CN103467679A - POSS (Polyhedral Oligomeric Silsesquioxane) fluorine-silicon acrylate block copolymer as well as preparation method and application thereof - Google Patents
POSS (Polyhedral Oligomeric Silsesquioxane) fluorine-silicon acrylate block copolymer as well as preparation method and application thereof Download PDFInfo
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- CN103467679A CN103467679A CN2013104155736A CN201310415573A CN103467679A CN 103467679 A CN103467679 A CN 103467679A CN 2013104155736 A CN2013104155736 A CN 2013104155736A CN 201310415573 A CN201310415573 A CN 201310415573A CN 103467679 A CN103467679 A CN 103467679A
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Abstract
The invention discloses a POSS (Polyhedral Oligomeric Silsesquioxane) fluorine-silicon acrylate block copolymer as well as a preparation method and application thereof. The copolymer is composed of a PDMS (Polydimethylsiloxane) block and an FAC (Fluorinated Acrylate) block and has a structural formula shown in the specification. According to the preparation method, free-radical polymerization is carried out on acrylate monomers, hydroxyl-containing acrylic functional monomers, fluorinated functional acrylic monomers and (methyl) propylene acyloxy oligomeric silsesquioxane by utilizing a polydimethyl siloxane macromolecular initiator to obtain the POSS fluorine-silicon acrylate block copolymer. The preparation method disclosed by the invention has the advantage that the raw materials are easily available and the experimental conditions are gentle; the surface of the block copolymer has a micro-phase separating structure, so that the block copolymer has the characteristics of low surface energy, strong base material adhesive force and the like after being formed into a film, has certain crudeness and hardness, and is applied to a blood compatible material.
Description
Technical field
The present invention relates to a kind of (methyl) acryloxy oligomeric silsesquioxane (POSS) fluorine silica acrylic acid ester block copolymer and preparation and application, belong to the synthetic field of fluorine silica acrylic acid resin and biomedical materials field.
Background technology
Carrying out design of material from bionical angle, is strategy commonly used in the bio-medical material preparation.On blood vessel microcosmic in organism, be a heterogeneous structure, therefore, the macromolecular material with micro phase separation structure of certain roughness may have good blood compatibility.
Ye etc. have observed the heart valve of rabbit, find that its surface is comprised of similar pebbles and very thin fluff structures, and prepared the polydimethylsiloxane with layering micro nano structure by the method for soft etching, the surface that discovery has micro phase separation structure has better blood compatibility (Ye X, Shao YL, Zhou M, Li J, Cai L. Research on micro-structure and hemocompatibility of the artificial heart valve surface.Applied Surface Science, 2009,255:6686-6690).In general, the surface of urethane has micro phase separation structure.Lu etc. improve the blood compatibility of polyurethane material by soft section component in the change urethane raw, prepared hydrophilic polyurethane material (the Lu J that a kind of blood compatibility is good, Zhou HJ, Shi HT, Qian YF, He CL, Liang CX, Li L. A hydrophilic polyurethane material with good blood compatibility. Journal of Clinical Rehabilitative Tissue Engineering Research, 2011,15 (42): 7827-7830).
Segmented copolymer, due to thermodynamic (al) uncompatibility on its segment, makes its body or surface form phase separation structure on micron or nanoscale.The POSS compound with regular structure, be the silicoorganic compound of the special cage shape of having of class organic inorganic hybridization molecular structure, small-sized, and diameter is 1.5nm.POSS can introduce in polymkeric substance and form micro phase separation structure by methods such as physical blending or chemical bondings, increases roughness and the hardness of co-polymer membrane, improves the material hydrophobic performance.The research of acrylate and POSS multipolymer is at present still in the starting stage, mainly concentrate on the structural characterization of this analog copolymer and adding the several aspects of the impact of mechanics and thermostability (Escude NC of POSS, .Chen E Y-X. Stereoregular methacrylate-POSS hybrid polymers:syntheses and nanostructured assemblies. Chemistry of materials, 2009,21:5743-5753).
