CN1166712C - Process for synthesizing polyurethane elastomer containing poly-beta-hydroxybutyrate block - Google Patents
Process for synthesizing polyurethane elastomer containing poly-beta-hydroxybutyrate block Download PDFInfo
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- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 title claims description 5
- 229920001397 Poly-beta-hydroxybutyrate Polymers 0.000 title abstract 6
- 229920000331 Polyhydroxybutyrate Polymers 0.000 title abstract 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 27
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229920002635 polyurethane Polymers 0.000 claims description 11
- 239000004814 polyurethane Substances 0.000 claims description 11
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 10
- 238000000855 fermentation Methods 0.000 claims description 10
- 230000004151 fermentation Effects 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000005809 transesterification reaction Methods 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229920006311 Urethane elastomer Polymers 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- -1 saturated sodium bicarbonate, saturated sodium-chloride Chemical class 0.000 claims description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- 239000012620 biological material Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract 3
- 238000007171 acid catalysis Methods 0.000 abstract 1
- 125000005442 diisocyanate group Chemical group 0.000 abstract 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 abstract 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 21
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical class ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 19
- 229960001701 chloroform Drugs 0.000 description 16
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 9
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical class [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 9
- 239000000284 extract Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000001476 alcoholic effect Effects 0.000 description 6
- 229940051250 hexylene glycol Drugs 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 5
- 239000012362 glacial acetic acid Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 206010061218 Inflammation Diseases 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 3
- 230000004054 inflammatory process Effects 0.000 description 3
- 230000002503 metabolic effect Effects 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000002526 effect on cardiovascular system Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- WHBMMWSBFZVSSR-GSVOUGTGSA-N (R)-3-hydroxybutyric acid Chemical compound C[C@@H](O)CC(O)=O WHBMMWSBFZVSSR-GSVOUGTGSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CWHJIJJSDGEHNS-MYLFLSLOSA-N Senegenin Chemical compound C1[C@H](O)[C@H](O)[C@@](C)(C(O)=O)[C@@H]2CC[C@@]3(C)C(CC[C@]4(CCC(C[C@H]44)(C)C)C(O)=O)=C4[C@@H](CCl)C[C@@H]3[C@]21C CWHJIJJSDGEHNS-MYLFLSLOSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000002429 anti-coagulating effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003384 small molecules Chemical group 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 239000009871 tenuigenin Substances 0.000 description 1
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- Materials For Medical Uses (AREA)
Abstract
The present invention relates to a synthetic method for a polyurethane elastomer with a PHB embedded section, which belongs to the field of biological materials. The synthetic method of the present invention is a method for preparing a biodegradable polyurethane elastomer and comprises the following steps that poly-beta-hydroxybutyrate (PHB) is used as a raw material, beta-hydroxybutyrate (3HB) is manufactured by an acid catalysis alcoholysis method, PHB glycol is manufactured by ester interchange reaction, and finally, the PHB glycol reacts with 2, 6-ethyl diisocyanate caproate. The polyurethane elastomer manufactured by the synthetic method of the present invention has fine biocompatibility and degradability, and a degraded product has no toxic or side effect to a biological body; thereby, the present invention can be used for various medical fields.
Description
Technical field
The invention belongs to technical field of biological material, relate to and utilize poly-beta-hydroxy-butyrate (PHB) as raw material, make beta-hydroxy-butanoic acid ester (3HB) by alcoholysis method, make the PHB glycol by transesterification reaction then, at last again with 2, the elastomeric method of a kind of biodegradable polyurethane of 6-vulcabond ethyl hexanoate (HDI) prepared in reaction.
