CN104387553B - A kind of biodegradable unsaturated polyurethanes material and preparation method thereof - Google Patents
A kind of biodegradable unsaturated polyurethanes material and preparation method thereof Download PDFInfo
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- CN104387553B CN104387553B CN201410667130.0A CN201410667130A CN104387553B CN 104387553 B CN104387553 B CN 104387553B CN 201410667130 A CN201410667130 A CN 201410667130A CN 104387553 B CN104387553 B CN 104387553B
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- small molecule
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- fumaric acid
- propylene glycol
- glycol ester
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 63
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 63
- 239000000463 material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims description 18
- -1 poly- fumaric acid propylene glycol ester Chemical class 0.000 claims abstract description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000012948 isocyanate Substances 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 229920006305 unsaturated polyester Polymers 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 8
- 150000003384 small molecules Chemical class 0.000 claims abstract description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 48
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 23
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 150000002513 isocyanates Chemical class 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 claims description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000005442 diisocyanate group Chemical group 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 150000004702 methyl esters Chemical class 0.000 claims description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims 1
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000004970 Chain extender Substances 0.000 abstract description 4
- 230000002950 deficient Effects 0.000 abstract description 2
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 229920003225 polyurethane elastomer Polymers 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 7
- BTNYBNHUZOZYTA-TYYBGVCCSA-N (e)-but-2-enedioic acid;propane-1,2-diol Chemical compound CC(O)CO.OC(=O)\C=C\C(O)=O BTNYBNHUZOZYTA-TYYBGVCCSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000005292 vacuum distillation Methods 0.000 description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- 235000019082 Osmanthus Nutrition 0.000 description 3
- 241000333181 Osmanthus Species 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000711 cancerogenic effect Effects 0.000 description 3
- 231100000315 carcinogenic Toxicity 0.000 description 3
- 238000007306 functionalization reaction Methods 0.000 description 3
- KPNBUPJZFJCCIQ-LURJTMIESA-N methyl L-lysinate Chemical compound COC(=O)[C@@H](N)CCCCN KPNBUPJZFJCCIQ-LURJTMIESA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- 229920006264 polyurethane film Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 description 1
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 1
- 101710130081 Aspergillopepsin-1 Proteins 0.000 description 1
- 102100031007 Cytosolic non-specific dipeptidase Human genes 0.000 description 1
- HTTJABKRGRZYRN-UHFFFAOYSA-N Heparin Chemical compound OC1C(NC(=O)C)C(O)OC(COS(O)(=O)=O)C1OC1C(OS(O)(=O)=O)C(O)C(OC2C(C(OS(O)(=O)=O)C(OC3C(C(O)C(O)C(O3)C(O)=O)OS(O)(=O)=O)C(CO)O2)NS(O)(=O)=O)C(C(O)=O)O1 HTTJABKRGRZYRN-UHFFFAOYSA-N 0.000 description 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- 239000004425 Makrolon Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229960000633 dextran sulfate Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 1
- 238000001415 gene therapy Methods 0.000 description 1
- 229960002897 heparin Drugs 0.000 description 1
- 229920000669 heparin Polymers 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001308 poly(aminoacid) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
-
- 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
- C08G2230/00—Compositions for preparing biodegradable polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Biodegradable unsaturated polyurethanes material disclosed by the invention includes soft section and hard section, described soft section is the poly- fumaric acid propylene glycol ester of unsaturated polyester (UP) polyalcohol, and described hard section is representative examples of saturated aliphatic isocyanates and small molecule diol chain-extension agent or small molecule diamine chain stretching agent.The material, with representative examples of saturated aliphatic isocyanates as raw material, with small molecule glycol or small molecule diamines as chain extender, is prepared with poly- fumaric acid propylene glycol ester as macromolecule dihydric alcohol using two step chain extension methods.Polyurethane elastomer prepared by the present invention has biodegradability, and material is in itself and catabolite is harmless, with good biocompatibility.Polyurethane backbone structure is easy to further be modified material with a large amount of unsaturation electron deficient double bonds, has a good application prospect.
