Search

CN-116672515-B - Coating system comprising hydrophilic polymers, bilayer coating system, hydrophilic coating and use

CN116672515BCN 116672515 BCN116672515 BCN 116672515BCN-116672515-B

Abstract

The invention relates to a coating system containing hydrophilic polymers, a double-layer coating system, a hydrophilic coating and application. The hydrophilic polymer-containing coating system comprises a reactive hydrophilic polymer Poly1 and a reactive monomer Rm1, can be used as a top coating system of a double-layer coating system or used singly, wherein the Poly1 has a large number of carbon-carbon double bonds, can form a compact crosslinked network, rm1 can further provide a more compact crosslinked network of physical interpenetrating or chemical secondary crosslinking, so that the formed coating can form a large number of chemical bond connection with a base coat or a substrate layer, and the hydrophilic polymer-containing double-layer coating further comprises a base coat system comprising a reactive hydrophilic polymer Poly2 and a reactive monomer Rm2, and can further strengthen the adhesion firmness of the hydrophilic coating. The hydrophilic coating prepared from the coating system and the double-layer coating system can be used as a hydrophilic lubricating layer of a medical instrument, and has good lubricity, low friction and high firmness.

Inventors

  • JIANG HONGYAN
  • YANG JINGXUAN
  • KANG YAHONG
  • LI SHIYANG
  • LUO QIYI

Assignees

  • 上海发微医用材料有限公司

Dates

Publication Date
20260508
Application Date
20221226

Claims (17)

