CN104744661A - Hydrophilic degradable segmented polyurethane as well as preparation method and application thereof - Google Patents
Hydrophilic degradable segmented polyurethane as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to hydrophilic degradable segmented polyurethane as well as a preparation method and application thereof. The segmented polyurethane provided by the invention is a polymer of tri-block polyester polyol, diisocyanate, a chain extender and a catalyst, wherein the tri-block polyester polyol is a polymer of e-caprolactone monomer and polyethylene glycol with the molecular weight of 2000 according to a mol ratio of (8.75-70):1. The preparation method comprises the following steps: sufficiently mixing the e-caprolactone monomer, the polyethylene glycol and the catalyst, and polymerizing to form the tri-block polyester polyol; dissolving the tri-block polyester polyol in an organic solvent, adding the diisocyanate and the catalyst to obtain a prepolymer; and finally adding the organic solvent and the chain extender, sufficiently stirring and mixing for 7h, pouring into a mould and evaporating the organic solvent to obtain the product. The segmented polyurethane provided by the invention is excellent in tensile strength, hydrophilia and biodegradability, suitable for use in the tissue engineering and tissue repair, and particularly suitable for use as a rack and a rack coating.
Description
Technical field
The invention belongs to polymer medical material and synthetic method technical field, relate to a kind of wetting ability, degradable block polyurethane and its production and use.
Background technology
Urethane is the very important medical science macromolecular material of a class.Because it has multiple premium properties as toughness, elasticity, thermostability, biocompatibility and hypotoxicity etc., thus the support base material of the biomaterial providing performance various for life science or organizational project and regenerative medicine.Traditional polyurethane material wetting ability is poor, thus degradation property is poor, and along with material implanted extensive medical use, degradable in vivo material, as medical tissue support, can avoid patient's second operation, for patient reduces misery and funds.
The polyurethane material adopting normal polyester polyvalent alcohol to prepare has excellent physics, chemical property, but there is the defects such as stronger hydrophobicity, poor degradation property.Therefore, retaining as far as possible on polyurethane material premium properties basis, improving its hydrolysis rate and have very important significance.
At present, correlative study and worker have carried out certain research to degradable polyurethane and have reported.Wherein, publication number: CN102977330A, denomination of invention is: a kind of preparation method of degradable polyurethane material, and the method adopts the blend of liquefying biomass and starch to be polyol masses synthesis of polyurethane, to improve the degradation property of urethane; CN 103910846A in addition, denomination of invention is: a kind of degradable polyurethane and preparation method thereof.The method adopts carbonic acid gas and propylene oxide copolymer body-poly (propylene carbonate) polyvalent alcohol to be the correlative study that source of degradation prepares degradable polyurethane.But, yet there are no and utilize hydrophilic polyoxyethylene glycol and hydrophobic 6-caprolactone monomer copolymerization to produce block polyester polyvalent alcohol for source of degradation to prepare the correlative study of wetting ability, degradable block polyurethane, the catalyzer that preparation process is used simultaneously is iron class catalyzer, substitute traditional Heavy Metal, Sn class, there is better biological safety.
Summary of the invention
One object of the present invention is to provide a kind of degradable polyurethane, and the urethane prepared not only mechanical property is good, and biological safety also has good degradation property.
Degradable block polyurethane of the present invention is polymkeric substance, and this polymkeric substance main component comprises triblock polyester polyvalent alcohol, vulcabond, chainextender, catalyzer; Wherein the mol ratio of triblock polyester polyvalent alcohol, vulcabond and chainextender is 1:2 ~ 20:1 ~ 10; Catalyzer accounts for 0.1 ~ 2 ﹪ of this total polymer mass; Described triblock polyester polyvalent alcohol is centered by the polyoxyethylene glycol of molecular weight 2000 (PEG) or initial, cause three block polyvalent alcohols (PCL-PEG-PCL) of 6-caprolactone (CL) monomer ring-opening polymerization, molecular weight is 3000 ~ 20000, has following general formula:
Wherein k is corresponding cyclic ester free carbon atomicity 5, m, n is arbitrary integer, final gained three block polyol molecular weight 3000 ~ 20000.