Description
Technical field
The present invention relates to a kind of biodegradable unsaturated polyurethanes material and preparation method thereof, belong to bio-medical material
Technical field.
Background technology
Biodegradable material is led due to its degradable and safety non-toxic characteristic in agricultural, environmental protection, food and medical treatment etc.
Domain has important application.Especially in bio-medical field, the material that degradable in vivo and catabolite have no toxic side effect is planted
Second operation taking-up need not be carried out after entering in vivo, therefore in drug delivery, organizational project and regenerative medicine and gene therapy side
Face application is particularly extensive.Biodegradable material particularly may be divided into natural origin material and synthetic material.Natural degradable
Material mainly including dextran sulfate, shitosan, heparin and protein etc., typically with excellent biocompatibility, but is grown
Phase is implanted with potential induction variation risk.Comparatively speaking, artificial synthesized degradation material does not have the potential danger of this respect, raw
Thing compatibility also meets concrete application requirement, while the physical and chemical performance of material can obtain fine regulation and control, thus in spy
Fixed field have more be widely applied prospect.
Artificial synthesized Biodegradable material is mainly including polyester, polyethers, condensing model, polyurethane and polyaminoacid etc..Its
In, it is polyurethane material prepared by raw material by degradable polyester, with excellent mechanical property, moulding process and bio-compatible
Property, and controllable degradation rate and surface property, therefore there is important application at aspects such as Bone Defect Repari, cardiovascular reparations.
Biodegradable polyurethane material is general with tetramethylene diisocyanate or hexamethylene diisocyanate or 4,4 '-two hexamethylenes
The representative examples of saturated aliphatic such as dicyclohexylmethane diisocyanate or 1B diisocyanate isocyanates is raw material, is lured in case producing and having
Become carcinogenic Biodegradation of PAHs product.It is chain extender to use small molecule dihydroxylic alcohols or diamine simultaneously, is prepared by two step chain extension methods
Obtain HMW polyurethane.Substantial amounts of degradable polyurethane product is synthesized and has been used widely at present.For example, passing through
The degradable polyester such as poly- (6-caprolactone) (PCL), makrolon (PC), poly-β-hydroxybutyric acid (PHB) is soft section, and cooperation is obtained
A series of degradable polyurethane material.
At present, the research of biological medical degradable polyurethane material is extensive, typically concentrates on saturated polyol polyester for raw material,
Thus the material for preparing, with good mechanical property and biological safety, but lacks enough bioactivity.While by
In lacking the functional group that is available for reaction on main polymer chain, therefore material modification needed by plasma, amine solution, photo-grafting
Realized etc. method so that the functionalization of material becomes difficult complex steps, so as to limit further applying for material.Therefore, make
It is standby a kind of with excellent biocompatibility, while having the Biodegradable polyurethane material of easy modified and functional method
Material, has great importance.
The content of the invention
The invention aims to solve the problems, such as that it is effectively modified that existing medical degradable polyurethane material is difficult to, there is provided
It is a kind of can easy functionalization biodegradable unsaturated polyurethanes material and preparation method thereof.
The purpose of the present invention is achieved through the following technical solutions.
Biodegradable unsaturated polyurethanes material of the invention, including soft section and hard section, described soft section are unsaturated
The poly- fumaric acid propylene glycol ester of PEPA, described hard section is representative examples of saturated aliphatic isocyanates and small molecule diol chain-extension agent
Or small molecule diamine chain stretching agent.
The number-average molecular weight of above-mentioned poly- fumaric acid propylene glycol ester is 500-3000.
Above-mentioned aliphatic isocyanates can be tetramethylene diisocyanate or hexamethylene diisocyanate (HDI)
Or 4,4 '-dicyclohexyl methyl hydride diisocyanate (HMDI) or 1B diisocyanate (LDI)；Described small molecule glycol
Chain extender can be 1,4- butanediols (BDO)；Small molecule diamine chain stretching agent can be 1B methyl esters (Lys-OMe).
