CN106589290A - High-biocompatibility phosphorylcholine-modified polyurethane material and prepration method thereof - Google Patents
High-biocompatibility phosphorylcholine-modified polyurethane material and prepration method thereof Download PDFInfo
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- CN106589290A CN106589290A CN201611238672.1A CN201611238672A CN106589290A CN 106589290 A CN106589290 A CN 106589290A CN 201611238672 A CN201611238672 A CN 201611238672A CN 106589290 A CN106589290 A CN 106589290A
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/428—Lactides
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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
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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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
- C08G2230/00—Compositions for preparing biodegradable polymers
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Abstract
The invention relates to a high-biocompatibility phosphorylcholine-modified polyurethane material and a preparation method thereof. The prepration method comprises the following steps that (1) a isocyanate group-terminated prepolymer is prepared, specifically, a hydroxyl-terminated prepolymer is blended with excess diisocyanate for reaction, and the isocyanate group-terminated prepolymer is obtained; and (2) phosphorylcholine-modified polyurethane is prepared, specifically, a propyl dimethicone phosphorylcholine compound is dissolved into a solvent, and dropwise added into the isocyanate group-terminated prepolymer, the isocyanate group-terminated prepolymer is subjected to a chain extension reaction, and the phosphorylcholine-modified polyurethane material is obtained. A membrane prepared through the material is excellent in mechanical property, side-chained phosphorylcholine groups can form a hydrophilic interface in an aqueous solution, and the absorbing capacity for protein in blood is low; and meanwhile, the material has biodegradability. The material can be applied to a living body for a long term as a tissue engineering repair stent material and the like, and degradation products at the later stage can be absorbed by the living body.
Description
Technical field
The invention belongs to can medical macromolecular materials field, and in particular to a kind of high-biocompatibility Phosphorylcholine is modified poly-
Urethane material and preparation method thereof.
Background technology
Polyurethane material relies on its excellent mechanical property, is widely used in biomedical neck as biomaterial
Domain.The primary articles of medical polyurethane have:Cardiac valve prosthesiss, artificial lung, bone cementum, artificial skin, burn dressing, heart
Pacemaker, covered wire, suture, various clamping plates, catheter, grafting vessel, trachea, dental material, insertion material etc..But, though
So polyurethane found with preferable biocompatibility, but Jing long-term Clinical practice compared with other materials, polyurethane material
Caused vascular restenosiss and thrombosiss are remained and limit its wide variety of subject matter.
Ingredient of the Phosphorylcholine group as cell membrane, its interaction with various biotic components in blood is very
Little, i.e., Phosphorylcholine group is able to maintain that the normal conformation of biotic component in blood, has the outer surface of hemocyte cell membrane
Good blood compatibility.Polymer comprising phosphocholine group can form similar biomembranous double points under certain condition
Sublayer, polymer surfaces represent good lubricity in aqueous medium, therefore show good opposing albumen in vivo
Matter is adsorbed and the ability sticked of its anti-histiocyte, exempts from so as to significantly decrease the formation of thrombosis, cytotoxic reaction, inflammation etc.
Epidemic disease is reacted.Therefore, Phosphorylcholine group is incorporated on polyurethane matrix, the biofacies of polyurethane material can be increased substantially
Capacitive, so as to widen polyurethane material application medically.
The polymer containing Phosphorylcholine group is prepared for containing phosphinylidyne gallbladder with polyurethane material blending in prior art
The method of modifying of the polyurethane of base groups can substantially reduce the mechanical performance of polyurethane material, the surface grafting phosphorus to polyurethane film
The modified method operation in the surface of phatidylcholine group is extremely complex, and is only applicable to some polyurethanes material.Using two Carbimide .s
The choline group that main chain prepared by ester chain extension contains Phosphorylcholine group polyurethane is embedded in material internal, it is difficult to be enriched in material
The surface of material, the utilization rate for producing Phosphorylcholine group is low, biocompatibility of material improve it is limited, have poisonous material drop
The problems such as solution.The block polymers of polyurethane blocked by double bond and methylacryoyloxyethyl Phosphorylcholine monomer radical copolymerization
Modified polyurethane material biodegradability it is very poor, can not be absorbed by organism, hydrogel can only be prepared, this is greatly limit
Material application medically.
The content of the invention
According to above the deficiencies in the prior art, a kind of preparation process is simple, good mechanical property, biocompatibility are needed at present badly
Nontoxic absorbable etc. the Phosphorylcholine modified polyurethane material of high, catabolite.
It is an object of the invention to provide a kind of preparation side of the modified polyurethane material of Phosphorylcholine of high-biocompatibility
Method, the Phosphorylcholine modified polyurethane material of preparation for it is complete synthesis, without potential animal derived, while with higher biofacies
Capacitive and good mechanical properties, and the material has biological degradability, catabolite is nontoxic, can be absorbed by organism.
