CN1108319C - Method for preparation of fluorosilicic block copolymer - Google Patents
Method for preparation of fluorosilicic block copolymer Download PDFInfo
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- CN1108319C CN1108319C CN97106780A CN97106780A CN1108319C CN 1108319 C CN1108319 C CN 1108319C CN 97106780 A CN97106780 A CN 97106780A CN 97106780 A CN97106780 A CN 97106780A CN 1108319 C CN1108319 C CN 1108319C
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- vinyl monomers
- prepolymer
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Abstract
The present invention discloses a method for the preparation of fluorosilicic block copolymers by a living radical polymerization technology. The method for the preparation of fluorosilicic block copolymers comprises the following steps: prepolymers containing halogen end groups are obtained by the atactic copolymerization of vinyl monomers containing silicon and vinyl monomers without silicon under the action of catalysts; the prepolymers are used as macromolecule initiators to trigger off the polymerization of fluoroalkyl vinyl monomers in order to obtain block polymers. The method of the present invention has the advantages of wide selection range of the monomers, proper reaction conditions, high reaction yield and simple technology; the prepared block polymers have the advantages of clear structure, controllable molecular weight, wide application range, favorable industrial prospects, etc.
Description
Fluoropolymer has excellent high-and low-temperature resistance, chemical proofing, weathering resistance and hydrophobic and lyophobic property, thereby fluor resin coating is a kind of ideal surfacecti proteon, anti-fouling material.But, cause being easy to come off poor durability a little less than the cohesive force between fluoro-containing copolymer film and base material because the orientations of fluoro-containing group produces minimum surface tension.On the other hand, silicon polymer not only has good adhesivity with most of base materials (as glass, paper, fiber, timber, metal etc.), and has good hydrophobic nature, but does not have oil repellency.Therefore the fluorine-silicon copolymer thing is expected to become the hydrophobic and oleophobic agent of superior performance.The clear 61-209286 of day disclosure special permission communique has reported fluorine silicon random copolymers, but because the consistency of silicon polymer and fluoropolymer is poor, has hindered giving full play to of the two function, and hydrophobic and lyophobic property and weather resistance are still undesirable.Segmented copolymer is compared with other type polymer has clearly structure segment, can control better such as structure sequence, chain length and important parameters such as spacing, polymolecularity, obtains good structure properties.But segmented copolymer is difficult to preparation, and relevant bibliographical information is very few.The clear 61-209287 of day disclosure special permission communique has reported that (polymeric peroxide, PPO) technology is synthesized fluorosilicic block copolymer with the macromole superoxide.PPO mainly is the macromolecular compound that contains a plurality of peroxide bridges on the molecular chain, under the condition of illumination or heating, peroxide bridge is non-to be decomposed and the trigger monomer polymerization fully, thereby the high-molecular copolymer that contains remnants-O-O-key on the formation main chain, remnants-O-O-the key that ruptures under another condition then causes second monomer polymerization, form segmented copolymer, but the multi-block polymer often that forms like this.Because PPO and prepolymer thereof are easy to blast, and solvability is not good in monomer, is restricted in the application.
The present invention then is the weak point at above-mentioned synthetic method, has proposed a kind of preparation method of fluorosilicic block copolymer.This method reaction conditions gentleness, product postprocessing technology is simple, and reaction yield height not only can be prepared the pure segmented copolymer that does not contain homopolymer, also can realize effective control of block copolymer amount, molecular weight distribution and segmented structure.
Design of the present invention is such:
Siliceous prepolymer with halide end group causes the fluoroalkyl vinyl monomers polymerization under certain temperature and catalyst action, generate fluorosilicic block copolymer.