Acrylate and POSS multipolymer are studied less aspect biomaterial, Korea S scholar J.H.Lee has reported that acrylate and POSS multipolymer can be used as the artificial tooth material, there is good biocompatibility (Kim SK, Heo SJ, Koak JY, Lee JH, Lee YM, Chung DJ, Lee JI, Hong SD. A biocompatibility study of a reinforced acrylic-based hybrid denture composite resin with polyhedraloligosilsesquioxane. Journal of Oral Rehabilitation, 2007, 34:389-395).The polymkeric substance that contains POSS has than traditional tetrafluoroethylene and the better biologically stable of organosilicon biomaterial.
(methyl) acryloxy oligomeric silsesquioxane fluorine silica acrylic acid ester block copolymer prepared by the present invention, centre is the PDMS macromole, and both sides are the fluorinated acrylate monomer and (methyl) acryloxy oligomeric silsesquioxane (POSS) multipolymer with crosslinking functionality.About take PDMS as soft section, fluorinated acrylate function monomer and the POSS multipolymer fluorosilicic block copolymer that is hard section is synthetic and research on the blood compatibility direction there is not yet report in the literature.
Summary of the invention
The object of the present invention is to provide a kind of (methyl) acryloxy oligomeric silsesquioxane (POSS) fluorine silica acrylic acid ester block copolymer and preparation method and application.Described copolymer sheet mask has micro phase separation structure, and certain roughness and hardness are arranged, and its preparation method process is simple, raw material is easy to get, reaction conditions is gentle, controlled, and this multipolymer can be applicable to blood compatibility material.
The present invention is achieved by the following technical solutions, a kind of (methyl) acryloxy oligomeric silsesquioxane fluorine silica acrylic acid ester block copolymer, it is characterized in that, the structural formula of this polymkeric substance as shown in Equation 1, this polymkeric substance is comprised of polydimethylsiloxane (PDMS) block and (methyl) acryloxy oligomeric silsesquioxane fluorinated acrylate (FAC) block, wherein, polydimethylsiloxane (PDMS) block accounts for 5% ~ 50% of multipolymer content, (methyl) acryloxy oligomeric silsesquioxane fluorinated acrylate (FAC) block accounts for 50% ~ 95% of multipolymer content, in (methyl) acryloxy oligomeric silsesquioxane fluorinated acrylate (FAC) block, the mass content that acrylate monomer accounts for this block is 55% ~ 80%, the mass content that fluorochemical monomer accounts for this block is 10% ~ 30%, the mass content that (methyl) acryloxy oligomeric silsesquioxane accounts for this block is 5% ~ 20%, the number-average molecular weight Mn of this multipolymer is 20000 ~ 50000, molecular weight distribution is 1.8 ~ 2.8,
Formula 1
In formula: X is-CH
3or-CH
2cH
3or-(CH
2)
3cH
3or-CH
2cH
2oH or-CH
2cHOHCH
3
Or be-CH
2cF
2cHFCF
3or-CH
2cF (CF
3) CFHCF (CF
3)
2or-CH
2cH
2(CF
2)
5cF
3or-CH
2cF
3;
R is C
1-C
8alkane or fluor alkaline;
Respectively the do for oneself independent integer of 1-1000 of y, z, p, q;
The independent integer that n is 20-300, the independent integer that k is 1-18.
