CN1461764A - Organic poly-molecular polymer containing fluorine, silicon and its production technology - Google Patents
Organic poly-molecular polymer containing fluorine, silicon and its production technology Download PDFInfo
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- CN1461764A CN1461764A CN 02115294 CN02115294A CN1461764A CN 1461764 A CN1461764 A CN 1461764A CN 02115294 CN02115294 CN 02115294 CN 02115294 A CN02115294 A CN 02115294A CN 1461764 A CN1461764 A CN 1461764A
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Abstract
An organic poly-molecular polymer containing F and Si is prepared from double-bond organic fluorolefin monomer, double-bond organosilicon monomer and/or organic siloxyborane polycondensate, double-bond lipocarboxylic acid and its ester, and double-bond epoxy ethane-epoxy propane addition through polymerizing under action of trigger to obtain multi-element block copolymer. Its advantages are high weatherability, high resistance to corrosion, dirt, chemical, salty fog and ageing, long service life and wide application fields.
Description
The present invention relates to a kind of fluorine-containing, silicon organic poly-molecular polymer and production technique thereof.
The like product kind is a lot of at present, and roughly having of having patented is following several:
Chinese patent (ZL 95 1 11961.3) is reported a kind of fluoro-containing coating, is to use trifluorochloroethylene, vinyl fatty ester, quarternary copolymerized the forming of aliphatic olefin alcohols and fatty olefin(e) acid.Polymerization is to add solvent and monomer, initiator in autoclave, reacts 20～60h and form under 70 ± 2 ℃, 0.80～0.55MPa condition.This invention is mainly used in building coating.
Chinese patent (97106780.5) the present invention has announced a kind of method for preparing fluorosilicic block copolymer with living radical polymerization technique.Its method is siliceous vinyl monomer and not siliceous vinyl monomer, and random copolymerization gets halogen-containing client-based prepolymer under catalyst action; With this prepolymer is that the polymerization of macromole evocating agent initiation fluoroalkyl vinyl monomers gets segmented copolymer.
Chinese patent 94191165.9 WO94.18253 English 94.8.18 disclose the monomer of new fluorine-containing siloxanes, and described monomer is particularly suitable for preparing the biomedical material such as contact lens one class.
WO95.33001 day 95.12.7 has the new fluosilicic oxyalkane compound of at least 2 hydroxyls and the solidification compound that contains this compound and solidifying agent commonly used for one kind in its molecule.
Chinese patent 89100669.9 relates to a kind of preparation method of high-strength tear-resistant trifluoropropyl siloxane auxiliary agent, specifically, it is by 3,3, the preparation method of 3-trifluoro propyl methyl cyclotrisiloxane, tetramethyl-tetrem thiazolinyl cyclotetrasiloxane and divinyl tetramethyl disiloxane terpolymer (being designated hereinafter simply as C glue), this patented method is the ring-opening polymerization method.
All there is the shortcoming and defect part at used reaction monomers, chemical reaction mechanism, catalyst type and application, polymer type and structural characterization etc. in above existing patent of lifting aspect many.As: Fluorine containing olefine monomer and other organic monomer intermiscibility is bad, organic fluorine, organosilicon material are not strong or the like to the ground bonding force.
Given this, the purpose of this invention is to provide a kind of fluorine-containing, silicon organic poly-molecular polymer and production technique thereof, solve the shortcoming and defect part of existing like product.
Advantage of the present invention and characteristics:
1, the present invention relates to contain fluorine, silicon, double bond containing aliphatic carboxylic acid and ester class thereof, the quarternary copolymerized reaction of double bond containing ethylene oxide/propylene oxide affixture.
2, the present invention has been owing to introduced organic fluorine, organosilane monomer or prepolymer, thereby multipolymer has plurality of advantages such as splendid weathering resistance, contamination resistance, salt fog resistance and ageing resistance.
3, the present invention has hydrophilic ethylene oxide/propylene oxide affixture owing to having introduced, and makes the surface tension of multipolymer of the present invention reduce, and has good hydrophilicity, and levelling property, multipolymer can be made into the product of water base or low organic volatile part (VOC).
4, the present invention makes multipolymer of the present invention have good sticking power and glossiness owing to introduced double bond containing aliphatic carboxylic acid and ester class thereof.