The present invention realizes according to such design:
In the presence of small molecules initiator, catalyzer, solvent 1 (also not solubilizing agent), siliceous vinyl monomer (A component) carries out random copolymerization with not siliceous vinyl monomer (B component) and gets prepolymer, through the absorption of neutral alumina post (the mass polymerization product is earlier with solvent 2 dissolvings), be deposited in the solvent 3, filter, dry, be dissolved in the solvent 4, the solution that obtains is added in the reactor that contains catalyzer, adds fluoroalkyl vinyl monomers and carries out polyreaction.The molecular weight and the molecular weight distribution of prepolymer are measured with GPC, the molecular weight nuclear magnetic resonance measuring of segmented copolymer.
Described small molecules initiator be benzyl chloride, bromotoluene, neighbour, to ,-2-halogenated aromatic compounds such as xylylene bromide, 2-halo carbonyl compounds such as 2-chloropropionate, 2 bromopropionic acid ethyl ester, 2-isobutyl ethyl bromide, and arylsulfonyl halogenation things such as benzene sulfonyl chloride and benzene sulfonyl bromine.
Described catalyzer is CuCl (or CuBr) and 2,2 '-bipyridine, o-phenanthroline, triphenylphosphine, 1, the coordination compound of 4-diaza-1,3-butadiene etc.
Described solvent 1 does not have particular restriction.As arenes such as benzene,toluene,xylenes; Ester such as vinyl acetic monomer, N-BUTYL ACETATE class and phenyl ether etc.
Described A component is the silane coupling agent of using always, as CH
2=CHSi (OCH
3)
3, CH
2=C (CH
3) Si (OCH
3)
3, CH
2=CHSi (OC
2H
5)
3, CH
2=CCH
3CCO (CH
2)
3Si (OCH
3)
3Deng.Its ratio shared in segmented copolymer is 1～89wt%, preferably accounts for 3～75wt%.
Described B component be can with the vinyl monomer of A component generation copolymerization, as methyl acrylate, methyl methacrylate, butyl acrylate, acrylate such as butyl methacrylate or methyl acrylic ester and vinylbenzene, vinyl cyanide etc.Its ratio shared in segmented copolymer is not more than 89wt%.
Described fluoroalkyl vinyl monomers is fluorine-containing (methyl) acrylic ester monomer of using always, as CF
3(CF
2)
m(CH
2)
nOCOCH=CH
2, CF
3(CF
2)
m(CH
2)
nOCO (CH
3)=CH
2, CF
3(CF
2)
mOCO-(CH
2)
nOCOCH=CH
2, CF
3(CF
2)
mOCO (CH
2)
nOCOC (CH
3)=CH
2, m=0～20 wherein, n=1～10, optimum value is m=3～12, n=1～4.Its ratio shared in segmented copolymer is 10～80wt%.
The molecular weight of described prepolymer is 4,000～20,000.
Described solvent 2 is benzene, tetrahydrofuran (THF) or chloroform.
Described solvent 3 can be alcoholic solvent and aliphatic saturated hydrocarbons such as sherwood oil, normal hexane, normal heptane or Skellysolve A such as methyl alcohol, ethanol.
Described solvent 4 is with solvent 1.
The temperature of reaction of described system is 30～160 ℃.
The synthesis technique of fluorosilicic block copolymer is such:
(1) block synthesizing with prepolymer
With a certain amount of CuCl (or CuBr), 2; 2 '-bipyridine and initiator add in the reaction flask; after vacuumizing, fill 3～4 circulations of nitrogen; under nitrogen protection; add a certain amount of A component and B constituent monomers and drum nitrogen a certain amount of solvent 30 minute or more of drum nitrogen more than 30 minutes; in 80～160 ℃ oil bath, reacted 1～30 hour under stirring, be deposited in the solvent 4 filtration, 60 ℃ of oven dry through neutral alumina post absorption purification (the mass polymerization product is earlier with solvent 2 dissolvings).
(2) block polymerization reaction
Prepolymer, the catalyzer of above-mentioned preparation are added in vacuumizing, fill 3～4 round-robin reaction flasks of nitrogen, add the fluorine-containing vinyl monomer of drum nitrogen more than 30 minutes and the solvent 4 of drum nitrogen more than 30 minutes again, stir down and in 80～160 ℃ oil bath, react.
