CN104829772B - A kind of normal temperature cure Fluorocoating resin and preparation method thereof - Google Patents
A kind of normal temperature cure Fluorocoating resin and preparation method thereof Download PDFInfo
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- CN104829772B CN104829772B CN201510251924.3A CN201510251924A CN104829772B CN 104829772 B CN104829772 B CN 104829772B CN 201510251924 A CN201510251924 A CN 201510251924A CN 104829772 B CN104829772 B CN 104829772B
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Abstract
The invention discloses a kind of normal temperature cure Fluorocoating resin and preparation method thereof, this resin is by CTFE, pi-allyl tetrafluoro ether, vinyl acetate base ester, hydroxy butyl vinyl ether, undecylenic acid is polymerized in the organic solvent containing initiator, outward appearance is colourless and light yellow transparent liquid, hydroxyl value is 30～90mgKOH/g, its acid number is 0～10mgKOH/g, utilizing painting 4 flow cups to record its viscosity at 25 DEG C is 60～90, Oil repellent >=18% of dried resin, the product of the present invention has higher Oil repellent, and there is preferable weatherability, chemical-resistant.
Description
Technical field
The invention belongs to coating raw material technical field, relate to a kind of normal temperature cure Fluorocoating resin.
Background technology
Fluoro coatings (also known as fluorocarbon coating) is a kind of emerging high-performance coating, and durability, up to more than 20 years, has again prominent
The contaminated resistance gone out, is described as " coating king ", is preferable exterior coating product, and its core substance is organo-fluorine polymer tree
Fat, it is desirable to first this resin should have enough Oil repellent, it is ensured that the preferable weatherability of coating, chemical-resistant；Resin simultaneously
Molecular flexibility to be got well, and degree of crystallinity is low, makes resin have excellent room temperature film-forming and solubility, it is possible to preferable with face, filler
Compatible, there is good rheological characteristic, workability.
The research of curing type fluoro coatings resin at present mainly has:
1, Japan AGC company at the beginning of last century with CTFE as principal monomer, succeeded in developing cold curing and built
Building fluoro coatings resin (Japan Patent JP58136662), its resin structure is CTFE-alkyl vinyl ether-cycloalkyl second
The quadripolymer of alkene ether-light alkyl vinyl ether.Chinese patent CN1145386 in 1997 has been carried out
The research work of the Fluorocoating resin of main body, the method uses the monomer with carboxylic acid functional to synthesize CTFE
Quadripolymer.
Oil repellent with the quarternary copolymerized fluoro coatings resin of CTFE synthesis is low, and difficult raising, the fluorine of low fluorine content
Resin can not play the high-performance benefits of fluoro coatings.And resin pigment bad dispersibility synthesized in Japan Patent, resistance to toluene
Solvent nature is low；Although Chinese patent improves fluororesin to the wettability of coating pigment and dispersibility, but alcohol resistance and Nai Qi
Its solvent borne also reduces.The subject matter of above two method or Oil repellent deficiency, thus had influence on resistance index.
2, using tetrafluoroethene is principal monomer synthetic type cold curing fluoro coatings resin.China disclosed in 2000
Patent application CN1244556A is prepared for a kind of tetrafluoroethene-aliphatic ester based on tetrafluoroethene and/or isomeric olefine-fat
Fat enol and/or the multiple copolymer of alkene ether dihydroxylic alcohols-fat olefin(e) acid, this coating resin corrosion resistance, good weatherability；China is specially
Profit application CN1629230A disclosed a kind of tetrafluoroethene-alkyl vinyl ether-light alkyl vinyl ether-vinyl in 2005
The synthetic method of the soluble fluorine-containing copolymer coating resin of ester, resin has higher Oil repellent and fabulous weatherability and resistance to
Solvent borne.
Main comonomer owing to using in the synthesis of resin is tetrafluoroethene, and this is the fluorine list of a kind of high fluorinated volume
Body, can make, with enough fluorine atoms on the macromolecular chain of fluororesin, to give fluororesin and fluoro coatings high-weatherability, Gao Naihua
The property learned and surface water repellent, refuse the performance such as oil, stain resistant.
Relation be-tween structure and properties according to fluoro coatings resin and Fluoro Contained Coatings Abroad research experience, fluoro coatings resin
Oil repellent is the highest, and the performance of fluoro coatings is the best.But tetrafluoroethene belongs to " hard monomer ", tetrafluoroethene is single with vinyl acetate base ester etc.
Tetrafluoroethylene units in the copolymer molecule chain of body is the most, then macromolecule chain rigidity is the strongest, fluoro coatings resin dissolubility
The poorest, fluoro coatings the most easily layering, application property is poor.When the molar fraction of tetrafluoroethylene units reaches 50%, fluoro coatings resin molten
Solution property and processability are the most very poor.Improving Oil repellent and then cause the decreased solubility of fluororesin, fluoro coatings application property is bad.