Background technology
Because polyurethane elastomer has good mechanical performance and excellent biocompatibility and anticoagulant property, so polyurethane elastomer can be used for cardiovascular organization engineering aspect.Polyurethane material is that the degraded product amine of isocyanic ester has bio-toxicity as the subject matter of bioabsorbable material.The degraded intermediate of HDI and PHB is small molecules or the human body metabolic product nontoxic to human body.Select the metabolic product of human body to become the guiding theory of the bioabsorbable material of synthetic safety as the monomer of synthetic nontoxicity bioabsorbable material.Select cross-linked structure can more freely adjust the mechanical property and the degradation rate of bioabsorbable material.At present biodegradable polyurethane synthetic mainly contains following several approach:
1 oligosaccharide derivatives urethane
2 xylogen, tannin and the bark urethane of deriving
3 cellulose-derived urethane
The 4 starch urethane of deriving
More than several biodegradable polyurethane synthetic thinkings be to utilize the high reactivity of isocyanate groups of isocyanate component of urethane and the biodegradable performance of natural high moleculer eompound, the natural high moleculer eompound that contains a plurality of hydroxyls as one of polyurethane polyol component, make various polyurethane materials, can give its biological degradability and biocompatibility preferably.But this type of polyurethane degraded product mostly is harmful or can't be absorption of human body, thereby can not be used for medical field.In addition, can also with the polymkeric substance of fully biodegradable for example poly(lactic acid), polylactone, polymerized thylene carbonate ethyl ester etc. as the polyol component of urethane, react synthesizing biological degradable urethane with vulcabond one, this class urethane is particularly suitable for being applied to medical field, but their degraded product mostly is acidic substance, causes inflammation easily.The degraded product that contains a certain amount of PHB in the metabolic product of human body.
Summary of the invention
It is good to the purpose of this invention is to provide a kind of manufacturing biological degradability, the method for synthesizing urethane elastomer that good biocompatibility, degraded product have no side effect.
Poly-beta-hydroxy-butyrate (PHB) is the optical active polymer of a kind of D (-)-3-hydroxybutyric acid, can be generated by various bacteria, and it is assembled with particle form in tenuigenin as the storage material of carbon and energy in a kind of cell.The chemical structure of PHB is as shown below.
PHB is a kind of polymkeric substance with good biocompatibility, and is good with the tissue consistency, do not cause inflammation, and do not have rejection and easily degraded, and this makes it can be used for biomedical sector.The application of PHB in medical science at present is a lot, for example is used for medicine sustained release, operation examination, and bandage also can be used as the film of blood compatibility and used in tissue engineering porous support or the like.As medical material, the most outstanding advantage of PHB is to have biocompatibility, and the allosome rejection is very little, and degradation speed is slow in human body, and its degraded product does not cause inflammation and toxic side effect.
Because PHB has excellent biological compatibility and totally biodegradable, the polyurethane elastomer that is synthesized by it should have excellent biological compatibility and certain biological degradability, and the good mechanical property that had of polyurethane elastomer itself in addition, the biodegradable type polyurethane of this class are bound to be widely used in organizational project and medical field such as cardiovascular.
The method for synthesizing urethane elastomer that the present invention contains the PHB block is stated as: use poly-beta-hydroxy-butyrate (PHB) as raw material, make beta-hydroxy-butanoic acid ester (3HB) by acid-catalyzed alcoholysis method, make the PHB glycol by transesterification reaction then, at last again with 2, the elastomeric method of a kind of biodegradable polyurethane of 6-vulcabond ethyl hexanoate (HDI) prepared in reaction.
Its preparation process is as follows:
1. will be dissolved in the mixing solutions of organic solvent and monohydroxy-alcohol by the PHB that biological fermentation makes, make catalyzer, heating reflux reaction 24 to 72 hours with acid.
2. the above-mentioned yellow oil dress liquid that obtains is used semi-saturation sodium-chlor successively, saturated sodium bicarbonate, the saturated sodium-chloride washing, gained water organic solvent extraction, extraction liquid and front oil phase are mixed, and gained oily matter is fractionated out organic solvent, remain to be 3HB.
3. in reaction flask, add 3HB, transesterification catalyst, glycol reacted 3 hours down in 130 ℃, was warming up to 140 ℃ then, and was decompressed to 0.5mmHg gradually, reacted 5 hours, obtained PHB glycol oligopolymer.
4. in reaction flask, add PHB glycol oligopolymer, under nitrogen protection, be heated to 110-150 ℃, in three hours, drip the HDI. reaction gradually and carried out again 2 hours.
5. reaction product is poured into and obtained white elastomerics in the cold deionized water, this is the polyurethane elastomer that the present invention contains the PHB block.
The polyurethane elastomer of using present method preparation has following characteristics and advantage:
PHB block molecule amount and content can be regulated in the 1 gained urethane.
It is nontoxic to organism that the polyurethane elastomer of 2 gained has excellent biological compatibility and degradation property and degraded product.
3 gained polyurethane molecular amounts are adjustable.
Embodiment
Embodiment 1
1. the PHB20 gram that biological fermentation is made is dissolved in the mixing solutions of 250 milliliters of trichloromethanes and 250 ml methanol, reflux 24 hours, and catalyzer is toluene sulfonic acide (10g).
