CN1448144A - Coating liquid for improving anticoagulant performance of surface of biomedical device and coating method - Google Patents
Coating liquid for improving anticoagulant performance of surface of biomedical device and coating method Download PDFInfo
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- CN1448144A CN1448144A CN 03116747 CN03116747A CN1448144A CN 1448144 A CN1448144 A CN 1448144A CN 03116747 CN03116747 CN 03116747 CN 03116747 A CN03116747 A CN 03116747A CN 1448144 A CN1448144 A CN 1448144A
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Abstract
The present invention is the coating liquid and coating process for improving the surface anticoagulant performance of biomedicine device. The coating liquid consists of heparin quaternary ammonium salt composite prepared through the reaction between heparin and quaternary ammonium salt 0.1-30 wt%, hydrophobic polymer cellulose ester, polyurethane, polylactate or rosin ester 0.01-20 wt% and solvent in the balance amount. The composite coating forming process includes the following steps: adding polyacrylate or similar polymer with carboxyl group and hydroxyl group capable of cross-linked in 1-20 wt% into the coating liquid; coating biomedicine device with complicated structure; and curing at 30-100 deg.c to form the cross-linked heparin polymer coating. The coating has excellent anticoagulant performance and stability.
Description
Technical field
The present invention relates to a kind of coating liquid and coating that improves biomedical devices surface anticoagulant performance.
Background technology
The medical apparatus that contacts with blood, for example all kinds of artificial blood vessels, artificial heart, interposing catheter, guide wire, support etc. have been widely used in the modern medicine treatment.These devices are normally made with metal, pottery, polymeric material, and itself does not have anticoagulant characteristic.After blood contacts with it, can produce a series of physiological reaction, the activation of for example hematoblastic absorption and activation, complement, the activation of interior external source coagulation system etc. finally cause the formation of thrombosis.Therefore pass through the finishing to the medical apparatus of blood contact, improving its blood compatibility is that such installs the major issue in using.
Heparin is a kind of well-known anticoagulative substance, and it can reach anticoagulant effect by some step that stops in the blood coagulation system.But heparin is a water-soluble substances, and when directly being coated in material surface simply, heparin can rapidly disappear under environment for use, can't stable existence in apparatus surface, therefore do not have effective anticoagulant effect.
Summary of the invention
The purpose of this invention is to provide a kind of coating liquid and coating that improves biomedical devices surface anticoagulant performance.
The percentage by weight component that is used to improve the coating liquid of bio-medical material anticoagulant property is heparin quaternary ammonium compound 0.1-30%, hydrophobic polymer cellulose esters or polyurethane or polylactic acid or Colophonium fat 0.01-20%, and solvent supplies 100%.
The step of signal layer coating method of coating liquid that is used to improve the bio-medical material anticoagulant property is as follows:
1) adopts claims 1 described coating liquid, utilize spin coating, dip-coating, spraying method, the biomedical devices with complex shape structure is carried out coating modifying;
2) and at 30～100 ℃ solidify down, be 1-48 hour hardening time, forms the heparin polymer coating;
The step of composite coating method of coating liquid that is used to improve the bio-medical material anticoagulant property is as follows:
1) add the 1-20% acrylic acid esters co-polymer in claims 1 described coating liquid, its acrylic acid esters co-polymer is carboxyl and the hydroxyl that contains the crosslinkable reaction simultaneously;
2) utilize spin coating, dip-coating, spraying method, the biomedical devices with complex shape structure is carried out coating modifying;
3) and at 30～100 ℃ solidify down, assimilation time is 1-48 hour, forms crosslinked heparin polymer coating.
Advantage of the present invention:
1. the coating solution preparation is simple, and raw material is easy to get.
2. but coating can form stable coating in the biomedical devices with complex shape structure by the means of industrial realization such as spin coating, dip-coating and spraying.
3. the anticoagulation function of the coating of gained is good, and can keep long-time stable.
The specific embodiment
Having invented a kind of anticoagulant coatings liquid that improves biomedical devices surface anticoagulant performance forms.This coating liquid contain heparin quaternary ammonium compound and hydrophobic polymer.Wherein the heparin quaternary ammonium compound is to make by heparin and quaternary ammonium salt reaction.Hydrophobic polymer is cellulose esters or polyurethane or polylactic acid or Colophonium fat.The weight content of heparin quaternary ammonium compound in coating solution is 0.1-30%.The weight content of hydrophobic polymer in coating solution is 0.01-20%.Typical solvent comprises alcohol, ester, ketone, carboxylic acid, aromatic solvent, amide solvent.
