CN101177485B - Low surface-energy fluorosiloxane containing double parallel main-chain structure and method for synthesizing the same - Google Patents
Low surface-energy fluorosiloxane containing double parallel main-chain structure and method for synthesizing the same Download PDFInfo
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- CN101177485B CN101177485B CN2007101579238A CN200710157923A CN101177485B CN 101177485 B CN101177485 B CN 101177485B CN 2007101579238 A CN2007101579238 A CN 2007101579238A CN 200710157923 A CN200710157923 A CN 200710157923A CN 101177485 B CN101177485 B CN 101177485B
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Abstract
The invention discloses a synthesis method by compounded with free radical solution polymerization and sol-gel method, which belongs to the technical field of functional materials. Acrylic fluoroalkyl and ethylene silane are compounded to be fluorosilicone oxysilane copolymer; then silane is applied to be inorganic-phase precursor and fluorosilicone oxysilane polymer solution and silane hydrolysis are condensed by sol-gel method to coexist in the same orgaic solvent, and a novel numerators compounded fluorosilicone oxysilane copolymer is directly prepared using a C-C chain and a siloxane network structure respectively as the cocurrent double main chians and introducing CF3 group with a certain concentration into the side chain, all the steps form the synthesis method. The material prepared by the invention is not only provided with the property of super low surface energy as for the CF3 group, but also combined with substrate material in a bonding mode to have excellent combination intensity; simultaneously coating thickness and durability of hybrid material is enhanced with the inorganic sillicone network structure, which greatly extends the application field for fluorosilicone oxysilane polymers.
Description
Technical field
The invention belongs to the functional material technical field, relate to the synthetic method of new polymeric composition and this polymkeric substance.Be particularly related to a kind of molecular level compound, introduce certain density CF with carbon carbochain and silica network structure for parallel two backbone structures, side chain respectively
3The high-durability low surface energy fluorine siloxane oligomer material of group.
Background technology
The low surface free energy material has many particular performances, has obtained at aspects such as printing, non-stick pan, vehicle glass, weaving and anti-dirts using widely.The surface free energy of material depends on the outermost chemical constitution of material surface, and the outermost layer chemical constitution is the CF of tight ordered arrangement
3Solid surface have minimum surface free energy.Fluorine material is generally the long-chain fluorocarbon, the bond energy of carbon-fluorine bond is bigger, more stable, fluorine atom not only combines with carbon atom firmly, and it is very tight in the outer arrangement of carbon skeleton, prevented the exposure of carbon atom and carbochain effectively, so fluorocarbon shows performances such as remarkable low surface energy, chemical stability, weathering resistance, erosion resistance, oxidation-resistance.But, when looking after second-order transition temperature, easily cause the resistance to soiling variation because thermoplasticity own is limited; And lack cross-linking set on its linear molecule, and be difficult to form three-dimensional cross-linked netted filming, easily chap during low temperature, efflorescence, and scoring resistance, hardness are low.Want to widen the Application Areas and the over-all properties of fluorocarbon, must carry out modification to it as required.
The relevant fluorosiloxane copolymer material of report is a main chain with the silica chain at present, introduces certain density CF in side chain
3Group, this group is because its great surfactivity is oriented in the surface with strictness, and whole macromole had both kept the snappiness and the high workability of linear polysiloxane, had absorbed CF again
3The ultra-low surface energy characteristic of group simultaneously, combines with base material by covalent linkage, and hybrid material has good bonding force.The advantage that it combines organosilicon and organo-fluorine polymer becomes the new focus in polymer materials field, at present at fabric, paper, leather finishing composition, and coating, aspects such as releasing agent and lubricant all have wide practical use.Referring to Chinese patent application numbers 97106780.5,00108172.1,02124034.5,200510101356.5,200610122270.5, U.S. Patent number US6265515B1 etc.
The fluorochemical monomer commonly used of synthetic silicon-fluorine polymer thing mainly contains monomers such as (methyl) vinylformic acid fluoroalkyl ester class, fluoroalkyl vinyl ethers and fluoroolefin.Silicon-containing compound mainly contains monomers such as silane-group containing esters of acrylic acid, vinyl silanes class, cyclosiloxane class.Synthesis technique adopts traditional polymerization such as letex polymerization, solution polymerization, mass polymerization to implement generally by radical polymerization, can reach to introduce the few but purpose of the better performance of tool of carbon-fluorine bond (C-F).Used initiator great majority are water soluble starters, as ammonium persulphate ((NH
3)
2S
2O
8), Potassium Persulphate (K
2S
2O
8), Sodium Persulfate (Na
2S
2O
8) and Sodium Persulfate-sodium bisulfite (Na
2S
2O
8-NaHSO
3); Also available oil-soluble initiator is as Diisopropyl azodicarboxylate (AIBN), dibenzoyl peroxide (BPO); Or with the azo macromole as initiator.
