CN112831013B - Functionalized polyurethane and preparation method and application thereof - Google Patents
Functionalized polyurethane and preparation method and application thereof Download PDFInfo
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 52
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims description 11
- 150000002009 diols Chemical class 0.000 claims abstract description 54
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 35
- 239000004417 polycarbonate Substances 0.000 claims abstract description 35
- 229920002367 Polyisobutene Polymers 0.000 claims abstract description 25
- 239000004970 Chain extender Substances 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 17
- 230000007062 hydrolysis Effects 0.000 claims abstract description 16
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 16
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 11
- 150000004985 diamines Chemical class 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 4
- 238000012662 bulk polymerization Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 2
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 2
- 229940051250 hexylene glycol Drugs 0.000 claims description 2
- 238000002513 implantation Methods 0.000 claims description 2
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 claims description 2
- -1 pentylene diamine Chemical class 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 238000004132 cross linking Methods 0.000 abstract description 4
- 210000003709 heart valve Anatomy 0.000 abstract description 4
- 210000004204 blood vessel Anatomy 0.000 abstract description 3
- 238000001727 in vivo Methods 0.000 abstract description 3
- 239000002473 artificial blood Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 18
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 7
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical group C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920003225 polyurethane elastomer Polymers 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000010100 anticoagulation Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009661 fatigue test Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 210000002540 macrophage Anatomy 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- XURVRZSODRHRNK-UHFFFAOYSA-N o-quinodimethane Chemical group C=C1C=CC=CC1=C XURVRZSODRHRNK-UHFFFAOYSA-N 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 230000002792 vascular Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6204—Polymers of olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
Abstract
The invention provides a functionalized polyurethane, which is obtained by copolymerizing a flexible chain segment consisting of polycarbonate diol and polyisobutylene diol with a rigid chain segment consisting of diisocyanate and a chain extender; the chain extender comprises a component A and a component B; the component A is dihydric alcohol containing a 4-benzocyclobutene-based structure; the component B is other low molecular dihydric alcohol and/or low molecular diamine. The functionalized polyurethane provided by the invention has the advantages that the polycarbonate structure in the soft segment has a hydrolysis resistance function, the polyisobutylene structure has an oxidation resistance function, and the 4-benzocyclobutene structure in the rigid segment chain extender can perform self-crosslinking reaction at elevated temperature (preferably higher than 190 ℃). Therefore, the functional polyurethane has good hydrolysis resistance, oxidation resistance and creep resistance, can realize the durability of medical polyurethane in vivo and is used for manufacturing devices such as artificial heart valves, artificial blood vessels, interventional medical catheters and the like which are implanted into the body for a long time.
Description
Technical Field
The invention relates to the technical field of medical materials, in particular to functionalized polyurethane and a preparation method and application thereof.
Background
The medical polyurethane elastomer is composed of polyether, polyester diol and the like as soft segments and diisocyanate as hard segments, the flexibility of the soft segments endows the polyurethane with good elasticity, the rigidity of the hard segments forms a crystalline region, and the soft segments and the hard segments belong to a thermodynamically incompatible system and have polarity difference, so that microphase separation can be caused. The polyurethane material is made by adjusting the proportion, structure, molecular distribution and the like of soft and hard segmentsThe material has the characteristics of proper mechanical strength, abrasion resistance, rebound resilience, biocompatibility, anticoagulation and the like. Medical polyurethanes can be used in implantable interventional medical devices such as central venous catheters, peripheral venous catheters, arterial catheter sheaths, balloon dilatation catheters, peritoneal dialysis catheters, balloon catheters, ports of fluid infusion, heart valves, vascular prostheses, and the like. Because of the existence of ester group, carbamate group and carbamido group in polyurethane, water can cause the molecular chain of polyurethane to be hydrolyzed under the complex environment of human body; the substance released by macrophage includes H+And oxidation media such as enzymes and in vivo free radicals are easy to cause polyurethane oxidative degradation, and the degradation of polyurethane molecular chains caused by hydrolysis and oxidation reaction leads to the reduction of the mechanical property of the polyurethane molecular chains, so that the polyurethane molecular chains are difficult to be applied to instruments implanted/intervened in human body environment for a long time. In addition, the polyurethane materials and articles, such as those used in long-term implantable devices, can creep when subjected to long-term fatigue stresses, which can limit their further use. Therefore, the preparation of medical polyurethane elastomer with oxidation resistance, hydrolysis resistance and creep resistance becomes a research hotspot which is widely concerned in the industry.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a functionalized polyurethane, and a preparation method and an application thereof, wherein the prepared functionalized polyurethane has hydrolysis resistance, oxidation resistance and creep resistance.