Described vulcabond is the one in tolylene diisocyanate, aromatic series diphenylmethanediisocyanate, aliphatics dicyclohexyl methane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, lysinediisocyanate;
Described catalyzer is ferric acetyl acetonade;
Described chainextender is conventional chain extender, has conventional polyol or the Diamines of two or more hydroxyls, has the compound with the functional group of described vulcabond generation esterification.As ethylene glycol, quadrol, 1B ethyl ester, Isosorbide-5-Nitrae-cyclohexanediol, amino-terminated polypeptide chain, hydroxy aliphatic acids, and polyol crosslink agent is as glycerine, the one in TriMethylolPropane(TMP), trolamine, tetramethylolmethane, ethoxylation tetramethylolmethane, castor-oil plant wet goods material.
Another object of the present invention is to the method that above-mentioned degradable polyurethane is provided, specifically according to following steps:
Step (1), 6-caprolactone, polyoxyethylene glycol are put into reaction vessel and carried out vacuumizing processed, obtain the raw material after dewatering; The mol ratio of polyoxyethylene glycol and 6-caprolactone is 1:8.75 ~ 70;
Step (2), by the raw material after dehydration in step (1) and catalyst mix, under nitrogen protection, be polymerized 19 ~ 29 hours at 130 ~ 140 DEG C, after being cooled to normal temperature, obtain triblock polyester polyvalent alcohol;
In step (2), the add-on of catalyzer is 0.1 ~ 2 ﹪ of polyoxyethylene glycol in step (1), 6-caprolactone total mass;
After step (3), triblock polyester polyvalent alcohol vacuum hydro-extraction that step (2) is obtained, be dissolved in organic solvent, then add vulcabond, catalyzer, 60 ~ 70 DEG C are reacted 1.5 ~ 3.5 hours under nitrogen protection, obtain performed polymer;
Described triblock polyester polyvalent alcohol and the mol ratio of vulcabond are 1:2 ~ 20;
In step (3), the add-on of catalyzer is 0.1 ~ 2 ﹪ of triblock polyester polyvalent alcohol, vulcabond, chainextender total mass;
Add organic solvent, chainextender in step (4), the prepolymer that obtains in step (3), after being fully uniformly mixed 2 ~ 12 hours, throw in mould, after organic solvent volatilization, prepare degradable block polyurethane.
The mol ratio of described chainextender and triblock polyester polyvalent alcohol is 1 ~ 10:1;
In step (2), (3), the add-on of organic solvent maintains 5 ~ 20 ﹪ with the mass volume ratio of solute and solvent, and unit is that g/mL is as the criterion.Described organic solvent is DMF.
Another object of the present invention is to provide the purposes of above-mentioned degradable block polyurethane.
The aspects such as a kind of wetting ability, degradable polymer support comprise degradable block polyurethane, and it is used for the treatment of the inner support of coronary heart disease, Soft-tissue operation, drug release, wound dressings, and tissue defect is alternative.
A kind of wetting ability, degradable polymer support also can introduce biotic component, and described composition is repaired according to auxiliary body inner tissue or produced and is used for Quick-forming object and selects, as introduced medicine or carrying out surface modification to it;
Described degradable block polyurethane in rapid shaping technique as the purposes in fusion sediment moulding.
Described degradable block polyurethane is in a patient in need for the treatment of for the purposes in tissue repair or organizational project, described purposes comprises in patient body described in stenter to implant, described support is the wetting ability prepared by Rapid Prototyping technique, degradable block polyurethane or polyurethane-urea.
Beneficial effect of the present invention is:
(1) degradable polyurethane of the present invention has the mechanical strength of 0.05 ~ 50MPa, reach the extension elongation rate of 100 ~ 500 ﹪, 15 ~ 70 DEG C of contact angles and faster degradation rate, good biocompatibility, can be used as degradable implantable support in medical use, and organizational project and tissue repair application.
