CN1450091A - Ultralow surface energy type fluorocarbon resin - Google Patents
Ultralow surface energy type fluorocarbon resin Download PDFInfo
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- CN1450091A CN1450091A CN 03112337 CN03112337A CN1450091A CN 1450091 A CN1450091 A CN 1450091A CN 03112337 CN03112337 CN 03112337 CN 03112337 A CN03112337 A CN 03112337A CN 1450091 A CN1450091 A CN 1450091A
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- fluorocarbon resin
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Abstract
The present invention relates to a kind ultra low surface energy type fluorocarbon resin. It adopts the flurochloroethylene, olefin ester, olefine acid, olefine ethyl and inititator, and uses ethyl ester and ketone as solvnt, and introduces organosilicon olefine acid ester when the polymerization production is made so as to make paint containing fluorocarbon resin have lower surface tension when said paint is film-formed, so that it can further raise the self-cleaning property of pint film.
Description
Technical field
The present invention relates to a kind of New Chemical Materials, specifically is a kind of low surface energy type fluorocarbon resin.
Background technology
Coating mainly is coated on various skins or other body surface as a kind of surface decoration material, plays the protection decoration function.Because long-term exposure is very easy to be subjected to dust outside, smeary pollutes.In order to make body surface more easy to clean, be badly in need of a kind of resin of exploitation, it has lower surface tension when film forming, further improve the self-cleaning of paint film.
Summary of the invention
Low surface energy type fluorocarbon resin of the present invention promptly is to introduce organosilicon olefin(e) acid ester when the fluorocarbon resin polymerization is produced, and makes fluorocarbon resin have lower surface tension when film forming, further improves the self-cleaning of paint film.
Ultra-low surface energy type fluorocarbon resin adopts following prescription polymerization to generate:
Raw material weight per-cent (%)
Fluorine vinylchlorid 25-40
Alkene ester 18-24
Ether-ether 20-30
Ketone 7-10
Olefin(e) acid 1-3
Alkene ether 4-10
Initiator 1-2
Organosilicon olefin(e) acid ester 3-8
Wherein fluorine vinylchlorid is the skeleton that constitutes fluorocarbon resin, makes it have extraordinary weather resistance, weather resisteant; Usually select inclined to one side fluorine vinylchlorid, tetrafluoro vinylchlorid, trifluorochloroethylene for use.
The alkene ester is the degree of crystallinity that is used for reducing multipolymer, increases the molecular weight of multipolymer; Usually select butyl methacrylate, Jia Jibingxisuanyizhi, methyl methacrylate, vinyl acetate for use.
Ether-ether and ketone are as solvent and thinner; Ether-ether is selected from propylene glycol monomethyl ether, propylene-glycol ethyl ether, propylene glycol butyl ether;
Ketone is selected from ketone, ethyl ketone, methylethylketone, methyl iso-butyl ketone (MIBK).
The effect of olefin(e) acid is to introduce carboxyl, strengthens fluorocarbon resin to the wettability of pigment and dispersiveness with to the good tack of base material; Olefin(e) acid is selected from: acrylic acid, 11 diluted acids, stearic acid.
The effect of alkene ether is to introduce reactive hydroxyl groups, make the fluorocarbon resin can be at normal temperatures and the cured with isocyanates film forming, give the solubility of fluorocarbon resin multipolymer to solvent, to dispersing of pigments, to the consistency and the reactivity of solidifying agent, the transparency of filming and glossiness, hardness, flexibility reach the performances such as tack to base material.Alkene ether commonly used has: butyleneglycol Vinyl Ether, ethylene glycol vinyl ether, propylene glycol vinyl ether.
Initiator is selected from: azo, benzoyl peroxide.
Organosilicon olefin(e) acid ester is preferred: organic silicon acrylic ester.
