WO2023125100A1 - 一种材料表面改性的方法和基于该方法得到的表面改性的材料 - Google Patents

一种材料表面改性的方法和基于该方法得到的表面改性的材料 Download PDF

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WO2023125100A1
WO2023125100A1 PCT/CN2022/139960 CN2022139960W WO2023125100A1 WO 2023125100 A1 WO2023125100 A1 WO 2023125100A1 CN 2022139960 W CN2022139960 W CN 2022139960W WO 2023125100 A1 WO2023125100 A1 WO 2023125100A1
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substrate
monomer
solution
mmol
monomers
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French (fr)
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唐增超
雷杰华
黄佳磊
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江苏百赛飞生物科技有限公司
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    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12Chemical modification
    • C08J7/123Treatment by wave energy or particle radiation
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    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L29/00Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
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    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
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    • C08L27/02Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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    • C08J2327/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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    • C08J2383/00Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
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    • C08J2425/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
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    • C08J2433/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/14Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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    • C08J2433/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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    • C08J2439/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
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    • C08J2439/04Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08J2439/06Homopolymers or copolymers of N-vinyl-pyrrolidones

Definitions

  • the invention relates to a material surface modification method and a surface modified material obtained based on the method, belonging to the field of material surface modification or modification.
  • the modification (modification) of the material surface can usually introduce or improve different functions of the material, such as improving hydrophilic function, lubricating function, antibacterial function, antifouling function, anticoagulant function, anti-protein adsorption function, etc.
  • various methods have been used to functionalize the surface of materials, mainly through surface grafting of polymers or coating of functional coatings.
  • the traditional modification method of grafting polymer on the surface of the material usually needs to modify the initiator on the surface of the material first, and then initiate the polymerization in the solution.
  • the process takes at least several hours or even more than ten hours.
  • Disadvantages such as complexity, high risk, and low productivity; in addition, it is not universal for substrates that are difficult to modify and have complex shapes.
  • Another way of modifying the surface grafted polymer needs to be modified first to introduce some reactive groups, such as polyphenols or PU base coats, which also involve some of the above-mentioned problems.
  • Another method of directly applying the coating usually has the problem that the coating is not firm and easy to fall off due to the lack of bonding force with the surface.
  • Microwave polymerization is a new polymerization method, which has the advantages of fast heating rate, fast reaction rate, and high monomer conversion rate.
  • the polymerization can be completed in a few minutes, while the traditional solution polymerization may take several hours or even dozens of hours. .
  • the microwave polymerization method generates heat through the self-motion of the monomer molecules, and completes the polymerization reaction more uniformly and efficiently without reacting at high temperature.
  • microwave polymerization in solution which is mainly used in the field of chemical synthesis, but less used in the field of material surface modification.
  • the prior art is based on firstly applying an initiator on the surface of the material, and then using microwave radiation to carry out subsequent polymerization.
  • CA2252877A1 discloses a graft polymerization method for modifying the surface of an object, wherein the object is coated with an initiator and at least one compound selected from hydrophilic polymers, hydrophobic polymers, biofunctional compounds or combinations thereof, and infrared radiation is used , microwave radiation, or high-pressure polymerization to modify the surface of a material to give it desired properties.
  • this method requires the use of special microwave grafting initiators, complicated steps, special radiation facilities and expensive gamma ray sources.
  • the grafting of initiators is also limited to different substrate surfaces, which is not universal in industrial production.
  • Literature 1 Haensch, C.; Erdmenger, T.; Fijten, M.W.; Hoeppener, S.; Schubert, U.S., Fast surface modification by microwave assisted click reactions on silicon substrates, Langmuir 2009, 25(14), 8019-24.
  • Literature 3 Lee, M.; Lee, S.H.; Oh, I.K.; Lee, H., Microwave-Accelerated Rapid, Chemical Oxidant-Free, Material-Independent Surface Chemistry of Poly(dopamine), Small 2017, 13(4).
  • the present invention relates to the following technical solutions.
  • [1] a kind of method for material surface modification, it comprises the following steps:
  • reaction solution (1) dissolving, suspending or dispersing the polymerized monomer, coupling agent and initiator in a solvent to prepare a reaction solution;
  • step (1) The method according to [1], wherein the polymerized monomers in step (1) are selected from (meth)acrylamide monomers, cationic monomers, heparin monomers, heparin-like monomers One or more of monomer, sodium styrene sulfonate, N-vinylpyrrolidone, (meth)acrylic monomer, (meth)acrylate monomer, fibrinolytic monomer, zwitterionic monomer kind.
  • step (1) The method according to [1] or [2], wherein the coupling agent in step (1) is selected from one or more of silane coupling agents and titanate coupling agents.
  • step (1) The method according to [1] or [2], wherein the initiator in step (1) is selected from one or more of azo initiators and peroxide initiators.
  • step (2) The method according to [1] or [2], wherein the substrate in step (2) is preliminarily subjected to one or more of plasma treatment, corona treatment, radiation treatment, ozone treatment, and chemical reagent treatment Multiple.
  • step (3) the microwave radiation is carried out for 0.5 ⁇ 30min, the temperature of microwave radiation polymerization is 50 ⁇ 200 °C, and the power of microwave radiation is 50 ⁇ 2500w.
  • the present invention realizes the modification of the surface of the material by using a microwave polymerization method and a one-step method.
  • the polymerization reaction of the present invention is rapid (the polymerization reaction can be completed within 5 minutes), which is different from the existing traditional coating coating method, which can greatly increase the output value and output, and the polymerization monomer is well grafted on the material surface to realize the material surface
  • the effect of modification; the solvent used is non-toxic and harmless; the types of substrates available for use are wide, and the processing and molding of the final material is not limited; the invention is easy to operate, the preparation method and equipment are simple, the production cost is low, and it is easy to Industrialization; the method of the present invention can be widely used in various fields, and is particularly suitable for modification of surfaces such as medical devices (such as pipes, guide wires, etc.), polymer materials, metal substrates, inorganic materials, etc., thereby changing the affinity of the material surface. / Hydrophobicity, lubricity, increased biological functionality, anti-protein adsorption performance, antibacterial and anticoagulant properties, etc.
  • FIG. 1 is an infrared image of a substrate obtained by microwave polymerization on a silicone rubber (polydimethylsiloxane, PDMS) substrate in Example 1 at different polymerization times.
  • PDMS polydimethylsiloxane
  • Fig. 2 is that embodiment two, embodiment six, embodiment ten, embodiment fourteen, embodiment eighteen and embodiment twenty-two are obtained by microwave polymerization on a silicone rubber (polydimethylsiloxane, PDMS) substrate The infrared image of the base material and the PDMS base material (comparative example 3) that did not carry out microwave polymerization as a control.
  • a silicone rubber polydimethylsiloxane, PDMS
  • Fig. 3 is the base material obtained by microwave polymerization on the nylon elastomer (Pebax) base material of embodiment 3, embodiment 7, embodiment 11, embodiment 15, embodiment 19, embodiment 23 and as contrast Infrared image of the Pebax substrate (comparative example 4) that was not subjected to microwave polymerization.
  • Fig. 4 is the base material that embodiment 4, embodiment 8, embodiment 12, embodiment 16, embodiment 20, embodiment 24 obtain by microwave polymerization on thermoplastic polyurethane (TPU) base material and as contrast Infrared image of the TPU substrate (comparative example 5) not subjected to microwave polymerization.
  • TPU thermoplastic polyurethane
  • Fig. 5 is the base material that embodiment five, embodiment nine, embodiment thirteen, embodiment seventeen, embodiment twenty-one, embodiment twenty-five obtain by microwave polymerization on polyvinyl chloride (PVC) base material and as Infrared image of a control PVC substrate (comparative example 6) that has not undergone microwave polymerization.
  • PVC polyvinyl chloride
  • Fig. 6 is a graph showing the bactericidal effect of the surface coating of the microcatheter measured by the flat plate coating method of Example 26 and the unmodified stainless steel material (comparative example 7).