The most above-mentioned two patents employ vinyl alkyl ethers or aliphatic ester monomer structure in polymerization process
Unit participates in copolymerization, to reduce the crystallinity of fluoropolymer, gives its dissolubility, tack etc.；Whether the former fat
Vinyl ethers and vinyl ester monomers that race's monomer or the latter use are the most fluorine-containing comonomer, when they participate in poly-
After conjunction process is prepared as Fluorocoating resin, copolymer segment will contain substantial amounts of non-fluorine segment.Depositing of non-fluorine segment
The performance of fluoro coatings will certainly affected, and owing to tetrafluoro can be made when the non-fluorine polymerization monomer of said method use participates in polymerization
Vinyl monomer segment skewness in the polymer, this also can affect the performance of resin.
Summary of the invention
The present invention is in order to overcome the drawbacks described above of prior art, it is provided that weatherability that what a kind of Oil repellent was higher have concurrently and good
The normal temperature cure Fluorocoating resin of good processing characteristics.
Present invention is specific as follows:
A kind of normal temperature cure Fluorocoating resin, is gathered in the organic solvent containing initiator by the monomer of following weight portion
Conjunction forms:
A: CTFE: 45～50；
B: pi-allyl tetrafluoro ether, structural formula is CH2=CH-CH2-O-CF2-CF2H:1～5；
C: vinyl acetate base ester: 15～20；
D: hydroxy butyl vinyl ether, structural formula is CH2=CH-O-C4H8-OH:3～8；
E: undecylenic acid, structural formula is CH2=CH-C8H16-COOH:0.5～3.
Preferably, described initiator is oleosoluble radical initiators, and its weight portion is 0.5～1.
Preferably, described oleosoluble radical initiators is azodiisobutyronitrile.
Preferably, the weight portion of described organic solvent is 30～40.
Preferably, described organic solvent is the mixture of dimethylbenzene and butyl acetate, and its mass ratio is 1:1～3.
The hydroxyl value of described normal temperature cure Fluorocoating resin is 30～90mgKOH/g, and its acid number is 3～10mgKOH/g, its
Viscosity is 60～90, Oil repellent >=18% of dried resin.
The preparation method of normal temperature cure Fluorocoating resin described above, comprises the steps:
1) will by above-mentioned weight portion load weighted pi-allyl tetrafluoro ether, vinyl acetate base ester, hydroxy butyl vinyl ether, ten
Monoenoic acid, organic solvent and initiator fully mix；
2) reaction raw materials that step 1) mixes is joined in polymerization autoclave；
3) air in polymerization autoclave is replaced into nitrogen；
4) load weighted CTFE monomer is added in polymerization autoclave；
5) opening stirring, heat up, control polymerization temperature 65～75 DEG C, controlling polymerization pressure is 0.6～0.9MPa, polymerization
Time is 18～22 hours；
6) it is cooled to room temperature, stops stirring, blowing.
Above-mentioned steps 1) specifically, by load weighted pi-allyl tetrafluoro ether, vinylacetate, hydroxy butyl vinyl ether,
Undecylenic acid and organic solvent add in the container of band stirring, open stirring, are slowly added into load weighted initiator, and stirring is all
Even.
Above-mentioned steps 2) specifically, polymerization autoclave is evacuated down to 90～95KPa after, by the monomer in step 1), draw
Send out agent, the mixed solution of solvent is drawn in polymerization autoclave.
Above-mentioned steps 3) specifically, to polymerization autoclave evacuation, in making polymerization autoclave, vacuum is to 90～95KPa,
Inflated with nitrogen, to gauge pressure+0.05MPa, so repeats 2～4 times.
The polyreaction of the present invention is carried out in organic solvent, for solution polymerization.
Although playing a decisive role according to high molecular rigidity and solubility backbone structure, but its side base or side chain are to macromolecule
Rigidity and the principle that also has a major impact of the various performances such as solubility, the present invention suitably adds a certain proportion of pi-allyl four
Fluorine ether, before avoiding affecting Fluorocoating resin rigidity and solubility and ensureing that Fluorocoating resin has higher molecular weight
Put, improve the Oil repellent of Fluorocoating resin by increasing side chain Oil repellent further, thus it is resistance to further increase it
Hou Xing.