In order to solve above technical problem, the technical scheme is that：
A kind of preparation method of high-biocompatibility Phosphorylcholine modified polyurethane material, comprises the following steps：
(1) preparation of both-end isocyanate group prepolymer
Both-end hydroxy polymer is mixed with the diisocyanate room temperature of excess and (is such as mixed uneven, is suitably added anhydrous
Dimethyl sulfoxide), temperature reaction obtains both-end isocyanate group prepolymer (containing the compound of-N=C=O functional groups in two ends)；
(2) preparation of Phosphorylcholine modified polyurethane
It is dissolved in after solvent with the Phosphorylcholine compound of double amino, is added drop-wise in both-end isocyanate group prepolymer, to both-end
Isocyanate group prepolymer carries out chain extending reaction, obtains Phosphorylcholine modified polyurethane material.
Preferred both-end hydroxy polymer synthesize by the mixture of ring-type lactide or annular lactone or both with cause
There is vacuum ring-opening polymerization in agent and catalyst mixing, the ring-type lactide or annular lactone, both-end hydroxy polymer is obtained.
Preferably, described initiator is Polyethylene Glycol, and the consumption of Polyethylene Glycol is the 10%～30% of gross mass, described
The vacuum of vacuum ring-opening reaction is 10～30Pa, and polymerization temperature is 120～150 DEG C, and polymerization time is 12～72h.
Preferably, described lactone is the lactone that MU (methylene unit) number is 4～7, and described lactide is that Acetic acid, hydroxy-, bimol. cyclic ester or third are handed over
Ester, the catalyst is organic tin catalyst or zinc class catalyst, the consumption of catalyst for mixture quality 0.1%～
0.5%.
Preferably, the both-end hydroxy polymer in step (1) is polyether ester type glycol, specially polyester-polyether-polyester-type
Triblock polymer, molecular weight are 800～5000, and wherein content of the polyethers in three block is 10wt%～30wt%.
Preferably, in polyester-polyether-polyester-type triblock polymer, polyester segment is the segment containing-COO- groups, excellent
PGA, PLLA, poly DL-lactide, poly-epsilon-caprolactone, or wherein both copolymers, polyethers is selected to contain for segment
There are the segment of C-O-C, preferred Polyethylene Glycol.
Preferably, the diisocyanate in step (1) is aliphatic diisocyanate, and more preferably 1,6- hexa-methylenes two are different
Cyanate, Isosorbide-5-Nitrae-tetramethylene diisocyanate, 1,6- hexamethylene diisocyanate-BDO -1,6- hexa-methylenes
Diisocyanate.
Preferably, the addition of the excess diisocyanate described in step (1) is-NCO:- OH=1.3～2.0 (mole
Than).
Preferably, in step (1), reaction temperature is 60～90 DEG C, and the response time is 2.5～5.5h.
Preferably, the Phosphorylcholine compound of the double amino described in step (2) for concrete structure is：Lys-PC is (such as 1 institute of formula
Show) or Lys-EG-PC (as shown in Equation 2).
Preferably, in step (2), the addition of the Phosphorylcholine compound of double amino is：-NH2Molal quantity=- NCO
The molal quantity of molal quantity-- OH.Reaction temperature is 10～20 DEG C, and the response time is 1.0～2.0h.
Preferably, described in step (2), the purification process of Phosphorylcholine modified polyurethane is：With dichloromethane or dioxy six
Ring dissolves, the sedimentation of ice ether, sucking filtration, and normal-temperature vacuum drying is to constant weight.
Preferably, the Phosphorylcholine modified polyurethane material obtained in step (2) is dissolved in organic solvent, is made into dense
The solution for 3～7% (g/mL) is spent, Jing solvents evaporate into film preparation and obtain polyurethane film material.
Preferably, described organic solvent is chloroform, dichloromethane, acetone, dioxane or its mixed solvent, is waved
It is 15-30 DEG C to send out temperature, and normal pressure 48～96h of volatilization, Jing normal-temperature vacuums are dried to obtain membrane material preferably, polyurethane material injection
Teflon mould volatilization film forming.
Preferably, the thickness of gained polyurethane film material membrane is 0.18～0.22mm.
Preferably, gained Phosphorylcholine modified polyurethane material can make dosage form needed for organism, including film or sponginum
Type.
The present invention Advantageous Effects be：
1. the material be complete synthesis material, inanimate object originality.
2. Phosphorylcholine group be located at polymer side chain, in organism (aqueous environments) using when can be gathered in material
Surface, greatly improve the biocompatibility of material.
3. the soft section of polyurethane has biodegradable polyester segment, therefore the last degradable of the material is small molecule,
Avoid the problem that second operation is drawn off.