(2) degradable block polyurethane of the present invention, hydrophilic polyoxyethylene glycol and hydrophobic 6-caprolactone monomer copolymerization is utilized to produce triblock polyester polyvalent alcohol for source of degradation, prepare block polyurethane, not only remain the process based prediction model of conventional urethane excellence, also improve normal polyester type polyurethane wetting ability simultaneously, improve its hydrolysis rate.Along with material implanted extensive medical use, degradable in vivo material, as medical tissue support, can avoid patient's second operation, for patient reduces misery and funds, meets very much current medical science and organizational project and tissue repair and applies.
Accompanying drawing explanation
Fig. 1 is embodiment stretching mechanical curve;
Fig. 2 is embodiment dynamic contact angle;
Fig. 3 is embodiment material degradation speed;
Fig. 4 is embodiment Biocompatibility.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.
Embodiment 1
Step (1), the polyoxyethylene glycol of 0.0875mol (10g) 6-caprolactone monomer, 0.01mol (20g) molecular weight 2000 is put into reaction vessel carry out vacuumizing processed, obtain the raw material after dewatering;
Step (2), by the raw material after dehydration in step (1) and 0.3g ferric acetyl acetonade catalyst mix, under nitrogen protection, at 135 DEG C, polymerization 24 hours, after being cooled to normal temperature, obtains triblock polyester polyvalent alcohol;
After step (3), triblock polyester polyvalent alcohol vacuum hydro-extraction that step (2) is obtained, get 3g (0.0005mol) and be dissolved in 45mlN, dinethylformamide organic solvent, then 1ml (1.05g is added, 0.006mol) hexamethylene diisocyanate, 0.042g catalyst acetyl acetone iron, 65 DEG C are reacted 2 hours under nitrogen protection, obtain performed polymer;
5ml organic solvent N is added in step (4), the prepolymer that obtains in step (3), dinethylformamide, 0.134g (0.001mol) TriMethylolPropane(TMP) chainextender, after being fully uniformly mixed 7 hours, throw in mould, after organic solvent volatilization, prepare degradable block polyurethane.
The material being prepared by embodiment 1 to gained carries out Mechanics Performance Testing, thin-film material is prepared into dumbbell shaped, stretch zones size is 0.2 ~ 0.3X 4mm, under normal temperature condition, on mechanics apparatus, (Instron 3366, USA) tests, and carries out tractive with 40mm speed per second, in triplicate, material final strength reaches 6.78 ± 0.76MPa as shown in Figure 1, and extension elongation rate can reach 333 ﹪, has the performances such as excellent anti-tractive and extension elongation rate; The material being prepared by embodiment 1 to gained carries out wetting ability test, and before test, thin-film material is dried into constant weight, then detects on Dataphysics OCA20 (Germany), deionized water droplet size is 1.0 μ L, in triplicate.Recording sheet material plane and water droplet angulation, prepare gained polyurethane material dynamic contact angle as shown in Figure 2 and can arrive 15 degree, shows that the material prepared has good wetting ability; The material being prepared by embodiment 1 to gained carries out degradation property test, material is inserted containing in dual anti-physiological saline, original quality is designated as (W0), (W1) is weighed after drying after taking out weekly, calculate the rear residual mass per-cent (W1/WO ﹪) of hydrolysis, wetting ability as shown in Figure 3, degradable polyurethane material can be hydrolyzed, and has degradation rate faster; The material being prepared by embodiment 1 to gained carries out Study on biocompatibility, by 5 × 10
4individual inoblast sowing is at material surface, and within 10 days, afterwards by confocal immunofluorescence microscopy imaging, qualitative observation cell growth condition, cell is in wetting ability as shown in Figure 4, and in order, therefore material has good biocompatibility to degradable polyurethane Material growth.