This method mild condition, reagent is easy to get, and is easy and simple to handle, and monomer is applied widely, and the hydrophobic and lyophobic property of gained segmented copolymer is good, can use at normal temperatures, has excellent industrial application foreground.Following example has illustrated the preparation method of this patent in more detail.Reaction method and the method that not only is confined in the example to be narrated.
Embodiment one: the preparation of poly-(vinylbenzene-methacryloxypropyl trimethoxy silane) prepolymer
Using nitrogen replacement three times, contain 0.23 gram CuBr, 0.42 gram to cyclite and 0.74 gram 2, in the reaction flask of 2 '-bipyridine, add 3 milliliters of 30 milliliters of 30 minutes vinylbenzene of drum nitrogen and methacryloxypropyl trimethoxy silane, 80 ℃ of stirring reactions 10 hours.With benzene solubilizing reaction thing, after neutral alumina post absorption, in sherwood oil, precipitate prepolymer, 60 ℃ of vacuum-dryings.Prepolymer number-average molecular weight (Mn)=6378, molecular weight distribution (MWD)=1.47.
Embodiment two: poly-(methyl methacrylate-methacryloxypropyl trimethoxy silane)
The preparation of prepolymer
Using nitrogen replacement three times, contain 0.17 gram CuBr, 0.45 gram Methyl benzenesulfonyl chlorine and 0.55 gram 2, in the reaction flask of 2 '-bipyridine, add 20 milliliters of 15 milliliters of 30 minutes methyl methacrylates of drum nitrogen, 1 milliliter of methacryloxypropyl trimethoxy silane and phenyl ether, 80 ℃ of stirring reactions 5 hours.With benzene solubilizing reaction thing, after neutral alumina post absorption, in methyl alcohol, precipitate prepolymer, 60 ℃ of vacuum-dryings.Prepolymer Mn=9430, MWD=1.3.
Embodiment three: the preparation of poly-15 fluorine octyl group methacrylic acid glycol esters-poly-(vinylbenzene-methacryloxypropyl trimethoxy silane)-poly-15 fluorine octyl group methacrylic acid glycol ester triblock copolymers
Using nitrogen replacement three times, contain 0.08 gram CuBr, 0.26 gram 2, in 2 '-bipyridine and 1.0 gram embodiment, the 1 gained prepolymer reaction flask, add drum nitrogen 5 milliliters of N-BUTYL ACETATEs and 1 milliliter of 15 fluorine octyl group methacrylic acid glycol ester of 30 minutes with syringe, stirring reaction is 20 hours in 100 ℃ oil bath.The Mn=14798 of triblock copolymer, productive rate 70%.
Embodiment four: poly-(methyl methacrylate-methacryloxypropyl trimethoxy silane)-poly-ten
The preparation of five fluorine octyl group methacrylic acid glycol ester Synthetic rubber, isoprene-styrene, hydrogenated, block, diblocks
Using nitrogen replacement three times, contain 0.07 gram CuBr, 0.22 gram 2, in the reaction flask of 2 '-bipyridine and 1.5 gram embodiment, 2 gained prepolymers, add drum nitrogen 8 milliliters of N-BUTYL ACETATEs and 1 milliliter of 15 fluorine octyl group methacrylic acid glycol ester of 30 minutes with syringe, stirring reaction is 15 hours in 110 ℃ oil bath.The Mn=12497 of Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, productive rate 60%.
Embodiment five: poly-Polyfluoroalkyl acrylate-poly-(vinylbenzene-methacryloxypropyl trimethoxy
Silane)-preparation of poly-Polyfluoroalkyl acrylate triblock copolymer
Using nitrogen replacement three times, containing 0.08 gram CuBr, 0.26 gram 2,2 '-bipyridine, 1.0 gram embodiment 1 gained prepolymers and 1.5 gram CF
3(CF
2)
m(CH
2)
2OCOCH=CH
2In the reaction flask of (m=7～11) Polyfluoroalkyl acrylate, add 5 milliliters of N-BUTYL ACETATEs of 30 minutes of drum nitrogen with syringe, stirring reaction is 20 hours in 110 ℃ oil bath, productive rate 95%.
