CN103468120B - POSS fluorine Si acrylate-urethane blood compatibility coating and preparation - Google Patents
POSS fluorine Si acrylate-urethane blood compatibility coating and preparation Download PDFInfo
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Abstract
The invention discloses a kind of POSS fluorine Si acrylate-urethane blood compatibility coating and preparation method.Described coating is formed on medical polyvinyl plate by one or both solidifying agent in (methyl) acryloxy oligomeric silsesquioxane fluorine Si acrylate copolymer and hexamethylene diisocyanate and isophorone diisocyanate.Its preparation method process comprises: mixing solutions POSS fluorine Si acrylate copolymer being mixed with methylene dichloride or ethyl acetate and normal hexane; Solution, by spray gun, is sprayed on surface of medical polyvinyl chloride, forms the coating that blood compatibility is good.Advantage of the present invention: preparation process technique is simple, and raw material is easy to get, and is easy to industrialization and scale operation; Prepared blood compatibility coating good film-forming property, hydrophobicity is good, has good blood compatibility, has higher practical value.
Description
Technical field
The present invention relates to one (methyl) acryloxy oligomeric silsesquioxane (POSS) fluorine Si acrylate-urethane blood compatibility coating and preparation method, belong to Surface Science and field of biomedical polymer materials.
Background technology
Along with scientific development, bio-medical material is more and more used in clinical medicine.Wherein anticoagulant biomaterial is the important component part of biomaterial, is widely used on the medical material that contacts with human blood and organizing.
The surface of super-hydrophobicity, because its surface free energy is low, low with the adsorptive power of composition each in blood, thus there is good blood compatibility.Khorasani etc. carry out super-hydrophobic or super hydrophilic modifying to polydimethylsiloxane (PDMS) film, the static adhesion experiment of external thrombocyte shows, compared with original PDMS film (water contact angle=105 °), the PDMS film (water contact angle=170 °) of modifying super hydrophobicity and the PDMS film (water contact angle=10 °) of super hydrophilic modifying all have outstanding blood compatibility (Khorasani MT, Mirzadeh H. In Vitro Blood compatibility of modified PDMS surfaces as superhydrophobic and superhydro-philic materials. Journal of Applied Polymer Science, 2004, 91:2042-2047).Fu Qiang etc. with array carbon nano tube film for template, prepare super-hydrophobic fluorochemical urethane film (water contact angle=163.6 ± 1.1 °), the static adhesion experiment of external thrombocyte shows, compared with same light synovial membrane (water contact angle=109.1 ± 1.5 °), this based superhydrophobic thin films has obvious antiplatelet adhesivity and excellent blood compatibility (Sun TL, Tan H, Han D, Fu Q, Jiang L. No platelet can adhere-largely improved blood compatibility on nanostructured superhydrophobic surfaces. Small, 2005, 1:959-963).Hou etc. also find that porous super hydrophobic polypropylene film has good blood compatibility (Hou XM, Wang XB, Zhu QS, Bao JC, Mao C, Jiang LC, Shen J. Preparation of polypropylene superhydro-phobic surface and its blood compatibility. Colloids and Surfaces B:Biointerfaces, 2010,80:247-250).
Method for preparing super-hydrophobic surface is numerous, as plasma processing method, etching method, sol-gel method, vapour deposition process, template, self-assembly method and solvent-nonsolvent method etc.Erbil etc. pass through the suitable solvent of selection polypropylene and film-forming temperature, prepare gelatinous porous super hydrophobic polypropylene film (Erbil HY on multiple base material, Demirel AL, Avc Y, Mert O. Transformation of a simple plastic into a superhydrophobic surface. Science, 2003,299:1377-1380).The silicon dioxide granule of hydrophobically modified and polymethylmethacrylate, polystyrene, epoxy resin mix by Yilgor etc., pass through multilayer of spin-on, prepare super-hydrophobic coat (Yilgor I on the glass substrate, Bilgin S, Isik M, Yilgor E. Facile preparation of superhydrophobic polymer surfaces. Polymer, 2012,53,1180-1188).But most of super hydrophobic surface complex manufacturing technology, be not suitable for a large amount of production, or there is not easily film forming, with shortcomings such as base material poor adhesive force.Fluorine-containing ester solution adopts the method for spraying on aluminium sheet, prepare fluorinated acrylate super-hydrophobic coat by our seminar, there is good resistance to low temperature (Li H, Zhao YH, Yuan XY. Facile preparation of superhydrophobic coating by spraying a fluorinated acrylic random copolymer micelle solution. Soft Matter, 2013,9,1005-1009).Relevant utilization is containing POSS fluorine silica acrylic acid ester solution, and there is not been reported in the literature to prepare the research of POSS fluorine Si acrylate-polyurethane superhydrophobic film on blood compatibility material by spraying.