In order to achieve the aim, the invention provides a functionalized polyurethane, which is obtained by copolymerizing a flexible chain segment consisting of polycarbonate diol and polyisobutylene diol with a rigid chain segment consisting of diisocyanate and a chain extender;
the chain extender comprises a component A and a component B;
the component A is dihydric alcohol containing a 4-benzocyclobutene-based structure; the component B is other low molecular dihydric alcohol and/or low molecular diamine.
In the invention, the polycarbonate diol is preferably polycarbonate diol with hydrolysis resistance.
In the present invention, the polyisobutylene diol is preferably a polyisobutylene diol having an oxidation resistance function.
In the invention, the molecular weight of the polycarbonate diol is preferably 400-8000, and more preferably 500-5000.
In the present invention, the polycarbonate diol is preferably a polycarbonate alcohol containing 1, 6-hexanediol and/or a polycarbonate alcohol containing 1, 4-cyclohexanedimethanol.
In some embodiments of the invention, the polycarbonate diol is selected from one or more of the group consisting of the polycarbonate diols UH-CARB50 (molecular weight 500), UH-CARB100 (molecular weight 1000), UH-CARB200 (molecular weight 2000), and 1, 4-cyclohexanedimethanol-containing polycarbonate UC-CARB100 (molecular weight 1000) from Japan containing 1, 6-hexanediol.
In a preferred embodiment of the present invention, the polyisobutylene diol contains a structure represented by formula ii:
wherein R is
n is a polymerization degree of 1 to 70, more preferably 2 to 50;
the source of the polyisobutylene diol is not particularly limited in the present invention, and may be generally commercially available or prepared according to a method well known to those skilled in the art.
In some embodiments of the invention, the polyisobutylene diol preparation method is described in Journarof Polymer Science, Polymer Chemistry Edition,1980,18, 3177-.
In the present invention, the diisocyanate is preferably an aliphatic diisocyanate or an aromatic diisocyanate. More preferably one or more of 2, 4-Tolylene Diisocyanate (TDI), 4 '-diphenylmethane diisocyanate (MDI), m-xylylene isocyanate (XDI), isophorone diisocyanate (IPDI), 1, 6-Hexamethylene Diisocyanate (HDI), 4' -dicyclohexylmethane diisocyanate (HMDI).
Preferably, the diol containing the 4-benzocyclobutene structure has a structure shown in a formula III:
m, y, k are preferably 0 to 20; more preferably 1 to 10, and still more preferably 1 to 5. In some embodiments of the present invention, m is 1, y is 1, and k is 1.
In the present invention, the 4-benzocyclobutene structure contained in the above diol structure, in which the four-membered ring having strain is present, is converted into o-xylylene at 190 ℃, so that the benzocyclobutene group reacts with a dienophile in Diels-Alder reaction to form a six-membered ring, or reacts with itself to form an eight-membered ring. The polyurethane molecular weight contains multiple benzocyclobutene groups that can be thermally crosslinked with a dienophile.
In some embodiments of the invention, the diol having a 4-benzocyclobutene-based structure is obtained by the following reaction.
Wherein m, y and k are 0-20; more preferably 1 to 10, and still more preferably 1 to 5. In some embodiments of the present invention, m is 1, y is 1, and k is 1.
Preferably, the other low molecular weight diol includes one or more of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, and hexylene glycol.
In a preferred embodiment of the present invention, the low molecular diamine includes one or more of ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, and hexylenediamine.
In the invention, the mass ratio of the total amount of the polycarbonate diol and the polyisobutylene diol to the diisocyanate, the component A and the component B is (20-85): (4-40): (0.2-40): (0.5 to 20).
The invention provides a preparation method of the functionalized polyurethane, which comprises the following steps:
the polycarbonate diol and the polyisobutylene diol, the diisocyanate and the chain extender are prepared by bulk polymerization or solvent polymerization of a one-step method, a two-step method or a semi-prepolymerization method according to the proportion.
Bulk or solvent polymerization, either one-step or two-step or semi-prepolymer, and the catalysts required for this invention are described in detail in CN 1371927A.
The invention provides the application of the functionalized polyurethane or the functionalized polyurethane prepared by the preparation method as a raw material of a medical implantation/intervention apparatus.
The implantable interventional medical devices include, but are not limited to, central venous catheters, peripheral venous catheters, arterial catheter sheaths, balloon dilatation catheters, peritoneal dialysis catheters, balloon catheters, ports of infusion, prosthetic heart valves, prosthetic blood vessels, and the like.