The concrete preparation method of heparin quaternary ammonium compound is:
1) quaternary ammonium salt is dissolved in the mixed solvent of isopropyl alcohol and deionized water, is made into the solution that the quaternary ammonium salt weight content is 1-60%.Quaternary ammonium salt can be benzalkonium chloride, three (dodecyl methyl ammonium chloride), cetyl pyridinium chlorine, polyethylene benzyltrimethylammonium chloride
2) heparin sodium is dissolved in the deionized water, is made into the solution that weight content is 1-50%;
3) above-mentioned two kinds of solution are mixed, stir 30-60 second fast, obtain the suspension of white compound; The centrifugal white compound that obtains;
4) white compound reuse deionized water wash is centrifugal; Vacuum drying is to constant weight.The compound method of coating liquid,
Heparin quaternary amine complex and hydrophobic polymer be dissolved in single or mixed solvent in, form the coating liquid of transparent and homogeneous.Typical solvent comprises alcohol, ester, ketone, carboxylic acid, aromatic solvent, amide solvent etc.
The present invention adopts the polymer hybrid technology, by with the effectively blend of the hydrophobic polymer of coupling of heparin quaternary ammonium compound, form stabilization of polymer heparin composite coating.Invention at first with heparin and quaternary ammonium salt reaction, makes a kind of water-insoluble heparin complex.Typical quaternary ammonium salt comprises benzalkonium chloride, three (dodecyl methyl ammonium chloride), cetyl pyridinium chlorine, polyethylene benzyltrimethylammonium chloride etc.
By with the effectively blend of the hydrophobic polymer of coupling of heparin quaternary ammonium compound, form stabilization of polymer heparin composite coating, thereby reduce the speed that heparin discharges, effectively prolong the anticoagulation time of coating.Typical hydrophobic polymer comprises: cellulose esters, for example cellulose acetate, ethyl cellulose, celluloid, cellulose butyl acetate; Polyurethane; Polylactic acid.
Concrete coating liquid preparation steps is, be dissolved in various materials such as heparin quaternary amine complex single or mixed solvent in, form the coating liquid of transparent and homogeneous.Typical solvent comprises alcohol, ester, ketone, carboxylic acid, aromatic solvent, amide solvent etc.(with top one section repetition, the suggestion deletion)
But this coating liquid can directly be adopted the mode of industrial realization such as utilizing spin coating, dip-coating, spraying, and the biomedical devices with complex shape structure is carried out coating modifying, and solidifies down at 30～100 ℃, and be 1-48 hour hardening time, forms the heparin polymer coating.Also can add 1-20% and contain the carboxyl of crosslinkable reaction and the acrylic acid esters co-polymer of hydroxyl simultaneously.But utilize the mode of industrial realization such as spin coating, dip-coating, spraying, the biomedical devices with complex shape structure is carried out coating modifying.And 30～200 ℃ of curing down, be 1-48 hour hardening time, forms crosslinked heparin polymer coating.Embodiment 1: the preparation of heparin-benzalkonium chloride complex
(1) benzalkonium chloride 1.7g is dissolved in the 6g isopropyl alcohol, then with deionized water 4g dilution;
(2) heparin sodium 1g is dissolved in the 10g deionized water;
(3) above-mentioned two kinds of solution are mixed, stirred fast 30 seconds, obtain the suspension of white compound;
(4) with the centrifugal suspension of centrifuge, obtaining white compound is heparin-benzalkonium chloride complex; Deionised water, with heparin-benzalkonium chloride complex lyophilizing to constant weight.Embodiment 2: the preparation of heparin-three (dodecyl methyl ammonium chloride) complex
(1) three (dodecyl methyl ammonium chloride) 3.4g is dissolved in the 6g isopropyl alcohol, then with deionized water 4g dilution;
(2) heparin sodium 4g is dissolved in the 10g deionized water;
(3) above-mentioned two kinds of solution are mixed, stirred fast 30 seconds, obtain the suspension of white compound;
(4) with the centrifugal suspension of centrifuge, obtaining white compound is heparin-three (dodecyl methyl ammonium chloride) complex;
(5) use deionized water wash, with heparin-three (dodecyl methyl ammonium chloride) complex lyophilizing to constant weight.Embodiment 3: the preparation of heparin-cetyl pyridinium chlorine complex
(6) cetyl pyridinium chlorine 5.7g is dissolved in the 6g isopropyl alcohol, then with deionized water 4g dilution;
(7) heparin sodium 3g is dissolved in the 10g deionized water;
(8) above-mentioned two kinds of solution are mixed, stirred fast 30 seconds, obtain the suspension of white compound;
(9) with the centrifugal suspension of centrifuge, obtaining white compound is heparin-three (dodecyl methyl ammonium chloride) complex;
(5) use deionized water wash, with heparin-three (dodecyl methyl ammonium chloride) complex lyophilizing to constant weight.