Summary of the invention
The object of the present invention is to provide one (methyl) acryloxy oligomeric silsesquioxane (POSS) fluorine Si acrylate-urethane blood compatibility coating and preparation method, this blood compatibility coating described can improve the anticoagulation ability of existing blood compatibility material, this coating is easy to form uniform coating, good with base material sticking power, its preparation method process is simple.
The present invention is realized by the following technical programs: a kind of (methyl) acryloxy oligomeric silsesquioxane (POSS) fluorine Si acrylate-urethane blood compatibility coating, this coating is coated on medical polyvinyl film and is formed, it is characterized in that, coating is made up of one or both solidifying agent in (methyl) acryloxy oligomeric silsesquioxane (POSS) fluorine Si acrylate copolymer and hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI), the mass ratio of (methyl) acryloxy oligomeric silsesquioxane (POSS) fluorine Si acrylate copolymer and solidifying agent is 1:0.05 ~ 0.2, coat-thickness is between 10 ~ 200 μm, Static water contact angles is greater than 145 °, in coating, as shown in Equation 1, number-average molecular weight is 20000 ~ 40000 to (methyl) acryloxy oligomeric silsesquioxane (POSS) fluorine Si acrylate structural formula, molecular weight distributing index in 1.8 ~ 2.5 scopes,
Formula 1
In formula: x, y, z, m, n are the independent integer of 1-1000 separately, k is the independent integer of 1-18;
R is C
1-C
8alkane or fluor alkaline;
R
1for-CH
3or-CH
2cH
3or-(CH
2)
3cH
3;
R
2for-CH
2cH
2oH or-CH
2cHOHCH
3;
R
3for-CH
2cF
3or-CH
2cF
2cHFCF
3or-CH
2cF (CF
3) CFHCF (CF
3)
2or-CH
2cH
2(CF
2)
5cF
3;
R
4for
wherein n is the independent integer of 20-300;
R
5, R
6, R
7, R
8, R
9be H or CH separately
3.
The preparation method of above-mentioned (methyl) acryloxy oligomeric silsesquioxane (POSS) fluorine Si acrylate-urethane blood compatibility coating, is characterized in that comprising following process:
(1) under temperature 10-50 ° of C, adding in methylene dichloride by (methyl) acryloxy oligomeric silsesquioxane fluorine Si acrylate or adding ethyl acetate and normal hexane is (1-9) in mass ratio: in 1 mixed solvent, be mixed with the solution that mass concentration is 5%-20%, mass ratio 1:(0.05-0.2 by (methyl) acryloxy oligomeric silsesquioxane fluorine Si acrylate in solution and solidifying agent) in solution, add solidifying agent, and in solution, add catalyzer by the mass ratio of (methyl) acryloxy oligomeric silsesquioxane fluorine Si acrylate and catalyzer 1000:1, described solidifying agent is one or both in hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI), described catalyzer is tin dilaurate diisobutyl alkene,
(2) with the medical polyvinyl of dried and clean for base material, polymers soln step (1) obtained is the spray gun of 0.1-0.2mm by nozzle diameter, with the air pressure of 0.05-0.2MPa for power, apart from substrate surface 2-20cm, spraying 5-30min, obtaining thickness is coating between 10 ~ 200 μm, then through drying at room temperature 10-48h, obtains (methyl) acryloxy oligomeric silsesquioxane fluorine Si acrylate-urethane blood compatibility coating.