The present invention is raw materials used to be had the following characteristics that
1. CTFE is the fluorine monomer of high fluorinated volume, makes on the macromolecular chain of Fluorocoating resin with enough
Fluorine atom, gives Fluorocoating resin high-weatherability, high chemical resistance and surface water repellent, refuses the performance such as oil, stain resistant；
2. pi-allyl tetrafluoro ether, this fluoropolymer monomer is prepared with tetrafluoroethene synthesis by 1-propenol-3, is characterized in
With the side chain that fluorinated volume is high, add fluorinated volume；
3. vinylacetate increases the dissolubility of Fluorocoating resin；
4. hydroxy butyl vinyl ether, the functional monomer of band cross-linkable solidifying group, providing for Fluorocoating resin can room
The functional group of temperature crosslinking curing；
5. undecylenic acid, the functional monomer of carboxylic acid functional group, give the Fluorocoating resin moistening to coating pigment
Property and the tack to base material.
The normal temperature cure Fluorocoating resin that the present invention prepares has higher fluorinated volume, its dried resin Oil repellent up to
More than 18%, the coating being made from has preferable weatherability, and molecular resin is flexible simultaneously, and degree of crystallinity is low, makes resin have excellent
Good room temperature film-forming and solubility, it is possible to the most compatible with face, filler, have good rheological characteristic, workability；Simultaneously
Preparation method in the present invention has the advantage that step is succinct, process is easily controllable.
Detailed description of the invention
Example 1
By pi-allyl tetrafluoro ether 18g, vinyl acetate base ester 200g, hydroxy butyl vinyl ether 50g, undecylenic acid 15g, vinegar
Acid butyl ester 200 grams, dimethylbenzene 260 grams join in the 2L glass beaker of band stirring, open stirring, are slowly added into initiator 10g
Azodiisobutyronitrile, is allowed to fully dissolve.2L polymeric kettle evacuation, makes vacuum in still mix above-mentioned to after 93KPa
Monomer, initiator, the mixed solution of solvent are drawn in 2L reactor, and to polymerization autoclave evacuation, in making still, vacuum arrives
93KPa, inflated with nitrogen to gauge pressure+0.05MPa, again the gas secondary in evacuation, nitrogen metathesis polymerizable device;Evacuation again
Rear unlatching autoclave stirs, and adds 550 grams of CTFE monomers.Start to warm up, control temperature in the kettle about 70 DEG C and enter
Row polyreaction.Primary response pressure is 0.8MPa, and after 20h, in still, reaction pressure will terminate reaction for 0.5MPa, be cooled to 30
DEG C, reclaim blowing after unreacted CTFE monomer, obtain the uniform thick liquid that colourless or micro-Huang is transparent.
Example 2
Use the method and apparatus identical with example 1, but be pi-allyl tetrafluoro ether 20g, acetic acid according to the consumption of monomer
Vinyl esters 180g, hydroxy butyl vinyl ether 80g, undecylenic acid 20g, CTFE 550 g, solvent load is butyl acetate
200 g, dimethylbenzene 260 g, initiator azodiisobutyronitrile consumption is 8g, carries out the synthesis of penta-component copolymerized fluororesin, prepares
There is the fluororesin of excellent performance.
Example 3
Use the method and apparatus identical with example 1, but be pi-allyl tetrafluoro ether 25g, acetic acid according to the consumption of monomer
Vinyl esters 180g, hydroxy butyl vinyl ether 120g, undecylenic acid 20g, CTFE 550 g, solvent load is acetic acid fourth
Ester 200 g, dimethylbenzene 260 g, initiator azodiisobutyronitrile consumption is 10g, carries out the synthesis of penta-component copolymerized fluororesin, prepares
There is the fluororesin of excellent performance.
Example 4
Use the method and apparatus identical with example 1, but be pi-allyl tetrafluoro ether 18g, acetic acid according to the consumption of monomer
Vinyl esters 200g, hydroxy butyl vinyl ether 50g, undecylenic acid 20g, CTFE 550 g, solvent load is butyl acetate
200 g, dimethylbenzene 260 g, initiator azodiisobutyronitrile consumption is 7g, carries out the synthesis of penta-component copolymerized fluororesin, prepares
There is the fluororesin of excellent performance.
The specific targets of product of the present invention are as shown in table 1:
Table 1
△: represent colourless or yellowish transparent, mechanical impurity, uniform liquid.
From this experimental result it can be seen that this product has higher fluorinated volume；Its viscosity maintains the water of about 60-70
Flat, compared to the levels of viscosity of usual resin, its viscosity also maintains relatively low level, thus ensures that it has and preferably can add
Work performance.
Application Example: after gained the said goods of the present invention is made coating, with existing coating in ambient temperature 50 DEG C, phase
The water-cooled xenon lamp of humidity 75, rainfall cycle 15min/h, 6KW light source is uninterruptedly irradiated accelerated ageing 5000h, its result such as table 2
Shown in:
Table 2
| Example 1 coating | Example 2 coating | Example 3 coating | Example 4 coating | Existing coating | |
| Experimental result after 5000h | ◆ | ◆ | ◆ | ◆ | ◇ |
◆ represent that this coating sample still can keep smooth, there is no be full of cracks, peel off and the phenomenon of efflorescence；
◇ represents this coating sample rough surface, has occurred in that be full of cracks, has peeled off or the phenomenon of efflorescence.