There is (methyl) acryloxy oligomeric silsesquioxane fluorine silica acrylic acid ester block copolymer its preparation method of said structure, it is characterized in that comprising the steps:
(1) adopt the both-end hydrogen silicone oil (H-PDMS-H) that molecular weight is 2000-20000 g/mol to pass through the addition of silicon hydrogen, synthetic two hydroxyl polydimethylsiloxane (HOR-PDMS-ROH), carry out again esterification and generate polydimethylsiloxane macromole evocating agent (PDMS-MAI), as shown in Equation 2:
Formula 2
In formula 2: the independent integer that n is 20-300, the independent integer that p is 1-1000;
(2) the polydimethylsiloxane macromole evocating agent (PDMS-MAI) prepared by step (1) is dissolved in solvent benzol, under nitrogen protection, stirs, and is made into the solution A that massfraction is 1%-25%, solution temperature is risen to 60-65 ℃, again by acrylic ester monomer, fluorine function monomer and (methyl) acryloxy oligomeric silsesquioxane are according to mass ratio (0.55 ~ 0.8): (0.1 ~ 0.3): (0.05 ~ 0.2) is dissolved in benzene, be made into the solution B that massfraction is 10%-50%, under 68-72 ℃, mass ratio according to polydimethylsiloxane macromole evocating agent (PDMS-MAI) and siliceous perfluoroalkyl acrylate esters monomer is (0.05-0.5): (0.5-0.95), solution B is added in solution A and reacts 8-12h, described acrylic ester monomer is methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, hydroxyethyl methylacrylate, one or more in Rocryl 410, described fluorine function monomer is one or more in methacrylic acid ten trifluoro monooctyl esters, dodecafluoroheptyl methacrylate, Hexafluorobutyl mathacrylate, described (methyl) acryloxy oligomeric silsesquioxane is (methyl) acryloxy isobutyl-oligomeric silsesquioxane, products therefrom is dropwise added in the normal hexane of volume ratio 1:2 and alcohol mixed solution and precipitates, vacuum-drying, to constant weight, obtains (methyl) acryloxy oligomeric silsesquioxane fluorine silica acrylic acid ester block copolymer.
(methyl) vinylformic acid acyloxy oligomeric silsesquioxane fluorine silica acrylic acid ester block copolymer described above or preparation is applied, and this multipolymer is applied to the coating of blood compatibility material.
The invention has the advantages that: (1) raw material is easy to get, the experiment condition gentleness, and easy control of reaction system, can produce in a large number.(2) (methyl) vinylformic acid acyloxy oligomeric silsesquioxane fluorine silica acrylic acid ester block copolymer prepared, polydimethylsiloxane wherein (PDMS) and (methyl) acryloxy oligomeric silsesquioxane fluorinated acrylate (FAC) block, due to the uncompatibility on segment thermodynamics, can cause the micro phase separation structure of multipolymer surface pattern, thereby there is blood compatibility preferably.(3) (methyl) vinylformic acid acyloxy oligomeric silsesquioxane fluorine Si acrylate copolymer prepared combines the advantage of silicone resin, fluoro-resin and acrylic resin, increased roughness and the hardness on co-polymer membrane surface, have low surface energy and with the characteristics such as base material strong adhesion.
Embodiment
Embodiment 1:
End hydrogen silicone oil (H-PDMS-H) 10g that the peek average molecular weight is 10000, vinylcarbinol 0.12g, platinum vinylsiloxane inner complex 50 μ l, add the 10g Virahol, room temperature reaction 15min.Get the synthetic HO-PDMS-OH of 10g, 0.28g ACVA, 0.12g DPTS joins in the mixed solvent that methylene dichloride 50g, DMF12g mix, and until completely dissolved, gets 0.83g DCC and is dissolved in the 10g methylene dichloride, adds in mixed system.After stirring at room reaction 24h, mixed solution is dripped in a large amount of methyl alcohol and precipitates, obtain polydimethylsiloxane macromole evocating agent (PDMS-MAI).
Get the 3.5g PDMS-MAI that said process makes, be dissolved in the 40g benzene solvent, stir half an hour under nitrogen protection after it dissolves fully, system temperature is risen to 65 ℃, after temperature-stable, add 2.7g methyl methacrylate (MMA), 2.2g butyl acrylate (BA), 0.7g hydroxyethyl methylacrylate (HEMA), 1.7g dodecafluoroheptyl methacrylate, 0.7g methacryloxy isobutyl-oligomeric silsesquioxane (MAPOSS) is to reaction system, be warming up to 70 ℃, reaction 8h, the gained reaction solution is slowly splashed in the mixing solutions of a large amount of normal hexanes and ethanol volume ratio 1:2 and precipitate, purify.Obtain (methyl) acryloxy oligomeric silsesquioxane fluorine silica acrylic acid ester block copolymer.