The invention has the advantages that: (methyl) acryloxy oligomeric silsesquioxane (POSS) fluorine Si acrylate-urethane blood compatibility coating provided, have good hydrophobicity, Static water contact angles is greater than 145 °; Blood compatibility is good, and platelet adhesion reaction amount can reduce by 80%; Good film-forming property, the adhesive power forming coating is good.This coating preparation process technique is simple, and raw material is easy to get, and is easy to industrialization and scale operation, has higher practical value.
Embodiment
Embodiment 1:
(1) preparation of POSS fluorine Si acrylate copolymer:
Raolical polymerizable is taked to prepare POSS fluorine Si acrylate copolymer: in four-hole bottle, first to add butylacetate (BA) 5g and hexone (MIBK) 5g as mixed solvent, and add with 0.15g azo-bis-isobutyl cyanide (AIBN) for initiator.After temperature rises to 78 DEG C, in four-hole bottle, methyl methacrylate (MMA) 5.5g, butyl acrylate (BA) 4.5g, hydroxyethyl methylacrylate (HEMA) 1.5g, dodecafluoroheptyl methacrylate (DFMA) 3.5g, methacrylic acid polydimethylsiloxane base ester (PDMS-MA) 0.8g is dripped with the speed of 7ml/h, the each 2g of methacryloxy oligomeric silsesquioxane (POSS) 1.5g, AIBN 0.02g and BA and MIBK.Be added dropwise to complete rear reaction 2-3h, then in four-hole bottle, add BA and MIBK each 2g and 0.06g initiator A IBN, reaction 2-3h.Whole reaction is carried out under nitrogen atmosphere protection.Excessive methanol precipitates three times, is placed in the dry 48h of vacuum drying oven to constant weight.
(2) preparation of copolymer solution:
Get the obtained 1g POSS fluorine Si acrylate copolymer of step (1) to be dissolved in 9g and to dewater in dichloromethane solvent, be mixed with the solution that concentration is 10wt%, after room temperature magnetic agitation 2h extremely dissolves completely, add 0.1g isophorone diisocyanate (IPDI), the massfraction adding 0.1ml is the dichloromethane solution that dewaters of the tin dilaurate diisobutyl alkene of 1%, obtains the copolymer solution that mass concentration is 10%.
(3) preparation of coating:
At temperature 15 DEG C, be of a size of 10cm × 2cm medical polyvinyl plate for base material with dried and clean, during spraying, atmospheric moisture is 30%.With the spray gun of nozzle diameter 0.1mm, with the air pressure of 0.1MPa for power.At distance base material polyvinyl chloride 10cm place spraying 5min.Drying at room temperature 12h, obtains the coating that thickness is 50 μm.
(4) performance test:
Zhong Chen equipment and technology company limited JC2000D Static Contact angle measuring instrument is adopted to carry out static contact angle and the dynamic contact angle test on testing coating surface.Static water contact angles reaches 156
o, dynamic contact angle hysteresis is 8
o.
Extracorporeal blood compatibility test adopts platelet adhesion reaction experiment: coating is dipped in phosphate buffer solution (PBS at 37 DEG C, pH=7.4) balance 2h in, platelet rich plasma is dropped in coating, 1h is hatched at 37 DEG C, with PBS solution concussion flushing three times after coating is taken out, the thrombocyte that removing sample surfaces does not adsorb, then at 4 DEG C, glutaraldehyde phosphate buffered saline buffer (2.5% is used, volume fraction) fixing more than 10h, then through different concns (30%, 50%, 70%, 90%, 100%, volume fraction) ethanolic soln serial dehydration, soak 30min respectively, final sample is metal spraying under vacuum, observe hematoblastic adhesive capacity and state of aggregation under a scanning electron microscope.Compared with carrying out with the medical PVC film being stained with blood, the surface of POSS fluorine Si acrylate-polyurethane coating, platelet adhesion reaction obviously reduces 70%, and the thrombocyte adhered to is substantially without distortion, and blood compatibility is good.