The objective of the invention is to realize by following solution:
1. solve problem, particularly Fluorine containing olefine monomer and the bad difficult problem of other organic monomer intermiscibility of the intermolecular copolymerization of heterology organic monomer;
2. introduce the cementability chain link, as aliphatic carboxylic acid and ester class thereof, organosilicon alcoxyl base monomer, organic silica borine polycondensate has solved organic fluorine, weakness that organosilicon material is not strong to the ground bonding force.
3. introduce organic fluorine and organosilicon, particularly utilize the shielding protection effect of organic fluorine chain link, make multipolymer have fabulous weathering resistance, ageing resistance.
4. introduce double bond containing aliphatic carboxylic acid and ester class thereof, make multipolymer of the present invention have good sticking power and glossiness.
5. introducing has hydrophilic ethylene oxide/propylene oxide affixture, makes the surface tension of multipolymer of the present invention reduce, and has good hydrophilicity, and levelling property, multipolymer can be made into the product of water base or low organic volatile part (VOC).
As:
1. the general formula of fluorochemical monomer is: CFR
1=CR
2R
3
Wherein: R
1=H, F or other halogen atom,
R
2=H, F or other halogen atom
R
3=H, F or other halogen alkyl are as CF
3Deng.
For example: vinyl fluoride (CHF=CH
2), vinylidene (CF
2=CH
2), trifluorochloroethylene (CF
2=CFCl), tetrafluoroethylene (CF
2=CF
2), R 1216 (CF
2=CF-CF
3) etc.
2. the general formula of double bond containing silicon monomer or performed polymer is:
Wherein: R4=H or low carbon number (C1-C3) alkyl
R7=is H or C1～C18 alkylene base, i.e. C
nH
2n, n=0～18, n=0 usually.
R10, R11 can be following identical group or other organo-siloxane monomer with R12 simultaneously:
(1) C1 ~ C6 alkoxyl group is as methoxyl group, oxyethyl group, isopropoxy, n-butoxy, isobutoxy, short butoxy, tert.-butoxy, pentyloxy etc., many preferential methoxyl group, oxyethyl group, isopropoxies selected.
(2) polymerization degree is polymethyl siloxane-[Si (Me) of 10-200
2-O-]-, n=10-200
(3) resin type sesquialter organo-siloxane and/or organic silica borine polycondensate.
3. double bond containing aliphatic carboxylic acid and ester class formation general formula thereof are as follows:
Wherein R5=H, or CH
3,
R8=is H or C1～C18 alkylene base, i.e. C
nH
2n, n=0～18, n=0 usually
R
13=H, CH
3-, CH
3CH
2-, CH
3CH
2CH
2CH
2-, CH
3CH (OH) CH
2-etc.
4. the ethylene oxide/propylene oxide affixture structural formula that contains two keys is as follows:
R6=H wherein, CH
3Deng, comparatively commonly used with H
R9: for C1～C18 alkylene base as-CH
2-,-CH
2-CH
2-,-CH
2-CH
2-CH
2-etc., with-CH
2-
Comparatively suitable, i.e. C
nH
2n, be advisable with n=1 in n=1～18, i.e. allyl group.
R14=H, CH
3, CH
3CH
2-, CH
3CH
2CH
2CH
2-, CH
3CO-etc.
A=1-40, for obtaining the active effect of surface of good, with 5-25 the best, b=1-40 is with 5-25 the best.
5. copolyreaction formula of the present invention is as follows:
6. polymerization starter involved in the present invention comprises: peroxide initiator, and as ammonium persulphate, Potassium Persulphate, benzoyl peroxide, hydrogen peroxide, diethyl (ethyl peroxidation) boron and dibutyl (butyl peroxyization) boron, Diisopropyl azodicarboxylate etc.The beneficial effect that the present invention produces:
Block type multipolymer involved in the present invention has advantages such as high-weatherability, anticorrosion, anti-contamination, chemicals-resistant, salt spray resistance, use length.
The scope that the present invention uses comprises but not only is confined to coating, paint, material of construction, protection type coating, lubricant, fiber treatment agent, hide finishes, remover, water and oil repellent agent, didirtresistance coating agent, Abherent coating agent, optics with applying fields such as agent and sealing agent.