  • Example 7 is a graph showing the thrombolytic ability of the surface of Examples 22 to 25 and an unmodified TPU substrate (Comparative Example 5).
  • the present invention relates to a kind of method of material surface modification, it comprises the following steps:
  • reaction solution (1) dissolving, suspending or dispersing the polymerized monomer, coupling agent and initiator in a solvent to prepare a reaction solution;
  • the present invention is described step by step below.
  • the polymerizable monomer involved in the microwave polymerization method of the present invention is not particularly limited as long as it has a double bond capable of polymerizing.
  • the polymerizable monomers in step (1) can be selected from, for example, (meth)acrylamide monomers, cationic monomers, heparin monomers, heparan monomers, sodium styrene sulfonate, N-vinylpyrrolidone , one or more of (meth)acrylic monomers, (meth)acrylate monomers, cellosolve monomers, and zwitterionic monomers.
  • Examples of (meth)acrylamide monomers include methacrylamide, acrylamide, methoxymethylmethacrylamide, methoxymethylacrylamide, n-butoxymethylmethacrylamide Amide, n-butoxymethacrylamide, isobutoxymethylmethacrylamide, isobutoxymethacrylamide, tert-butylaminopropylmethacrylamide, tert-butylaminopropylacrylamide , dimethylaminopropyl methacrylamide and dimethylaminopropyl acrylamide and so on.
  • quaternary ammonium salt monomers such as diallylamine, dimethyl diallyl ammonium chloride, diethyl diallyl ammonium chloride, (methyl) Acryloyloxyethyltrimethylammonium chloride, acryloyloxyethyldimethylbenzylammonium chloride, 3-[[2-(methacryloyloxy)ethyl]dimethylammonio]propane- 1-sulfonate, etc.; guanidine monomers such as guanidine, metformin, diphenylguanidine, tetramethylguanidine, etc.; quaternary phosphorus salt monomers such as triphenylphosphine, tetraphenylphosphine bromide, methyltriphenyl Phosphine bromide, ethyltriphenylphosphine bromide, benzyltriphenylphosphine chloride, etc.;
  • heparin-like monomers and heparin-like monomers examples include unfractionated heparin (such as mucopolysaccharide sulfate alternately composed of D-glucosamine, L-iduronic acid, and D-glucuronic acid), low-molecular-weight Heparin (such as enoxaparin, dalteparin, nadroparin, etc.), heparin derivatives (such as fondaparinux sodium), heparin analogs (such as danaparinux sodium), and the like.
  • unfractionated heparin such as mucopolysaccharide sulfate alternately composed of D-glucosamine, L-iduronic acid, and D-glucuronic acid
  • low-molecular-weight Heparin such as enoxaparin, dalteparin, nadroparin, etc.
  • heparin derivatives such as fondaparinux sodium
  • heparin analogs such as
  • Examples of (meth)acrylic monomers and (meth)acrylate monomers include (meth)acrylic acid, acrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, Methyl acrylate, ethyl acrylate, n-butyl acrylate, etc.
  • fibrinolytic monomer examples include vinyl lysine monomer and the like.
  • zwitterionic monomers examples include phosphorylcholine, carboxybetaine, sulfobetaine and the like.
  • the coupling agent described in step (1) is not particularly limited.
  • the coupling agent is a coupling agent with a double bond, which can be selected from silane coupling agents with double bonds, One or more of titanate coupling agents.
  • silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethyl Oxysilane, Anilinomethyltriethoxysilane, Anilinomethyltrimethoxysilane, (3-Mercaptopropyl)trimethoxysilane, 3-Isocyanatotrimethoxysilane, 3-Isocyanatotriethyl Oxysilane, Epoxytrimethoxysilane, Epoxytriethoxysilane, etc.
  • titanate coupling agents include isopropyl tris(dioctyl pyrophosphate acyloxy) titanate, monoalkoxy unsaturated fatty acid titanate, isopropyl dioleate acyloxy (dioctylphosphonyloxy)titanate, isopropyltris(dioctylphosphonyloxy)titanate, and the like.
  • the initiator in step (1) is not particularly limited, and may be selected from one or more of azo initiators and peroxide initiators.
  • the initiator can be selected from azodicyanovaleric acid, cyclohexanone peroxide, benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, ammonium persulfate, azobisiso One or more of butamidine hydrochloride.
  • the consumptions of the polymerized monomer, the coupling agent and the initiator in the step (1) are respectively: the molar ratio of the polymerized monomer to the coupling agent is (1-100): 1, so The molar ratio of the polymerizable monomer to the initiator is (10-1000):1. If the ratio of the polymerized monomer to the coupling agent is too small, the grafting amount of the polymerized monomer is small, and the surface coating with the desired function cannot be obtained. If the ratio of the polymerized monomer to the coupling agent is too large, the The lack of bonding between the coupling agent and the surface of the substrate results in weak bonding between the coating and the surface of the substrate.
  • the ratio of the polymerized monomer to the initiator is too small, the molecular weight of the polymer surface is limited; if the ratio of the polymerized monomer to the initiator is too large, the graft density on the polymer surface may decrease.
  • the concentration of the polymerized monomer in the reaction solution in step (1) is 0.001-10 g/ml, preferably 0.005-0.5 g/ml. If the concentration of the polymerized monomer is too small, the graft density on the surface of the polymer will decrease, and if the concentration of the polymerized monomer is too high, an excessively thick gel layer will be formed on the surface of the polymer.
  • the solvent used in step (1) is not particularly limited, for example, water or organic solvents such as methanol, ethanol, acetone, methyl ethyl ketone, isopropanol and the like can be used.
  • the step (2) of the present invention involves using the reaction solution obtained in the step (1) to contact the substrate.
  • the substrate of the present invention is not particularly limited, for example, silicone rubber substrates such as polydimethylsiloxane (PDMS) substrates, nylon elastomer (Pebax) substrates, thermoplastic polyurethane (TPU) substrates, polyvinyl chloride substrates, etc. (PVC) substrates, polyolefin substrates, polyester substrates and other polymer substrates can also be inorganic materials such as ceramic materials and glass materials, or metal materials such as stainless steel materials, nickel-titanium alloys, and copper.
  • PDMS polydimethylsiloxane
  • TePU thermoplastic polyurethane
  • PVC polyvinyl chloride substrates
  • polyester substrates and other polymer substrates can also be inorganic materials such as ceramic materials and glass materials, or metal materials such as stainless steel materials, nickel-titanium alloys, and copper.
  • the substrate is preferably pre-treated with one or more of plasma treatment, radiation treatment (such as ultraviolet radiation, ray radiation), ozone treatment, and chemical reagent treatment.
  • plasma treatment such as ultraviolet radiation, ray radiation
  • radiation treatment such as ultraviolet radiation, ray radiation
  • ozone treatment ozone treatment
  • chemical reagent treatment can adopt those conventionally used, for example, can adopt Plasma technology to clean the surface of the substrate to remove the release agent and additives on the surface of the substrate; use hydrochloric acid, nitric acid, etc. to acidify the surface of the substrate and/or use sodium hydroxide, potassium hydroxide, etc. to treat the surface of the substrate Alkali treatment is carried out to achieve the purpose of cleaning the surface of the substrate.
  • known microwave equipment can be used to irradiate the reaction solution on the surface of the substrate with microwaves. Through microwave radiation, the polymerized monomers, the polymerized monomers and the coupling agent, and the coupling agent and the surface of the substrate can all be connected.
  • the microwave radiation is carried out for 0.5-30 min, preferably 1-20 min, the temperature of the microwave radiation is 50-200°C, preferably 50-100°C, and the power of the microwave radiation is 50-2500w, preferably 500-1500w . If the microwave radiation time is short, the polymerization reaction efficiency may be low and the degree of grafting is not high; if the microwave radiation time, temperature or power are too large, the substrate may be damaged to a certain extent.