Embodiment 2:
(1) preparation of POSS fluorine Si acrylate copolymer
Raolical polymerizable is taked to prepare POSS fluorine Si acrylate copolymer: in four-hole bottle, first to add butylacetate (BA) 5g and hexone (MIBK) 5g as mixed solvent, and add with 0.12g azo-bis-isobutyl cyanide (AIBN) for initiator.After temperature rises to 78 DEG C, in four-hole bottle, methyl methacrylate (MMA) 6g, butyl acrylate (BA) 4g, hydroxyethyl methylacrylate (HEMA) 2g, dodecafluoroheptyl methacrylate (DFMA) 3g, methacrylic acid polydimethylsiloxane base ester (PDMS-MA) 1g is dripped with the speed of 5ml/h, the each 3g of methacryloxy oligomeric silsesquioxane (POSS) 2g, AIBN 0.03g and BA and MIBK.Be added dropwise to complete rear reaction 2-3h, then in four-hole bottle, add BA and MIBK each 3g and 0.06g initiator A IBN, reaction 2-3h.Whole reaction is carried out under nitrogen atmosphere protection.Excessive methanol precipitates three times, is placed in the dry 48h of vacuum drying oven to constant weight.
(2) preparation of copolymer solution:
6g dewaters after ethyl acetate and the mixing of 3g normal hexane, adds the 1gPOSS fluorine Si acrylate copolymer that step (1) is obtained, adds magneton and stirs 2h, make it dissolve.Add 0.1g hexamethylene diisocyanate (HDI), add the ethyl acetate of tin dilaurate diisobutyl alkene and the mixing solutions of normal hexane that 0.1ml massfraction is 1%, obtain the copolymer solution that mass concentration is 10%.
(3) preparation of coating:
At temperature 20 DEG C, be of a size of the medical polyvinyl plate of 10cm × 2cm for base material with dried and clean, during spraying, atmospheric moisture is 30%.Take diameter as the spray gun of 0.2mm nozzle, with the air pressure of 0.2MPa for power.At distance base material 20cm place, spraying 10min.Drying at room temperature 24h, obtains the coating that thickness is 90 μm.
(4) performance test:
Zhong Chen equipment and technology company limited JC2000D Static Contact angle measuring instrument is adopted to carry out static contact angle and the dynamic contact angle test on testing coating surface.Static contact angle reaches 159 °, and contact angle hysteresis is 7 °.
Extracorporeal blood compatibility test adopts platelet adhesion reaction experiment: coating is dipped in phosphate buffer solution (PBS at 37 DEG C, pH=7.4) balance 2h in, platelet rich plasma is dropped in coating, 1h is hatched at 37 DEG C, with PBS solution concussion flushing three times after sample is taken out, the thrombocyte that removing sample surfaces does not adsorb, then at 4 DEG C, glutaraldehyde phosphate buffered saline buffer (2.5% is used, volume fraction) fixing more than 10h, then through different concns (30%, 50%, 70%, 90%, 100%, volume fraction) ethanolic soln serial dehydration, soak 30min respectively, final sample is metal spraying under vacuum, observe hematoblastic adhesive capacity and state of aggregation under a scanning electron microscope.Compared with carrying out with the medical PVC film being stained with blood, the surface of POSS fluorine Si acrylate-polyurethane coating, platelet adhesion reaction obviously reduces 80%, and the thrombocyte adhered to is substantially without distortion, and blood compatibility is good.
Embodiment 3:
(1) preparation of POSS fluorine Si acrylate copolymer:
Raolical polymerizable is taked to prepare POSS fluorine Si acrylate copolymer: in four-hole bottle, first to add butylacetate (BA) 6g and hexone (MIBK) 6g as mixed solvent, and add with 0.17g azo-bis-isobutyl cyanide (AIBN) for initiator.After temperature rises to 78 DEG C, in four-hole bottle, methyl methacrylate (MMA) 6.5g, butyl acrylate (BA) 5.5g, hydroxyethyl methylacrylate (HEMA) 1.5g, dodecafluoroheptyl methacrylate (DFMA) 3.5g, each 2g of (methyl) acryloxy oligomeric silsesquioxane (POSS) 1.5g, AIBN 0.03g and BA and MIBK is dripped with the speed of 8ml/h.Be added dropwise to complete rear reaction 2-3h, then in four-hole bottle, add BA and MIBK each 3g and 0.06g initiator A IBN, reaction 2-3h.Whole reaction is carried out under nitrogen atmosphere protection.Excessive methanol precipitates three times, is placed in the dry 48h of vacuum drying oven to constant weight.