But above-mentioned fluoroalkyl silane low-surface-energy material is a main chain with individual layer silica chain, introduces certain density CF in side chain
3Group, the hybrid material applied thickness of its formation is thinner, and endurance quality is poor.Simultaneously, because other group has uncompatibility in fluorine-containing side chain and the molecule, the compound that causes containing perfluoroalkyl side chain can spontaneously form laminate structure.Repeatedly its bonding force of coating back is relatively poor, and easily layering, be full of cracks can't improve its thickness and weather resistance by repeatedly applying.The problem of endurance quality difference has limited it and has used under some particular surroundingss.Improve the endurance quality of fluorosiloxane copolymer material by suitable technology, can improve its over-all properties greatly and promote the fluorosiloxane copolymer material in multi-field practical application, anticorrosion as large bridge and Highrise buildings, naval vessels is antifouling, the finishing composition of antifog vehicle glass, fabric and leather etc.
Summary of the invention
The object of the invention provide a kind of to various base materials excellent bonding force is arranged, applied thickness is thick, endurance quality is strong, finishing is with the low surface energy fluorine siloxane polymer material of fluorine-containing side chain.
Another object of the present invention provides the synthetic method of above-mentioned fluorosiloxane copolymer material.One step of this method finishes, product be intermolecular compound, technology simple, product does not need to purify, add water or organic solvent diluting can directly use to needs concentration.
Technical scheme of the present invention is as follows:
The synthetic method of above-mentioned fluorosiloxane copolymer emulsion provided by the invention is that free-radical emulsion polymerization and sol-gel method are compound.Adopt fluorine-containing alkyl ester of methacrylic acid or the fluorine-containing alkyl ester of vinylformic acid and vinyl silanes free-radical emulsion polymerization to synthesize the fluorosilicone multipolymer, adopting silane again is inorganic phase presoma, by sol-gel method with fluorosiloxane copolymer solution and silane cohydrolysis and polycondensation directly prepared a kind of molecular level compound, introduce certain density CF with carbon carbochain and silica network structure for parallel two backbone structures, side chain respectively
3The fluorosiloxane copolymer emulsion material of group.
Synthetic method of the present invention may further comprise the steps:
A) adopt free radical solution copolymerization to prepare the fluorosilicone multipolymer, wherein fluorochemical monomer is a vinylsiloxane for containing fluorine-containing alkyl ester of methacrylic acid or the fluorine-containing alkyl ester of vinylformic acid, containing siloxanyl monomers, and its basic structure formula is:
Wherein,
m，n＞1；
R is H or CH
3
Rf is C
1-12Hydrogen atom in the alkyl is by the part or all of metathetical Polyfluoroalkyl of fluorine atom;
D is CH
3Or C
2H
5
B) adopt sol-gel technology that above-mentioned fluorosilicone copolymer solution and the polycondensation of inorganic silicon presoma cohydrolysis are prepared the fluorosilicone oligopolymer that bottom is the silicon network structure, its basic structure formula is:
Rf is C
1-12Hydrogen atom in the alkyl is by the part or all of metathetical Polyfluoroalkyl of fluorine atom;
R is H or CH
3
m，n＞1；
x≥1
Concrete synthesis technique is, at first the fluorine-containing alkyl ester of methacrylic acid or the fluorine-containing alkyl ester of vinylformic acid and vinylsiloxane are dissolved in the organic cosolvent, slowly drip initiator in the there-necked flask of band cooling and reflux device, 60 ℃ of powerful stirring polyreactions of constant temperature 3 hours form fluoroalkyl polymerizable silane solution.Add inorganic silicon presoma, H again
2O and an amount of acid for adjusting pH continue to stir hydrolysis reaction 4 hours about 3.5, obtain transparent fluorosilicone hybrid material colloidal solution.Concrete reaction process is as follows.