4. in the soft section of polyurethane, the catabolite of polyester can be absorbed by the body, and polyether segment can directly by organism generation
Thank, it is logical be the diisocyanate for using be aliphatic diisocyanate, its catabolite is aliphatic diamine, the degraded of chain extender
Product is also aliphatic diamine, can be absorbed by organism.
5. the material has good mechanical performance simultaneously, can be applied to as organizational project renovating bracket material etc. for a long time
Organism.
Specific embodiment
With reference to specific embodiment, the invention will be further described.
Embodiment 1
(1) preparation of both-end Hydroxyl Prepolymers：
By 15g (0.05mol) PEG300 in vacuum response bottle, magneton stirring is 100 DEG C in reaction temperature, vacuum
(30Pa) after eliminating water 4h, room temperature is cooled to, nitrogen balance is passed through toward vacuum response bottle.Then add in vacuum response bottle
60g L- lactides and 0.3g dibutyltin diacetates.Again by vacuum response bottle evacuation, lead to drying nitrogen balance afterwards, repeatedly three
It is secondary.30Pa is evacuated to finally, containing vacuum reaction bulb, oil bath heating obtain both-end hydroxyl pre-polymerization to 130 DEG C, after reacting 24 hours
Thing PLLA-polyethylene glycol L- lactide (PLLA-PEG-PLLA, Mn=1500, PEGwt%=20%).
(2) preparation of both-end isocyanate group prepolymer
By the PLLA-PEG-PLLA prepared in 15g (0.01mol) (1) and 2.52g (0.015mol) 1,6- hexa-methylenes two
Isocyanates are placed in there-necked flask, drying nitrogen protection, mechanical agitation, are warming up to 80 DEG C, after reaction 3.5h, are cooled to 20
℃。
(3) preparation of Phosphorylcholine modified polyurethane
The dichloromethane solution (1g/6mL) of Deca 1.345g (0.005mol) Lys-PC, stirring, when system viscosity becomes big
When normally cannot stir, dichloromethane being added in right amount, after stirring 1h, adding dichloromethane to concentration about 15wt%, ice ether sinks
Drop, sucking filtration, normal-temperature vacuum drying obtain Phosphorylcholine modified polyurethane A1 to constant weight.
(4) preparation of membrane material
6g polyurethane materials are weighed, is dissolved in 100mL acetone, using Teflon mould, film forming of volatilizing at 30 DEG C,
Normal pressure volatilization 50h, film is removed from mould, and normal-temperature vacuum drying obtains polyurethane film material to constant weight.
Embodiment 2
(1) preparation of both-end Hydroxyl Prepolymers：
By 10.0g (0.05mol) PEG200 in vacuum response bottle, magneton stirring is 100 DEG C in reaction temperature, vacuum
(30Pa) after eliminating water 4h, room temperature is cooled to, nitrogen balance is passed through toward vacuum response bottle.Then add in vacuum response bottle
40g 6-caprolactones and 0.2g stannous octoates.Again by vacuum response bottle evacuation, lead to drying nitrogen balance afterwards, repeatedly for three times.Finally
Be evacuated to 30Pa, containing vacuum reaction bulb, oil bath heating to 140 DEG C, after reaction 24 hours the poly- ε of both-end Hydroxyl Prepolymers-
Caprolactone-polyethylene glycol 6-caprolactone (PCL-PEG-PCL, Mn=1000, PEGwt%=20%).
(2) preparation of both-end isocyanate group prepolymer
Two Carbimide. of PCL-PEG-PCL and 3.39g (0.015mol) 1B that will be prepared in 10g (0.01mol) (1)
Ester is placed in there-necked flask, drying nitrogen protection, mechanical agitation, is warming up to 85 DEG C, after reaction 3h, is cooled to 22 DEG C.
(3) preparation of Phosphorylcholine modified polyurethane
The dichloromethane solution (1g/6mL) of Deca 1.345g (0.005mol) Lys-PC, stirring, when system viscosity becomes big
When normally cannot stir, dichloromethane being added in right amount, after stirring 1h, adding dichloromethane to concentration about 15wt%, ice ether sinks
Drop, sucking filtration, normal-temperature vacuum drying obtain Phosphorylcholine modified polyurethane A2 to constant weight.
(4) preparation of membrane material
6g polyurethane materials are weighed, is dissolved in 100mL acetone, using Teflon mould, film forming of volatilizing at 25 DEG C,
Normal pressure volatilization 48h, film is removed from mould, and normal-temperature vacuum drying obtains polyurethane film material to constant weight.