Compared with the prior art, the invention provides the functionalized polyurethane, which is obtained by copolymerizing a flexible chain segment consisting of polycarbonate diol and polyisobutylene diol with a rigid chain segment consisting of diisocyanate and a chain extender; the chain extender comprises a component A and a component B; the component A is dihydric alcohol containing a 4-benzocyclobutene-based structure; the component B is other low molecular dihydric alcohol and/or low molecular diamine. The polycarbonate diol structure in the functionalized polyurethane soft segment provided by the invention has a hydrolysis resistance function, the polyisobutylene diol structure has an oxidation resistance function, and the 4-benzocyclobutene structure in the rigid segment chain extender can perform self-crosslinking reaction at elevated temperature (preferably higher than 180 ℃). Therefore, the functional polyurethane has good hydrolysis resistance and oxidation resistance, does not change greatly even under the corrosion of an oxidizing medium and a hydrolyzing medium, has creep resistance, can realize the durability of internal service of the medical polyurethane, and is used for manufacturing devices such as artificial heart valves, artificial blood vessels, interventional medical catheters and the like which are implanted/intervened in vivo for a long time. In addition, the preparation method adopted by the invention adopts the conventional synthetic methods except the raw material monomer formula, and the method is simple, mature and easy to control.
The test result shows that the mechanical property of the functional polyurethane provided by the invention is not changed greatly under the hydrolysis and oxidation conditions, and the strain of the synthesized polyurethane is smaller under the action of certain stress after the synthetic polyurethane is subjected to heat treatment and self-crosslinking, so that the functional polyurethane is hydrolysis-resistant and oxidation-resistant, and has better creep resistance.
Detailed Description
For further illustration of the present invention, the functionalized polyurethanes provided by the present invention, as well as methods of making and using the same, are described in detail below with reference to examples, but it is to be understood that such descriptions are merely intended to further illustrate features and advantages of the present invention, and are not intended to limit the scope of the claims.
EXAMPLE 1 one-step solvent polymerization
400ml of tetrahydrofuran/N, N-dimethylacetamide (volume ratio: 1:6) solvent, 30g of polycarbonate diol (polycarbonate alcohol UH-CARB50 (molecular weight: 500) containing 1, 6-hexanediol in Japan) and 30g of polyisobutylene diol (molecular weight: 1000) were put into a four-necked flask, stirred, and heated to 70 ℃; adding 10g of ethylene glycol serving as a chain extender and 10g of 4-benzocyclobutene diol (m is 1, y is 1, and k is 1), and fully stirring to completely dissolve the reactants; then 20g of 4,4' -diphenylmethane diisocyanate (MDI) is added, the temperature is raised to 100 ℃, the reaction is carried out for 6 hours, the stirring is stopped, and the polyurethane solution with the solid content of about 25 percent is obtained after cooling.
EXAMPLE 2 one-step solvent polymerization
400ml of tetrahydrofuran/N, N-dimethylacetamide (volume ratio: 1:6) solvent, 30g of polycarbonate diol (polycarbonate alcohol UH-CARB200 (molecular weight 2000) containing 1, 6-hexanediol in Japan) and 30g of polyisobutylene diol (molecular weight 2000) were put into a four-necked flask, stirred, and heated to 70 ℃; adding chain extender 10g butanediol and 10g 4-benzocyclobutene dihydric alcohol (m is 1, y is 1, k is 1), and fully stirring to completely dissolve the reactants; then 20g of 4,4' -diphenylmethane diisocyanate (MDI) is added, the temperature is raised to 100 ℃, the reaction is carried out for 6 hours, the stirring is stopped, and the polyurethane solution with the solid content of about 26 percent is obtained after cooling.
Example 3 two-step solvent polymerization
Adding 400ml of N, N-dimethylacetamide solvent, 30g of polycarbonate diol (polycarbonate alcohol UH-CARB100 (molecular weight 1000) containing 1, 6-hexanediol in Japan) and 30g of polyisobutylene diol (molecular weight 1000) in sequence into a four-neck flask, stirring, heating to 70 deg.C, and dissolving completely; adding 20g of 4,4' -diphenylmethane diisocyanate (MDI) to react for 60 minutes, measuring the content of the isocyanate in the reaction process, adding 10g of ethylene glycol and 10g of 4-benzocyclobutene diol (m is 1, y is 1, and k is 1) when the content of the isocyanate is reduced to the theoretical amount, adding a chain extender to react for 5 hours, stopping stirring, and cooling to obtain the polyurethane solution with the solid content of about 23 percent.