The preparation method of ultra-low surface energy type fluorocarbon resin of the present invention is: make each the material polymerization reaction take place in the prescription, generate fluorocarbon resin.The synthetic method of optimizing is: in reactor, add ether-ether, ketone, organosilicon olefin(e) acid ester, initiator, alkene ester, olefin(e) acid, the alkene ether of formula ratio successively, reactor is airtight, to system vacuumize, pressure is-0.08～-0.1Mpa; Logical nitrogen to pressure is 0.1Mpa, secondary to system vacuumize, pressure is-0.08～-0.1Mpa; Add fluorine vinylchlorid and open stirring, reinforced finishing is warming up to 70 ± 5 ℃, isothermal reaction; Being cooled to 60 ℃ after reaction finishes reclaims the residual reaction gas thing; Further be cooled to 30 ℃ with bottom discharge; Filter solid material slag, drive bubble enhancing product transparency away, obtain fluorocarbon resin.
Innovative point of the present invention is to introduce organosilicon olefin(e) acid ester, makes fluorocarbon resin have lower surface tension when film forming, further improves film forming self-cleaning.Fluorocarbon resin can be used for various protective systems, as the coating of building, bridge, TV tower, automobile etc. owing to have excellent weather resistance, weather resisteant.Fluorocarbon resin of the present invention is owing to have stronger anti-a staining property, and its decoration, barrier propterty are stronger.
Embodiment
Embodiment 1
Butyl methacrylate 24%, propylene-glycol ethyl ether 25%, ketone 7.5%, vinylformic acid 3%, ethylene glycol vinyl ether 8.5%, azo 1%, organic silicon acrylic ester 3%, add in the closed reaction kettle, to system vacuumize make pressure be-0.08～-0.1Mpa, add trifluorochloroethylene (CTFE) 28%, and open stirring, reinforced finishing is warming up to 70 ± 5 ℃, isothermal reaction 24 hours, being cooled to 60 ℃ after reaction finishes reclaims the residual reaction gas thing, further be cooled to 30 ℃ with bottom discharge, filter solid material slag, drive bubble away and strengthen the product transparency, obtain fluorocarbon resin.It is as follows to detect its capability and performance index: viscosity 45 seconds, solid content 52.8%, acid number 8.1mgKOH/g, hydroxyl value 50mgKOH/g, the content of benzene class material is zero in the resin.With the coating making sheet of the fluorocarbon resin that contains present embodiment, hydrophobic (surface energy) situation of observation paint film: very slight getting wet arranged.
Embodiment 2
Raw materials used: methyl methacrylate 22%, propylene glycol monomethyl ether 25%, methylethylketone 8%, undecylenic acid 3%, ethylene glycol vinyl ether 8.5%, azo 2%, organic silicon acrylic ester 3.5%, trifluorochloroethylene (CTFE) 28%, the preparation method is with embodiment 1, the capability and performance index of the fluorocarbon resin that obtains is as follows: viscosity 50 seconds, solid content 49%, acid number 7.6mgKOH/g, hydroxyl value 54.1mgKOH/g, benzene class substances content is zero in the resin.With the coating making sheet of the fluorocarbon resin that contains present embodiment, hydrophobic (surface energy) situation of observation paint film: the globule tumbles entirely, does not get wet.
Embodiment 3
Raw materials used: vinyl acetate 20%, propylene-glycol ethyl ether 20.5%, ketone 7.5%, undecylenic acid 3%, ethylene glycol vinyl ether 8.5%, azo 1.5%, organic silicon acrylic ester 4%, trifluorochloroethylene (CTFE) 35%, the preparation method is with embodiment 1, the capability and performance index of the fluorocarbon resin that obtains is as follows: viscosity 105 seconds, solid content 58%, acid number 7.8mgKOH/g, hydroxyl value 52mgKOH/g, benzene class substances content is zero in the resin.With the coating making sheet of the fluorocarbon resin that contains present embodiment, hydrophobic (surface energy) situation of observation paint film: the globule almost tumbles entirely, does not get wet.Annotate: making sheet is carried out making sheet by GB GB1727-92.
Viscosity adopts the method for GB1724-89 to detect.
Solid content adopts the method for GB6751-86 to detect.