  1. 1. The hydrophilic polymer-containing coating system is characterized by comprising, by dry weight, 45-90 parts by weight of reactive hydrophilic polymer Poly1, 9.9-50 parts by weight of reactive monomer Rm1, 0.1-5 parts by weight of initiator In1 and solvent So1, wherein the dry weight is 100 parts by weight; the reactive hydrophilic polymer Poly1 has a general structure shown in a formula (2); Formula (2); The reactive monomer Rm1 is capable of intermolecular crosslinking, the reactive monomer Rm1 has a polymer chain and a plurality of reactive groups F 1 which are covalently connected to the polymer chain, the reactive groups F 1 in the reactive monomer Rm1 are selected from carbon-carbon unsaturated bonds; The initiator In1 is Norrish type I initiator or free radical photoinitiator; the mass percentage of the solvent So1 in the coating system is more than or equal to 50%; in the formula (2), the amino acid sequence of the compound, M is an integer selected from 10 to 50; n is an integer selected from 4 to 30; the ratio of m to n is selected from 1:1 to 8:1, and the number average molecular weight of the reactive monomer Rm1 is 900-5000 Da; R 1 is ; Each a 1 is independently H or methyl; each a 2 is independently C 2-8 alkylene; Each L 11 is independently-O-or-NH-; each R 3 is independently-O-or-NH-; each B 2 is independently C 2-8 alkylene; Each L 13 is independently-O-or-NH-; Each B 1 is independently H or methyl; ", indicates the site of attachment to the end group.
  2. 2. The coating system of claim 1, wherein formula (1) satisfies any one or more of the following characteristics: m is an integer selected from 15 to 40; n is an integer selected from 4 to 20; the ratio of m to n is selected from 1:1 to 7:3; Each A 2 is independently- (CH 2 ) q1 -), wherein q1 is an integer selected from 2-4; l 11 is-O-; L 13 is-O-; the number average molecular weight of the reactive hydrophilic polymer Poly1 is selected from 1.5 kDa-15 kDa.
  3. 3. The coating system of claim 2, wherein formula (1) satisfies any one or more of the following characteristics: m is an integer selected from 20 to 28; n is an integer selected from 12 to 20; the ratio of m to n is selected from 1:1 to 7:3; each a 1 is independently methyl; each B 1 is independently methyl; Each A 2 is independently 1, 2-ethylene; Each B 2 is independently 1, 2-ethylene; The number average molecular weight of the reactive hydrophilic polymer Poly1 is selected from 3 kDa-10 kDa.
  4. 4. The coating system of claim 1, wherein one or more of the following characteristics are satisfied: In the same molecule, A 2 is the same, B 2 is the same, and B 1 is the same; in the same molecule, L 11 are the same; In the same molecule, L 13 are the same; the number average molecular weight of the reactive hydrophilic polymer Poly1 is selected from 3 kDa-6 kDa.
  5. 5. The coating system of any one of claims 1-4, wherein each R 3 in the reactive hydrophilic polymer Poly1 is independently-O-.
  6. 6. The coating system of any one of claims 1-4, wherein the reactive hydrophilic polymer Poly1 has a general structure represented by formula (2 b): (2b); Wherein A 1 is methyl, A 2 is 1, 2-ethylene, R 3 is-O-, B 2 is 1, 2-ethylene, and B 1 is methyl.
  7. 7. The coating system of any one of claims 1-4, wherein one or more of the following characteristics are satisfied: 2) The number average molecular weight of the reactive monomer Rm1 is 900-2000 Da; 3) The initiator In1 is selected from one or more of benzoin initiator, 4-benzoyl-1, 3-dioxavaleric initiator, benzyl ketal, alpha-dialkoxyacetophenone, alpha-hydroxy alkyl benzophenone, alpha-amino alkyl benzophenone, acyl phosphorus oxide, diacyl phosphine oxide, acyl phosphine sulfide and halogenated acetophenone initiator; 4) The solvent So1 is selected from one or more of alcohol, acetone, methyl ethyl ketone, tetrahydrofuran, dichloromethane and toluene, or is a solution or emulsion formed by one or more of alcohol, acetone, methyl ethyl ketone, tetrahydrofuran, dichloromethane and toluene and water, or is water; 5) The mass percentage of the reactive hydrophilic polymer Poly1 in the dry weight of the coating system is 45% -85%; 6) The mass percentage of the reactive monomer Rm1 in the dry weight of the coating system is 14.5% -50%; 7) Based on dry weight, the mass percentage of the initiator In1 In the dry weight of the coating system is 0.5% -5%; 8) The mass percentage of the reactive hydrophilic polymer Poly1 in the coating system is 4% -30%; 9) The mass percentage of the reactive monomer Rm1 in the coating system is 1.9% -19%; 10 The mass percentage of the initiator In1 In the coating system is 0.05% -1%; 11 The mass percentage of the solvent So1 in the coating system is 50% -90%.
  8. 8. The coating system of claim 7, wherein one or more of the following characteristics are satisfied: the number average molecular weight of the reactive monomer Rm1 is 900-1100 Da; the mass percentage of the reactive hydrophilic polymer Poly1 in the dry weight of the coating system is 75-85% -80%; The mass percentage of the reactive monomer Rm1 in the dry weight of the coating system is 14.5% -20%; the mass percentage of the initiator In1 In the dry weight of the coating system is 0.5% -2%; the mass percentage of the reactive hydrophilic polymer Poly1 in the coating system is 6% -10%; The mass percentage of the reactive monomer Rm1 in the coating system is 1% -4%; the mass percentage of the initiator In1 In the coating system is 0.05% -0.15%; the mass percentage of the solvent So1 in the coating system is 86% -90%.
  9. 9. The coating system of claim 7, wherein one or more of the following characteristics are satisfied: 1) The reactive monomer Rm1 is polyethylene glycol diacrylate or polyethylene glycol dimethacrylate; 2) The number average molecular weight of the reactive monomer Rm1 is 900-1100 Da; 3) The mass percentage of the reactive hydrophilic polymer Poly1 in the dry weight of the coating system is 47% -80%; 4) The mass percentage of the reactive monomer Rm1 in the dry weight of the coating system is 19% -48%; 5) The mass percentage of the initiator In1 In the dry weight of the coating system is 0.9% -5%; 6) The mass percentage of the reactive hydrophilic polymer Poly1 in the coating system is 5% -8%; 7) The mass percentage of the reactive monomer Rm1 in the coating system is 2% -5%; 8) The mass percentage of the initiator In1 In the coating system is 0.1% -0.5%; 9) The mass percentage of the solvent So1 in the coating system is 86.5% -90%.