  • the temperature at which polymerization by microwave radiation refers to the temperature at which polymerization by microwave radiation actually occurs.
  • the invention also relates to surface-modified materials prepared by the method according to the invention.
  • the surface-modified material prepared by the method of the invention can be widely used in various fields, especially in the field of medical devices.
  • NVP 1-vinyl-2-pyrrolidone
  • TAC Methacryloyloxyethyltrimethylammonium Chloride
  • Example 1 studies the results of microwave polymerization under different reaction times in the present invention. It can be seen from Figure 1 that there are strong absorption peaks in the infrared diagram at a reaction time of more than 60s, which shows that after microwave radiation, graft polymerization has occurred between silicone rubber, MEDSA and vinyltrimethoxysilane reaction, MEDSA successfully modified the surface of silicone rubber.
  • embodiment two changed the consumption and the reaction time of vinyltrimethoxysilane, MEDSA and ACVA, and the result shows that graft polymerization reaction has taken place between silicone rubber, MEDSA and vinyltrimethoxysilane, MEDSA successfully modified the surface of silicone rubber (Fig. 2).
  • Comparative Example 1 the ratio of polymerized monomer to coupling agent was 0.5:1, which would lead to insufficient grafting amount of polymerized monomer.
  • the ratio of initiator to polymerized monomer is 1:1, which also leads to insufficient grafting amount of monomer.
  • the fibrinogen was labeled with 125 I by the iodine chloride (ICl) method, and the fibrinogen was passed through an AG1-X4 anion exchange resin column to remove free iodine.
  • the labeled protein is added to platelet-free plasma at a concentration approximately 10% of the plasminogen concentration in normal plasma. Take the substrate and put it into the above protein solution for 3h incubation, rinse it with phosphate buffer solution three times, 10min each time, blot it dry with filter paper, transfer it to a clean tube, and test its radioactivity with an automatic gamma particle counter. The amount of protein adsorption is calculated as the mass per unit area.
  • Example 7 Use the friction testing machine (model FW-01) of Jiangsu Best Biotechnology Co., Ltd. to test the friction of different sample catheters under the action of 300g holding force and increase the speed by 1cm/s to judge the lubricity of the coating.
  • the products of Example 7 and Comparative Example 1 were placed in a clip-type friction tester to test the lubricating performance, and the results are shown in Table 2.
  • Example 27 proves that the surface modification can also be completed without pretreatment of the substrate, and the water contact angle of the unmodified Pebax substrate under normal conditions is reduced from 102 to about 72.
  • Example 26 and Comparative Example 7 utilize the plate coating method to determine the bactericidal effect of the microcatheter surface coating. It can be seen from Figure 6 that the bacteria collected from the microwave-modified substrate were basically dead, and no colony was formed, while a large number of colonies formed on the unmodified substrate, and the antibacterial effect was poor.