(2) preparation of copolymer solution:
4.5g dewaters after ethyl acetate and the mixing of 4g normal hexane, add the POSS fluorine Si acrylate copolymer 1.5g that step (1) is obtained, be mixed with the solution that concentration is 15wt%, after magnetic agitation 3h extremely dissolves completely, add 0.1g isophorone diisocyanate (IPDI), add the mixing solutions that 0.1ml massfraction is dewater ethyl acetate and the normal hexane of the tin dilaurate diisobutyl alkene of 1%, obtain the polymers soln that mass concentration is 15%.
(3) preparation of coating:
At temperature 25 DEG C, be of a size of the medical polyvinyl plate of 10cm × 2cm for base material with dried and clean, during spraying, atmospheric moisture is 30%.With the spray gun of nozzle diameter 0.1mm, with the air pressure of 0.1MPa for power.At distance base material polyvinyl chloride 10cm place spraying 10min.Drying at room temperature 36h, obtains the coating that thickness is 150 μm.
(4) performance test:
Zhong Chen equipment and technology company limited JC2000D Static Contact angle measuring instrument is adopted to carry out static contact angle and the dynamic contact angle test on testing coating surface.Static water contact angles reaches 160
o, dynamic Contact angular lag is 5
o.
Extracorporeal blood compatibility test adopts platelet adhesion reaction experiment: coating is dipped in phosphate buffer solution (PBS at 37 DEG C, pH=7.4) balance 2h in, platelet rich plasma is dropped in coating, 1h is hatched at 37 DEG C, with PBS solution concussion flushing three times after sample is taken out, the thrombocyte that removing sample surfaces does not adsorb, then at 4 DEG C, glutaraldehyde phosphate buffered saline buffer (2.5% is used, volume fraction) fixing more than 10h, then through different concns (30%, 50%, 70%, 90%, 100%, volume fraction) ethanolic soln serial dehydration, soak 30min respectively, final sample is metal spraying under vacuum, observe hematoblastic adhesive capacity and state of aggregation under a scanning electron microscope.Compared with carrying out with the medical PVC film being stained with blood, the surface of POSS fluorine Si acrylate-polyurethane coating, platelet adhesion reaction obviously reduces 80%, and the thrombocyte adhered to is substantially without distortion, and blood compatibility is good.
Claims (2)
1. (methyl) acryloxy oligomeric silsesquioxane fluorine Si acrylate-urethane blood compatibility coating, this coating is coated on medical polyvinyl film and is formed, it is characterized in that, coating is made up of one or both solidifying agent in (methyl) acryloxy oligomeric silsesquioxane fluorine Si acrylate copolymer and hexamethylene diisocyanate and isophorone diisocyanate, the mass ratio of (methyl) acryloxy oligomeric silsesquioxane fluorine Si acrylate copolymer and solidifying agent is 1:0.05-0.2, coat-thickness is between 10-200 μm, Static water contact angles is greater than 145 °, in coating, as shown in Equation 1, number-average molecular weight is 20000-40000 to (methyl) acryloxy oligomeric silsesquioxane fluorine Si acrylate structural formula, and molecular weight distributing index is within the scope of 1.8-2.5
Formula 1
In formula: x, y, z, m, n are the independent integer of 1-1000 separately, k is the independent integer of 1-18;
R is C
1-C
8alkane or fluor alkaline;
R
1for-CH
3or-CH
2cH
3or-(CH
2)
3cH
3;
R
2for-CH
2cH
2oH or-CH
2cHOHCH
3;
R
3for-CH
2cF
3or-CH
2cF
2cHFCF
3or-CH
2cF (CF
3) CFHCF (CF
3)
2or-CH
2cH
2(CF
2)
5cF
3;
R
4for
, wherein n is the independent integer of 20-300;
R
5, R
6, R
7, R
8, R
9be H or CH separately
3.
