COO-R
2 (2)
Wherein, R
1, R
2Independently be the alkyl of 1-4 separately for carbonatoms, R
3Be H, hydroxyethyl or hydroxypropyl, R
4Be H or methyl, the hydroxyl value of described fluorocarbon resin is 30～70, and acid value is 2～6mgKOH/g, and fluorine content is 24%～40%, and molecular weight is 5000～30000.
2. the preparation method of fluorinated copolymer as claimed in claim 1 is characterized in that methacrylic ester is the mixture of the arbitrary proportion of methyl methacrylate and Jia Jibingxisuanyizhi or butyl methacrylate.
3. the preparation method of fluorinated copolymer as claimed in claim 1 is characterized in that acrylate is ethyl propenoate or butyl acrylate.
4. the preparation method of fluorinated copolymer as claimed in claim 1 is characterized in that functional monomer is the mixture of methacrylic acid and Hydroxyethyl acrylate or Propylene glycol monoacrylate, and wherein the consumption of methacrylic acid is 0.1～1 weight part.
5. the preparation method of fluorinated copolymer as claimed in claim 1, the solids content that it is characterized in that the gained fluorinated copolymer is 50 ± 2%.
6. as the preparation method of each described fluorinated copolymer among the claim 1-5, it is characterized in that described organic solvent is the good solvent of fluorocarbon resin.
7. the preparation method of fluorinated copolymer as claimed in claim 6, it is characterized in that described organic solvent is the mixture of dimethylbenzene, N-BUTYL ACETATE, 1-Methoxy-2-propyl acetate and pimelinketone, the consumption of dimethylbenzene, N-BUTYL ACETATE, 1-Methoxy-2-propyl acetate and pimelinketone is respectively 5～12 parts, 12～20 parts, 5～10 parts, 1～5 part, and described umber is a weight part.
8. as the preparation method of each described fluorinated copolymer among the claim 1-5, it is characterized in that described graft copolymerization is a Raolical polymerizable.
9. the preparation method of fluorinated copolymer as claimed in claim 8 is characterized in that comprising the steps:
A. fluorocarbon resin is dissolved in the organic solvent, obtains fluorocarbon resin solution;
B. fluorocarbon resin solution is warming up to 100～110 ℃;
C. drip the mixture of monomer and part initiator in 3～4h, be incubated 1～1.5h then, wherein said part initiator accounts for 4/5～7/8 of initiator total amount;
D. add remaining initiator, be incubated 1.5～2h then, obtain fluorinated copolymer,
Described initiator is a benzoyl peroxide.
10. the preparation method of fluorinated copolymer as claimed in claim 9 is characterized in that described initiator amount is 0.2～1 weight part.
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| CN2009100312695A CN101544732B (en) | 2009-04-30 | 2009-04-30 | Preparation method of fluorine-containing multipolymer |
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|---|---|---|---|
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| CN101544732B true CN101544732B (en) | 2011-04-06 |
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| CN105037637A (en) * | 2015-07-07 | 2015-11-11 | 苏州嘉祥树脂有限公司 | Method for synthesizing fluorocarbon-acrylic resin from PVDF |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1117979A (en) * | 1994-06-01 | 1996-03-06 | 埃勒夫阿托化学有限公司 | Stable aqueous dispersive body of hydroxyleste fluoridated copolymer and acrylic copolymer and preparation and application as aqueous pait of same |
| EP1411085B1 (en) * | 2001-06-28 | 2006-11-02 | Daikin Industries, Ltd. | Aqueous emulsion resin compositions |
| CN101238153A (en) * | 2005-08-04 | 2008-08-06 | 大金工业株式会社 | Process for producing aqueous dispersion of composite fluoropolymer particle, aqueous dispersion, and composite polymer particle |
-
2009
- 2009-04-30 CN CN2009100312695A patent/CN101544732B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1117979A (en) * | 1994-06-01 | 1996-03-06 | 埃勒夫阿托化学有限公司 | Stable aqueous dispersive body of hydroxyleste fluoridated copolymer and acrylic copolymer and preparation and application as aqueous pait of same |
| EP1411085B1 (en) * | 2001-06-28 | 2006-11-02 | Daikin Industries, Ltd. | Aqueous emulsion resin compositions |
| CN101238153A (en) * | 2005-08-04 | 2008-08-06 | 大金工业株式会社 | Process for producing aqueous dispersion of composite fluoropolymer particle, aqueous dispersion, and composite polymer particle |
Non-Patent Citations (2)
| Title |
|---|
| JP特开2003-171520A 2003.06.20 |
| JP特开平5-170909A 1993.07.09 |
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