  • FIG. 7 shows the thrombolytic ability of the surface of Examples 22 to 25 and the unmodified TPU substrate (Comparative Example 5). With time, the absorbance gradually increased to the maximum value, which indicated that the thrombus was completely formed during this period. After the thrombus is completely formed, the absorbance of various substrates after microwave surface modification gradually decreases, which proves that the generated thrombus is being dissolved until the thrombus is completely dissolved and the absorbance returns to the initial value. This proves that after microwave modification, the surface of the substrate has a certain ability of thrombolysis and anticoagulation.

Abstract

本发明涉及一种材料表面改性的方法和基于该方法得到的表面改性的材料。本发明的方法包括以下步骤: (1)将聚合单体、偶联剂和引发剂溶解、悬浮或分散在溶剂中制得反应液;(2)将基材与所述反应液接触;(3)经微波辐射使基材表面的反应液进行聚合,得到表面改性的基材。通过本发明的方法,聚合单体可以成功地改性材料表面,从而改变材料表面的亲/疏水性、润滑性,增加生物功能性、抗蛋白吸附性能、抗菌性和抗凝性等。

Description

一种材料表面改性的方法和基于该方法得到的表面改性的材料 技术领域
本发明涉及一种材料表面改性的方法和基于该方法得到的表面改性的材料,属于材料表面改性或修饰领域。
背景技术
对材料表面的修饰(改性)通常能够为材料带来不同功能的引入或提升,例如提升亲水功能、润滑功能、抗菌功能、防污功能、抗凝血功能、抗蛋白吸附功能等。目前已经通过各种方法对材料表面进行功能化的修饰,主要通过表面接枝聚合物或者涂覆功能性涂层来实现。
传统的材料表面接枝聚合物的改性方式通常需要先在材料表面修饰引发剂,然后在溶液中引发聚合,过程至少需要几小时甚至十几小时,在实际工艺生产中存在涉及多步骤、工艺复杂、危险性高、产能低等劣势;另外,对于一些难以修饰及复杂形状的基材来说,并不具有普适性。另一种表面接枝聚合物的改性方式需要先通过底层修饰,引入一些具有反应活性的基团,例如多酚类或者PU类的底涂层,这就同样涉及上述的一些问题。另一种直接涂覆涂层的方法由于缺少与表面的结合力,通常具有涂层不牢固、易于脱落的问题。
微波聚合是一种新的聚合方式,其具有加热速率快,反应速率快,单体转化率高等优势,在几分钟内即可完成聚合,而传统的溶液聚合可能需要几个小时甚至几十小时。微波聚合方法通过单体分子的自身运动产生热,更均匀高效地完成聚合反应,不需要在高温下反应。
目前,微波的利用主要是通过溶液中的微波聚合,其集中应用在化学合成领域,而较少应用于材料表面修饰领域。而在少量的材料表面修饰方面,现有技术都是基于先在材料表面修饰上引发剂后,再利用微波辐射的方式进行后续聚合。
CA2252877A1公开了一种改性物体表面的接枝聚合方法,其中用引发剂和至少一种选自亲水聚合物、疏水聚合物、生物功能化合物或其组合的化合物涂覆物体,并且采用红外辐射、微波辐射或高压聚合来改性材料表面以赋予其所需的特性。但是该方法需要采用特殊的微波接枝引发剂,步骤复杂并且需要使用特殊的辐射设施和昂贵的伽马射线源。同时引发剂的接枝也受限于不同的基材表面,在工业生产中不具有普适性。
文献1中,Schubert等人在微波辐照下,利用CuAAC成功地将具有乙炔官能团的低摩尔质量分子(炔丙醇)和高摩尔质量分子(聚(2-乙基-2-噁唑啉))偶联到叠氮化硅基材表面。(反应条件:50w,75-120℃,5-45min)
文献2中,Cai等人首先将三甲基锗(TMG)基团保护的炔基链光接枝到活化的硅基材表面,形成“可点击”的单分子层。在微波辐照下基于铜催化的“点击”化学,将叠氮化低聚环氧乙烷(OEG)偶联到硅基材表面。其原理也是先接枝引发剂后微波辐照聚合。
文献3中,Lee等人提出微波辅助涂层工艺(Microwave-Assisted Coating process,MAC),证明了 微波辐射可以显著地加速多巴胺(PDA)的涂层速度,并提出机理:微波产生自由基以及自由基参与氧化的协同作用。但是该文献不涉及聚合反应。
综上,现有技术中没有将微波聚合一步法应用于材料表面改性的相关技术。
文献1:Haensch,C.;Erdmenger,T.;Fijten,M.W.;Hoeppener,S.;Schubert,U.S.,Fast surface modification by microwave assisted click reactions on silicon substrates,Langmuir 2009,25(14),8019-24。
文献2:Li,Y.;Wang,J.;Cai,C.,Rapid grafting of azido-labeled oligo(ethylene glycol)s onto an alkynyl-terminated monolayer on nonoxidized silicon via microwave-assisted"click"reaction,Langmuir 2011,27(6),2437-45。
文献3:Lee,M.;Lee,S.H.;Oh,I.K.;Lee,H.,Microwave-Accelerated Rapid,Chemical Oxidant-Free,Material-Independent Surface Chemistry of Poly(dopamine),Small 2017,13(4)。
发明内容
发明要解决的问题
因此,目前更需要的是将材料接枝到物体表面上的更方便的方法,该方法不需对材料进行复杂的预处理,仅采用一步法就能实现功能化改性。还需要一种快速且允许涂覆不能用常规方法涂覆的物体的方法。
用于解决问题的方案
基于以上,本发明涉及以下技术方案。
[1]、一种材料表面改性的方法,其包括以下步骤:
(1)将聚合单体、偶联剂和引发剂溶解、悬浮或分散在溶剂中制得反应液;
(2)将基材与所述反应液接触;
(3)经微波辐射使基材表面的反应液进行聚合,得到表面改性的基材。
[2]、根据[1]所述的方法,其中,步骤(1)中所述聚合单体选自(甲基)丙烯酰胺类单体、阳离子类单体、肝素类单体、类肝素类单体、苯乙烯磺酸钠、N-乙烯吡咯烷酮、(甲基)丙烯酸类单体、(甲基)丙烯酸酯类单体、纤溶类单体、两性离子类单体中的一种或多种。
[3]、根据[1]或[2]所述的方法,其中,步骤(1)中所述偶联剂选自硅烷偶联剂、钛酸酯偶联剂中的一种或多种。
[4]、根据[1]或[2]所述的方法,其中,步骤(1)中所述引发剂选自偶氮类引发剂、过氧化物类引发剂中的一种或多种。
[5]、根据[4]所述的方法,其中,所述引发剂选自偶氮二氰基戊酸、过氧化环己酮、过氧化苯甲酰、过氧化二异丙苯、偶氮二异丁腈、过硫酸铵、偶氮二异丁脒盐酸盐中的一种或多种。
[6]、根据[1]或[2]所述的方法,其中,步骤(1)中所述聚合单体、所述偶联剂和所述引发剂的用量分别为:所述聚合单体与所述偶联剂的摩尔比例为(1-100):1,所述聚合单体与所述引发剂的摩尔比例为(10-1000):1。
[7]、根据[1]或[2]所述的方法,其中,步骤(1)中所述聚合单体在反应液中的浓度为0.001-10g/ml。
[8]、根据[1]或[2]所述的方法,其中,步骤(2)中所述基材预先进行等离子体处理、电晕处理、辐射处理、臭氧处理、化学试剂处理的一个或者多个。