Claims (9)
1. ultra-low surface energy type fluorocarbon resin is characterized in that, adopts following prescription polyreaction to generate:
Raw material weight per-cent (%)
Fluorine vinylchlorid 25-40
Alkene ester 18-24
Ether-ether 20-30
Ketone 7-10
Olefin(e) acid 1-3
Alkene ether 4-10
Initiator 1-2
Organosilicon olefin(e) acid ester 3-8
2. according to the ultra-low surface energy type fluorocarbon resin of claim 1, it is characterized in that described fluorine vinylchlorid is selected from inclined to one side fluorine vinylchlorid, tetrafluoro vinylchlorid, trifluorochloroethylene.
3. according to the ultra-low surface energy type fluorocarbon resin of claim 1, it is characterized in that described alkene ester is selected from butyl methacrylate, Jia Jibingxisuanyizhi, methyl methacrylate, vinyl acetate.
4. according to the ultra-low surface energy type fluorocarbon resin of claim 1, it is characterized in that described ether-ether is selected from propylene glycol monomethyl ether, propylene-glycol ethyl ether, propylene glycol butyl ether;
5. according to the ultra-low surface energy type fluorocarbon resin of claim 1, it is characterized in that described ketone is selected from: ketone, ethyl ketone, methylethylketone, methyl iso-butyl ketone (MIBK).
6. according to the ultra-low surface energy type fluorocarbon resin of claim 1, it is characterized in that described olefin(e) acid is selected from acrylic acid, 11 diluted acids, stearic acid.
7. according to the ultra-low surface energy type fluorocarbon resin of claim 1, it is characterized in that described alkene ether is selected from: butyleneglycol Vinyl Ether, ethylene glycol vinyl ether, propylene glycol vinyl ether.
8. according to the ultra-low surface energy type fluorocarbon resin of claim 1, it is characterized in that the preferred organic silicon acrylic ester of described organosilicon olefin(e) acid ester.
9. the preparation method of the ultra-low surface energy type fluorocarbon resin of claim 1 is: make each the material polymerization reaction take place in the prescription.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03112337 CN1200011C (en) | 2003-04-21 | 2003-04-21 | Ultralow surface energy type fluorocarbon resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03112337 CN1200011C (en) | 2003-04-21 | 2003-04-21 | Ultralow surface energy type fluorocarbon resin |
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| Publication Number | Publication Date |
|---|---|
| CN1450091A true CN1450091A (en) | 2003-10-22 |
| CN1200011C CN1200011C (en) | 2005-05-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03112337 Expired - Fee Related CN1200011C (en) | 2003-04-21 | 2003-04-21 | Ultralow surface energy type fluorocarbon resin |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702440A (en) * | 2012-05-14 | 2012-10-03 | 陕西宝塔山油漆股份有限公司 | High-adhesion fluorocarbon resin and synthesis process of high-adhesion fluorocarbon resin |
| CN103193920A (en) * | 2013-04-22 | 2013-07-10 | 济南华临化工有限公司 | Normal temperature cured type fluorine-silicon copolymerization coating resin and preparation method thereof |
| CN107418341A (en) * | 2017-09-26 | 2017-12-01 | 安徽喜宝高分子材料有限公司 | A kind of resistant fluorine carbon wall finiss and preparation method thereof |
-
2003
- 2003-04-21 CN CN 03112337 patent/CN1200011C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702440A (en) * | 2012-05-14 | 2012-10-03 | 陕西宝塔山油漆股份有限公司 | High-adhesion fluorocarbon resin and synthesis process of high-adhesion fluorocarbon resin |
| CN102702440B (en) * | 2012-05-14 | 2015-07-15 | 陕西宝塔山油漆股份有限公司 | High-adhesion fluorocarbon resin and synthesis process of high-adhesion fluorocarbon resin |
| CN103193920A (en) * | 2013-04-22 | 2013-07-10 | 济南华临化工有限公司 | Normal temperature cured type fluorine-silicon copolymerization coating resin and preparation method thereof |
| CN107418341A (en) * | 2017-09-26 | 2017-12-01 | 安徽喜宝高分子材料有限公司 | A kind of resistant fluorine carbon wall finiss and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1200011C (en) | 2005-05-04 |
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