CN103936946A - Method for one-kettle preparation of fluorosilicone block polymer-modified inorganic material - Google Patents
Method for one-kettle preparation of fluorosilicone block polymer-modified inorganic material Download PDFInfo
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- CN103936946A CN103936946A CN201310405400.6A CN201310405400A CN103936946A CN 103936946 A CN103936946 A CN 103936946A CN 201310405400 A CN201310405400 A CN 201310405400A CN 103936946 A CN103936946 A CN 103936946A
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Abstract
The invention belongs to the technical field of high-molecular chemistry synthesis, and particularly relates to a method for one-kettle preparation of a fluorosilicone block polymer-modified inorganic material. Activators regenerated by electron transfer for atom transfer radical polymerization are adopted to control a reaction, the concentration of a metal catalyst in a system is extremely low, side reactions between radicals and the catalyst and between the radicals can be effectively inhibited or reduced, and end group activity is better kept. Surface functionalized inorganic particles are used as an initiator, a first monomer and a reducing agent are added, and polymerization is initiated; and when the first monomer conversion rate is relatively high, a second monomer and the reducing agent are added and one-kettle preparation of the fluorosilicone block polymer-modified inorganic material can be achieved. The invention provides the technology of one-kettle preparation of the fluorosilicone block polymer-modified inorganic material, wherein the technology has the advantages of being low in catalyst concentration, mild in reaction conditions, simple in operation steps and suitable for industrialization. At the same time, the method has important significance in preparation of high-efficiency marine antifouling coatings, improvement of marine fishery industries, and even enhancement of naval power.
Description
Technical field
The invention belongs to polymer chemistry synthesis technical field, be specifically related to one still process and cause with surface the technology that transfer transport regeneration activator-atom transfer radical polymerization (Surface initiated activators regenerated by electron transfer atom transfer radical polymerization, SI-ARGET ATRP) is prepared fluorosilicic block copolymer modified inorganic material under low catalyst concentration.
Background technology
Marine biofouling has brought huge financial loss to the maintenance of ship and oceanographic equipment.Marine life, in pipeline, accelerates the corrosion of housing, causes serious harm, even can cause line clogging.The marine organisms such as marine alga, lime worm are attached on hull and water screw, and the friction resistance that can increase hull weight and travel causes the speed of a ship or plane to reduce, and energy consumption increases.
According to the literature, certain fast boat antifouling paint improper use, lower water then settled organism reach 17kg/m
2, the speed of a ship or plane is corresponding has reduced by 30%; Certain ocean-going freighter berths after 28 days at harbour, and hull bottom adheres to a large amount of marine lifes; Make a return voyage in way, fuel is multiplex 500 tons, speed is reduced to 13 joints from 18 joints, the course line time has increased by 10 days, (Zhang Hongrong, former training victory, naval vessel chemical defence, 2005,2,7-12).For general ship, can increase economical load, and for combat vessel, marine biofouling can directly have influence on speed and time, and then have influence on fighting capacity.Therefore, prepare efficient marine antifouling coating, even strengthening sea power for enhancing fishery has important meaning.
Self-cleaning coating is that wherein the low surface energy of base-material and surperficial roughness are key factors when previous study hotspot.Fluorine silicon block polymer multiple advantage in paint field, such as low surface energy, hydrophobicity, erosion resistance, ageing-resistant etc.The inorganic materials of its modification can, simultaneously in conjunction with the feature of the roughness of inorganics own, have good application prospect in paint field.If poly-3-methyl allyl acyloxypropyl trimethoxysilane-b-polymethyl acrylic acid seven fluorine butyl esters are the novel fluorine silicon of one block polymers of reporting in the recent period, its improved silica has super-hydrophobicity (Yu H.; Luo Z.; J.Polym.Sci., Part A:Polym.Chem., 2010,48,5570-5580; Luo Zhenghong, Yu Haijiang, Zhou Yinning; China Patent Publication No.: CN101805434A).
Fluorine silicon block polymer improved silica for nanoparticle surperficial Atom Transfer Radical Polymerization (ATRP) obtain.Its ultimate principle of ATRP is taking Organohalogen compounds as initiator, transition metal complex is halogen atom carrier, pass through redox reaction, between spike and dormancy kind, set up running balance, by the reversible active free radical dormancy kind that becomes passivation, extend its life-span, reduce number of free radical, irreversible chain termination reaction is minimized, thereby realize " activity "/controllable free-radical polymerisation.