[9]、根据[1]或[2]所述的方法,其中,步骤(3)中微波辐射进行0.5~30min,微波辐射进行聚合的温度为50~200℃,微波辐射的功率为50~2500w。
[10]、一种通过前述任一项所述的方法制备得到的表面改性的材料。
发明的效果
与现有技术中需要先在材料表面接枝引发剂、然后再进行聚合的复杂工艺不同,本发明利用微波聚合方法、采用一步法实现了材料表面的改性。
本发明的聚合反应迅速(可以实现在5min内结束聚合反应),区别于现有传统的涂层涂覆方法,可以大大增加产值产量、聚合单体良好地接枝在材料表面上实现了材料表面改性的效果;使用的溶剂无毒无害;可供使用的基材类型广泛,并且最终得到的材料的加工成型不受限制;本发明易于操作、制备方法和设备简单、生产成本低并且易于工业化;本发明的方法可广泛用于各种领域,特别适合于医疗器械(例如管材、导丝等)、高分子材料、金属基材、无机材料等表面的改性,从而改变材料表面的亲/疏水性、润滑性,增加生物功能性、抗蛋白吸附性能、抗菌性和抗凝性等。
附图说明
图1是实施例一在不同的聚合时间下在硅橡胶(聚二甲基硅氧烷,PDMS)基材上微波聚合得到的基材的红外图。
图2是实施例二、实施例六、实施例十、实施例十四、实施例十八和实施例二十二在硅橡胶(聚二甲基硅氧烷,PDMS)基材上微波聚合得到的基材以及作为对照的未进行微波聚合的PDMS基材(对比例3)的红外图。
图3是实施例三、实施例七、实施例十一、实施例十五、实施例十九、实施例二十三在尼龙弹性体(Pebax)基材上微波聚合得到的基材以及作为对照的未进行微波聚合的Pebax基材(对比例4)的红外图。
图4是实施例四、实施例八、实施例十二、实施例十六、实施例二十、实施例二十四在热塑性聚氨酯(TPU)基材上微波聚合得到的基材以及作为对照的未进行微波聚合的TPU基材(对比例5)的红外图。
图5是实施例五、实施例九、实施例十三、实施例十七、实施例二十一、实施例二十五在聚氯乙烯(PVC)基材上微波聚合得到的基材以及作为对照的未进行微波聚合的PVC基材(对比例6)的红外图。
图6是显示实施例二十六及未经改性的不锈钢材料(对比例7)利用平板涂布法测定微导管表面涂层的杀菌效果的图。
图7是显示实施例二十二至二十五以及未改性的TPU基材(对比例5)表面的溶栓能力的图。
具体实施方式
为了更好地说明本发明,在下文的具体实施方式中给出了众多的具体细节。本领域技术人员应当理解,在没有某些具体细节的情况下本发明同样可以实施。在另外一些实例中,对于本领域技术人员熟知的方法、手段、器材和步骤未作详细描述,以便于凸显本发明的主旨。
如果没有特别说明,在本发明的方法中使用的各种反应物料可以商购获得。
本发明涉及一种材料表面改性的方法,其包括以下步骤:
(1)将聚合单体、偶联剂和引发剂溶解、悬浮或分散在溶剂中制得反应液;
(2)将基材与所述反应液接触;
(3)经微波辐射使基材表面的反应液进行聚合,得到表面改性的基材。
下面分步骤阐述本发明。
步骤(1)
参与本发明的微波聚合方法的聚合单体没有特别限制,只要其具有可发生聚合反应的双键即可。
步骤(1)中所述聚合单体可以选自例如(甲基)丙烯酰胺类单体、阳离子类单体、肝素类单体、类肝素类单体、苯乙烯磺酸钠、N-乙烯吡咯烷酮、(甲基)丙烯酸类单体、(甲基)丙烯酸酯类单体、溶纤类单体、两性离子类单体中的一种或多种。
作为(甲基)丙烯酰胺类单体,可以列举出例如甲基丙烯酰胺、丙烯酰胺、甲氧基甲基甲基丙烯酰胺、甲氧基甲基丙烯酰胺、正丁氧基甲基甲基丙烯酰胺、正丁氧基甲基丙烯酰胺、异丁氧基甲基甲基丙烯酰胺、异丁氧基甲基丙烯酰胺、叔丁基氨基丙基甲基丙烯酰胺、叔丁基氨基丙基丙烯酰胺、二甲氨基丙基甲基丙烯酰胺和二甲氨基丙基丙烯酰胺等等。
作为阳离子类单体,可以列举出例如季铵盐类单体,如二烯丙基胺、二甲基二烯丙基氯化铵、二乙基二烯丙基氯化铵、(甲基)丙烯酰氧乙基三甲基氯化铵、丙烯酰氧乙基二甲基苄基氯化铵、3-[[2-(甲基丙烯酰氧基)乙基]二甲铵基]丙烷-1-磺酸盐等;胍类单体如胍、二甲双胍、二苯胍、四甲基胍等;季磷盐类单体如三苯基膦、四苯基溴化膦、甲基三苯基溴化膦、乙基三苯基溴化膦、苄基三苯基氯化膦等;壳聚糖等等。
作为肝素类单体和类肝素类单体,可以列举出普通肝素(例如由D-葡糖胺、L-艾杜糖醛酸及D-葡萄糖醛酸交替组成的黏多糖硫酸酯)、低分子肝素(例如依诺肝素、达肝素、那曲肝素等)、肝素衍生物(例如磺达肝癸钠)、肝素类似物(例如达那肝素钠)等等。
作为(甲基)丙烯酸类单体和(甲基)丙烯酸酯类单体,可以列举出(甲基)丙烯酸、丙烯酸、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯等等。
作为纤溶类单体,可以例举出乙烯基赖氨酸类单体等等。
作为两性离子类单体,可以列举出例如磷酰胆碱、羧基甜菜碱、磺基甜菜碱等等。
步骤(1)中所述偶联剂没有特别限制,在本发明的一些具体实施方式中,偶联剂为带有双键的偶联剂,可以选自带有双键的硅烷偶联剂、钛酸酯偶联剂中的一种或多种。
作为硅烷偶联剂,可以列举出例如乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三乙酰氧基硅烷、γ-氨丙基三乙氧基硅烷、γ-氨丙基三甲氧基硅烷、苯氨基甲基三乙氧基硅烷、苯氨基甲基三甲氧基硅烷、(3-巯基丙基)三甲氧基硅烷、3-异氰酸酯基三甲氧基硅烷、3-异氰酸酯基三乙氧基硅烷、环氧基三甲氧基硅烷、环氧基三乙氧基硅烷等等。
作为钛酸酯偶联剂,可以列举出例如异丙基三(二辛基焦磷酸酰氧基)钛酸酯、单烷氧基不饱和脂肪酸钛酸酯、异丙基二油酸酰氧基(二辛基磷酸酰氧基)钛酸酯、异丙基三(二辛基磷酸酰氧基)钛酸酯等等。
步骤(1)中所述引发剂没有特别限制,可以选自偶氮类引发剂、过氧化物类引发剂中的一种或多种。优选地,引发剂可以选自偶氮二氰基戊酸、过氧化环己酮、过氧化苯甲酰、过氧化二异丙苯、偶氮二异丁腈、过硫酸铵、偶氮二异丁脒盐酸盐中的一种或多种。
步骤(1)中所述聚合单体、所述偶联剂和所述引发剂的用量分别为:所述聚合单体与所述偶联剂的摩尔比例为(1-100):1,所述聚合单体与所述引发剂的摩尔比例为(10-1000):1。若聚合单体与偶联剂的比例过小,则聚合单体的接枝量较小,不能获得具有所希望的功能的表面涂层,若聚合单体与偶联剂的比例过大,则缺少偶联剂与基材表面的粘合,导致涂层与基材表面的结合力不牢固。另外,若聚合单体与引发剂的比例过小,则聚合物表面的分子量受限;若聚合单体与引发剂的比例过大,则可能聚合物表面的接枝密度下降。
步骤(1)中所述聚合单体在反应液中的浓度为0.001-10g/ml,优选为0.005-0.5g/ml。若聚合单体浓度过小,则聚合物表面的接枝密度下降,若聚合单体浓度过大,则会在聚合物表面形成过厚的凝胶层。
步骤(1)中使用的溶剂没有特别限制,例如可以采用水或有机溶剂,如甲醇、乙醇、丙酮、甲乙酮、异丙醇等等。
步骤(2)
本发明的步骤(2)涉及使用步骤(1)得到的反应液接触基材。
本发明的基材没有特别限制,例如可以使用硅橡胶基材如聚二甲基硅氧烷(PDMS)基材、尼龙弹性体(Pebax)基材、热塑性聚氨酯(TPU)基材、聚氯乙烯(PVC)基材、聚烯烃基材、聚酯基材等等高分子类基材,也可以是陶瓷材料、玻璃材料等无机材料,也可以是不锈钢材料、镍钛合金、铜等金属材料。
所述基材优选预先进行等离子体处理、辐射处理(例如紫外辐射、射线辐射)、臭氧处理、化学试剂处理的一个或者多个。这些处理可以采用常规使用的那些,例如可以采用
Figure PCTCN2022139960-appb-000001
等离子体技术对基材表面进行清洗以清除基材表面的脱模剂和添加剂等;采用盐酸、硝酸等对基材表面进行酸处理和/或采用氢氧化钠、氢氧化钾等对基材表面进行碱处理以达到清洗基材表面的目的。
步骤(3)
本发明中可以采用已知的微波设备对基材表面的反应液进行微波辐射。通过微波辐射,聚合单体之间、聚合单体与偶联剂之间以及偶联剂与基材表面之间都可以连接。