Embodiment 3
(1) preparation of both-end Hydroxyl Prepolymers：
By 10.0g (0.05mol) PEG200 in vacuum response bottle, magneton stirring is 100 DEG C in reaction temperature, vacuum
(30Pa) after eliminating water 4h, room temperature is cooled to, nitrogen balance is passed through toward vacuum response bottle.Then add in vacuum response bottle
40g 6-caprolactones and 0.2g stannous octoates.Again by vacuum response bottle evacuation, lead to drying nitrogen balance afterwards, repeatedly for three times.Finally
30Pa is evacuated to, containing vacuum reaction bulb, oil bath heating obtain the poly- (L- of both-end Hydroxyl Prepolymers to 130 DEG C, after reacting 36 hours
Lactide coglycolide)-polyethylene glycol (L- lactide coglycolides) (PLGA-PEG-PLGA, Mn=1000, PEGwt%=
20%).
(2) preparation of both-end isocyanate group prepolymer
Two isocyanide of PLGA-PEG-PLGA and 3.39g (0.015mol) 1B that will be prepared in 10g (0.01mol) (1)
Acid esters is placed in there-necked flask, drying nitrogen protection, mechanical agitation, is warming up to 85 DEG C, after reaction 3h, is cooled to 20 DEG C.
(3) preparation of Phosphorylcholine modified polyurethane
The dichloromethane solution (1g/6mL) of Deca 1.345g (0.005mol) Lys-PC, stirring, when system viscosity becomes big
When normally cannot stir, dichloromethane is added in right amount, after stirring 1.5h, add dichloromethane to concentration about 15wt%, ice ether
Sedimentation, sucking filtration, normal-temperature vacuum drying obtain Phosphorylcholine modified polyurethane A3 to constant weight.
(4) preparation of membrane material
6g polyurethane materials are weighed, is dissolved in 100mL acetone, using Teflon mould, film forming of volatilizing at 27 DEG C,
Normal pressure volatilization 55h, film is removed from mould, and normal-temperature vacuum drying obtains polyurethane film material to constant weight.
Embodiment 4
(1) preparation of both-end Hydroxyl Prepolymers：
By 10.0g (0.05mol) PEG200 in vacuum response bottle, magneton stirring is 100 DEG C in reaction temperature, vacuum
(30Pa) after eliminating water 4h, room temperature is cooled to, nitrogen balance is passed through toward vacuum response bottle.Then add in vacuum response bottle
20g 6-caprolactones, 20g L- lactides and 0.2g stannous octoates.Again by vacuum response bottle evacuation, lead to drying nitrogen balance afterwards,
Repeatedly for three times.20Pa is evacuated to finally, containing vacuum reaction bulb, oil bath heating obtain both-end hydroxyl to 135 DEG C, after reacting 36 hours
Poly- (L- lactide-epsilon-coprolactones)-polyethylene glycol (L- lactide-epsilon-coprolactones) (PLCA-PEG-PLCA, the M of based prepolymersn
=1000, PEGwt%=20%).
(2) preparation of both-end isocyanate group prepolymer
Two Carbimide. of PLCA-PEG-PLCA and 3.39g (0.015mol) 1B will be prepared in 10g (0.01mol) (1)
Ester is placed in there-necked flask, drying nitrogen protection, mechanical agitation, is warming up to 80 DEG C, after reaction 3.5h, is cooled to 20 DEG C.
(3) preparation of Phosphorylcholine modified polyurethane
The dichloromethane solution (1g/6mL) of Deca 1.345g (0.005mol) Lys-PC, stirring, when system viscosity becomes big
When normally cannot stir, dichloromethane is added in right amount, after stirring 1.5h, add dichloromethane to concentration about 15wt%, ice ether
Sedimentation, sucking filtration, normal-temperature vacuum drying obtain Phosphorylcholine modified polyurethane A4 to constant weight.
(4) preparation of membrane material
5g polyurethane materials are weighed, is dissolved in 100mL dichloromethane, using Teflon mould, volatilized at 20 DEG C
Film forming, normal pressure volatilization 80h, film is removed from mould, and normal-temperature vacuum drying obtains polyurethane film material to constant weight.
Embodiment 5
The preparation of both-end Hydroxyl Prepolymers：
By 12.5g (0.05mol) PEG250 in vacuum response bottle, magneton stirring is 100 DEG C in reaction temperature, vacuum
(30Pa) after eliminating water 4h, room temperature is cooled to, nitrogen balance is passed through toward vacuum response bottle.Then add in vacuum response bottle
18.75g 6-caprolactones, 18.75g L- lactides and 0.18g stannous octoates.Again by vacuum response bottle evacuation, lead to dry nitrogen afterwards
Gas is balanced, repeatedly for three times.Finally be evacuated to 20Pa, containing vacuum reaction bulb, oil bath heating to 130 DEG C, after reaction 36 hours
Obtain poly- (L- lactide-epsilon-coprolactones)-polyethylene glycol (L- the lactide-epsilon-coprolactones) (PLCA- of both-end Hydroxyl Prepolymers
PEG-PLCA, Mn=1000, PEGwt%=25%).