Embodiment 4:
With application example 1 described heparin quaternary ammonium compound 0.33g, hydrophobic polymer cellulose acetate 0.16g, rosin ester 0.05g are dissolved in dimethyl acetylamide 5.0g, isopropyl alcohol 3.7g, 3-ethoxy ethyl acrylate 0.6g, ethyl acetate 0.1g is in the mixed solvent that butyl acetate 0.5g forms.Dip coating is applied to coating liquid on the polyurethane small pieces, after the drying, at room temperature soaked 30 days with the PBS buffer under the room temperature, test is multiple calcification clotting time (RT) result do not coagulate for blood plasma.
The multiple calcification clotting time (RT) of test, concrete steps are: at first base material is cut into the small pieces of 5mm * 30mm, scribbles coating of the present invention on it; Place 10mm * 75mm in vitro above-mentioned small pieces and 1ml fresh plasma, test tube places 37 ℃ of water-baths, balance 3-5 minute; Be injected into 1ml0.25M CaCl then
2Solution picks up counting, and observes clotting of plasma required time and is RT.The typical RT that is not coated with the small pieces of coating liquid of the present invention is 2-8 minute.
Embodiment 5:
With application example 1 heparin quaternary ammonium compound 0.4g, hydrophobic polymer cellulose acetate 0.2g, rosin ester 0.05g are dissolved in N '-N dimethyl formamide 5.0g, isopropyl alcohol 3.7g 3-ethoxy ethyl acrylate 0.7g, ethyl acetate 0.1g is in the mixed solvent that butyl acetate 0.5g forms.Coating liquid employing spin coating mode is applied on the polyurethane small pieces, and 60 ℃ drying is after 30 minutes down, and with Tris-HCl (PH=7.4) buffer immersion 40 days, RT the results are shown in following table under 37 ℃.
Embodiment 6:
| The 10th day | The 20th day | The 30th day | The 35th day | The 40th day | |
| PCT | Do not coagulate | Do not coagulate | Do not coagulate | ＞1 hour | ＞10 minutes |
With application example 2 described heparin quaternary ammonium compound 3.3g, hydrophobic polymer cellulose acetate 1.6g, polyurethane 0.5g are dissolved in dimethyl acetylamide 5.0g, isopropyl alcohol 3.7g, 3-ethoxy ethyl acrylate 0.6g, ethyl acetate 0.1g is in the mixed solvent that butyl acetate 0.5g forms.Adopt spraying process that coating liquid is applied on the 316L rustless steel porous support, after the drying, at room temperature soaked 30 days under the room temperature with the PBS buffer, the multiple calcification clotting time (RT) of test, the result does not coagulate for blood plasma.Embodiment 7: the preparation of crosslinkable acrylic copolymer is with acrylic acid 10 grams, butyl acrylate 15 grams, methymethacrylate 20 grams, hydroxyethyl methacrylate second fat 5 grams and initiator azo-bis-isobutyl cyanide 0.24 gram are dissolved in 30 gram isopropyl alcohols and the 45 gram ethylene glycol mixed solvents, reacted 6 hours down at 64-66 ℃, water precipitating is analysed, wash white acrylic copolymer
Embodiment 8:
With application example 3 described heparin quaternary ammonium compound 1.3g, hydrophobic polymer ethyl cellulose 1.6g, polylactic acid 0.6g, application example 7 described crosslinkable acrylic copolymer 1.6 grams, be dissolved in dimethyl acetylamide 5.0g, isopropyl alcohol 3.7g, 3-ethoxy ethyl acrylate 0.6g, ethyl acetate 0.1g is in the mixed solvent that butyl acetate 0.5g forms.Dip coating is applied to coating liquid on the polyurethane small pieces, under the room temperature after the drying,, obtains crosslinked heparin polymer coating in 150 ℃ of crosslinking curings 6 hours.The polyurethane small pieces of this coating modifying at room temperature soaked 30 days with the PBS buffer, and test is multiple calcification clotting time (RT) result do not coagulate for blood plasma.