The preparation method of biodegradable unsaturated polyurethanes material of the invention, comprises the following steps：
1) the poly- fumaric acid propylene glycol ester for poly- fumaric acid propylene glycol ester and dry toluene being configured into mass fraction 30% is molten
Liquid, the molal quantity of hydroxyl in solution is determined using ISO 2554-1974 methods；
2) by step 1) obtained by poly- fumaric acid propylene glycol ester solution be added to and dry there-necked flask, removal of solvent under reduced pressure
Toluene and residual moisture, are subsequently adding solvent anhydrous dioxane and dissolve again, add representative examples of saturated aliphatic isocyanates, and urge
Agent dibutyl tin laurate, reacts 2~5h in 60~80 DEG C under nitrogen protection, obtains isocyanate-terminated pre-polymerization
Thing；The molal quantity of the molal quantity of NCO and hydroxyl in poly- fumaric acid propylene glycol ester wherein in representative examples of saturated aliphatic isocyanates
The ratio between be 1.1~1.6：1, dibutyl tin laurate consumption is the 0.2mol% of hydroxyl moles in solution；
3) in step 2) prepare isocyanate-terminated prepolymer in add small molecule glycol or small molecule diamines, in
60 DEG C of chain extending reaction at least 6h, obtain polyurethane solutions, and the molal quantity of small molecule glycol or small molecule diamines is representative examples of saturated aliphatic
In isocyanates in NCO molal quantity and poly- fumaric acid propylene glycol ester hydroxyl moles difference；
4) keep 60 DEG C, in step 3) prepare polyurethane solutions in add ethanol end-blocking；
5) by through step 4) treatment polyurethane solutions pour into ethanol precipitate, centrifugation, collect, the polyurethane of collection is consolidated
Body is again dissolved in dioxane, and pours into precipitation in ethanol again, is repeated several times, and the urethane solid of gained finally is used into two
The ring of oxygen six dissolves, and freeze-drying obtains biodegradable unsaturated polyurethanes material.
Compared with existing medical polyurethane, the present invention has advantages below：
1) poly- fumaric acid propylene glycol ester has excellent biodegradability and biocompatibility, and its catabolite is mainly
Fumaric acid and propane diols, can be circulated by tricarboxylic in human body and exclude external, be had no toxic side effect, therefore with poly- fumaric acid the third two
Alcohol ester is that polyurethane prepared by raw material has biodegradable performance.
2) with representative examples of saturated aliphatic isocyanates as raw material so that hard section catabolite is without the toxic and side effect such as carcinogenic.
3) with small molecule glycol or diamines as chain extender so that hard section catabolite is without the toxic and side effect such as carcinogenic.
4) polyurethane molecular backbone structure retains a large amount of unsaturation electron deficient carbon-to-carbon double bonds, can carry under mild conditions
For efficient reaction site so that the modified and functionalization of material is more easy and effective.
Brief description of the drawings
Fig. 1 is the synthetic line figure of biodegradable unsaturated polyurethanes material of the invention.
Specific embodiment
The present invention is further illustrated below in conjunction with example, but these examples are not intended to limit the present invention.Life of the invention
Synthetic line such as Fig. 1 of Biodegradable unsaturated polyurethanes material.
Embodiment 1
Biodegradable unsaturated polyurethanes material (PPFU/HDI 1.6+Lys-OMe), including soft section and hard section, it is described
Soft section be the poly- fumaric acid propylene glycol ester PPF of unsaturated polyester (UP) polyalcohol, described hard section be aliphatic isocyanates HDI and
Small molecule diamine chain stretching agent Lys-OMe.
With following structure.
Its preparation is comprised the following steps：
The PPF that number-average molecular weight is 1000 is configured to the poly- fumaric acid propylene glycol ester solution of mass fraction 30%, according to
ISO 2554-1974 methods, it is determined that it is 14.68mmol to obtain hydroxyl moles in solution.