(2) preparation of both-end isocyanate group prepolymer
Two isocyanide of PLCA-PEG-PLCA and 3.39g (0.015mol) 1B that will be prepared in 10g (0.01mol) (1)
Acid esters is placed in there-necked flask, drying nitrogen protection, mechanical agitation, is warming up to 80 DEG C, after reaction 3.5h, is cooled to 18 DEG C.
(3) preparation of Phosphorylcholine modified polyurethane
The dichloromethane solution (1g/6mL) of Deca 1.345g (0.005mol) Lys-PC, stirring, when system viscosity becomes big
When normally cannot stir, dichloromethane is added in right amount, after stirring 1.5h, add dichloromethane to concentration about 15wt%, ice ether
Sedimentation, sucking filtration, normal-temperature vacuum drying obtain Phosphorylcholine modified polyurethane A5 to constant weight.
(4) preparation of membrane material
4g polyurethane materials are weighed, is dissolved in 100mL chloroform, using Teflon mould, volatilized at 25 DEG C
Film forming, normal pressure volatilization 60h, film is removed from mould, and normal-temperature vacuum drying obtains polyurethane film material to constant weight.
Embodiment 6
(1) preparation of both-end Hydroxyl Prepolymers：
By 10.0g (0.05mol) PEG200 in vacuum response bottle, magneton stirring is 100 DEG C in reaction temperature, vacuum
(30Pa) after eliminating water 4h, room temperature is cooled to, nitrogen balance is passed through toward vacuum response bottle.Then add in vacuum response bottle
50g 6-caprolactones and 0.22g dibutyltin diacetates.Again by vacuum response bottle evacuation, lead to drying nitrogen balance afterwards, repeatedly three
It is secondary.20Pa is evacuated to finally, containing vacuum reaction bulb, oil bath heating obtain both-end hydroxyl pre-polymerization to 140 DEG C, after reacting 24 hours
Thing poly-epsilon-caprolactone-polyethylene glycol 6-caprolactone (PCL-PEG-PCL, Mn=1200, PEGwt%=16.7%).
(2) preparation of both-end isocyanate group prepolymer
Will be the PCL-PEG-PCL and 2.52g (0.018mol) 1,4- tetramethylenes two that prepare in 10g (0.01mol) (1) different
Cyanate is placed in there-necked flask, drying nitrogen protection, mechanical agitation, is warming up to 75 DEG C, after reaction 3h, is cooled to 18 DEG C.
(3) preparation of Phosphorylcholine modified polyurethane
The dichloromethane solution (1g/6mL) of Deca 2.70g (0.008mol) Lys-EG-PC, stirring, when system viscosity becomes
When normally cannot stir greatly, dichloromethane is added in right amount, after stirring 1h, add dichloromethane to concentration about 15wt%, ice ether
Sedimentation, sucking filtration, normal-temperature vacuum drying obtain Phosphorylcholine modified polyurethane A6 to constant weight.
(4) preparation of membrane material
6g polyurethane materials are weighed, is dissolved in 100mL acetone, using Teflon mould, film forming of volatilizing at 30 DEG C,
Normal pressure volatilization 50h, film is removed from mould, and normal-temperature vacuum drying obtains polyurethane film material to constant weight.
Embodiment 7
(1) preparation of both-end Hydroxyl Prepolymers：
By 6.0g (0.05mol) PEG120 in vacuum response bottle, magneton stirring is 100 DEG C in reaction temperature, vacuum
(30Pa) after eliminating water 4h, room temperature is cooled to, nitrogen balance is passed through toward vacuum response bottle.Then add in vacuum response bottle
44g 6-caprolactones and 0.20g stannous octoates.Again by vacuum response bottle evacuation, lead to drying nitrogen balance afterwards, repeatedly for three times.Most
After be evacuated to 20Pa, containing vacuum reaction bulb, oil bath heating to 145 DEG C, after reaction 20 hours both-end Hydroxyl Prepolymers gather
6-caprolactone-polyethylene glycol 6-caprolactone (PCL-PEG-PCL, Mn=1000, PEGwt%=12%).
(2) preparation of both-end isocyanate group prepolymer
Will be the PCL-PEG-PCL and 2.52g (0.018mol) 1,4- tetramethylenes two that prepare in 10g (0.01mol) (1) different
Cyanate is placed in there-necked flask, drying nitrogen protection, mechanical agitation, is warming up to 75 DEG C, after reaction 3h, is cooled to 18 DEG C.