Embodiment 2
Step (1), the polyoxyethylene glycol of 0.175mol (20g) 6-caprolactone, 0.01mol (20g) molecular weight 2000 is put into reaction vessel carry out vacuumizing processed, obtain the raw material after dewatering;
Step (2), mixed with 0.4g catalyst acetyl acetone iron by the raw material after dehydration in step (1), under nitrogen protection, at 130 DEG C, polymerization 29 hours, after being cooled to normal temperature, obtains triblock polyester polyvalent alcohol;
Step (3), the triblock polyester polyvalent alcohol that step (2) is obtained, after vacuum hydro-extraction, get 4g (0.0006mol) and be dissolved in 50mL organic solvent N, dinethylformamide, then 0.002mol (0.3483g) tolylene diisocyanate, 0.0044g catalyst acetyl acetone iron is added, 60 DEG C are reacted 3.5 hours under nitrogen protection, obtain performed polymer;
5mL organic solvent N is added in step (4), the prepolymer that obtains in step (3), dinethylformamide, 0.001mol (0.062g) glycol chain extender, after being fully uniformly mixed 2 hours, throw in mould, degradable block polyurethane is prepared after the volatilization of organic solvent DMF.
Embodiment 3
Step (1), the polyoxyethylene glycol of 0.35mol (40g) 6-caprolactone, 0.01mol (20g) molecular weight 2000 is put into reaction vessel carry out vacuumizing processed, obtain the raw material after dewatering;
Step (2), mixed with 0.6g catalyst acetyl acetone iron by the raw material after dehydration in step (1), under nitrogen protection, at 140 DEG C, polymerization 19 hours, after being cooled to normal temperature, obtains triblock polyester polyvalent alcohol;
After step (3), triblock polyester polyvalent alcohol vacuum hydro-extraction that step (2) is obtained, get 10g (0.001mol) and be dissolved in 77mL organic solvent N, dinethylformamide, then 5g (0.02mol) diphenylmethanediisocyanate, 0.33g catalyst acetyl acetone iron is added, 70 DEG C are reacted 1.5 hours under nitrogen protection, obtain performed polymer;
9mL organic solvent N is added in step (4), the prepolymer that obtains in step (3), dinethylformamide, 1.44g (0.01mol) chainextender 1,4-cyclohexanediol, after being fully uniformly mixed 12 hours, throw in mould, after organic solvent volatilization, prepare degradable block polyurethane.
Embodiment 4
Step (1), the polyoxyethylene glycol of 0.7mol (80g) 6-caprolactone, 0.01mol (20g) molecular weight 2000 is put into reaction vessel carry out vacuumizing processed, obtain the raw material after dewatering;
Step (2), mixed with 0.1g catalyst acetyl acetone iron by the raw material after dehydration in step (1), under nitrogen protection, at 135 DEG C, polymerization 26 hours, after being cooled to normal temperature, obtains triblock polyester polyvalent alcohol;
After step (3), triblock polyester polyvalent alcohol vacuum hydro-extraction that step (2) is obtained, get 10g (0.001mol) and be dissolved in 80mL organic solvent N, dinethylformamide, then 1.32g (0.005mol) dicyclohexyl methane diisocyanate, 0.118g catalyst acetyl acetone iron is added, 65 DEG C are reacted 2.5 hours under nitrogen protection, obtain performed polymer;
10mL organic solvent N is added in step (4), the prepolymer that obtains in step (3), dinethylformamide, 0.46g (0.005mol) chainextender glycerine, after being fully uniformly mixed 12 hours, throw in mould, after organic solvent volatilization, prepare degradable block polyurethane.