Take during above-mentioned PPF toluene solutions add and dry there-necked flask, 110 DEG C of decompression 1h remove solvent toluene and residual water
Point.Add solvent anhydrous dioxane 30mL to dissolve again, add 1.9752g hexamethylene diisocyanates (HDI),
0.03mmol catalyst dibutyltin dilaurylates, react 3h in 70 DEG C under nitrogen protection.60 DEG C are cooled to, are added
1.0267g lysine methyl ester dihydrochlorides, 1.3369g triethylamines, chain extending reaction 6h at 60 DEG C are added after stirring 15min.Add
3g ethanol synthesis 1h is blocked.Polyurethane dioxane solution is poured into ethanol is after completion of the reaction precipitated, 3 times repeatedly.Most
It is dissolved in dioxane solution eventually, freeze-drying 24h obtains polyurethane.
Obtained polyurethane is dissolved in dioxane, in pouring into polytetrafluoro mould, air atmosphere normal temperature volatilization 72h, after
48h is vacuum dried in 35 DEG C and removes residual solvent, obtain polyurethane film.In order to investigate the mechanics of the polyurethane of present invention preparation
Performance, tests the tensile strength and elongation at break of polyurethane, and batten size is：Length x width x thickness=50mm ×
5mm×0.5mm.Rate of extension is 100mm/min.Mechanics Performance Testing gained polyurethane fracture strength is 4.9MPa, and fracture is stretched
Rate long is 960%.
In order to investigate the degradation property of the polyurethane of present invention preparation, external degradation experiment is carried out, degraded medium is
5mol/L sodium hydroxide solutions.The polyurethane film of 10mm × 10mm is put into 20mL seed bottles, 15mL NaOH is added
Solution, shakes in 37 DEG C of waters bath with thermostatic control.Hydrolysis takes out sample after 15 days, with water washing is distilled 3 times, is dried in 40 DEG C of vacuum drying ovens
24h.Degraded is represented using mass loss percentage：Mass loss (%)=(W0-W1)/W0× 100%.Wherein W0And W1Respectively
Quality before polyurethane samples degraded and after degraded.Mass loss is after being degraded 15 days in degradation experiment display potassium hydroxide solution
76.48%.
Embodiment 2
Biodegradable unsaturated polyurethanes material (PPFU/HMDI 1.6+Lys-OMe), including soft section and hard section, it is described
Soft section be the poly- fumaric acid propylene glycol ester PPF of unsaturated polyester (UP) polyalcohol, described hard section be aliphatic isocyanates HMDI with
And small molecule diamine chain stretching agent Lys-OMe.
With following structure.
Its preparation is comprised the following steps：
The PPF that number-average molecular weight is 1000 is configured to the poly- fumaric acid propylene glycol ester solution of mass fraction 30%, according to
ISO 2554-1974 methods, it is determined that it is 14.68mmol to obtain hydroxyl moles in solution.
Take during above-mentioned PPF toluene solutions add and dry there-necked flask, 110 DEG C of vacuum distillation 1h, remove solvent toluene and residual
Remaining moisture.Add solvent anhydrous dioxane 30mL to dissolve again, add 3.0810g 4, the isocyanic acid of 4 '-dicyclohexyl methyl hydride two
Ester (HMDI), 0.03mmol catalyst dibutyltin dilaurylates react 3h in 70 DEG C under nitrogen protection.60 DEG C are cooled to,
1.0267g lysine methyl ester dihydrochlorides are added, 1.3369g triethylamines, chain extending reaction 6h at 60 DEG C are added after stirring 15min.
3g ethanol synthesis 1h is added to be blocked.Polyurethane dioxane solution is poured into ethanol is after completion of the reaction precipitated, repeatedly 3
It is secondary.Finally it is dissolved in dioxane solution, freeze-drying 24h obtains polyurethane.
Gained polyurethane fracture strength is 5.8MPa, and elongation at break is 640%；After being degraded 15 days in sodium hydroxide solution
Mass loss is 46.89%.