(3) preparation of Phosphorylcholine modified polyurethane
The dichloromethane solution (1g/6mL) of Deca 2.70g (0.008mol) Lys-EG-PC, stirring, when system viscosity becomes
When normally cannot stir greatly, dichloromethane is added in right amount, after stirring 1h, add dichloromethane to concentration about 15wt%, ice ether
Sedimentation, sucking filtration, normal-temperature vacuum drying obtain Phosphorylcholine modified polyurethane A7 to constant weight.
(4) preparation of membrane material
6g polyurethane materials are weighed, is dissolved in 100mL acetone, using Teflon mould, film forming of volatilizing at 30 DEG C,
Normal pressure volatilization 50h, film is removed from mould, and normal-temperature vacuum drying obtains polyurethane film material to constant weight.
Embodiment 8
(1) preparation of both-end Hydroxyl Prepolymers：
By 6.0g (0.05mol) PEG120 in vacuum response bottle, magneton stirring is 100 DEG C in reaction temperature, vacuum
(30Pa) after eliminating water 4h, room temperature is cooled to, nitrogen balance is passed through toward vacuum response bottle.Then add in vacuum response bottle
44g 6-caprolactones and 0.20g stannous octoates.Again by vacuum response bottle evacuation, lead to drying nitrogen balance afterwards, repeatedly for three times.Most
After be evacuated to 20Pa, containing vacuum reaction bulb, oil bath heating to 145 DEG C, after reaction 20 hours both-end Hydroxyl Prepolymers gather
6-caprolactone-polyethylene glycol 6-caprolactone (PCL-PEG-PCL, Mn=1000, PEGwt%=12%).
(2) preparation of both-end isocyanate group prepolymer
Will be the PCL-PEG-PCL and 7.67g (0.018mol) 1,6- hexa-methylenes two that prepare in 10g (0.01mol) (1) different
Cyanate-BDO -1,6- hexamethylene diisocyanates (HDI-BDO-HDI) are placed in there-necked flask, plus a small amount of nothing
Water dimethyl sulfoxide dissolves, and drying nitrogen protection, mechanical agitation are warming up to 85 DEG C, after reaction 4h, is cooled to 22 DEG C, obtains both-end
Isocyanate group prepolymer.
(3) preparation of Phosphorylcholine modified polyurethane
The dichloromethane solution (1g/6mL) of Deca 2.70g (0.008mol) Lys-EG-PC, stirring, when system viscosity becomes
When normally cannot stir greatly, dichloromethane is added in right amount, after stirring 1h, add dichloromethane to concentration about 15wt%, ice ether
Sedimentation, sucking filtration, normal-temperature vacuum drying obtain Phosphorylcholine modified polyurethane A8 to constant weight.
(4) preparation of membrane material
6g polyurethane materials are weighed, is dissolved in 100mL acetone, using Teflon mould, film forming of volatilizing at 30 DEG C,
Normal pressure volatilization 50h, film is removed from mould, and normal-temperature vacuum drying obtains polyurethane film material to constant weight.
Embodiment 9
(1) preparation of both-end Hydroxyl Prepolymers：
By 12.5g (0.05mol) PEG250 in vacuum response bottle, magneton stirring is 100 DEG C in reaction temperature, vacuum
(30Pa) after eliminating water 4h, room temperature is cooled to, nitrogen balance is passed through toward vacuum response bottle.Then add in vacuum response bottle
87.5g 6-caprolactones and 0.35g dibutyltin diacetates.Again by vacuum response bottle evacuation, lead to drying nitrogen balance afterwards, repeatedly
Three times.Finally be evacuated to 18Pa, containing vacuum reaction bulb, oil bath heating to 145 DEG C, after reaction 20 hours both-end hydroxyl is pre-
Polymers poly-epsilon-caprolactone-polyethylene glycol 6-caprolactone (PCL-PEG-PCL, Mn=2000, PEGwt%=12.5%).
(2) preparation of both-end isocyanate group prepolymer
Will be the PCL-PEG-PCL and 7.67g (0.018mol) 1,6- hexa-methylenes two that prepare in 20g (0.01mol) (1) different
Cyanate-BDO -1,6- hexamethylene diisocyanates (HDI-BDO-HDI) are placed in there-necked flask, plus a small amount of nothing
Water dimethyl sulfoxide dissolves, and drying nitrogen protection, mechanical agitation are warming up to 85 DEG C, after reaction 4h, is cooled to 22 DEG C.
(3) preparation of Phosphorylcholine modified polyurethane
The dichloromethane solution (1g/6mL) of Deca 2.70g (0.008mol) Lys-EG-PC, stirring, when system viscosity becomes
When normally cannot stir greatly, dichloromethane is added in right amount, after stirring 1h, add dichloromethane to concentration about 15wt%, ice ether
Sedimentation, sucking filtration, normal-temperature vacuum drying obtain Phosphorylcholine modified polyurethane A9 to constant weight.