In the time that inorganic material surface is prepared block polymer, normally synthesize respectively each segment by traditional ATRP technology.After first paragraph polyreaction finishes, need to purify and remove metal ion, otherwise a large amount of passivator can have a strong impact on the polymerization of second segment; After the second monomer polymerization reactions finishes, need to again purify, just can obtain purer product.The step of this operating process is more, in industrialization, can increase greatly cost.
ARGET ATRP is a progress of traditional ATRP.Continue again the passivator in reduction system with excessive weak reductant, original position generates the atom transfer radical polymerization of activator catalysis monomer.In whole process, the concentration of metal ions of system is very low, in a lot of Application Areass, does not need to remove and can reach service requirements.Secondly, in system, a small amount of oxygen can be reacted and be consumed gradually in enclosed system, and it is harsh and strict that this result makes ATRP not pass by for another example to the requirement of oxygen.
For particle surface SI-ATRP reaction, because surperficial amount of initiator is less, and after activator reaction, the passivation dosage generating is less, cannot effectively the free radical in system be become to dormancy kind, produce irreversible free radical coupling reaction, introduce a small amount of homopolymer to system.This part polymkeric substance cannot trigger monomer polymerization, therefore, will give in block polymerization objects system and introduce impurity component.(Wu?T.，Zhang?Y.，Wang?X.，Liu?S.，Chem.Mater.，2008，20，101-109)。ARGET ATRP is in building-up process, and what add is exactly passivator; Secondly, polymerization system uses the catalyzer of minute quantity significantly to reduce and even eliminates the side reaction of free radical and catalyzer and the coupled reaction of free radical and free radical.In this case, even in the time of high conversion, still can keep the activity of end group, be beneficial to abundant use monomer.(Matyjaszewski?K.；Jakubowski?W.；Min?K.；Tang?W.；Huang?J.；Braunecker?W.A.；Tsarevsky?N.V.，PNAS，2006，103，15309-15314；Matyjaszewski?K.；Dong，H.；Jakubowski，W.；Pietrasik，J.；Kusumo，A.，Langmuir2007，23，4528-4531.)
Summary of the invention
Under this background, the SI-ARGET ATRP that utilizes under extremely low concentration catalyzer with one still process that this patent proposes prepares the technology of fluorosilicic block copolymer modified inorganic material, can fully use monomer, reduce reactions steps, avoid purification process, reduce to a greater degree the cost of industrialization process, have great significance for the development in silicon fluoride paint field; And the self-cleaning coating taking fluorosilicic block copolymer modified inorganic material as base-material, for improving, marine fishery and naval vessel strength are all significant.
Described one still process is prepared the method for the inorganic materials of fluorine silicon block polymer modification, step is as follows: the modified inorganic material that surface is had to 1mol initiator site, 0.0025～0.1mol transition metal salt, 0.01～0.4mol part and 50～500mol solvent join in reaction flask together, pass into nitrogen 10～60 minutes, be heated to 60～95 DEG C, then add the mixture of 100～500mol3-methyl allyl acyloxypropyl trimethoxysilane and 0.025～1mol reductive agent, in the time that monomer conversion reaches 85～95%, slowly add 100～500mol methacrylic acid, the seven fluorine butyl esters of 100～500mol solvent cut and the mixture of 0.05～1mol reductive agent in reaction flask, pass into nitrogen 10～60 minutes, be heated to 60～95 DEG C, enclosed system reacts while reaching 85～95% to monomer conversion, uncovered stirring, obtaining product main component is the inorganic materials of poly-3-methyl allyl acyloxypropyl trimethoxysilane-b-polymethyl acrylic acid seven fluorine butyl ester modifications.
Described solvent is that one or more in tetrahydrofuran (THF), ethyl acetate, N-BUTYL ACETATE, methylene dichloride, trichloromethane, benzene, toluene, methyl-phenoxide, dimethylbenzene, DMF are mixed arbitrarily.