Wherein,
m，n＞1；
x≥1；
R is H or CH
3
D is CH
3Or C
2H
5
Rf is C
1-12Hydrogen atom in the alkyl is by the part or all of metathetical Polyfluoroalkyl of fluorine atom;
A is alkyl or the alkylidene group with at least one carbon atom;
B is-O-Si-
Each component charging capacity in molar ratio is:
Organic cosolvent 30.00～75.00
The fluorine-containing alkyl ester 0.5～2 of fluorine-containing alkyl ester of methacrylic acid or vinylformic acid
Vinylsiloxane 0.5～2
Inorganic silicon pioneer's liquid 0.5～60
Deionized water 1～120
Initiator 0.005～0.01
Catalyzer 0.025～3
In technique scheme,
Fluorine-containing alkyl ester of methacrylic acid or the fluorine-containing alkyl ester of vinylformic acid are following general formulas:
In the formula:
R=H or CH
3
Rf is C
1-12Hydrogen atom in the alkyl is by the part or all of metathetical Polyfluoroalkyl of fluorine atom.
Vinylsiloxane is meant vinyl silicane coupling agent commonly used, as CH
2=CHSi (OCH
3)
3, CH
2=C (CH
3) Si (OCH
3)
3, CH
2=CHSi (OC
2H
5)
3Deng.
Inorganic silicon pioneer's liquid is meant tetraethoxy (Si (OC
2H
5)
4, TEOS) or methyl silicate (Si (OCH
3)
4, TMOS).
Initiator is water-soluble persulphate, as K
2S
2O
8Na
2S
2O
8(NH
4)
2S
2O
8Deng; Or azo-initiator, as AIBN etc.; Or organic peroxy class initiator, as BPO etc.
Organic cosolvent does not have particular restriction, as arenes such as benzene,toluene,xylenes; Tetrahydrofuran (THF), vinyl acetic monomer, ethanol, butanols, trieline or methyl ethyl ketone etc.
Hydrolyst is an acidic catalysts such as acetic acid, hydrochloric acid or nitric acid.
Effect of the present invention and benefit be by free radical solution polymerization and the compound employing of sol-gel method with a kind of organic cosolvent directly prepared a kind of molecular level compound, introduce certain density CF with carbon carbochain and silica network structure for parallel two backbone structures, side chain respectively
3The fluorosiloxane copolymer material of group.Synthetic fluorosiloxane copolymer material had both absorbed CF
3The ultra-low surface energy characteristic of group, combine with covalent with base material again, good bonding strength is arranged, improved the applied thickness and the weather resistance of hybrid material simultaneously by the structure of bottom inorganic silicon network structure, can expand the Application Areas of fluorosiloxane copolymer material greatly.
One step of synthesis technique of the present invention finishes, and product is intermolecular compound, and technology is simple, and product does not need to purify, and can directly use.
Embodiment
The present invention will be described to enumerate the part specific embodiment below, is necessary to point out that at this following embodiment only is used for further specifying the present invention, rather than the present invention specifically is limited in illustrated mode of embodiment and Application Areas.Those skilled in the relevant art will appreciate that comprise embodiment of the invention content and beyond do not deviate from the modification of essence of the present invention and scope and perfect.
Embodiment 1:
At first methacrylic acid ten difluoro heptyl esters (FA) and vinyltriethoxysilane (VTES) are dissolved in tetrahydrofuran (THF) (THF) solvent, slowly drip initiator dibenzoyl peroxide (BPO) in the there-necked flask of band cooling and reflux device, 60 ℃ of powerful stirring polyreactions of constant temperature 3 hours form fluoroalkyl polymerizable silane solution.Add tetraethoxy (TEOS), H again
2O and appropriate hydrochloric acid are regulated pH about 3.5, continue to stir hydrolysis reaction 4 hours, obtain transparent fluorosilicone hybrid material colloidal solution.Concrete composition (mol ratio) is FA: VTES: THF: BPO: TEOS: H
2O: HCl=1: 1: 60: 0.01: 1: 6: 0.05.Every performance measurement of polymeric solution the results are shown in Table 1.
Embodiment 2:
At first methacrylic acid ten difluoro heptyl esters (FA) and vinyltriethoxysilane (VTES) are dissolved in ethanol (ETOH) solvent, slowly drip initiator dibenzoyl peroxide (BPO) in the there-necked flask of band cooling and reflux device, 60 ℃ of powerful stirring polyreactions of constant temperature 3 hours form fluoroalkyl polymerizable silane solution.Add tetraethoxy (TEOS), H again
2O and an amount of nitric acid are regulated pH about 3.5, continue to stir hydrolysis reaction 4 hours, obtain transparent fluorosilicone hybrid material colloidal solution.Concrete composition (mol ratio) is FA: VTES: ETOH: BPO: TEOS: H
2O: HNO
3=1: 1: 60: 0.01: 1: 6: 0.05.Every performance measurement of polymeric solution the results are shown in Table 1.