Embodiment 5
Step (1), the polyoxyethylene glycol of 0.3mol (34.2g) 6-caprolactone, 0.01mol (20g) molecular weight 2000 is put into reaction vessel carry out vacuumizing processed, obtain the raw material after dewatering;
Step (2), mixed with 1.084g catalyst acetyl acetone iron by the raw material after dehydration in step (1), under nitrogen protection, at 132 DEG C, polymerization 28 hours, after being cooled to normal temperature, obtains triblock polyester polyvalent alcohol;
After step (3), triblock polyester polyvalent alcohol (molecular weight is 8000) vacuum hydro-extraction that step (2) is obtained, get 8g (0.001mol) and be dissolved in 195.6mL organic solvent N, dinethylformamide, then 1.68g (0.01mol) hexamethylene diisocyanate, 0.1g catalyst acetyl acetone iron is added, 62 DEG C are reacted 3 hours under nitrogen protection, obtain performed polymer;
13.6mL organic solvent N is added in step (4), the prepolymer that obtains in step (3), dinethylformamide, 0.68g (0.005mol) chainextender tetramethylolmethane, after being fully uniformly mixed 10 hours, throw in mould, after organic solvent volatilization, prepare degradable block polyurethane.
Embodiment 6
Step (1), the polyoxyethylene glycol of 0.4mol (45.6g) 6-caprolactone, 0.01mol (20g) molecular weight 2000 is put into reaction vessel carry out vacuumizing processed, obtain the raw material after dewatering;
Step (2), mixed with 0.656g catalyst acetyl acetone iron by the raw material after dehydration in step (1), under nitrogen protection, at 136 DEG C, polymerization 22 hours, after being cooled to normal temperature, obtains triblock polyester polyvalent alcohol;
After step (3), triblock polyester polyvalent alcohol vacuum hydro-extraction that step (2) is obtained, get 6.5g (0.001mol) and be dissolved in 110mL organic solvent N, dinethylformamide, then 2.22g (0.01mol) isophorone diisocyanate, 0.1148g catalyst acetyl acetone iron is added, 67 DEG C are reacted 2.2 hours under nitrogen protection, obtain performed polymer;
33mL organic solvent N is added in step (4), the prepolymer that obtains in step (3), dinethylformamide, 2.76g (0.008mol) chainextender Viscotrol C, after being fully uniformly mixed 8 hours, throw in mould, after organic solvent volatilization, prepare degradable block polyurethane.
Embodiment 7
Step (1), the polyoxyethylene glycol of 0.1mol (11.4g) 6-caprolactone, 0.01mol (20g) molecular weight 2000 is put into reaction vessel carry out vacuumizing processed, obtain the raw material after dewatering;
Step (2), mixed with 0.314g catalyst acetyl acetone iron by the raw material after dehydration in step (1), under nitrogen protection, at 140 DEG C, polymerization 19 hours, after being cooled to normal temperature, obtains triblock polyester polyvalent alcohol;
After step (3), triblock polyester polyvalent alcohol vacuum hydro-extraction that step (2) is obtained, get 3g (0.001mol) and be dissolved in 58mL organic solvent N, dinethylformamide, then 0.456g (0.002mol) lysinediisocyanate, 0.0792g catalyst acetyl acetone iron is added, 60 DEG C are reacted 3.5 hours under nitrogen protection, obtain performed polymer;
3.75mL organic solvent N is added in step (4), the prepolymer that obtains in step (3), dinethylformamide, 0.15g (0.001mol) chainextender trolamine, after being fully uniformly mixed 6 hours, throw in mould, after organic solvent volatilization, prepare degradable block polyurethane.
Above-described embodiment is not that the present invention is not limited only to above-described embodiment for restriction of the present invention, as long as meet application claims, all belongs to protection scope of the present invention.
Claims (10)
1. a wetting ability, degradable block polyurethane, for polymkeric substance, it is characterized in that this polymkeric substance main component comprises triblock polyester polyvalent alcohol, vulcabond, chainextender, catalyzer, wherein the mol ratio of triblock polyester polyvalent alcohol, vulcabond and chainextender is 1:2 ~ 20:1 ~ 10, and catalyzer accounts for 0.1 ~ 2 ﹪ of this total polymer mass;
Described triblock polyester polyvalent alcohol is centered by the polyoxyethylene glycol of molecular weight 2000 or initial, and cause three block polyvalent alcohols of 6-caprolactone monomer ring-opening polymerization, molecular weight is 3000 ~ 20000, has following general formula:
Wherein k is corresponding cyclic ester free carbon atomicity 5, m, n is arbitrary integer, final gained three block polyol molecular weight 3000 ~ 20000.