Embodiment 3
Biodegradable unsaturated polyurethanes material (PPFU/LDI 1.6+Lys-OMe), including soft section and hard section, it is described
Soft section be the poly- fumaric acid propylene glycol ester PPF of unsaturated polyester (UP) polyalcohol, described hard section be aliphatic isocyanates LDI and
Small molecule diamine chain stretching agent Lys-OMe.
With following structure.
Its preparation is comprised the following steps：
The PPF that number-average molecular weight is 1000 is configured to the poly- fumaric acid propylene glycol ester solution of mass fraction 30%, according to
ISO 2554-1974 methods, it is determined that it is 14.68mmol to obtain hydroxyl moles in solution.
Take during above-mentioned PPF toluene solutions add and dry there-necked flask, 110 DEG C of vacuum distillation 1h, remove solvent toluene and residual
Remaining moisture.Add solvent anhydrous dioxane 30mL to dissolve again, add 2.6568g 1Bs diisocyanate (LDI),
0.03mmol catalyst dibutyltin dilaurylates, react 3h in 70 DEG C under nitrogen protection.60 DEG C are cooled to, are added
1.0267g lysine methyl ester dihydrochlorides, 1.3369g triethylamines, chain extending reaction 6h at 60 DEG C are added after stirring 15min.Add
3g ethanol synthesis 1h is blocked.Polyurethane dioxane solution is poured into ethanol is after completion of the reaction precipitated, 3 times repeatedly.Most
It is dissolved in dioxane solution eventually, freeze-drying 24h obtains polyurethane.
Gained polyurethane fracture strength is 1.3MPa, and elongation at break is 950%；After being degraded 15 days in sodium hydroxide solution
Mass loss is 100%.
Embodiment 4
Biodegradable unsaturated polyurethanes material (PPFU/HDI 1.6+BDO), including soft section and hard section, described is soft
Section is the poly- fumaric acid propylene glycol ester PPF of unsaturated polyester (UP) polyalcohol, and described hard section is aliphatic isocyanates HDI and small point
Sub- diol chain-extension agent BDO.
With following structure.
Its preparation is comprised the following steps：
The PPF that number-average molecular weight is 1000 is configured to the poly- fumaric acid propylene glycol ester solution of mass fraction 30%, according to
ISO 2554-1974 methods, it is determined that it is 14.68mmol to obtain hydroxyl moles in solution.
Take during above-mentioned PPF toluene solutions add and dry there-necked flask, 110 DEG C of vacuum distillation 1h, remove solvent toluene and residual
Remaining moisture.Add solvent anhydrous dioxane 30mL to dissolve again, add 1.9752g HDI, 0.03mmol catalyst dibutyltins osmanthus
Sour dibutyl tin, reacts 3h in 70 DEG C under nitrogen protection.60 DEG C are cooled to, 0.3969g BDOs (BDO), 60 is added
Chain extending reaction 6h at DEG C.3g ethanol synthesis 1h is added to be blocked.Polyurethane dioxane solution is poured into second after completion of the reaction
Precipitated in alcohol, 3 times repeatedly.Finally it is dissolved in dioxane solution, freeze-drying 24h obtains polyurethane.
Gained polyurethane fracture strength is 4.3MPa, and elongation at break is 480%；After being degraded 15 days in sodium hydroxide solution
Mass loss is 78.64%.
Embodiment 5
Biodegradable unsaturated polyurethanes material (PPFU/HDI 1.3+BDO), including soft section and hard section, described is soft
Section is the poly- fumaric acid propylene glycol ester PPF of unsaturated polyester (UP) polyalcohol, and described hard section is aliphatic isocyanates HDI and small point
Sub- diol chain-extension agent BDO.
With following structure.
Its preparation is comprised the following steps：
The PPF that number-average molecular weight is 1000 is configured to the poly- fumaric acid propylene glycol ester solution of mass fraction 30%, according to
ISO 2554-1974 methods, it is determined that it is 14.68mmol to obtain hydroxyl moles in solution.