Embodiment 2:
Both-end hydrogen silicone oil (H-PDMS-H) 10g that the peek average molecular weight is 5000g/mol, vinylcarbinol 0.23g, platinum vinylsiloxane inner complex 100 μ l, add the 10g Virahol, room temperature reaction 30min.Get the synthetic HO-PDMS-OH of 10g, 0.56g ACVA, 0.235g DPTS joins in the mixed solvent that methylene dichloride 50g, DMF15g mix, and until completely dissolved, gets 1.65g DCC and is dissolved in the 10g methylene dichloride, adds in mixed system.After stirring at room reaction 24h, mixed solution is dripped in a large amount of methyl alcohol and precipitates.Obtain polydimethylsiloxane macromole evocating agent (PDMS-MAI).
Get the 3g PDMS-MAI that said process makes, be dissolved in the 40g benzene solvent, stir half an hour under nitrogen protection after it dissolves fully, system temperature is risen to 65 ℃, after temperature-stable, add 2.5g methyl methacrylate (MMA), 2.1g butyl acrylate (BA), 0.7g hydroxyethyl methylacrylate (HEMA), 1.6g Hexafluorobutyl mathacrylate, 1.0g methacrylic acid acyloxy isobutyl-oligomeric silsesquioxane (MAPOSS) is to reaction system, be warming up to 70 ℃, reaction 10h, the gained reaction solution is slowly splashed in the mixing solutions of a large amount of normal hexanes and ethanol volume ratio 1:2 and precipitate, purify.Obtain (methyl) acryloxy oligomeric silsesquioxane fluorine silica acrylic acid ester block copolymer.
Embodiment 3:
Both-end hydrogen silicone oil (H-PDMS-H) 10g that the peek average molecular weight is 2000g/mol, vinylcarbinol 0.72g, platinum vinylsiloxane inner complex 200 μ l, add the 10g Virahol, room temperature reaction 60min.Get the synthetic HO-PDMS-OH of 10g, 1.15g ACVA, 0.5g DPTS joins in the mixed solvent that methylene dichloride 50g, DMF10g mix, and until completely dissolved, gets 3.1g DCC and is dissolved in the 10g methylene dichloride, adds in mixed system.After stirring at room reaction 24h, mixed solution is dripped in a large amount of methyl alcohol and precipitates.Obtain polydimethylsiloxane macromole evocating agent (PDMS-MAI).
Get the 3g PDMS-MAI that said process makes, be dissolved in the 40g benzene solvent, stir half an hour under nitrogen protection after it dissolves fully, system temperature is risen to 65 ℃, after temperature-stable, add 3g methyl methacrylate (MMA), 1.9g ethyl propenoate, 0.8g hydroxyethyl methylacrylate (HEMA), 1.2g methacrylic acid ten trifluoro monooctyl esters in heptan, methacryloxy isobutyl-oligomeric silsesquioxane (MAPOSS) is to reaction system, be warming up to 70 ℃, reaction 10h, the gained reaction solution is slowly splashed in the mixing solutions of a large amount of normal hexanes and ethanol volume ratio 1:2 and precipitate, purify.Obtain (methyl) acryloxy oligomeric silsesquioxane fluorine silica acrylic acid ester block copolymer.
Claims (3)
1. (methyl) acryloxy oligomeric silsesquioxane fluorine silica acrylic acid ester block copolymer, it is characterized in that, the structural formula of this polymkeric substance as shown in Equation 1, this polymkeric substance is comprised of polydimethylsiloxaneblock block and (methyl) acryloxy oligomeric silsesquioxane fluorinated acrylate block, wherein, polydimethylsiloxaneblock block accounts for 5% ~ 50% of multipolymer content, (methyl) acryloxy oligomeric silsesquioxane fluorinated acrylate block accounts for 50% ~ 95% of multipolymer content, in (methyl) acryloxy oligomeric silsesquioxane fluorinated acrylate block, the mass content that acrylate monomer accounts for this block is 55% ~ 80%, the mass content that fluorochemical monomer accounts for this block is 10% ~ 30%, the mass content that (methyl) acryloxy oligomeric silsesquioxane accounts for this block is 5% ~ 20%, the number-average molecular weight Mn of this multipolymer is 20000 ~ 50000, molecular weight distribution is 1.8 ~ 2.8,
Formula 1
In formula: X is-CH
3or-CH
2cH
3or-(CH
2)
3cH
3or-CH
2cH
2oH or-CH
2cHOHCH
3
Or be-CH
2cF
2cHFCF
3or-CH
2cF (CF
3) CFHCF (CF
3)
2or-CH
2cH
2(CF
2)
5cF
3or-CH
2cF
3;
R is C
1-C
8alkane or fluor alkaline;
Respectively the do for oneself independent integer of 1-1000 of y, z, p, q;
The independent integer that n is 20-300, the independent integer that k is 1-18.