Claims (5)
1. coating liquid that is used to improve the bio-medical material anticoagulant property, it is characterized in that: its percentage by weight component is heparin quaternary ammonium compound 0.1-30%, hydrophobic polymer cellulose esters or polyurethane or polylactic acid or Colophonium fat 0.01-20%, solvent supplies 100%.
2. a kind of coating liquid that is used to improve the bio-medical material anticoagulant property according to claim 1 is characterized in that said solvent is alcohol, ester, ketone, carboxylic acid, aromatic solvent, amide solvent.
3. a kind of coating liquid that is used to improve the bio-medical material anticoagulant property according to claim 1 is characterized in that the step of said heparin quaternary ammonium compound preparation method is as follows:
1) quaternary ammonium salt is dissolved in the mixed solvent of isopropyl alcohol and deionized water, is made into the solution that the quaternary ammonium salt weight content is 1-60%.Quaternary ammonium salt can be benzalkonium chloride, three (dodecyl methyl ammonium chloride), cetyl pyridinium chlorine, polyethylene benzyltrimethylammonium chloride;
2) heparin sodium is dissolved in the deionized water, is made into the solution that weight content is 1-50%;
3) above-mentioned two kinds of solution are mixed, stir 30-60 second fast, obtain the suspension of white compound;
4) with the centrifugal suspension of centrifuge, obtain white compound, the reuse deionized water wash, centrifugal again; With heparin quaternary ammonium compound vacuum drying or lyophilizing to constant weight.
4. signal layer coating method that is used to improve the coating liquid of bio-medical material anticoagulant property, its step is as follows:
1) adopts claims 1 described coating liquid, utilize spin coating, dip-coating, spraying method, the biomedical devices with complex shape structure is carried out coating modifying;
2) and at 30～100 ℃ solidify down, be 1-48 hour hardening time, forms the heparin polymer coating;
5. composite coating method that is used to improve the coating liquid of bio-medical material anticoagulant property, its step is as follows:
1) add the 1-20% acrylic acid esters co-polymer in claims 1 described coating liquid, its acrylic acid esters co-polymer is carboxyl and the hydroxyl that contains the crosslinkable reaction simultaneously;
2) utilize spin coating, dip-coating, spraying method, the biomedical devices with complex shape structure is carried out coating modifying;
3) and at 30～100 ℃ solidify down, be 1-48 hour hardening time, forms crosslinked heparin polymer coating.
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100335506C (en) * | 2004-05-20 | 2007-09-05 | 汕头市金丰医疗器械科技有限公司 | Heparin compound, and its preparing method and use |
| CN100345601C (en) * | 2005-07-12 | 2007-10-31 | 浙江大学 | Method for improving biocompatibility of biological medical stainless steel device |
| CN100371033C (en) * | 2005-12-16 | 2008-02-27 | 南京师范大学 | Polymer/graphite oxide anticoagulant nano composite material and preparation method thereof |
| CN102127204A (en) * | 2011-01-28 | 2011-07-20 | 苏州大学 | Preparation method of novel antibiotic anticoagulant polyurethane material |
| CN102344521A (en) * | 2011-07-12 | 2012-02-08 | 天津市塑料研究所 | Polymethyl polyglycol methacrylate containing sorbitol ester mononitrate structure as well as preparation method and use method thereof |
| CN102671240A (en) * | 2012-05-17 | 2012-09-19 | 浙江大学 | Method for preparing multifunctional antibacterial chitosan stable gel coat |
| CN102671239A (en) * | 2012-05-03 | 2012-09-19 | 浙江大学 | Method for preparing broad-spectrum antibacterial effect chitosan nano composite gel coating |
| CN101146558B (en) * | 2005-03-03 | 2012-11-07 | 科维蒂恩股份公司 | Medical treatment device and its making method |
| WO2015188716A1 (en) * | 2014-06-09 | 2015-12-17 | 上海微创医疗器械（集团）有限公司 | Anticoagulation coating and applying method therefor |