Take during above-mentioned PPF toluene solutions add and dry there-necked flask, 110 DEG C of vacuum distillation 1h, remove solvent toluene and residual
Remaining moisture.Add solvent anhydrous dioxane 30mL to dissolve again, add 1.6049g HDI, 0.03mmol catalyst dibutyltins osmanthus
Sour dibutyl tin, reacts 3h in 70 DEG C under nitrogen protection.60 DEG C are cooled to, 0.1985g BDOs (BDO), 60 is added
Chain extending reaction 6h at DEG C.3g ethanol synthesis 1h is added to be blocked.Polyurethane dioxane solution is poured into second after completion of the reaction
Precipitated in alcohol, 3 times repeatedly.Finally it is dissolved in dioxane solution, freeze-drying 24h obtains polyurethane.
Gained polyurethane fracture strength is 2.6MPa, and elongation at break is 780%；After being degraded 15 days in sodium hydroxide solution
Mass loss is 100%.
Embodiment 6
Biodegradable unsaturated polyurethanes material (PPFU/HDI 1.3+BDO), including soft section and hard section, described is soft
Section is the poly- fumaric acid propylene glycol ester PPF of unsaturated polyester (UP) polyalcohol, and described hard section is aliphatic isocyanates HDI and small point
Sub- diol chain-extension agent BDO.
With following structure.
Its preparation is comprised the following steps：
The PPF that number-average molecular weight is 2000 is configured to the poly- fumaric acid propylene glycol ester solution of mass fraction 30%, according to
ISO 2554-1974 methods, it is determined that it is 7.35mmol to obtain hydroxyl moles in solution.
Take during above-mentioned PPF toluene solutions add and dry there-necked flask, 110 DEG C of vacuum distillation 1h, remove solvent toluene and residual
Remaining moisture.Add solvent anhydrous dioxane 30mL to dissolve again, add 0.8025g HDI, 0.015mmol catalyst dibutyltins osmanthus
Sour dibutyl tin, reacts 3h in 70 DEG C under nitrogen protection.60 DEG C are cooled to, 0.09931,4- butanediols (BDO), 60 DEG C is added
Lower chain extending reaction 6h.3g ethanol synthesis 1h is added to be blocked.Polyurethane dioxane solution is poured into ethanol after completion of the reaction
Middle precipitation, repeatedly 3 times.Finally it is dissolved in dioxane solution, freeze-drying 24h obtains polyurethane.
Gained polyurethane fracture strength is 2.1MPa, and elongation at break is 850%；After being degraded 15 days in sodium hydroxide solution
Mass loss is 100%.
Claims (3)
1. a kind of preparation method of biodegradable unsaturated polyurethanes material, the material includes soft section and hard section, and described is soft
Section is the poly- fumaric acid propylene glycol ester of unsaturated polyester (UP) polyalcohol, and described hard section is representative examples of saturated aliphatic isocyanates and small molecule
Diol chain-extension agent or small molecule diamine chain stretching agent, its preparation are comprised the following steps：
1）Poly- fumaric acid propylene glycol ester and dry toluene are configured to the poly- fumaric acid propylene glycol ester solution of mass fraction 30%, are adopted
The molal quantity of hydroxyl in solution is determined with ISO 2554-1974 methods；
2）By step 1）The poly- fumaric acid propylene glycol ester solution of gained is added in drying there-necked flask, removal of solvent under reduced pressure toluene
And residual moisture, it is subsequently adding solvent anhydrous dioxane and dissolves again, add representative examples of saturated aliphatic isocyanates, and catalyst
Dibutyl tin laurate, reacts 2 ~ 5h in 60 ~ 80 °C under nitrogen protection, obtains isocyanate-terminated prepolymer；Its
The ratio between the molal quantity of NCO and molal quantity of hydroxyl in poly- fumaric acid propylene glycol ester in middle saturation aliphatic isocyanates
It is 1.1 ~ 1.6：1, dibutyl tin laurate consumption is 0.2 mol% of hydroxyl moles in solution；
3）In step 2）Small molecule glycol or small molecule diamines are added in the isocyanate-terminated prepolymer for preparing, in 60 °C
Chain extending reaction at least 6h, obtains polyurethane solutions, and the molal quantity of small molecule glycol or small molecule diamines is representative examples of saturated aliphatic isocyanide
In acid esters in NCO molal quantity and poly- fumaric acid propylene glycol ester hydroxyl moles difference；
4）Kept for 60 °C, in step 3）Ethanol end-blocking is added in the polyurethane solutions of preparation；
5）Will be through step 4）The polyurethane solutions for the treatment of are poured into ethanol and precipitated, centrifugation, collection, and the urethane solid that will be collected is again
It is secondary to be dissolved in dioxane, and precipitation in ethanol is poured into again, it is repeated several times, finally by the urethane solid of gained dioxy six
Ring dissolves, and freeze-drying obtains biodegradable unsaturated polyurethanes material.