2. the above-mentioned yellow oil dress liquid that obtains is used semi-saturation sodium-chlor successively, saturated sodium bicarbonate, the saturated sodium-chloride washing, the gained water extracts with trichloromethane/ethylene dichloride, and extraction liquid and front oil phase are mixed.Gained oily matter is fractionated out trichloromethane/ethylene dichloride, remain and be 3HB.
3. in reaction flask, add 3HB130g, catalyzer (Glacial acetic acid zinc) 0.5g, butyleneglycol 4.506g reacted 3 hours down in 130 ℃, was warming up to 140 ℃ then, and was decompressed to 0.5mmHg gradually, reacted 5 hours, obtained PHB glycol oligopolymer.
4. in the 250ml there-necked flask, add PHB glycol oligopolymer (molecular weight is 1810) 18.1 grams, under nitrogen protection, be heated to 110-150 ℃, in three hours, drip HDI (2,6-vulcabond ethyl hexanoate) 1.686 grams gradually.Reaction was carried out 2 hours again.
5. reaction product is poured into and obtained white elastomerics in the cold deionized water.
Embodiment 2
The 1 PHB20 gram that biological fermentation is made is dissolved in 250 milliliters of trichloromethanes and the 250 milliliters of alcoholic acid mixing solutionss, reflux 24 hours, catalyzer p-methyl benzenesulfonic acid (10g).
2 adorn liquid with the above-mentioned yellow oil that obtains uses semi-saturation sodium-chlor successively, saturated sodium bicarbonate, and the saturated sodium-chloride washing, the gained water extracts with trichloromethane/ethylene dichloride, and extraction liquid and front oil phase are mixed.Gained oily matter is fractionated out trichloromethane/ethylene dichloride, remain and be 3HB.
3 add 3HB130g in reaction flask, catalyzer (Dibutyltin oxide) 0.5g, and butyleneglycol 4.506g reacted 3 hours down in 130 ℃, was warming up to 140 ℃ then, and was decompressed to 0.5mmHg gradually, reacted 5 hours, obtained PHB glycol oligopolymer.
4 add PHB glycol prepolymer (molecular weight is 1830) 18.3 grams in the 250ml there-necked flask, be heated to 110-150 ℃ under nitrogen protection, drip HDI (2,6-vulcabond ethyl hexanoate) 1.686 grams in three hours gradually.Reaction was carried out 2 hours again.
5 pour reaction product into and obtain white elastomerics in the cold deionized water.
Embodiment 3
The 1 PHB20 gram that biological fermentation is made is dissolved in the mixing solutions of 250 milliliters of trichloromethanes and 250 ml methanol reflux 24 hours, catalyzer p-methyl benzenesulfonic acid (10g).
2 adorn liquid with the above-mentioned yellow oil that obtains uses semi-saturation sodium-chlor successively, saturated sodium bicarbonate, and the saturated sodium-chloride washing, the gained water extracts with trichloromethane/ethylene dichloride, and extraction liquid and front oil phase are mixed.Gained oily matter is fractionated out trichloromethane/ethylene dichloride, remain and be 3HB.
3 add 3HB130g in reaction flask, catalyzer (Dibutyltin oxide) 0.5g, and hexylene glycol 5.906g reacted 3 hours down in 130 ℃, was warming up to 140 ℃ then, and was decompressed to 0.5mmHg gradually, reacted 5 hours, obtained PHB glycol oligopolymer.
4 add PHB glycol prepolymer (molecular weight is 1830) 18.3 grams in the 250ml there-necked flask, be heated to 110-150 ℃ under nitrogen protection, drip HDI (2,6-vulcabond ethyl hexanoate) 1.686 grams in three hours gradually.Reaction was carried out 2 hours again.
5 pour reaction product into and obtain white elastomerics in the cold deionized water.
Embodiment 4
The 1 PHB20 gram that biological fermentation is made is dissolved in 250 milliliters of ethylene dichloride and the 250 milliliters of alcoholic acid mixing solutionss, reflux 24 hours, and catalyzer is toluene sulfonic acide (10g).。
2 adorn liquid with the above-mentioned yellow oil that obtains uses semi-saturation sodium-chlor successively, saturated sodium bicarbonate, and the saturated sodium-chloride washing, the gained water extracts with trichloromethane/ethylene dichloride, and extraction liquid and front oil phase are mixed.Gained oily matter is fractionated out trichloromethane/ethylene dichloride, remain and be 3HB.