2. prepare the method for a kind of wetting ability as claimed in claim 1, degradable block polyurethane, it is characterized in that the method comprises the following steps:
Step (1), 6-caprolactone, polyoxyethylene glycol are put into reaction vessel and carried out vacuumizing processed, obtain the raw material after dewatering; The mol ratio of polyoxyethylene glycol and 6-caprolactone is 1:8.75 ~ 70;
Step (2), by the raw material after dehydration in step (1) and catalyst mix, under nitrogen protection, be polymerized 19 ~ 29 hours at 130 ~ 140 DEG C, after being cooled to normal temperature, obtain triblock polyester polyvalent alcohol;
In step (2), the add-on of catalyzer is 0.1 ~ 2 ﹪ of polyoxyethylene glycol in step (1), 6-caprolactone total mass;
After step (3), triblock polyester polyvalent alcohol vacuum hydro-extraction that step (2) is obtained, be dissolved in organic solvent, then add vulcabond, catalyzer, 60 ~ 70 DEG C are reacted 1.5 ~ 3.5 hours under nitrogen protection, obtain performed polymer;
Described triblock polyester polyvalent alcohol and the mol ratio of vulcabond are 1:2 ~ 20;
In step (3), the add-on of catalyzer is 0.1 ~ 2 ﹪ of triblock polyester polyvalent alcohol, vulcabond, chainextender total mass;
Add organic solvent, chainextender in step (4), the prepolymer that obtains in step (3), after being fully uniformly mixed 2 ~ 12 hours, throw in mould, after organic solvent volatilization, prepare degradable block polyurethane;
The mol ratio of described chainextender and triblock polyester polyvalent alcohol is 1 ~ 10:1.
3. the preparation method of a kind of wetting ability as claimed in claim 1, degradable block polyurethane or a kind of wetting ability as claimed in claim 2, degradable block polyurethane, is characterized in that described vulcabond is the one in tolylene diisocyanate, aromatic series diphenylmethanediisocyanate, aliphatics dicyclohexyl methane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, lysinediisocyanate.
4. the preparation method of a kind of wetting ability as claimed in claim 1, degradable block polyurethane or a kind of wetting ability as claimed in claim 2, degradable block polyurethane, is characterized in that described catalyzer is ferric acetyl acetonade.
5. the preparation method of a kind of wetting ability as claimed in claim 1, degradable block polyurethane or a kind of wetting ability as claimed in claim 2, degradable block polyurethane, it is characterized in that described chainextender is conventional polyol or the Diamines with two or more hydroxyls, there is the compound with the functional group of described vulcabond generation esterification.
6. the preparation method of a kind of wetting ability as claimed in claim 2, degradable block polyurethane, it is characterized in that the add-on of organic solvent in step (2), (3) maintains 5 ~ 20 ﹪ with the mass volume ratio of solute and solvent, unit is that g/mL is as the criterion; Described organic solvent is DMF.
7. wetting ability, a degradable polymer support, comprise degradable block polyurethane as claimed in claim 1 and be prepared from, the purposes in tissue repair or organizational project, as support or bracket coating.
8. a kind of wetting ability as claimed in claim 7, degradable polymer support, it is characterized in that for the inner support as treatment coronary heart disease, Soft-tissue operation, drug release, wound dressings, tissue defect substitutes.
9. a kind of wetting ability as claimed in claim 7, degradable polymer support, is characterized in that also can introducing biotic component; Described composition is repaired according to auxiliary body inner tissue or is produced and is used for Quick-forming object and selects.
10. a kind of wetting ability as claimed in claim 1, the purposes of degradable block polyurethane in rapid shaping technique.
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