2., by a preparation method for (methyl) according to claim 1 acryloxy oligomeric silsesquioxane fluorine Si acrylate-urethane blood compatibility coating, it is characterized in that comprising following process:
(1) at temperature 10-50 DEG C, adding in methylene dichloride by (methyl) acryloxy oligomeric silsesquioxane fluorine Si acrylate or adding ethyl acetate and normal hexane is (1-9) in mass ratio: in 1 mixed solvent, be mixed with the solution that mass concentration is 5%-20%, mass ratio 1:(0.05-0.2 by (methyl) acryloxy oligomeric silsesquioxane fluorine Si acrylate in solution and solidifying agent) in solution, add solidifying agent, and in solution, add catalyzer by the mass ratio of (methyl) acryloxy oligomeric silsesquioxane fluorine Si acrylate and catalyzer 1000:1, described solidifying agent is one or both in hexamethylene diisocyanate and isophorone diisocyanate, described catalyzer is tin dilaurate diisobutyl tin,
(2) with the medical polyvinyl of dried and clean for base material, polymers soln step (1) obtained is the spray gun of 0.1-0.2mm by nozzle diameter, with the air pressure of 0.05-0.2MPa for power, apart from substrate surface 2-20cm, spraying 5-30min, obtaining thickness is coating between 10-200 μm, then through drying at room temperature 10-48h, obtains (methyl) acryloxy oligomeric silsesquioxane fluorine Si acrylate-urethane blood compatibility coating.
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| EP3149012B1 (en) * | 2014-05-30 | 2020-10-21 | Commonwealth Scientific and Industrial Research Organisation | Ice adhesion reducing prepolymers and polymers |
| 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 |
| CN110331458A (en) * | 2019-08-13 | 2019-10-15 | 湖南工业大学 | A kind of preparation method of the biomass-based fiber of high intensity |
| KR102291336B1 (en) * | 2020-09-08 | 2021-08-20 | 주식회사 에스와이테크 | Deck plate coated with inorganic resin for enhanced non-flammability and corrosion resistance |
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| EP1355963B1 (en) * | 2000-12-19 | 2006-04-12 | Bausch & Lomb Incorporated | Polymeric biomaterials containing silsesquioxane monomers |
| WO2011133847A2 (en) * | 2010-04-22 | 2011-10-27 | Syracuse University | Polyhedral oligomeric silsesquioxane polyurethanes |
| CN102277060A (en) * | 2011-08-10 | 2011-12-14 | 天津大学 | Hydrophobic ice-snow preventing coating material of fluorosilicone acrylate copolymer and preparation method of coating layer thereof |
| CN102604309A (en) * | 2012-03-07 | 2012-07-25 | 厦门大学 | Hydrophobic and oleophobic polymer film and preparing method thereof |
| CN102775567A (en) * | 2012-07-20 | 2012-11-14 | 天津大学 | POSS (polyhedral oligomeric silsesquioxane) contained polyacrylate-polysiloxane block copolymer and preparation method thereof |
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| EP1355963B1 (en) * | 2000-12-19 | 2006-04-12 | Bausch & Lomb Incorporated | Polymeric biomaterials containing silsesquioxane monomers |
| WO2011133847A2 (en) * | 2010-04-22 | 2011-10-27 | Syracuse University | Polyhedral oligomeric silsesquioxane polyurethanes |
| CN102277060A (en) * | 2011-08-10 | 2011-12-14 | 天津大学 | Hydrophobic ice-snow preventing coating material of fluorosilicone acrylate copolymer and preparation method of coating layer thereof |
| CN102604309A (en) * | 2012-03-07 | 2012-07-25 | 厦门大学 | Hydrophobic and oleophobic polymer film and preparing method thereof |
| CN102775567A (en) * | 2012-07-20 | 2012-11-14 | 天津大学 | POSS (polyhedral oligomeric silsesquioxane) contained polyacrylate-polysiloxane block copolymer and preparation method thereof |
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