Example 4 bulk polymerization
Adding 30g of polycarbonate diol (polycarbonate diol UC-CARB100 (molecular weight 1000) containing 1, 4-cyclohexanedimethanol in Japan) and 30g of polyisobutylene diol (molecular weight 2000) into a four-mouth bottle, stirring and heating to 100 ℃, carrying out vacuum degassing for 30 minutes under stirring, cooling to 50 ℃, sequentially adding 10g of ethylene glycol and 10g of 4-benzocyclobutene diol (m is 1, y is 1, k is 1) chain extender and 4,4' -diphenylmethane diisocyanate (MDI), stirring and heating to 100 ℃, reacting for 20 minutes, transferring the reaction mixture into a preheated polytetrafluoroethylene disc at 100 ℃, carrying out after-ripening for 5 hours in an oven at 110 ℃, cooling and pelletizing to obtain the product.
Comparative example 1
Adding 400ml tetrahydrofuran/N, N-dimethylacetamide (volume ratio 1:6) solvent and 60g polycarbonate diol (polycarbonate alcohol UH-CARB100 (molecular weight 1000) containing 1, 6-hexanediol in Japan) into a four-neck flask, stirring, and heating to 70 deg.C; adding 10g of ethylene glycol serving as a chain extender and 10g of 4-benzocyclobutene diol (m is 1, y is 1, and k is 1), and fully stirring to completely dissolve the reactants; then 20g of 4,4' -diphenylmethane diisocyanate (MDI) is added, the temperature is raised to 100 ℃, the reaction is carried out for 6 hours, the stirring is stopped, and the polyurethane solution with the solid content of about 24 percent is obtained.
Comparative example 2
Adding 400ml of tetrahydrofuran/N, N-dimethylacetamide (volume ratio is 1:6) solvent and 60g of polyisobutene diol (molecular weight is 1000) into a four-mouth bottle, stirring, and heating to 70 ℃; adding 10g of ethylene glycol serving as a chain extender and 10g of 4-benzocyclobutene diol (m is 1, y is 1, and k is 1), and fully stirring to completely dissolve the reactants; then 20g of 4,4' -diphenylmethane diisocyanate (MDI) is added, the temperature is raised to 100 ℃, the reaction is carried out for 6 hours, the stirring is stopped, and the polyurethane solution with the solid content of about 26 percent is obtained after cooling.
Comparative example 3
Adding 400ml of tetrahydrofuran/N, N-dimethylacetamide (volume ratio of 1:6) solvent, 30g of polycarbonate diol (polycarbonate alcohol UH-CARB100 (molecular weight 1000) containing 1, 6-hexanediol in Japan) and 30g of polyisobutylene diol (molecular weight 1000) into a four-necked flask, stirring, and heating to 70 deg.C; adding 20g of glycol serving as a chain extender, and fully stirring to completely dissolve reactants; then 20g of 4,4' -diphenylmethane diisocyanate (MDI) is added, the temperature is raised to 100 ℃, the reaction is carried out for 6 hours, the stirring is stopped, and the polyurethane solution with the solid content of about 25 percent is obtained after cooling.
Test experiments:
the prepared polyurethane is cast into a film by adopting 10 percent solution, the film thickness is about 1mm, and a dumbbell type standard sample knife is adopted to prepare a sample wafer.
And (3) hydrolysis resistance testing: the samples were placed in a 0.1MNaAc/HAc (pH 3.3-3.5) hydrolytic aging at 37 ℃ for half a year and then tested for tensile properties with the hydrolytic medium replaced twice a week.
And (3) testing oxidation resistance: place the sample in 3% H2O2And 0.1MCoCl2The oxidative media was aged for half a year at 37 ℃ and then tested for tensile properties, with the oxidative media being changed twice a week.
And (3) testing tensile property: the tensile properties of the mechanical sample polyurethane before and after aging were measured on an Instron-5869 type tensile tester at a tensile speed of 10mm/min and 10 specimens of each sample, and the results were averaged.
Creep test: the dumbbell type sample piece is aged at 180 ℃ for 10min, then a creep test is carried out under the action of 12MPa stress by using an electromagnetic fatigue test system, the test temperature is carried out at 20 ℃, and the strain capacity of the sample at 30000 seconds is recorded.
For examples 1 to 4 and comparative examples 1 to 3, the samples were subjected to hydrolysis, oxidation and heat treatment, and the results are shown in tables 1 and 2.