Described transition metal salt is the one in mantoquita, molysite, nickel salt.Described part is pentamethyl-diethylenetriamine (PMDETA), three (2-pyridine) methylamine (TPMA), three (2-methyl amido) ethamine (Me
6tREN) one in.
Described reductive agent is that one or more in stannous octoate, glucose, lactose, fructose, hydrazine, phenylhydrazine, xitix are mixed arbitrarily.
In the time that described transition metal salt is 50～200ppm with the amount of substance ratio of monomer 3-methyl allyl acyloxypropyl trimethoxysilane, methacrylic acid seven fluorine butyl esters respectively, it prepares best results.
Described one still process is prepared the method for the inorganic materials of fluorine silicon block polymerization modification, and the polymkeric substance of prepared acquisition is poly-3-methyl allyl acyloxypropyl trimethoxysilane-b-polymethyl acrylic acid seven fluorine butyl esters, its following structural features:
Wherein, Particle is inorganic materials, and x is the poly-of poly-3-methyl allyl acyloxypropyl trimethoxysilane
Right, y is the polymerization degree of polymethyl acrylic acid seven fluorine butyl esters.
Wherein, described surface has the preparation method of modified inorganic material in initiator site as follows:
(1) described inorganic materials is first by silane coupling agent processing: 1mol inorganic materials, 5～10mol silane coupling agent and 100～500mol solvent are joined in container, reflux 1～24 hour, centrifugation goes out inorganic materials, and repeatedly wash with solvent, obtain silane coupler modified inorganic materials;
(2) introduce again initiator site: have the modified inorganic material of 1mol silane coupling agent and 1.1～10mol alkali to join in 1～100mol solvent on surface, and stir at low temperatures, then slowly drip the raw material that contains 1.1～10mol initiator site through 1～100mol solvent cut; After 1～3 hour, system is returned to room temperature, continue to stir 1～24 hour, centrifugation, and repeatedly washing with solvent, obtaining surface after dry has the inorganic materials in initiator site.
Described in above-mentioned steps (1), solvent is the one in ethanol, methyl alcohol, Virahol, toluene, dimethylbenzene.Described inorganic materials is silicon-dioxide, Z 250, cobalt oxide, nickel oxide, calcium carbonate, titanium oxide, polynite, diatomite, kaolin, wollastonite, talcum powder, ground barium sulfate, wilkinite, the one in hydroxyapatite, rectorite leng.
Solvent described in above-mentioned steps (2) is the one in tetrahydrofuran (THF), methylene dichloride, trichloromethane, benzene,toluene,xylene inert solvent.Described initiator site is that one or more in 2-bromine (chlorine) isobutyrate, 2-bromine (chlorine) isobutyramide, 2-bromine (chlorine) propionic ester, 2-bromine (chlorine) propionic acid amide, α-bromine (chlorine) phenylacetate, these functional groups of α-bromine (chlorine) phenylacetamide are mixed arbitrarily, and its structural representation as shown in Figure 3.
Compared with existing preparation method (as Chinese patent CN101805434A), the beneficial effect that the present invention has is:
1, the catalytic amount using in system is few, can avoid removing the step of catalyzer, reduces costs.
2, the transformation efficiency of monomer is higher, can fully use raw material, reduces costs, and is beneficial to the realization of one still process simultaneously.
3, obtain product with one still process, can greatly reduce production costs.
4, obtain after product with one still process, can be directly used in coating, do not need through being precipitated out from solvent, be then again dissolved in solvent, therefore, can further reduce costs.
Brief description of the drawings
Fig. 1, one still process are prepared fluorine silicon block polymer modified inorganic material route schematic diagram;
Fig. 2, one still process are prepared fluorine silicon block polymer modified inorganic material route schema;
Fig. 3, initiator site modified inorganic particle structure schematic diagram;
Embodiment
The invention is further illustrated by the following examples.