步骤(3)中,微波辐射进行0.5~30min,优选为1~20min,微波辐射的温度为50~200℃,优选为50~100℃,微波辐射的功率为50~2500w,优选为500~1500w。微波辐射时间若短,则可能导致聚合反应效率较低,接枝的程度不高;微波辐射的时间、温度或功率过大,则可能会对基材具有一定的损坏。在本说明书中,微波辐射进行聚合的温度是指实际发生微波辐射聚合的温度。
本发明还涉及通过本发明所述的方法制备得到的表面改性的材料。通过本发明的方法制备的表面改性的材料可以广泛应用于各个领域,特别是可以应用于医疗器械领域。
实施例
以下,通过实施例具体地对本发明进行说明,但本发明不受这些实施例的限定。实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用材料或仪器除非特别说明,均为可以使用通过市购获得的常规产品。
在实施例中,以下缩写表示的物质如下。
MEDSA:3-[[2-(甲基丙烯酰氧基)乙基]二甲铵基]丙烷-1-磺酸盐
AA:丙烯酰胺
SS:苯乙烯磺酸钠
NVP:1-乙烯基-2-吡咯烷酮
TAC:甲基丙烯酰氧乙基三甲基氯化铵
Lys:乙烯基赖氨酸
ACVA:偶氮二氰基戊酸
实施例一
[硅橡胶-MEDSA复合基材的制备]
将6μL(0.02%V/V,0.04mmol)乙烯基三甲氧基硅烷,111mg(0.4mmol)3-[[2-(甲基丙烯酰氧基)乙基]二甲铵基]丙烷-1-磺酸盐(MEDSA)和1.12mg(0.004mmol)的偶氮二氰基戊酸(ACVA)溶解在装有30mL 75%乙醇的三口烧瓶中得到溶液。将提前用氧气等离子体预处理5min的聚二甲基硅氧烷(PDMS)基材完全浸没在该溶液中,鼓N 2 15min。随后设置微波功率900w,加热温度75℃,反应时间分别为30s、60s、90s、120s和150s,得到表面带有涂层的复合基材。
实施例一研究了在本发明中在不同的反应时间下进行微波聚合的结果。从图1看出,在60s以上的反应时间下在红外图上均显示有强的吸收峰,这说明经过微波辐射后,硅橡胶、MEDSA和乙烯基三甲氧基硅烷之间发生了接枝聚合反应,MEDSA成功地改性了硅橡胶的表面。
实施例二
[硅橡胶-MEDSA复合基材的制备]
将60μL(0.2%V/V,0.4mmol)乙烯基三甲氧基硅烷,1110mg(4mmol)3-[[2-(甲基丙烯酰氧基)乙基]二甲铵基]丙烷-1-磺酸盐(MEDSA)和11.2mg(0.04mmol)的偶氮二氰基戊酸(ACVA)溶解在装有30mL 75%乙醇的三口烧瓶中得到溶液。将提前用氧气等离子体预处理10min的聚二甲基硅 氧烷(PDMS)基材完全浸没在该溶液中,鼓N 2 30min。随后设置微波功率900w,加热温度75℃,反应时间为5min,得到表面带有涂层的复合基材。
相比于实施例一,实施例二改变了乙烯基三甲氧基硅烷、MEDSA和ACVA的用量以及反应时间,结果显示硅橡胶、MEDSA和乙烯基三甲氧基硅烷之间发生了接枝聚合反应,MEDSA成功地改性了硅橡胶的表面(图2)。
实施例三
[Pebax-MEDSA复合基材的制备]
将60μL(0.2%V/V,0.4mmol)乙烯基三甲氧基硅烷,1110mg(4mmol)3-[[2-(甲基丙烯酰氧基)乙基]二甲铵基]丙烷-1-磺酸盐(MEDSA)和11.2mg的偶氮二氰基戊酸(ACVA)溶解在装有30mL75%乙醇的三口烧瓶中得到溶液。将提前用氧气等离子体预处理10min的尼龙弹性体(Pebax)基材完全浸没在该溶液中,鼓N 2 30min。随后设置微波功率900w,加热温度75℃,反应时间为5min,得到表面带有涂层的复合基材。
实施例四
[TPU-MEDSA复合基材的制备]
将60μL(0.2%V/V,0.4mmol)乙烯基三甲氧基硅烷,1110mg(4mmol)3-[[2-(甲基丙烯酰氧基)乙基]二甲铵基]丙烷-1-磺酸盐(MEDSA)和11.2mg的偶氮二氰基戊酸(ACVA)溶解在装有30mL75%乙醇的三口烧瓶中得到溶液。将提前用氧气等离子体预处理10min的热塑性聚氨酯(TPU)基材完全浸没在该溶液中,鼓N 2 30min。随后设置微波功率900w,加热温度75℃,反应时间为5min,得到表面带有涂层的复合基材。
实施例五
[PVC-MEDSA复合基材的制备]
将60μL(0.2%V/V,0.4mmol)乙烯基三甲氧基硅烷,1110mg(4mmol)3-[[2-(甲基丙烯酰氧基)乙基]二甲铵基]丙烷-1-磺酸盐(MEDSA)和11.2mg的偶氮二氰基戊酸(ACVA)溶解在装有30mL75%乙醇的三口烧瓶中得到溶液。将提前用氧气等离子体预处理10min的聚氯乙烯(PVC)基材完全浸没在该溶液中,鼓N 2 30min。随后设置微波功率900w,加热温度75℃,反应时间为5min,得到表面带有涂层的复合基材。
实施例六
[硅橡胶-AA复合基材的制备]
将30μL(0.2%V/V,0.2mmol)乙烯基三甲氧基硅烷,285mg(4mmol)丙烯酰胺(AA)和11.2mg的偶氮二氰基戊酸(ACVA)溶解在装有30mL 75%乙醇的三口烧瓶中得到溶液。将提前用氧气等离子体预处理10min的聚二甲基硅氧烷(PDMS)基材完全浸没在该溶液中,鼓N 2 30min。随后设置微波功率900w,加热温度75℃,反应时间为5min,得到表面带有涂层的复合基材。
实施例七
[Pebax-AA复合基材的制备]
将60μL(0.2%V/V,0.4mmol)乙烯基三甲氧基硅烷,285mg(4mmol)丙烯酰胺(AA)和11.2mg的偶氮二氰基戊酸(ACVA)溶解在装有30mL 75%乙醇的三口烧瓶中得到溶液。将提前用氧气等离子体预处理10min的尼龙弹性体(Pebax)基材完全浸没在该溶液中,鼓N 2 30min。随后设置微波功率900w,加热温度75℃,反应时间为5min,得到表面带有涂层的复合基材。
实施例八
[TPU-AA复合基材的制备]
将90μL(0.2%V/V,0.6mmol)乙烯基三甲氧基硅烷,285mg(4mmol)丙烯酰胺(AA)和11.2mg的偶氮二氰基戊酸(ACVA)溶解在装有30mL 75%乙醇的三口烧瓶中得到溶液。将提前用氧气等离子体预处理10min的热塑性聚氨酯(TPU)基材完全浸没在该溶液中,鼓N 2 30min。随后设置微波功率900w,加热温度75℃,反应时间为5min,得到表面带有涂层的复合基材。
实施例九
[PVC-AA复合基材的制备]
将120μL(0.2%V/V,0.8mmol)乙烯基三甲氧基硅烷,285mg(4mmol)丙烯酰胺(AA)和11.2mg的偶氮二氰基戊酸(ACVA)溶解在装有30mL 75%乙醇的三口烧瓶中得到溶液。将提前用氧气等离子体预处理10min的聚氯乙烯(PVC)基材完全浸没在该溶液中,鼓N 2 30min。随后设置微波功率900w,加热温度75℃,反应时间为5min,得到表面带有涂层的复合基材。
实施例十
[硅橡胶-SS复合基材的制备]
将60μL(0.2%V/V,0.4mmol)乙烯基三甲氧基硅烷,825mg(4mmol)苯乙烯磺酸钠(SS)和11.2mg的偶氮二氰基戊酸(ACVA)溶解在装有30mL 75%乙醇的三口烧瓶中得到溶液。将提前用氧气等离子体预处理10min的聚二甲基硅氧烷(PDMS)基材完全浸没在该溶液中,鼓N 2 30min。随后设置微波功率900w,加热温度75℃,反应时间为2min,得到表面带有涂层的复合基材。
实施例十一
[Pebax-SS复合基材的制备]
将60μL(0.2%V/V,0.4mmol)乙烯基三甲氧基硅烷,825mg(4mmol)苯乙烯磺酸钠(SS)和11.2mg的偶氮二氰基戊酸(ACVA)溶解在装有30mL 75%乙醇的三口烧瓶中得到溶液。将提前用氧气等离子体预处理10min的尼龙弹性体(Pebax)基材完全浸没在该溶液中,鼓N 2 30min。随后设置微波功率500w,加热温度75℃,反应时间为10min,得到表面带有涂层的复合基材。
实施例十二
[TPU-SS复合基材的制备]
将60μL(0.2%V/V,0.4mmol)乙烯基三甲氧基硅烷,825mg(4mmol)苯乙烯磺酸钠(SS)和11.2mg的偶氮二氰基戊酸(ACVA)溶解在装有30mL 75%乙醇的三口烧瓶中得到溶液。将提前用氧气等离子体预处理10min的热塑性聚氨酯(TPU)基材完全浸没在该溶液中,鼓N 2 30min。随后设置微波功率900w,加热温度60℃,反应时间为5min,得到表面带有涂层的复合基材。