3 add 3HB130g in reaction flask, catalyzer (Glacial acetic acid zinc) 0.5g, and hexylene glycol 5.906g reacted 3 hours down in 130 ℃, was warming up to 140 ℃ then, and was decompressed to 0.5mmHg gradually, reacted 5 hours, obtained PHB glycol oligopolymer.
4 add PHB glycol prepolymer (molecular weight is 1830) 18.3 grams in the 250ml there-necked flask, be heated to 110-150 ℃ under nitrogen protection, drip HDI (2,6-vulcabond ethyl hexanoate) 1.686 grams in three hours gradually. and reaction was carried out 2 hours again.
5 pour reaction product into and obtain white elastomerics in the cold deionized water.
Embodiment 5
The 1 PHB20 gram that biological fermentation is made is dissolved in 250 milliliters of ethylene dichloride and the 250 milliliters of alcoholic acid mixing solutionss, reflux 24 hours, and catalyzer is phosphoric acid (2ml).。
2 adorn liquid with the above-mentioned yellow oil that obtains uses semi-saturation sodium-chlor successively, saturated sodium bicarbonate, and the saturated sodium-chloride washing, the gained water extracts with trichloromethane/ethylene dichloride, and extraction liquid and front oil phase are mixed.Gained oily matter is fractionated out trichloromethane/ethylene dichloride, remain and be 3HB.
3 add 3HB130g in reaction flask, catalyzer (Glacial acetic acid zinc) 0.5g, and hexylene glycol 5.906g reacted 3 hours down in 130 ℃, was warming up to 140 ℃ then, and was decompressed to 0.5mmHg gradually, reacted 5 hours, obtained PHB glycol oligopolymer.
4 add PHB glycol prepolymer (molecular weight is 1830) 18.3 grams in the 250ml there-necked flask, be heated to 110-150 ℃ under nitrogen protection, drip HDI (2,6-vulcabond ethyl hexanoate) 1.686 grams in three hours gradually.Reaction was carried out 2 hours again.
5 pour reaction product into and obtain white elastomerics in the cold deionized water.
Embodiment 6
The 1 PHB20 gram that biological fermentation is made is dissolved in 250 milliliters of ethylene dichloride and the 250 milliliters of alcoholic acid mixing solutionss, reflux 24 hours, and catalyzer is hydrochloric acid (2ml).。
2 adorn liquid with the above-mentioned yellow oil that obtains uses semi-saturation sodium-chlor successively, saturated sodium bicarbonate, and the saturated sodium-chloride washing, the gained water extracts with trichloromethane/ethylene dichloride, and extraction liquid and front oil phase are mixed.Gained oily matter is fractionated out trichloromethane/ethylene dichloride, remain and be 3HB.
3 add 3HB130g in reaction flask, catalyzer (Glacial acetic acid zinc) 0.5g, and hexylene glycol 5.906g reacted 3 hours down in 130 ℃, was warming up to 140 ℃ then, and was decompressed to 0.5mmHg gradually, reacted 5 hours, obtained PHB glycol oligopolymer.
4 add PHB glycol prepolymer (molecular weight is 1830) 18.3 grams in the 250ml there-necked flask, be heated to 110-150 ℃ under nitrogen protection, drip HDI (2,6-vulcabond ethyl hexanoate) 1.686 grams in three hours gradually. and reaction was carried out 2 hours again.
5 pour reaction product into and obtain white elastomerics in the cold deionized water.
Embodiment 7
The 1 PHB20 gram that biological fermentation is made is dissolved in 250 milliliters of ethylene dichloride and the 250 milliliters of alcoholic acid mixing solutionss, reflux 24 hours, and catalyzer is sulfuric acid (2ml).。
2 adorn liquid with the above-mentioned yellow oil that obtains uses semi-saturation sodium-chlor successively, saturated sodium bicarbonate, and the saturated sodium-chloride washing, the gained water extracts with trichloromethane/ethylene dichloride, and extraction liquid and front oil phase are mixed.Gained oily matter is fractionated out trichloromethane/ethylene dichloride, remain and be 3HB.
3 add 3HB130g in reaction flask, catalyzer (Glacial acetic acid zinc) 0.5g, and hexylene glycol 5.906g reacted 3 hours down in 130 ℃, was warming up to 140 ℃ then, and was decompressed to 0.5mmHg gradually, reacted 5 hours, obtained PHB glycol oligopolymer.