Embodiment 1:
Surface is had to the silicon-dioxide of 1mol2-isobutyl bromide ester group modification, 0.0025mol cupric bromide, 0.01mol TPMA and 50mol toluene join in reaction flask together, pass into nitrogen 10 minutes, be heated to 60 DEG C, then add the mixture of 100mol3-methyl allyl acyloxypropyl trimethoxysilane (MPTS) and 0025mol stannous octoate, in the time that monomer conversion reaches 85%, slowly add the 100mol methacrylic acid seven fluorine butyl esters (HFBMA) of 100mol dilution with toluene and the mixture of 0.05mol stannous octoate in reaction flask, pass into nitrogen 10 minutes, be heated to 60 DEG C, enclosed system reacts while reaching 85% to monomer conversion, uncovered stirring, obtaining product main component is the silicon-dioxide of poly-3-methyl allyl acyloxypropyl trimethoxysilane-b-polymethyl acrylic acid seven fluorine butyl ester modifications.
Embodiment 2:
Surface is had to the diatomite of 1mol2-bromine isobutyramide group modification, 0.05mol cupric bromide, 0.2molMe
6tREN and 250mol dimethylbenzene join in reaction flask together, pass into nitrogen 30 minutes, be heated to 80 DEG C, then add the mixture of 250mol3-methyl allyl acyloxypropyl trimethoxysilane (MPTS) and 0.025～1mol xitix, in the time that monomer conversion reaches 90%, slowly add the 250mol methacrylic acid seven fluorine butyl esters (HFBMA) of 250mol dimethylbenzene dilution and the mixture of 0.5mol xitix in reaction flask, pass into nitrogen 10～60 minutes, be heated to 80 DEG C, enclosed system reacts while reaching 90% to monomer conversion, uncovered stirring, obtaining product main component is the silicon-dioxide of poly-3-methyl allyl acyloxypropyl trimethoxysilane-b-polymethyl acrylic acid seven fluorine butyl ester modifications.
Embodiment 3:
Surface is had to the polynite of 1mol2-bromo-propionic acid ester group modification, 0.1mol cupric bromide, 0.4molTPMA and 500mol methyl-phenoxide join in reaction flask together, pass into nitrogen 60 minutes, be heated to 95 DEG C, then add the mixture of 500mol3-methyl allyl acyloxypropyl trimethoxysilane (MPTS) and 1mol stannous octoate, in the time that monomer conversion reaches 95%, slowly add the 500mol methacrylic acid seven fluorine butyl esters (HFBMA) of 500mol methyl-phenoxide dilution and the mixture of 1mol stannous octoate in reaction flask, pass into nitrogen 60 minutes, be heated to 95 DEG C, enclosed system reacts while reaching 95% to monomer conversion, uncovered stirring, obtaining product main component is the silicon-dioxide of poly-3-methyl allyl acyloxypropyl trimethoxysilane-b-polymethyl acrylic acid seven fluorine butyl ester modifications.
Claims (9)
1. one still process is prepared the method for the inorganic materials of fluorine silicon block polymer modification, and step is as follows:
Surface is had to the modified inorganic material in 1mol initiator site, 0.0025～0.1mol transition metal salt, 0.01～0.4mol part and 50～500mol solvent join in reaction flask together, pass into nitrogen 10～60 minutes, be heated to 60～95 DEG C, then add the mixture of 100～500mol3-methyl allyl acyloxypropyl trimethoxysilane and 0.025～1mol reductive agent, in the time that monomer conversion reaches 85～95%, slowly add 100～500mol methacrylic acid, the seven fluorine butyl esters of 100～500mol solvent cut and the mixture of 0.05～1mol reductive agent in reaction flask, pass into nitrogen 10～60 minutes, be heated to 60～95 DEG C, enclosed system reacts while reaching 85～95% to monomer conversion, uncovered stirring, obtaining product main component is the inorganic materials of poly-3-methyl allyl acyloxypropyl trimethoxysilane-b-polymethyl acrylic acid seven fluorine butyl ester modifications.
2. one still process is prepared the method for the inorganic materials of fluorine silicon block polymer modification as claimed in claim 1, it is characterized in that described inorganic materials is the one in silicon-dioxide, Z 250, cobalt oxide, nickel oxide, calcium carbonate, titanium oxide, polynite, diatomite, kaolin, wollastonite, talcum powder, ground barium sulfate, wilkinite, hydroxyapatite, rectorite leng.