(4) preparation of membrane material
6g polyurethane materials are weighed, is dissolved in 100mL dioxane, using Teflon mould, volatilized at 30 DEG C
Film forming, normal pressure volatilization 50h, film is removed from mould, and normal-temperature vacuum drying obtains polyurethane film material to constant weight.
Analysis method
Analysis below method is used for all of embodiment, unless otherwise indicated.
Molecular weight：Using Water companies of the U.S. Alpha type gel permeation chrommatographs (GPC) determine polyurethane molecular weight and
Molecular weight distribution, solvent are tetrahydrofuran, and standard specimen is monodisperse polystyrene.
Mechanical performance：Surveyed using the computermatic single-column tensile testing machine of the HY939C types of Dongguan, Guangdong Heng Yu Instrument Ltd.
Determine the tensile strength and elongation at break of film.Before on-test, sample is soaked into 3min in normal saline first, is then made mute
Bell pattern type, the method specified according to GB GB13022-91 are measured.
Degradation property：Membrane material is immersed in 37 DEG C of normal saline, the saturation that absorbs water is thought after 6 hours, surface is dried
Moisture, uses electronic balance weighing quality, using this data as initial mass.With one day quality as period measuring membrane material, when
Membrane material is crushed when cannot weigh, it is believed that degraded is completed, it is determined as degradation time.
Water contact angle measurement：Water contact angle test is carried out with air contact one side in thin film, distilled water (droplet size:2μ
), L temperature:250 DEG C, contact angle numerical value of the water drop contact surface in about 1min is determined, 5 points is taken and is made meansigma methodss.
Protein adsorbance:Fill during the polymeric film of 1cm × 1cm to be soaked in the phosphate buffer (PBS) of pH=7.4
Divide swelling equilibrium, be placed on after taking-up in the bovine serum albumen solution (BSA) that concentration is 0.6g/L, in 37 DEG C of water bath with thermostatic control
Middle immersion 2h.Polymeric film is taken out after end, with the abundant drip washing of PBS buffer solution 3 times.Then with the SDS solution of 1% (w/w)
(PBS solution) is cleaned by ultrasonic 20min, accurately pipettes same volume cleanout fluid in tool plug test tube, adds Micro-BcATMEgg
(PierceInc., Rockford, 23235), are sufficiently mixed white matter detection kit working solution, sealing, 60 DEG C of constant temperature water bath lh.
Finally naturally cool to room temperature, using ultraviolet-visible spectrophotometer at the 562nm wavelength mensuration absorbance, according to standard
Curve calculates adsorbance, takes the meansigma methodss of 3 samples.
In embodiment 1-9, the performance of Phosphorylcholine modified polyurethane membrane material is as shown in table 1.
In embodiment 1-9, the biological assessment test of polyurethane film material is as shown in table 2.
The machinery of 1 Phosphorylcholine modified polyurethane film of table is energy, surface hydrophilicity and protein adsorbance
As shown in Table 1, Phosphorylcholine modified polyurethane prepared by the method provided by this patent has higher molecular weight
(MnIt is all higher than 1.3 × 105), its corresponding membrane material has very high fracture strength and elongation at break, and fracture strength is more than
14MPa, elongation at break are more than 950%, meet the demand of bio-tissue engineering renovating bracket material.As hard section (contains ammonia
Carbamate or urine base segment) content increase, fracture strength increase；With the increase of PEG content in soft section, extension at break
Rate increases.The degradation time of membrane material is all higher than five weeks, up to nine weeks, examine prepared by film it is relatively thin, specific surface area compared with
Greatly, if dosage form is prepared into the shape required for organizational project renovating bracket material, its degradation time can be greatly increased.The drop of film
The solution time is relevant with the content of PEG content in material and Phosphorylcholine, with the increase of PEG content, the increasing of Phosphorylcholine content
Plus and shorten.Also, the crystallinity of polyester-polyether-polyester is higher in raw material, degrade slower, i.e., when polyester segment is homopolymer,
Degree of crystallinity is high, and degraded is slow；Polyester segment is trackless copolymer, and degree of crystallinity is low, and degraded is fast.Its water contact angle and protein adsorbance
Rule it is consistent：Contact angle is less, more hydrophilic surface, and protein adsorbance is less.With the increasing of Phosphorylcholine group content
Plus, in water, the Phosphorylcholine group of side chain forms hydrophilic interface, simultaneously because Phosphorylcholine due to the mutual aggressiveness of hydrophilic
The high biocompatibility of group, its adsorbance to protein are also reduced.The contact angle of the sample in this patent embodiment is less than
42, the adsorbance of protein is less than 3 μ g/cm2, even less than 1.5 μ g/cm2, show that the material shows splendid bio-compatible
Property, organism can be long-term used in.