2. press (methyl) claimed in claim 1 acryloxy oligomeric silsesquioxane fluorine silica acrylic acid ester block copolymer its preparation method for one kind, it is characterized in that comprising the steps:
(1) adopt the both-end hydrogen silicone oil that molecular weight is 2000-20000 g/mol to pass through the addition of silicon hydrogen, synthetic two hydroxyl polydimethylsiloxanes, then carry out esterification generation polydimethylsiloxane macromole evocating agent, as shown in Equation 2:
Formula 2
In formula 2: the independent integer that n is 20-300, the independent integer that p is 1-1000;
(2) the polydimethylsiloxane macromole evocating agent prepared by step (1) is dissolved in solvent benzol, under nitrogen protection, stirs, and is made into the solution A that massfraction is 1%-25%, solution temperature is risen to 60-65 ℃, again by acrylic ester monomer, fluorine function monomer and (methyl) acryloxy oligomeric silsesquioxane are according to mass ratio (0.55 ~ 0.8): (0.1 ~ 0.3): (0.05 ~ 0.2) is dissolved in benzene, be made into the solution B that massfraction is 10%-50%, under 68-72 ℃, mass ratio according to polydimethylsiloxane macromole evocating agent and siliceous perfluoroalkyl acrylate esters monomer is (0.05-0.5): (0.5-0.95), solution B is added in solution A and reacts 8-12h, described acrylic ester monomer is methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, hydroxyethyl methylacrylate, one or more in Rocryl 410, described fluorine function monomer is one or more in methacrylic acid ten trifluoro monooctyl esters, dodecafluoroheptyl methacrylate, Hexafluorobutyl mathacrylate, described (methyl) acryloxy oligomeric silsesquioxane is (methyl) acryloxy isobutyl-oligomeric silsesquioxane, products therefrom is dropwise added in the normal hexane of volume ratio 1:2 and alcohol mixed solution and precipitates, vacuum-drying, to constant weight, obtains (methyl) acryloxy oligomeric silsesquioxane fluorine silica acrylic acid ester block copolymer.
3. apply by (methyl) claimed in claim 1 vinylformic acid acyloxy oligomeric silsesquioxane fluorine silica acrylic acid ester block copolymer for one kind, be applied to the coating of blood compatibility material.
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| CN108159477A (en) * | 2017-12-25 | 2018-06-15 | 中国人民解放军陆军军医大学第附属医院 | The preparation method and application of poly- seven fluorine butyl propyleneglycol acid esters-pla-pcl block polymer nano fibrous membrane of anticoagulation anti-adhesive |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632923A (en) * | 2016-12-09 | 2017-05-10 | 境洁环保科技（上海）有限公司 | Fluorosilicone polyurethane and polyacrylic ester four-block copolymer and preparation method thereof |
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| CN108159477A (en) * | 2017-12-25 | 2018-06-15 | 中国人民解放军陆军军医大学第附属医院 | The preparation method and application of poly- seven fluorine butyl propyleneglycol acid esters-pla-pcl block polymer nano fibrous membrane of anticoagulation anti-adhesive |
| CN108159477B (en) * | 2017-12-25 | 2020-10-02 | 中国人民解放军陆军军医大学第一附属医院 | Preparation method and application of anticoagulant and anti-adhesion poly (heptafluoro butyl acrylate) -polycaprolactone block polymer nanofiber membrane |
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Application publication date: 20131225 |