| CN105194742A (en) * | 2015-09-17 | 2015-12-30 | 协和同仁科技（天津）有限责任公司 | Anticoagulation method for surface of medical high molecular material or product |
| CN106710416A (en) * | 2015-07-30 | 2017-05-24 | 上海微创医疗器械（集团）有限公司 | Vessel model, making method thereof, and device for making vessel model |
| CN107456611A (en) * | 2017-07-23 | 2017-12-12 | 北京化工大学 | A kind of preparation method of anticoagulation composite coating |
| CN109172877A (en) * | 2018-08-28 | 2019-01-11 | 杭州创元医疗科技有限公司 | A kind of bionical anticoagulation lotion and preparation method thereof and application method |
| CN111356911A (en) * | 2017-11-15 | 2020-06-30 | 雷迪奥米特医学公司 | Platelet activation free heparin-based blood sampler |
| CN113842507A (en) * | 2021-07-19 | 2021-12-28 | 浙江大学 | Polyelectrolyte hydrogel coating with super-strong substrate adhesion performance and preparation method thereof |
| CN114957564A (en) * | 2013-04-26 | 2022-08-30 | 生物相互作用有限公司 | Bioactive coating |
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- 2003-04-28 CN CN 03116747 patent/CN1448144A/en active Pending
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100335506C (en) * | 2004-05-20 | 2007-09-05 | 汕头市金丰医疗器械科技有限公司 | Heparin compound, and its preparing method and use |
| CN101146558B (en) * | 2005-03-03 | 2012-11-07 | 科维蒂恩股份公司 | Medical treatment device and its making method |
| CN100345601C (en) * | 2005-07-12 | 2007-10-31 | 浙江大学 | Method for improving biocompatibility of biological medical stainless steel device |
| CN100371033C (en) * | 2005-12-16 | 2008-02-27 | 南京师范大学 | Polymer/graphite oxide anticoagulant nano composite material and preparation method thereof |
| CN102127204A (en) * | 2011-01-28 | 2011-07-20 | 苏州大学 | Preparation method of novel antibiotic anticoagulant polyurethane material |
| CN102344521A (en) * | 2011-07-12 | 2012-02-08 | 天津市塑料研究所 | Polymethyl polyglycol methacrylate containing sorbitol ester mononitrate structure as well as preparation method and use method thereof |
| CN102671239A (en) * | 2012-05-03 | 2012-09-19 | 浙江大学 | Method for preparing broad-spectrum antibacterial effect chitosan nano composite gel coating |
| CN102671240A (en) * | 2012-05-17 | 2012-09-19 | 浙江大学 | Method for preparing multifunctional antibacterial chitosan stable gel coat |
| CN114957564A (en) * | 2013-04-26 | 2022-08-30 | 生物相互作用有限公司 | Bioactive coating |
| WO2015188716A1 (en) * | 2014-06-09 | 2015-12-17 | 上海微创医疗器械（集团）有限公司 | Anticoagulation coating and applying method therefor |
| CN106710416A (en) * | 2015-07-30 | 2017-05-24 | 上海微创医疗器械（集团）有限公司 | Vessel model, making method thereof, and device for making vessel model |
| CN105194742A (en) * | 2015-09-17 | 2015-12-30 | 协和同仁科技（天津）有限责任公司 | Anticoagulation method for surface of medical high molecular material or product |
| CN107456611A (en) * | 2017-07-23 | 2017-12-12 | 北京化工大学 | A kind of preparation method of anticoagulation composite coating |
| CN111356911A (en) * | 2017-11-15 | 2020-06-30 | 雷迪奥米特医学公司 | Platelet activation free heparin-based blood sampler |
| CN109172877A (en) * | 2018-08-28 | 2019-01-11 | 杭州创元医疗科技有限公司 | A kind of bionical anticoagulation lotion and preparation method thereof and application method |
| CN109172877B (en) * | 2018-08-28 | 2021-07-13 | 杭州忻元医疗科技合伙企业(有限合伙) | Bionic anticoagulant emulsion and preparation method and using method thereof |
| CN113842507A (en) * | 2021-07-19 | 2021-12-28 | 浙江大学 | Polyelectrolyte hydrogel coating with super-strong substrate adhesion performance and preparation method thereof |
| CN113842507B (en) * | 2021-07-19 | 2022-04-29 | 浙江大学 | Polyelectrolyte hydrogel coating with super-strong substrate adhesion performance and preparation method thereof |
| WO2023000713A1 (en) * | 2021-07-19 | 2023-01-26 | 浙江大学 | Strong-adhesive polyelectrolyte hydrogel coating and preparation method therefor |
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