The experimental result tested from this is it can be seen that this product has preferable weatherability.
Claims (8)
1. a normal temperature cure Fluorocoating resin, it is characterised in that be polymerized in organic solvent by the monomer of following weight portion
Form:
A: CTFE: 45～50；
B: pi-allyl tetrafluoro ether, structural formula is CH2=CH-CH2-O-CF2-CF2H: 1～5；
C: vinyl acetate base ester: 15～20；
D: hydroxy butyl vinyl ether, structural formula is CH2=CH-O-C4H8-OH: 3～8；
E: undecylenic acid, structural formula is CH2=CH-C8H16-COOH: 0.5～3；
Concrete preparation method is as follows:
1) will be by above-mentioned weight portion load weighted pi-allyl tetrafluoro ether, vinyl acetate base ester, hydroxy butyl vinyl ether, hendecene
Acid, organic solvent and initiator fully mix；
2) polymerization autoclave evacuation, is drawn into the reaction raw materials mixed in step 1) in polymerization autoclave；
3) by polymerization autoclave evacuation, inflated with nitrogen, so repeats 2～4 times；
4) load weighted CTFE monomer is added in polymerization autoclave；
5) opening stirring, heat up, control polymerization temperature 65～75 DEG C, controlling polymerization pressure is 0.6～0.9MPa, polymerization time
It is 18～22 hours；
6) it is cooled to room temperature, stops stirring, blowing.
Normal temperature cure Fluorocoating resin the most according to claim 1, it is characterised in that: described polyreaction adds
Initiator is oleosoluble radical initiators, and its weight portion is 0.5～1.
Normal temperature cure Fluorocoating resin the most according to claim 2, it is characterised in that: described oleosoluble radical causes
Agent is azodiisobutyronitrile.
Normal temperature cure Fluorocoating resin the most according to claim 1, it is characterised in that: the weight portion of described organic solvent
It is 30～40.
Normal temperature cure Fluorocoating resin the most according to claim 4, it is characterised in that: described organic solvent is acetic acid fourth
Ester and the mixture of dimethylbenzene, its mass ratio is 1:1～3.
Normal temperature cure Fluorocoating resin the most according to claim 1, it is characterised in that: described normal temperature cure fluoro-containing coating
The hydroxyl value of resin is 30～90mgKOH/g, and its acid number is 3～10mg KOH/g, and its viscosity is 60～90, the Oil repellent of dried resin
≥18%。
Normal temperature cure Fluorocoating resin the most according to claim 1, it is characterised in that: above-mentioned steps 2) in, high pressure gathers
After closing still evacuation, its pressure is 90～95KPa.
Normal temperature cure Fluorocoating resin the most according to claim 1, it is characterised in that: above-mentioned steps 3) in, high pressure gathers
After closing still evacuation, its pressure is 90～95KPa, inflated with nitrogen to gauge pressure+0.05MPa.
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| CN105670412A (en) * | 2016-03-07 | 2016-06-15 | 江苏梅兰化工有限公司 | Amphipathic normal-temperature curing fluorocarbon coating resin and preparation method thereof |
| CN107383264A (en) * | 2017-08-04 | 2017-11-24 | 安徽博泰氟材料科技有限公司 | Solvent-borne type F-C paint resin copolymerization technique |
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| JPH04258613A (en) * | 1991-02-12 | 1992-09-14 | Dainippon Ink & Chem Inc | Production of hydroxylated fluorocopolymer |
| JPH0532725A (en) * | 1991-06-18 | 1993-02-09 | Asahi Chem Ind Co Ltd | Fluorine-containing copolymer and coating material composed mainly of the same copolymer |
| CN1111571C (en) * | 1999-08-20 | 2003-06-18 | 大连塑料研究所 | Fluoric copolymer paint and method for making thereof based on tetrafluoroethylene |
| CN1294217C (en) * | 2003-12-15 | 2007-01-10 | 上海三爱富新材料股份有限公司 | Soluble fluorine-containing paint resin and method for preparing same |
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Effective date of registration: 20161226 Address after: 255000 Shandong Province, Zibo city Zhangdian District People's Road East business in Washington 1-3-202 Patentee after: Bi Yaping Address before: 255020 Zibo East Road, Zhangdian District, Shandong, No. 217 Patentee before: Shandong Senfu New Materials Co., Ltd. |
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Effective date of registration: 20180712 Address after: 256301 Qinghe Industrial Park, Gaoqing County, Zibo, Shandong Patentee after: Zibo Fei Yuan Chemical Co., Ltd. Address before: 255000 Zhangdian Road, Zhangdian City, Shandong Province, 1-3-202 Patentee before: Bi Yaping |
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