Test biology of 2 Phosphorylcholine modified polyurethane membrane material (sample A1-A9) of table
| Antibacterial is tested | It is aseptic | With reference to GB/T14233.2-2005 |
| Cytotoxicity | <I levels | With reference to GB/T14233.2-2005 |
| Intradermal zest | Stimulate without Intradermal | With reference to GB/T14233.10-2005 |
| Sensitization | Without sensitization | With reference to GB/T14233.10-2005 |
| Acute systemic toxicity | No significant difference | With reference to GB/T14233.11-2011 |
As shown in Table 2, the biology performance testing result of the membrane material prepared by embodiment of the present invention 1-9 shows each embodiment
Nontoxic, non-stimulated, good biocompatibility can be obtained and meet the material of Clinical practice requirement.
Although giving detailed description above to the specific embodiment of the present invention and illustrating, it should be noted that
We can carry out various equivalent changes and modification according to the conception of the present invention to above-mentioned embodiment, and the function produced by which is made
With still without departing from description covered it is spiritual when, all should be within protection scope of the present invention.
Claims (10)
1. a kind of high-biocompatibility Phosphorylcholine modified polyurethane material, it is characterised in that：Phosphorylcholine group is located at polymerization
The side chain of thing, Phosphorylcholine modified polyurethane molecular weight are more than 1.3 × 105, membrane material fracture strength more than 14Mpa, fracture stretch
Long rate is less than 3 μ g/cm more than the adsorbance of 950%, protein2。
2. a kind of preparation method of high-biocompatibility Phosphorylcholine modified polyurethane material, comprises the following steps：
(1) preparation of both-end isocyanate group prepolymer
Both-end hydroxy polymer is mixed with the diisocyanate room temperature of excess, temperature reaction obtains both-end isocyanate group prepolymer；
(2) preparation of Phosphorylcholine modified polyurethane
It is dissolved in after solvent with the Phosphorylcholine compound of double amino, is added drop-wise in both-end isocyanate group prepolymer, to both-end isocyanide
Acidic group prepolymer carries out chain extension, and reaction, purification obtain Phosphorylcholine modified polyurethane material.
3. preparation method according to claim 2, it is characterised in that：Will be the Phosphorylcholine obtained in step (2) modified poly-
Urethane material is dissolved in organic solvent, is made into the solution that concentration is 3～7% (g/mL), and Jing solvents evaporate into film preparation and obtain
Polyurethane film material.
4. preparation method according to claim 2, it is characterised in that：Both-end hydroxy polymer in step (1) is polyethers
Ester type glycol, molecular weight are 800～5000, and content of the polyethers in polyethers esterdiol is 10～30wt%.
5. preparation method according to claim 4, it is characterised in that：Described polyether ester type glycol is polyester-polyether-poly-
Ester type triblock polymer, described polyester segment are PGA, polylactide, polycaprolactone or wherein both copolymerization
Thing, described polyether segment are Polyethylene Glycol.
6. preparation method according to claim 2, it is characterised in that：Diisocyanate in step (1) is aliphatic two
Isocyanates, described aliphatic diisocyanate is 1,6- hexamethylene diisocyanates, two Carbimide. of Isosorbide-5-Nitrae-tetramethylene
Ester, 1,6- hexamethylene diisocyanate-BDO -1,6- hexamethylene diisocyanates, described diisocyanate
Addition be-NCO and-OH mol ratios be 1.3～2.0, reaction temperature is 60～90 DEG C, and the response time is 2.5～5.5h.
7. the preparation method according to right wants 2, it is characterised in that：Double amino Phosphorylcholine chemical combination in the step (2)
It is Lys-PC (as shown in Equation 1) or Lys-EG-PC (as shown in Equation 2) that thing is structure, and addition is-NH2Molal quantity be two different
In cyanate in the molal quantity of-NCO and both-end Hydroxyl Prepolymers the molal quantity of-OH difference, reaction temperature is 10～20 DEG C, reaction
Time is 1.0～2.0h.
8. preparation method according to claim 2, it is characterised in that：Phosphorylcholine modified polyurethane described in step (2)
Purification process be：Dissolved with dichloromethane or dioxane, the sedimentation of ice ether, sucking filtration, normal-temperature vacuum drying is to constant weight.
9. preparation method according to claim 3, it is characterised in that：Described solvent be chloroform, dichloromethane, third
Ketone, dioxane or its mixed solvent, volatilization temperature are 15-30 DEG C, and normal pressure 48～96h of volatilization, Jing normal-temperature vacuums are dried to obtain
Membrane material, the thickness of described membrane material is 0.18～0.22mm.
10. the high-biocompatibility Phosphorylcholine modified polyurethane material obtained by the preparation method according to claim 2-9
Dosage form needed for organism, including film or sponge dosage form can be made.
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