TABLE 1 comparison of mechanical Properties before and after hydrolysis and Oxidation treatment of the materials obtained in examples and comparative examples
TABLE 2 comparison of mechanical Properties before and after self-crosslinking of the materials obtained in examples and comparative examples by Heat treatment
As can be seen from the test results in tables 1 and 2, the polyurethane obtained in the embodiments 1 to 4 of the present invention has good hydrolysis resistance, oxidation resistance and creep resistance. Compared with the effect of the comparative example 1, the polyisobutylene diol introduced in the invention has better oxidation resistance. Compared with the effect of the comparative example 2, the polycarbonate diol introduced by the invention has better hydrolysis resistance. Compared with the effect of the comparative example 3, the 4-benzocyclobutene diol introduced by the invention has better creep resistance.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A functional polyurethane is prepared by copolymerizing a flexible chain segment consisting of polycarbonate diol and polyisobutylene diol with a rigid chain segment consisting of diisocyanate and a chain extender;
the chain extender comprises a component A and a component B;
the component A is dihydric alcohol containing a 4-benzocyclobutene-based structure; the component B is other low molecular dihydric alcohol and/or low molecular diamine;
the dihydric alcohol containing the 4-benzocyclobutene structure has a structure shown in a formula III:
wherein m, y and k are 0-20.
2. The functionalized polyurethane of claim 1, wherein the polycarbonate diol is a polycarbonate diol having hydrolysis resistance;
the polyisobutylene dihydric alcohol is polyisobutylene dihydric alcohol with an oxidation resistance function;
the diisocyanate is aliphatic diisocyanate or aromatic diisocyanate.
3. The functionalized polyurethane of claim 1, wherein the polycarbonate diol has a molecular weight of 400 to 8000.
4. The functionalized polyurethane of claim 1, wherein the polyisobutylene diol has a structure represented by formula ii:
wherein R is
n is polymerization degree of 1-70.
5. The functionalized polyurethane of claim 1, wherein said other low molecular weight diol comprises one or more of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, and hexylene glycol.
6. The functionalized polyurethane of claim 1, wherein the low molecular weight diamine comprises one or more of ethylene diamine, propylene diamine, butylene diamine, pentylene diamine, and hexylene diamine.
7. The functionalized polyurethane of claim 1, wherein the mass ratio of the total amount of the polycarbonate diol and the polyisobutylene diol to the diisocyanate, the component A and the component B is (20-85): (4-40): (0.2-40): (0.5 to 20).
8. The process for the preparation of the functionalized polyurethane according to any one of claims 1 to 7, comprising the following steps:
the polycarbonate diol and the polyisobutylene diol, the diisocyanate and the chain extender are prepared by bulk polymerization or solvent polymerization of a one-step method, a two-step method or a semi-prepolymerization method according to the proportion.
9. The functionalized polyurethane of any one of claims 1 to 7, or the functionalized polyurethane prepared by the preparation method of claim 8, for use as a raw material of a medical device for implantation/intervention.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5391650A (en) * | 1992-12-30 | 1995-02-21 | The Dow Chemical Company | Bisbenzocyclobutene thermosetting compounds and process for preparing the same |
| CN1445254A (en) * | 2003-04-10 | 2003-10-01 | 四川大学 | Polyurethane material containing fluorin in its lateral chain and preparing method thereof |
| CN102131530A (en) * | 2008-06-27 | 2011-07-20 | 心脏起搏器公司 | Polyisobutylene urethane, urea and urethane/urea copolymers and medical devices containing same |
| CN108368229A (en) * | 2015-12-17 | 2018-08-03 | 心脏起搏器股份公司 | Polyisobutene-polyurethane and medical treatment device containing them |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US8986626B2 (en) * | 2008-07-28 | 2015-03-24 | ETH Zürich / ETH Transfer | Probe arrangement for exchanging in a controllable way liquids with micro-sized samples of material like biological cells |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5391650A (en) * | 1992-12-30 | 1995-02-21 | The Dow Chemical Company | Bisbenzocyclobutene thermosetting compounds and process for preparing the same |
| CN1445254A (en) * | 2003-04-10 | 2003-10-01 | 四川大学 | Polyurethane material containing fluorin in its lateral chain and preparing method thereof |
| CN102131530A (en) * | 2008-06-27 | 2011-07-20 | 心脏起搏器公司 | Polyisobutylene urethane, urea and urethane/urea copolymers and medical devices containing same |
| CN108368229A (en) * | 2015-12-17 | 2018-08-03 | 心脏起搏器股份公司 | Polyisobutene-polyurethane and medical treatment device containing them |
Non-Patent Citations (1)
| Title |
|---|
| 苯并环丁烯及其材料（II）;王靖等;《玻璃钢／复合材料》;20040108(第3期);第44-50页 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024015200A1 (en) * | 2022-07-13 | 2024-01-18 | Leonard Pinchuk | Polyisobutylene‐based polyurethanes for medical implant devices |
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