  10. 10. A hydrophilic polymer-containing bilayer coating system comprising a top coating system selected from the hydrophilic polymer-containing coating systems of any one of claims 1-9 and a base coating system; The primer coating system comprises, by dry weight, 45-90 parts of reactive hydrophilic polymer Poly2, 9.9-50 parts of reactive monomer Rm2, 0.1-5 parts of initiator In2 and solvent So2, wherein the mass percentage of the reactive hydrophilic polymer Poly2 In the dry weight of the primer coating system is 75% -85%, and the mass percentage of the reactive monomer Rm2 In the dry weight of the primer coating system is 14.5% -20%; the reactive hydrophilic polymer Poly2 has a general structure shown in a formula (4) Formula (4); The reactive monomer Rm2 is capable of intermolecular crosslinking, the reactive monomer Rm2 having a polymer chain and a plurality of reactive groups F 2 covalently linked to the polymer chain; the initiator In2 is Norrish type I initiator or free radical photoinitiator; The mass percentage of the solvent So2 in the bottom coating system is more than or equal to 50%; In the formula (4), the amino acid sequence of the compound, Each X is independently-O-or-NH-or-N (CH 3 ) -; Each Z is independently C 1-18 alkylene; L 21 and L 22 are each independently selected from the group consisting of absent, -C (=o) -and-C (=o) NH-, wherein X is directed to X; B 21 and B 22 are each independently C 1-18 alkylene; L 31 and L 32 are each independently-O-or-NH-; B 11 and B 12 are each independently H, methyl, ethyl or C 3-6 alkyl; k is an integer selected from 1 to 220.
  11. 11. The bilayer coating system of claim 10, wherein formula (4) satisfies one or more of the following characteristics: each X is independently-O-; Each Z is independently 1, 2-ethylene or 1, 4-butylene; L 21 and L 22 are both-C (=o) NH-, wherein X is pointing to X; b 21 and B 22 are each independently methylene, 1, 2-ethylene, 1, 3-propylene, 1, 4-butylene, 1, 5-pentylene, 1, 6-hexylene, 1, 7-heptylene or 1, 8-octylene; b 11 and B 12 are each independently H or methyl; k is an integer selected from 2 to 100; the number average molecular weight of the reactive hydrophilic polymer Poly2 is 500-5000 Da.
  12. 12. The bilayer coating system of claim 10, wherein the coating composition comprises, K is an integer selected from 4 to 50; The reactive monomer Rm2 has a polymer chain and a plurality of reactive groups F 2 which are connected with the polymer chain in a covalent way, wherein the polymer chain in the reactive monomer Rm2 is selected from one or more structures in the following groups, namely polyether, polyurethane, polyethylene, polypropylene, polyvinyl chloride, polyethylene oxide, polyamide, polyacrylamide, poly (methyl) acrylic acid, polyvinyl alcohol, polyethyleneimine, polyester and alkyd copolymer, polypeptide and polysaccharide, the reactive group F 2 in the reactive monomer Rm2 is selected from one or more structures in the following groups, namely carbon-carbon unsaturated bond, -NH 2 、-CONH 2 and-SH, and when the reactive monomer Rm2 comprises carbon-carbon unsaturated bond, the reactive monomer Rm2 comprises one or more structures in alkenyl, unsaturated ester, unsaturated ether, unsaturated amide and dry alkyd resin; The number average molecular weight of the reactive monomer Rm2 is 600-4000 Da; The initiator In2 is selected from one or more of benzoin initiator, 4-benzoyl-1, 3-dioxavaleric initiator, benzyl ketal, alpha-dialkoxyacetophenone, alpha-hydroxy alkyl benzophenone, alpha-amino alkyl benzophenone, acyl phosphorus oxide, diacyl phosphine oxide, acyl phosphine sulfide and halogenated acetophenone initiator; The solvent So2 is selected from one or more of alcohol, acetone, methyl ethyl ketone, tetrahydrofuran, dichloromethane and toluene, or is a solution or emulsion formed by one or more of alcohol, acetone, methyl ethyl ketone, tetrahydrofuran, dichloromethane and toluene and water, or is water; The mass percentage of the initiator In2 In the dry weight of the priming coating system is 0.5% -2%; The mass percentage of the reactive hydrophilic polymer Poly2 in the priming coating system is 4% -30%; the mass percentage of the reactive monomer Rm2 in the primer coating system is 1.9% -19%; the mass percentage of the initiator In2 In the primer coating system is 0.05% -1%; the mass percentage of the solvent So2 in the bottom coating system is 50% -90%.
  13. 13. The bilayer coating system according to claim 12, wherein one or more of the following characteristics are satisfied: the polymer chain in the reactive monomer Rm2 is selected from polyethylene oxide; k is an integer selected from 7 to 20; The reactive monomer Rm2 is selected from one or more of a plurality of carbon-carbon unsaturated bond modified polyethers, wherein the plurality of carbon-carbon unsaturated bond modified polyethers comprise a plurality of carbon-carbon unsaturated bond modified polyethylene glycols and a plurality of carbon-carbon unsaturated bond modified polytetrahydrofurans; The number average molecular weight of the reactive monomer Rm2 is 800-2000 Da; the reactive monomer Rm2 is polyethylene glycol diacrylate or polyethylene glycol dimethacrylate; the mass percentage of the reactive hydrophilic polymer Poly2 in the priming coating system is 5% -8%; the mass percentage of the reactive monomer Rm2 in the primer coating system is 2% -5%; The mass percentage of the initiator In2 In the primer coating system is 0.1% -0.5%; the mass percentage of the solvent So2 in the bottom coating system is 86.5% -90%.
  14. 14. A hydrophilic coating prepared according to the hydrophilic polymer-containing coating system of any one of claims 1 to 9 or prepared according to the hydrophilic polymer-containing bilayer coating system of any one of claims 10 to 13.
  15. 15. Use of a hydrophilic polymer containing coating system according to any one of claims 1 to 9 or a hydrophilic polymer containing bilayer coating system according to any one of claims 10 to 13 for the preparation of a hydrophilic lubricating layer for a medical device or of a hydrophilic coating according to claim 14 as a hydrophilic lubricating layer for a medical device.
  16. 16. The use of claim 15, wherein the hydrophilic coating is laminated to the surface of a plastic substrate of an implantable medical device, and wherein the substrate coated with the hydrophilic coating is a plastic substrate.
  17. 17. The method according to claim 16, wherein the plastic substrate is selected from the group consisting of nylon, block polyether amide resin products, polyurethane, polyethylene terephthalate, polyvinyl chloride, polymethyl methacrylate, polyether ether ketone, polydimethylsiloxane, polyethylene, polypropylene, polytetrafluoroethylene.