2. the preparation method of biodegradable unsaturated polyurethanes material according to claim 1, it is characterised in that：It is described
Poly- fumaric acid propylene glycol ester number-average molecular weight be 500-3000.
3. the preparation method of biodegradable unsaturated polyurethanes material according to claim 2, it is characterised in that：It is described
Aliphatic isocyanates be tetramethylene diisocyanate or hexamethylene diisocyanate or 4,4 '-dicyclohexyl methyl hydride two
Isocyanates or 1B diisocyanate；Described small molecule diol chain-extension agent is 1,4- butanediols；Small molecule diamines expands
Chain agent is 1B methyl esters.
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| CN106046309A (en) * | 2015-11-20 | 2016-10-26 | 徐永祥 | Completely-biodegradable cross-linked polyurethane and preparation method thereof, and porous sponge prepared from completely-biodegradable cross-linked polyurethane |
| CN106397721B (en) * | 2016-10-10 | 2019-01-11 | 同济大学 | A kind of preparation method of the Biodegradable polyurethane containing unsaturated bond |
| WO2018144849A1 (en) * | 2017-02-02 | 2018-08-09 | The University Of Akron | Functionalized poly(propylene fumarate) polymers made by ring opening polymerization using magnesium catalysts |
| CN107686546A (en) * | 2017-06-19 | 2018-02-13 | 许开天 | A kind of novel degradable polyurethane biomaterial and its preparation method and application |
| CN108409990B (en) * | 2018-03-20 | 2020-11-03 | 青岛科技大学 | Graphene/polyester thermoplastic elastomer composite material and preparation method thereof |
| CN109988280B (en) * | 2019-04-10 | 2020-07-14 | 浙江大学 | Active oxygen responsive degradable polyurethane material and preparation method thereof |
| CN110183608B (en) * | 2019-04-18 | 2020-10-02 | 浙江大学 | Active oxygen degradation polyurethane material containing polyketide thiol soft segment and preparation method thereof |
| CN113698908B (en) * | 2021-09-06 | 2022-11-11 | 合肥工业大学 | UV (ultraviolet) viscosity reducing adhesive and preparation method thereof |
| CN113845643B (en) * | 2021-09-17 | 2023-03-28 | 浙江大学 | Shape memory polyurethane material with active oxygen responsiveness and anti-adhesion dual functions |
| CN114984312A (en) * | 2022-05-30 | 2022-09-02 | 浙江大学 | Hyperbranched polylysine-containing polyurethane heart patch and preparation method thereof |
| CN115322123B (en) * | 2022-08-15 | 2024-02-02 | 万华化学集团股份有限公司 | Halogen modified azo diamine chain extender, preparation method and application thereof |
| CN118599504A (en) * | 2024-08-07 | 2024-09-06 | 山东得顺源石油科技有限公司 | Oil-based drilling fluid and preparation method thereof |
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| CN1720278A (en) * | 2002-12-03 | 2006-01-11 | 陶氏环球技术公司 | Sulfonate-functional polyester polyols |
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