Embodiment 3:
At first methacrylic acid ten difluoro heptyl esters (FA) and vinyltriethoxysilane (VTES) are dissolved in propyl carbinol (Butanol) solvent, slowly drip initiator potassium persulfate (K
2S
2O
8) in the there-necked flask of band cooling and reflux device, 60 ℃ of powerful stirring polyreactions of constant temperature 3 hours form fluoroalkyl polymerizable silane solution.Add tetraethoxy (TEOS), H again
2O and appropriate hydrochloric acid are regulated pH about 3.5, continue to stir hydrolysis reaction 4 hours, obtain transparent fluorosilicone hybrid material colloidal solution.Concrete composition (mol ratio) is FA: VTES: Butanol: K
2S
2O
8: TEOS: H
2O: HCl=1: 1: 60: 0.01: 1: 6: 0.05.Every performance measurement of polymeric solution the results are shown in Table 1.
Embodiment 4:
At first methacrylic acid ten difluoro heptyl esters (FA) and vinyltrimethoxy silane (VTMS) are dissolved in tetrahydrofuran (THF) (THF) solvent, slowly drip initiator dibenzoyl peroxide (BPO) in the there-necked flask of band cooling and reflux device, 60 ℃ of powerful stirring polyreactions of constant temperature 3 hours form fluoroalkyl polymerizable silane solution.Add tetraethoxy (TMOS), H again
2O and appropriate hydrochloric acid are regulated pH about 3.5, continue to stir hydrolysis reaction 4 hours, obtain transparent fluorosilicone hybrid material colloidal solution.Concrete composition (mol ratio) is FA: VTMS: THF: BPO: TMOS: H
2O: HCl=1: 1: 60: 0.01: 1: 6: 0.05.Every performance measurement of polymeric solution the results are shown in Table 1.
Embodiment 5:
At first methacrylic acid ten difluoro heptyl esters (FA) and vinyltriethoxysilane (VTES) are dissolved in tetrahydrofuran (THF) (THF) solvent, slowly drip initiator dibenzoyl peroxide (BPO) in the there-necked flask of band cooling and reflux device, 60 ℃ of powerful stirring polyreactions of constant temperature 3 hours form fluoroalkyl polymerizable silane solution.Add tetraethoxy (TEOS), H again
2O and appropriate hydrochloric acid are regulated pH about 3.5, continue to stir hydrolysis reaction 4 hours, obtain transparent fluorosilicone hybrid material colloidal solution.Concrete composition (mol ratio) is FA: VTES: THF: BPO: TEOS: H
2O: HCl=1: 1: 60: 0.01: 4: 12: 0.1.Every performance measurement of polymeric solution the results are shown in Table 1.
Embodiment 6:
At first methacrylic acid ten difluoro heptyl esters (FA) and vinyltriethoxysilane (VTES) are dissolved in tetrahydrofuran (THF) (THF) solvent, slowly drip initiator dibenzoyl peroxide (BPO) in the there-necked flask of band cooling and reflux device, 60 ℃ of powerful stirring polyreactions of constant temperature 3 hours form fluoroalkyl polymerizable silane solution.Add tetraethoxy (TEOS), H again
2O and appropriate hydrochloric acid are regulated pH about 3.5, continue to stir hydrolysis reaction 4 hours, obtain transparent fluorosilicone hybrid material colloidal solution.Concrete composition (mol ratio) is FA: VTES: THF: BPO: TEOS: H
2O: HCl=1: 1: 60: 0.01: 12: 72: 0.6.Every performance measurement of polymeric solution the results are shown in Table 1.
Embodiment 7:
The physicals of the low surface energy coat of embodiment 1～6 polymers soln preparation.
Adopt the membrane method to apply the fluorosiloxane copolymer coating as the aluminum alloy surface after minute surface and the ultrasonic cleaning gained embodiment 1～6 polymers soln in polishing.At first the aluminium substrate material is immersed in as a result in the solution 10 minutes, again with the speed membrane of 10cm/min.The aluminum metal film that scribbles coating is at room temperature air-dry, and then the temperature rise rate with 0.25 ℃/min is warmed up to 140 ℃ of dry solidifications processing in baking oven.Above applying step repeats respectively five times.Corrosion resistance nature adopts the electrokinetic potential anodic polarization curves to measure, and calculates corrosion current I with the Tafel method
Corr, erosion rate v
CorrAnd evaluate anti-corrosion grade according to general ten grade standards of metal solidity to corrosion.