Fig. 1 is a principle flow chart of the present invention.
The embodiment of the invention is described in detail below in detail: experimental example one:
Get α, ω bi-vinyl polysiloxane (contents of ethylene 2%, viscosity 2,000mPaS) 80-150g, 15: 15 grades of allyl group ethylene oxide/propylene oxide mole affixture 20-40g, vinyltriethoxysilane 4-8g, or vinyl three boron TMOS polycondensate 4-10g, benzene 30-60g, Diisopropyl azodicarboxylate 0.1-0.5g, trifluorochloroethylene (CF
2=CFCl) pressure is 0.1-1.0Mpa, temperature of reaction 50-100 ℃, 5-12hr, a polymkeric substance, not stratified and flow leveling is better.Experimental example two:
Get α, ω bi-vinyl polysiloxane (contents of ethylene 2%, viscosity 2,000mPaS) 80-150g, butyl acrylate 30-80g, vinylformic acid 5-10g, Propylene glycol monoacrylate 8-20g, benzene 30-60g, butanols 30-70g, butylacetate 20-100g, Diisopropyl azodicarboxylate 0.5-1.5g, trifluorochloroethylene (CF
2=CFCl) pressure is 0.1-1.0MPa, temperature of reaction 50-100 ℃, reaction 5-12hr, a solid content is 60% homogeneous polymkeric substance, not stratified and flow leveling is better.Experimental example three:
Get α, ω bi-vinyl polysiloxane (contents of ethylene 2%, viscosity 2,000mPaS) 120～160g, 15: 15 grades of allyl group ethylene oxide/propylene oxide mole affixture 16-40g, vinyltriethoxysilane 2～6g, benzene 20～80g, butyl acrylate 30-80g, vinylformic acid 5-10g, Propylene glycol monoacrylate 8-20g, benzene 30-60g, butanols 30-70g, butylacetate 20-100g, Diisopropyl azodicarboxylate 0.5-1.5g, trifluorochloroethylene (CF
2=CFCl) pressure is about 0.1～1.0Mpa, 50～100 ℃ of temperature of reaction, and reaction 5～12hr gets a polymkeric substance, and is not stratified, and flow leveling is better.
Claims (11)
1. fluorine-containing, silicon organic poly-molecular polymer and production technique thereof, it is characterized in that: employed polymeric chemical starting monomer comprises: the organic fluorine olefinic monomer of two keys; Double bond containing organosilane monomer and/or organic silica borine polycondensate; Double bond containing aliphatic carboxylic acid and ester class thereof; The epoxy ethane-epoxy propane affixture that contains two keys.
2. a kind of fluorine-containing, silicon organic poly-molecular polymer according to claim 1 and production technique thereof, it is characterized in that: its structural formula is:
3. a kind of fluorine-containing, silicon organic poly-molecular polymer according to claim 1 and production technique thereof, it is characterized in that: the general formula of fluorochemical monomer is: CFR
1=CR
2R
3
(wherein: R
1=H, F or other halogen atom,
R
2=H, F or other halogen atom
R
3=H, F or other halogen atom, CF
3Deng.)
4. a kind of fluorine-containing, silicon organic poly-molecular polymer according to claim 1 and production technique thereof, it is characterized in that: the general formula of double bond containing silicon monomer or performed polymer is:
(wherein: R4=H or low carbon number (C1-C3) alkyl
R7=is H or C1～C18 alkylene base, i.e. C
nH
2n, m=0～18.
R10, R11 can be following identical group or other organo-siloxane monomer with R12 simultaneously:
(1) 1～C6 alkoxyl group is as methoxyl group, oxyethyl group, isopropoxy, n-butoxy, isobutoxy, short butoxy, tert.-butoxy, pentyloxy etc., many preferential methoxyl group, oxyethyl group, isopropoxies selected.
(2) right is the polysiloxane of 10-200
(3) resin type sesquialter organo-siloxane and/or organic silica borine polycondensate)
5. a kind of fluorine-containing, silicon organic poly-molecular polymer according to claim 1 and production technique thereof, it is characterized in that: double bond containing aliphatic carboxylic acid and ester class formation general formula thereof are as follows:
(wherein R5=H, or CH
3,
R8=is H or C1～C18 alkylene base, i.e. C
nH
2n, n=0～18.