3. one still process is prepared the method for the inorganic materials of fluorine silicon block polymer modification as claimed in claim 1, it is characterized in that described inorganic materials is first by silane coupling agent processing, then introduces initiator site; Wherein initiator site is that one or more in 2-bromine (chlorine) isobutyrate, 2-bromine (chlorine) isobutyramide, 2-bromine (chlorine) propionic ester, 2-bromine (chlorine) propionic acid amide, α-bromine (chlorine) phenylacetate, α-bromine (chlorine) phenylacetamide functional group are mixed arbitrarily.
4. one still process is prepared the method for the inorganic materials of fluorine silicon block polymer modification as claimed in claim 1, it is characterized in that described solvent is that one or more in tetrahydrofuran (THF), ethyl acetate, N-BUTYL ACETATE, methylene dichloride, trichloromethane, benzene, toluene, methyl-phenoxide, dimethylbenzene, DMF are mixed arbitrarily.
5. one still process is prepared the method for the inorganic materials of fluorine silicon block polymer modification as claimed in claim 1, it is characterized in that described transition metal salt is the one in mantoquita, molysite, nickel salt.
6. one still process is prepared the method for the inorganic materials of fluorine silicon block polymer modification as claimed in claim 1, it is characterized in that described part is the one in pentamethyl-diethylenetriamine, three (2-pyridine) methylamine, three (2-methyl amido) ethamine.
7. one still process is prepared the method for the inorganic materials of fluorine silicon block polymer modification as claimed in claim 1, it is characterized in that described reductive agent is that one or more in stannous octoate, glucose, lactose, fructose, hydrazine, phenylhydrazine, xitix are mixed arbitrarily.
8. one still process is prepared the method for the inorganic materials of fluorine silicon block polymer modification as claimed in claim 1, the polymkeric substance that it is characterized in that prepared acquisition is poly-3-methyl allyl acyloxypropyl trimethoxysilane-b-polymethyl acrylic acid seven fluorine butyl esters, its following structural features:
Wherein, Particle is inorganic materials, and x is the polymerization degree of poly-3-methyl allyl acyloxypropyl trimethoxysilane, and y is the polymerization degree of polymethyl acrylic acid seven fluorine butyl esters.
9. one still process is prepared the method for the inorganic materials of fluorine silicon block polymer modification as claimed in claim 1, it is characterized in that it prepares best results in the time that described transition metal salt is 50～200ppm with the amount of substance ratio of monomer 3-methyl allyl acyloxypropyl trimethoxysilane, methacrylic acid seven fluorine butyl esters respectively.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104403065A (en) * | 2014-11-20 | 2015-03-11 | 南京工业大学 | Silicon fluoride block copolymer for big-core diameter energy fiber and preparation method for silicon fluoride block copolymer |
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| US20090171024A1 (en) * | 2005-12-21 | 2009-07-02 | Carnegie Mellon University | Preparation of block copolymers |
| CN101805434A (en) * | 2010-02-23 | 2010-08-18 | 厦门大学 | Super hydrophobic silicon-fluorine polymer/nanometer silica hybridization nanometer material and preparation method thereof |
| CN102964543A (en) * | 2012-10-17 | 2013-03-13 | 西北工业大学 | Amphiphilic fluorinated acrylate penta-block copolymer and preparation method thereof |
-
2013
- 2013-08-27 CN CN201310405400.6A patent/CN103936946A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090171024A1 (en) * | 2005-12-21 | 2009-07-02 | Carnegie Mellon University | Preparation of block copolymers |
| CN101805434A (en) * | 2010-02-23 | 2010-08-18 | 厦门大学 | Super hydrophobic silicon-fluorine polymer/nanometer silica hybridization nanometer material and preparation method thereof |
| CN102964543A (en) * | 2012-10-17 | 2013-03-13 | 西北工业大学 | Amphiphilic fluorinated acrylate penta-block copolymer and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104403065A (en) * | 2014-11-20 | 2015-03-11 | 南京工业大学 | Silicon fluoride block copolymer for big-core diameter energy fiber and preparation method for silicon fluoride block copolymer |
| CN104403065B (en) * | 2014-11-20 | 2016-09-28 | 南京工业大学 | A kind of big core diameter energy optical fiber fluorosilicic block copolymer and preparation method thereof |
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