Table 1 embodiment 1～6 resulting polymers solution properties
The every performance measurement result in table 2 embodiment 1～6 coating back
Claims (4)
1. the synthetic method that contains two parallel backbone structure low surface energy fluorine siloxane oligomers is characterized in that a kind of molecular level is compound, introduce certain density CF with carbon carbochain and silica network structure for parallel two backbone structures, side chain respectively
3The low surface energy fluorine siloxane oligomer preparation methods of group, this method may further comprise the steps:
A) adopt free radical solution copolymerization to prepare the fluorosilicone multipolymer, wherein fluorochemical monomer is a vinylsiloxane for containing fluorine-containing alkyl ester of methacrylic acid or the fluorine-containing alkyl ester of vinylformic acid, containing siloxanyl monomers, and its basic structure formula is:
Wherein,
m，n＞1；
R is H or CH
3
Rf is C
1-12Hydrogen atom in the alkyl is by the whole metathetical Polyfluoroalkyls of fluorine atom;
D is CH
3Or C
2H
5
B) adopt sol-gel technology that above-mentioned fluorosilicone copolymer solution and the polycondensation of inorganic silicon presoma cohydrolysis are prepared the fluorosilicone oligopolymer that bottom is the silicon network structure, its basic structure formula is:
x≥1；
Each component charging capacity in molar ratio is:
Organic cosolvent 30.00～75.00
The fluorine-containing alkyl ester 0.5～2 of fluorine-containing alkyl ester of methacrylic acid or vinylformic acid
Vinylsiloxane 0.5～2
Inorganic silicon precursor 0.5～60
Deionized water 1～120
Initiator 0.005～0.01
Catalyzer 0.025～3
Described inorganic silicon presoma is meant tetraethoxy or methyl silicate;
Concrete synthesis technique is, at first the fluorine-containing alkyl ester of methacrylic acid or the fluorine-containing alkyl ester of vinylformic acid and vinylsiloxane are dissolved in the organic cosolvent, slowly drip initiator in the there-necked flask of band cooling and reflux device, 60 ℃ of powerful stirring polyreactions of constant temperature 3 hours form fluoroalkyl polymerizable silane solution; Add inorganic silicon presoma, H again
2O and appropriate amount of acid catalyzer are regulated pH 3.5, continue to stir hydrolysis reaction 4 hours, obtain transparent fluorosilicone hybrid material colloidal solution.
2. it is characterized in that in accordance with the method for claim 1: described vinylsiloxane is meant CH
2=CHSi (OCH
3)
3Or CH
2=CHSi (OC
2H
5)
3
3. it is characterized in that in accordance with the method for claim 1: described initiator is water-soluble persulphate, azo-initiator or organic peroxy class initiator.
4. it is characterized in that in accordance with the method for claim 1: described catalyzer is acetic acid, hydrochloric acid or nitric acid.
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|---|---|---|---|
| CN2007101579238A CN101177485B (en) | 2007-10-31 | 2007-10-31 | Low surface-energy fluorosiloxane containing double parallel main-chain structure and method for synthesizing the same |
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|---|---|---|---|
| CN2007101579238A CN101177485B (en) | 2007-10-31 | 2007-10-31 | Low surface-energy fluorosiloxane containing double parallel main-chain structure and method for synthesizing the same |
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| CN102094329B (en) * | 2009-12-09 | 2013-07-03 | 北京服装学院 | Fluorine and silicon containing water and oil repellent finishing agent, preparation and application thereof |
| CN102453419B (en) * | 2010-10-26 | 2014-08-27 | 福建瑞森化工有限公司 | External insulation cleaning protective agent and preparation method thereof |
| CN103726308A (en) * | 2013-12-17 | 2014-04-16 | 江苏金太阳纺织科技有限公司 | Oil-repellent finishing liquid for woolen sweater and preparation method for oil-repellent finishing liquid |
| CN104073116B (en) * | 2014-07-08 | 2017-01-25 | 深圳大学 | Preparation method of super-amphiphobic coating |
| KR102543248B1 (en) * | 2019-08-08 | 2023-06-14 | 주식회사 엘지에너지솔루션 | Polymer for gel polymer electrolyte, gel polymer electrolyte and lithium secondary battery comprising the same |
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2007
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|---|---|---|---|---|
| US6350806B1 (en) * | 1997-10-24 | 2002-02-26 | Daikin Industries, Ltd. | Aqueous fluoropolymer dispersion composition |
| CN1690142A (en) * | 2004-04-19 | 2005-11-02 | 河南大学 | Process for preparing fluorine-containing nano SiO2 composite non-adhesive coating materials |
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