R
13=H, CH
3-, CH
3CH
2-, CH
3CH
2CH
2-, CH
3CH
2CH
2-, CH
3CH (OH) CH
2-etc.)
6. a kind of fluorine-containing, silicon organic poly-molecular polymer according to claim 1 and production technique thereof is characterized in that: the ethylene oxide/propylene oxide affixture structural formula that contains two keys is as follows:
(R6=H wherein, CH
3Deng, comparatively commonly used with H
R8=C1～C18 alkylene base, i.e. C
nH
2n, be advisable with n=1 in n=1～18, i.e. allyl group.
R9: for alkylene base as-CH
2-,-CH
2-CH
2-,-CH
2-CH
2-CH
2-etc., with-CH
2-comparatively suitable.
R14=H, CH
3, CH
3CH
2-, CH
3CH
2CH
2-, CH
3CH
2CH
2CH
2-, CH
3CO-etc.
A=1-40, for obtaining the active effect of surface of good, with 5-25 the best, b=1-40 is with 5-25 the best)
7. a kind of fluorine-containing, silicon organic poly-molecular polymer according to claim 1 and production technique thereof, it is characterized in that: polymerization starter comprises: peroxide initiator such as Oxybenzene formyl, hydrogen peroxide, diethyl (ethyl peroxidation) boron and dibutyl (butyl peroxyization) boron Diisopropyl azodicarboxylate.
8. a kind of fluorine-containing, silicon organic poly-molecular polymer according to claim 1 and production technique thereof, it is characterized in that: employed solvent comprises: benzene class (benzene,toluene,xylene, trimethylbenzene), dimethyl formamide, the positive structure of C1-C8 or different alcohols, ester class (ritalin, vinyl acetic monomer, N-BUTYL ACETATE), ketone (acetone, methylethylketone, pimelinketone)
9. a kind of fluorine-containing, silicon organic poly-molecular polymer according to claim 1 and production technique thereof, it is characterized in that: temperature of reaction is 50-100 ℃.
10. a kind of fluorine-containing, silicon organic poly-molecular polymer according to claim 1 and production technique thereof, it is characterized in that: the reaction times is 5-25 hour.
11 a kind of fluorine-containing, silicon organic poly-molecular polymer according to claim 1 and production technique thereof, it is characterized in that: reaction pressure is 0.1-1.0MPa.
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|---|---|---|---|
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942083A (en) * | 2010-09-10 | 2011-01-12 | 广东标美硅氟新材料有限公司 | Organic silicon compounds, and preparation method and application thereof |
| CN101684125B (en) * | 2008-09-26 | 2012-02-29 | 中国科学院兰州化学物理研究所 | Fluorine-containing silicon carbon hydrogen compound and preparation method thereof |
| CN108951180A (en) * | 2018-06-05 | 2018-12-07 | 福建宝利特科技股份有限公司 | A kind of antifouling rtificial leather and preparation method thereof |
| CN113667421A (en) * | 2021-08-13 | 2021-11-19 | 佛山市奥川顺新材料实业有限公司 | Friction-resistant PET (polyethylene terephthalate) protective film and preparation method thereof |
-
2002
- 2002-05-29 CN CN 02115294 patent/CN1461764A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101684125B (en) * | 2008-09-26 | 2012-02-29 | 中国科学院兰州化学物理研究所 | Fluorine-containing silicon carbon hydrogen compound and preparation method thereof |
| CN101942083A (en) * | 2010-09-10 | 2011-01-12 | 广东标美硅氟新材料有限公司 | Organic silicon compounds, and preparation method and application thereof |
| CN101942083B (en) * | 2010-09-10 | 2012-08-22 | 广东标美硅氟新材料有限公司 | Organic silicon compounds, and preparation method and application thereof |
| CN108951180A (en) * | 2018-06-05 | 2018-12-07 | 福建宝利特科技股份有限公司 | A kind of antifouling rtificial leather and preparation method thereof |
| CN113667421A (en) * | 2021-08-13 | 2021-11-19 | 佛山市奥川顺新材料实业有限公司 | Friction-resistant PET (polyethylene terephthalate) protective film and preparation method thereof |
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