实施例十三
[PVC-SS复合基材的制备]
将60μL(0.2%V/V,0.4mmol)乙烯基三甲氧基硅烷,825mg(4mmol)苯乙烯磺酸钠(SS)和11.2mg的偶氮二氰基戊酸(ACVA)溶解在装有30mL 75%乙醇的三口烧瓶中得到溶液。将提前用氧气等离子体预处理10min的聚氯乙烯(PVC)基材完全浸没在该溶液中,鼓N 2 15min。随后设置微波功率900w,加热温度75℃,反应时间为5min,得到表面带有涂层的复合基材。
实施例十四
[硅橡胶-NVP复合基材的制备]
将60μL(0.2%V/V,0.4mmol)乙烯基三甲氧基硅烷,445mg(4mmol)1-乙烯基-2-吡咯烷酮(NVP)和11.2mg的偶氮二氰基戊酸(ACVA)溶解在装有30mL 75%乙醇的三口烧瓶中得到溶液。将提前用氧气等离子体预处理10min的聚二甲基硅氧烷(PDMS)基材完全浸没在该溶液中,鼓N 230min。随后设置微波功率900w,加热温度75℃,反应时间为5min,得到表面带有涂层的复合基材。
实施例十五
[Pebax-NVP复合基材的制备]
将60μL(0.2%V/V,0.4mmol)乙烯基三甲氧基硅烷,445mg(4mmol)1-乙烯基-2-吡咯烷酮(NVP)和11.2mg的偶氮二氰基戊酸(ACVA)溶解在装有30mL 75%乙醇的三口烧瓶中得到溶液。将提前用氧气等离子体预处理10min的尼龙弹性体(Pebax)基材完全浸没在该溶液中,鼓N 2 30min。随后设置微波功率900w,加热温度75℃,反应时间为5min,得到表面带有涂层的复合基材。
实施例十六
[TPU-NVP复合基材的制备]
将60μL(0.2%V/V,0.4mmol)乙烯基三甲氧基硅烷,445mg(4mmol)1-乙烯基-2-吡咯烷酮(NVP)和11.2mg的偶氮二氰基戊酸(ACVA)溶解在装有30mL 75%乙醇的三口烧瓶中得到溶液。将提前用氧气等离子体预处理10min的热塑性聚氨酯(TPU)基材完全浸没在该溶液中,鼓N 2 30min。随后设置微波功率900w,加热温度75℃,反应时间为5min,得到表面带有涂层的复合基材。
实施例十七
[PVC-NVP复合基材的制备]
将60μL(0.2%V/V,0.4mmol)乙烯基三甲氧基硅烷,445mg(4mmol)1-乙烯基-2-吡咯烷酮(NVP)和11.2mg的偶氮二氰基戊酸(ACVA)溶解在装有30mL 75%乙醇的三口烧瓶中得到溶液。将提前用氧气等离子体预处理10min的聚氯乙烯(PVC)基材完全浸没在该溶液中,鼓N 2 30min。随后设置微波功率900w,加热温度75℃,反应时间为5min,得到表面带有涂层的复合基材。
实施例十八
[硅橡胶-TAC复合基材的制备]
将60μL(0.2%V/V,0.4mmol)乙烯基三甲氧基硅烷,830mg(4mmol)甲基丙烯酰氧乙基三甲基氯化铵(TAC)和11.2mg的偶氮二氰基戊酸(ACVA)溶解在装有30mL 75%乙醇的三口烧瓶中 得到溶液。将提前用氧气等离子体预处理10min的聚二甲基硅氧烷(PDMS)基材完全浸没在该溶液中,鼓N 2 30min。随后设置微波功率900w,加热温度75℃,反应时间为5min,得到表面带有涂层的复合基材。
实施例十九
[Pebax-TAC复合基材的制备]
将60μL(0.2%V/V,0.4mmol)乙烯基三甲氧基硅烷,830mg(4mmol)甲基丙烯酰氧乙基三甲基氯化铵(TAC)和11.2mg的偶氮二氰基戊酸(ACVA)溶解在装有30mL 75%乙醇的三口烧瓶中得到溶液。将提前用氧气等离子体预处理10min的尼龙弹性体(Pebax)基材完全浸没在该溶液中,鼓N 2 30min。随后设置微波功率900w,加热温度75℃,反应时间为5min,得到表面带有涂层的复合基材。
实施例二十
[TPU-TAC复合基材的制备]
将60μL(0.2%V/V,0.4mmol)乙烯基三甲氧基硅烷,830mg(4mmol)甲基丙烯酰氧乙基三甲基氯化铵(TAC)和11.2mg的偶氮二氰基戊酸(ACVA)溶解在装有30mL 75%乙醇的三口烧瓶中得到溶液。将提前用氧气等离子体预处理10min的热塑性聚氨酯(TPU)基材完全浸没在该溶液中,鼓N 2 30min。随后设置微波功率900w,加热温度75℃,反应时间为5min,得到表面带有涂层的复合基材。
实施例二十一
[PVC-TAC复合基材的制备]
将60μL(0.2%V/V,0.4mmol)乙烯基三甲氧基硅烷,830mg(4mmol)甲基丙烯酰氧乙基三甲基氯化铵(TAC)和11.2mg的偶氮二氰基戊酸(ACVA)溶解在装有30mL 75%乙醇的三口烧瓶中得到溶液。将提前用氧气等离子体预处理10min的聚氯乙烯(PVC)基材完全浸没在该溶液中,鼓N 2 30min。随后设置微波功率900w,加热温度75℃,反应时间为5min,得到表面带有涂层的复合基材。
实施例二十二
[硅橡胶-Lys复合基材的制备]
将60μL(0.2%V/V,0.4mmol)乙烯基三甲氧基硅烷,850mg(4mmol)乙烯基赖氨酸(Lys)和11.2mg的偶氮二氰基戊酸(ACVA)溶解在装有30mL 75%乙醇的三口烧瓶中得到溶液。将提前用氧气等离子体预处理10min的聚二甲基硅氧烷(PDMS)基材完全浸没在该溶液中,鼓N 2 30min。随后设置微波功率900w,加热温度75℃,反应时间为5min,得到表面带有涂层的复合基材。
实施例二十三
[Pebax-Lys复合基材的制备]
将60μL(0.2%V/V,0.4mmol)乙烯基三甲氧基硅烷,850mg(4mmol)乙烯基赖氨酸(Lys)和11.2mg的偶氮二氰基戊酸(ACVA)溶解在装有30mL 75%乙醇的三口烧瓶中得到溶液。将提前用 氧气等离子体预处理10min的尼龙弹性体(Pebax)基材完全浸没在该溶液中,鼓N 2 30min。随后设置微波功率900w,加热温度75℃,反应时间为5min,得到表面带有涂层的复合基材。
实施例二十四
[TPU-Lys复合基材的制备]
将60μL(0.2%V/V,0.4mmol)乙烯基三甲氧基硅烷,850mg(4mmol)乙烯基赖氨酸(Lys)和11.2mg的偶氮二氰基戊酸(ACVA)溶解在装有30mL 75%乙醇的三口烧瓶中得到溶液。将提前用氧气等离子体预处理10min的热塑性聚氨酯(TPU)基材完全浸没在该溶液中,鼓N 2 30min。随后设置微波功率900w,加热温度75℃,反应时间为5min,得到表面带有涂层的复合基材。
实施例二十五
[PVC-Lys复合基材的制备]
将60μL(0.2%V/V,0.4mmol)乙烯基三甲氧基硅烷,850mg(4mmol)乙烯基赖氨酸(Lys)和11.2mg的偶氮二氰基戊酸(ACVA)溶解在装有30mL 75%乙醇的三口烧瓶中得到溶液。将提前用氧气等离子体预处理10min的聚氯乙烯(PVC)基材完全浸没在该溶液中,鼓N 2 30min。随后设置微波功率900w,加热温度75℃,反应时间为5min,得到表面带有涂层的复合基材。
从图2至图5可以看出,在实施例二至实施例二十五中经过微波辐射后,聚合单体、偶联剂和基材表面之间发生了接枝聚合反应,聚合单体成功地改性了基材的表面。
实施例二十六
[不锈钢材料-TAC复合基材的制备]
将60μL(0.2%V/V,0.4mmol)乙烯基三甲氧基硅烷,830mg(4mmol)甲基丙烯酰氧乙基三甲基氯化铵(TAC)和11.2mg的偶氮二氰基戊酸(ACVA)溶解在装有30mL 75%乙醇的三口烧瓶中得到溶液。将提前用氧气等离子体预处理10min的不锈钢基材完全浸没在该溶液中,鼓N 2 30min。随后设置微波功率900w,加热温度75℃,反应时间为5min,得到表面带有涂层的复合基材。
实施例二十七
[硅胶导尿管-MPC复合基材的制备]