Description

Coating system comprising hydrophilic polymers, bilayer coating system, hydrophilic coating and use RELATED APPLICATIONS The present application is a divisional application of chinese patent application No. CN202211676225X, entitled "hydrophilic polymer containing coating system and bilayer coating system, hydrophilic coating and application", filed on month 26 of 2022, the entire contents of which are incorporated herein by reference. Technical Field The invention relates to the technical field of medical hydrophilic coatings, in particular to a coating system containing a hydrophilic polymer, a double-layer coating system containing the hydrophilic polymer, a hydrophilic coating and application. Background In the field of medical devices, interventional therapy is becoming more and more accepted. For many interventional medical devices, such as catheters, balloon dilation catheters, central venous catheters, intravascular contrast catheters, and the like, due to insufficient surface smoothness, there is a large resistance to insertion or extraction into the body, causing pain and lifting injuries. Wherein, the medical catheter (or guide wire) is mainly guided into the human body through a natural duct of the human body or a micro-wound of puncture, and needs to be contacted with human tissue for a short term or a long term. The catheter (or guide wire) is rubbed with the tissue in direct contact during insertion or extraction, which leads to frequent burning and pain feeling of the patient, and is easy to cause tissue damage and adhesion, which leads to easy occurrence of complications. In clinical practice, lubricating oil (such as paraffin oil, silicone oil, vaseline and the like) is often coated on the surface of a catheter or a guide wire to reduce the problems, however, in clinical use, the silicone oil cannot be stably attached to the surface of the catheter or the guide wire, the lubricating effect is poor, the duration is difficult, and the tissue is still damaged when the catheter or the guide wire is inserted into or pulled out of a body. Accordingly, related researchers have been working on developing a method capable of forming a stable hydrophilic lubricant layer on the surface of a medical catheter, a guide wire, and hopefully achieving multiple effects of 1, reducing discomfort to a patient and avoiding damage to mucous membrane and tissue cells during insertion, 2, reducing biological contamination such as adsorption accumulation of proteins, cells, bacteria, microorganisms, etc. on the surface of a substrate, 3, anticoagulation, and reducing influence on blood flow environment, 4, improving biocompatibility of an instrument such as improving blood compatibility, 5, imparting good trafficability to a medical instrument, improving surgical safety, 6, enriching applicability to various substrates such as making a hydrophilic coating suitable for a substrate of nylon, PEBAX (block polyether amide resin product), PU (polyurethane), PET (polyethylene terephthalate), PVC (polyvinyl chloride), PMMA (polymethyl methacrylate), PEEK (polyether ether ketone), PDMS (polydimethylsiloxane), PE (polypropylene), PTFE (polytetrafluoroethylene), etc. In general, hydrophilic coatings are required to have lubricity, resistance to biofouling, good adhesion, biocompatibility, and reliability. At present, few products capable of meeting the comprehensive performance requirements of a hydrophilic lubricating layer are available on the market, and the formula is complex. Therefore, there is still a need to further develop hydrophilic lubricating layers that have clinical application value. Disclosure of Invention Based on the above, the invention aims to provide a coating system containing hydrophilic polymer and a double-layer coating system thereof, wherein the two systems can be applied to the surface of a plastic substrate of a medical device, and the formed hydrophilic coating can be used as a hydrophilic lubricating layer to provide lower friction force, better lubricity and higher adhesion firmness for the medical device, so that important technical support can be provided for developing implantable medical device products. The above object of the present invention can be achieved by the following means. In a first aspect of the invention, a hydrophilic polymer-containing coating system is provided, which comprises, based on 100 parts by dry weight, 45-90 parts by weight of reactive hydrophilic polymer Poly1, 9.9-50 parts by weight of reactive monomer Rm1, 0.1-5 parts by weight of initiator In1 and solvent So1; the reactive hydrophilic polymer Poly1 has a general structure shown in a formula (1); the reactive monomer Rm1 is capable of intermolecular crosslinking; The initiator In1 is Norrish type I initiator or free radical photoinitiator; the mass percentage of the solvent So1 in the coating system is more than or equal to 50%; in the formula (1), the components are as follows, M is an integer selected fro