Embodiment six: poly-(methyl methacrylate-methacryloxypropyl trimethoxy silane)-and poly-many
The preparation of fluoroalkyl acrylate Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock
Using nitrogen replacement three times, containing 0.05 gram CuBr, 0.15 gram 2,2 '-bipyridine, embodiment 2 gained prepolymers, 1.0 grams and 1.0 gram CF
3(CF
2)
m(CH
2)
2OCOCH=CH
2In the reaction flask of (m=7～11) Polyfluoroalkyl acrylate, add the 8 milliliter N-BUTYL ACETATEs of drum nitrogen more than 30 minutes with syringe, stirring reaction is 10 hours in 100 ℃ oil bath, productive rate 80%.
Claims (8)
- The preparation method of 1 one kinds of fluorosilicic block copolymers, it is characterized in that: silicon prepolymer, catalyzer and the fluorochemical monomer of halogen-containing end group, reaction obtains segmented copolymer of the present invention under certain temperature and inert atmosphere nitrogen or argon gas, the silicon prepolymer of employed halogen-containing end group shared ratio in segmented copolymer is 1-89wt%, employed fluorochemical monomer is a fluoroalkyl vinyl monomers, and its ratio shared in segmented copolymer is 10-80wt%.
- 2 methods according to claim 1, the silicon prepolymer that it is characterized in that described halogen-containing end group are two or more monomeric multipolymers.
- 3 methods according to claim 1 is characterized in that containing at least in the described silicon prepolymer one or more hydrolyzable groups.
- 4 methods according to claim 1 is characterized in that described fluoroalkyl is perfluor or Polyfluoroalkyl.
- 5 methods according to claim 1 is characterized in that employed catalyzer is the coordination compound of transition metal ion.
- 6 methods according to claim 5 is characterized in that described transition metal ion is Cu (I), Fe (II), Ni (II), Ru (II).
- 7 methods according to claim 5 is characterized in that described ligand is the compound of nitrogenous or phosphorus.
- 8 methods according to claim 1, the temperature of reaction that it is characterized in that system is 30～160 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106780A CN1108319C (en) | 1997-12-16 | 1997-12-16 | Method for preparation of fluorosilicic block copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106780A CN1108319C (en) | 1997-12-16 | 1997-12-16 | Method for preparation of fluorosilicic block copolymer |
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| Publication Number | Publication Date |
|---|---|
| CN1220276A CN1220276A (en) | 1999-06-23 |
| CN1108319C true CN1108319C (en) | 2003-05-14 |
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ID=5168991
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97106780A Expired - Fee Related CN1108319C (en) | 1997-12-16 | 1997-12-16 | Method for preparation of fluorosilicic block copolymer |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235124B (en) * | 2008-01-08 | 2010-08-04 | 厦门大学 | Fluorine silicon di-block copolymers and preparation method thereof |
| CN111333793B (en) * | 2020-03-18 | 2022-12-13 | 山东应强新材料科技有限公司 | Multi-element triblock fluorosilicone copolymer electronic protective agent with sequence structure and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61209287A (en) * | 1985-03-14 | 1986-09-17 | Nippon Oil & Fats Co Ltd | Water and oil repellent |
| JPH04100877A (en) * | 1990-08-21 | 1992-04-02 | Ube Ind Ltd | Heat-resistant coating material |
-
1997
- 1997-12-16 CN CN97106780A patent/CN1108319C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61209287A (en) * | 1985-03-14 | 1986-09-17 | Nippon Oil & Fats Co Ltd | Water and oil repellent |
| JPH04100877A (en) * | 1990-08-21 | 1992-04-02 | Ube Ind Ltd | Heat-resistant coating material |
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|---|---|
| CN1220276A (en) | 1999-06-23 |
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