将60μL(0.2%V/V,0.4mmol)乙烯基三甲氧基硅烷,1180mg(4mmol)2-甲基丙烯酰氧乙基磷酸胆碱(MPC)和11.2mg的偶氮二氰基戊酸(ACVA)溶解在装有30mL 75%乙醇的三口烧瓶中得到溶液。将未经预处理的硅胶导尿管完全浸没在该溶液中,鼓N 2 30min。随后设置微波功率700w,加热温度60℃,反应时间为5min,得到表面带有涂层的复合基材。
反应式如下:
Figure PCTCN2022139960-appb-000002
对比例
对比例1
[硅橡胶-MEDSA复合基材的制备]
将120μL(0.2%V/V,0.8mmol)乙烯基三甲氧基硅烷,111mg(0.4mmol)3-[[2-(甲基丙烯酰氧基)乙基]二甲铵基]丙烷-1-磺酸盐(MEDSA)和1.12mg(0.004mmol)的偶氮二氰基戊酸(ACVA)溶解在装有30mL 75%乙醇的三口烧瓶中得到溶液。将提前用氧气等离子体预处理10min的聚二甲基硅氧烷(PDMS)基材完全浸没在该溶液中,鼓N 2 30min。随后设置微波功率900w,加热温度75℃,反应时间为5min,得到表面带有涂层的复合基材。
对比例1中,聚合单体与偶联剂的比例为0.5:1,会导致聚合单体的接枝量不足。
对比例2
[硅橡胶-MEDSA复合基材的制备]
将60μL(0.2%V/V,0.4mmol)乙烯基三甲氧基硅烷,1110mg(4mmol)3-[[2-(甲基丙烯酰氧基)乙基]二甲铵基]丙烷-1-磺酸盐(MEDSA)和1120mg(4mmol)的偶氮二氰基戊酸(ACVA)溶解在装有30mL 75%乙醇的三口烧瓶中得到溶液。将提前用氧气等离子体预处理10min的聚二甲基硅氧烷(PDMS)基材完全浸没在该溶液中,鼓N 2 30min。随后设置微波功率900w,加热温度75℃,反应时间为5min,得到表面带有涂层的复合基材。
对比例2中,引发剂与聚合单体的比例为1:1,也会导致单体的接枝量不足。
对比例3
取用未经改性的硅橡胶(PDMS)。
对比例4
取用未经改性的Pebax。
对比例5
取用未经改性的TPU。
对比例6
取用未经改性的PVC。
对比例7
取用未经改性的不锈钢材料。
对比例8
同实施例7,区别仅在于无微波步骤。
性能表征
1、水接触角表征
将待测样品水平放置于水接触角测试仪上,通过注射器将5μL体积的水滴接触到样品表面,待液滴在表面稳定2s后,测定由固-液-气三相接触点向液气界面走向的切线与液固界面之间的夹角,即 为样品的水接触角。
2、抗蛋白吸附表征测试纤维蛋白原吸附量
以氯化碘(ICl)方法用 125I标记纤维蛋白原,将纤维蛋白原通过AG1-X4阴离子交换树脂柱以除去游离碘。将标记的蛋白质加入无血小板的血浆中,浓度约为正常血浆中纤维蛋白溶酶原浓度的10%。取基材放入上述蛋白质溶液中培养3h,用磷酸缓冲溶液淋洗三次,每次10min,用滤纸吸干后将其转移到干净的管中利用自动伽玛粒子计数器测试其放射量。蛋白质吸附量以单位面积上的质量来计算。
3、测试润滑性能
使用江苏百赛飞生物科技有限公司的摩擦力测试机(型号FW-01),通过300g加持力作用下,提速1cm/s,测试不同样品导管的摩擦力来判断涂层润滑性。将实施例7和比较例1的产品置于夹片式摩擦力测试仪测试润滑性能,结果如表2所示。
根据表1所示的测试结果:相较于未改性的硅橡胶基材,微波改性之后由于功能性单体的引入,水接触角明显下降,且纤维蛋白原的吸附量也大大降低,证明经过微波改性之后的基材具有良好的亲水、抗污性能。实施例二十七证明,基材没有预处理的情况下,同样可以完成表面的改性,将正常情况下未改性的Pebax基材水接触角由102降低至72左右。
表1
组别 水接触角(°) Fg吸附量(μg/cm 2)
实施例二 36 0.08
实施例十四 38 0.10
实施例二十七 72
对比例3 85 0.86
对比例1 68 0.72
对比例2 72 0.82
根据表2所示的测试结果:在无微波条件下,Pebax管材的初始摩擦力为1.30N,第30次摩擦力为2.12N。相比之下,微波条件下获得的复合基材样品的初始摩擦力远小于对比例8的初始摩擦力,说明微波能够快速辅助基材的改性,并且在短时间内,改性的涂层能够达到一定厚度,并且在循环30次后依然能够保持良好的润滑性、稳定性。
表2
组别 初始摩擦力(N) 第30次循环摩擦力(N)
实施例七 0.12 0.14
对比例8 1.30 2.12
4、测试抗菌性能
将大肠杆菌种植于基材表面培养2-3h后,将基材取出,浸置于含1mL磷酸缓冲液(pH=7.4)的离心管中,5000rpm离心5min收集基材表面的细菌。取500μL收集的菌液以平板涂布法涂布于琼脂培养板上,置于37℃培养箱中培养18h,取出,拍照。
测试结果参见图6。图6显示了实施例二十六及对比例7利用平板涂布法测定微导管表面涂层的杀菌效果。从图6可以看出,从经过微波改性处理的基材上收集下来的细菌基本已经死亡,没有形成菌落,而未改性的基材上大量菌落形成,抗菌效果差。
5、测试血栓溶解性能
将基材样品浸泡于三羟甲基氨基甲烷缓冲液(pH=7.4)1h,取出后再浸泡于普通人体血浆中3h,取出基片,用三羟甲基氨基甲烷缓冲液淋洗三次。将样品浸泡于t-PA中10min。用三羟甲基氨基甲烷缓冲液淋洗片3次,取出基片,用滤纸吸干,加入100μL血浆后,再加入100μL 0.025M的氯化钙溶液。上述所有浸泡都在37℃恒温培养箱中进行,加入的血浆和t-PA需先在37℃培养箱中预热。用酶标仪测量405nm处的吸光度,时间间隔定为30s,测试总时长不得少于1h。
测试结果参见图7。图7显示了实施例二十二至二十五以及未改性的TPU基材(对比例5)表面的溶栓能力。随时间延长,吸光度逐渐增大直至最大值,这说明该期间内血栓完全形成。经微波表面改性之后的各类基材在血栓完全形成之后,吸光度又逐渐降低,证明生成的血栓正在被溶解,直至血栓被溶解完全,吸光度恢复至初始值。这证明经过微波改性之后,基材表面具有一定的溶栓能力、抗凝血能力。

Claims (10)

  1. 一种材料表面改性的方法,其特征在于包括以下步骤:
    (1)将聚合单体、偶联剂和引发剂溶解、悬浮或分散在溶剂中制得反应液;
    (2)将基材与所述反应液接触;
    (3)经微波辐射使基材表面的反应液进行聚合,得到表面改性的基材。
  2. 根据权利要求1所述的方法,其特征在于,步骤(1)中所述聚合单体选自(甲基)丙烯酰胺类单体、阳离子类单体、肝素类单体、类肝素类单体、苯乙烯磺酸钠、N-乙烯吡咯烷酮、(甲基)丙烯酸类单体、(甲基)丙烯酸酯类单体、纤溶类单体、两性离子类单体中的一种或多种。
  3. 根据权利要求1或2所述的方法,其特征在于,步骤(1)中所述偶联剂选自硅烷偶联剂、钛酸酯偶联剂中的一种或多种。
  4. 根据权利要求1或2所述的方法,其特征在于,步骤(1)中所述引发剂选自偶氮类引发剂、过氧化物类引发剂中的一种或多种。
  5. 根据权利要求4所述的方法,其特征在于,所述引发剂选自偶氮二氰基戊酸、过氧化环己酮、过氧化苯甲酰、过氧化二异丙苯、偶氮二异丁腈、过硫酸铵、偶氮二异丁脒盐酸盐中的一种或多种。
  6. 根据权利要求1或2所述的方法,其特征在于,步骤(1)中所述聚合单体、所述偶联剂和所述引发剂的用量分别为:所述聚合单体与所述偶联剂的摩尔比例为(1-100):1,所述聚合单体与所述引发剂的摩尔比例为(10-1000):1。
  7. 根据权利要求1或2所述的方法,其特征在于,步骤(1)中所述聚合单体在反应液中的浓度为0.001-10g/ml。
  8. 根据权利要求1或2所述的方法,其特征在于,步骤(2)中所述基材预先进行等离子体处理、电晕处理、辐射处理、臭氧处理、化学试剂处理的一个或者多个。
  9. 根据权利要求1或2所述的方法,其特征在于,步骤(3)中微波辐射进行0.5~30min,微波辐射进行聚合的温度为50~200℃,微波辐射的功率为50~2500w。
  10. 一种通过前述任一项权利要求所述的方法制备得到的表面改性的材料。
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