4 add PHB glycol prepolymer (molecular weight is 1830) 18.3 grams in the 250ml there-necked flask, be heated to 110-150 ℃ under nitrogen protection, drip HDI (2,6-vulcabond ethyl hexanoate) 1.686 grams in three hours gradually.Reaction was carried out 2 hours again.
5 pour reaction product into and obtain white elastomerics in the cold deionized water.
Embodiment 8
The 1 PHB20 gram that biological fermentation is made is dissolved in 250 milliliters of ethylene dichloride and the 250 milliliters of alcoholic acid mixing solutionss, reflux 24 hours, and catalyzer is hydrochloric acid (2ml).。
2 adorn liquid with the above-mentioned yellow oil that obtains uses semi-saturation sodium-chlor successively, saturated sodium bicarbonate, and the saturated sodium-chloride washing, the gained water extracts with trichloromethane/ethylene dichloride, and extraction liquid and front oil phase are mixed.Gained oily matter is fractionated out trichloromethane/ethylene dichloride, remain and be 3HB.
3 add 3HB130g in reaction flask, catalyzer (Dibutyltin oxide) 0.5g, and hexylene glycol 5.906g reacted 3 hours down in 130 ℃, was warming up to 140 ℃ then, and was decompressed to 0.5mmHg gradually, reacted 5 hours, obtained PHB glycol oligopolymer.
4 add PHB glycol prepolymer (molecular weight is 1830) 18.3 grams in the 250ml there-necked flask, be heated to 110-150 ℃ under nitrogen protection, drip HDI (2,6-vulcabond ethyl hexanoate) 1.686 grams in three hours gradually.Reaction was carried out 2 hours again.
5 pour reaction product into and obtain white elastomerics in the cold deionized water.
Claims (1)
1. a method for synthesizing urethane elastomer that contains the poly-beta-hydroxy-butyrate block is characterized in that: use poly-beta-hydroxy-butyrate as raw material, make beta-hydroxy-butanoic acid ester by acid-catalyzed alcoholysis method, make the poly-beta-hydroxy-butyrate glycol by transesterification reaction then, at last again with 2, a kind of biodegradable polyurethane elastomerics of 6-vulcabond ethyl hexanoate prepared in reaction;
Its preparation process is as follows:
(1) poly-beta-hydroxy-butyrate that is made by biological fermentation is dissolved in the mixing solutions of organic solvent and monohydroxy-alcohol, makees catalyzer with acid, heating reflux reaction 24 to 72 hours;
(2) the above-mentioned yellow oil dress liquid that obtains is used semi-saturation sodium-chlor, saturated sodium bicarbonate, saturated sodium-chloride washing successively, gained water organic solvent extraction, extraction liquid and front oil phase are mixed, and gained oily matter is fractionated out organic solvent, remain to be beta-hydroxy-butanoic acid ester;
(3) in reaction flask, add beta-hydroxy-butanoic acid ester, transesterification catalyst, glycol reacted 3 hours down in 130 ℃, was warming up to 140 ℃ then, and was decompressed to 66.66Pa gradually, reacted 5 hours, obtained poly-beta-hydroxy-butyrate glycol oligopolymer;
(4) in reaction flask, add poly-beta-hydroxy-butyrate glycol oligopolymer, under nitrogen protection, be heated to 110-150 ℃, in three hours, drip 2 gradually, 6-vulcabond ethyl hexanoate, reaction was carried out 2 hours again;
(5) reaction product is poured into obtained white elastomerics in the cold deionized water, this is the polyurethane elastomer that the present invention contains the poly-beta-hydroxy-butyrate block.
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| DK1864687T3 (en) * | 2006-06-09 | 2013-10-07 | Eidgenoess Tech Hochschule | Skeleton for artificial heart valves and vascular structures |
| JP5386798B2 (en) * | 2007-06-22 | 2014-01-15 | 東ソー株式会社 | Poly-3-hydroxybutyrate complex |
| CN103756288B (en) * | 2013-12-20 | 2016-10-12 | 苏州市万泰真空炉研究所有限公司 | A kind of preparation method of biodegradable environmental-friendrigid rigid foam plastic complex |
| CN107814896A (en) * | 2017-11-21 | 2018-03-20 | 深圳大学 | A kind of preparation method of polyurethane |
| CN112126050A (en) * | 2020-08-20 | 2020-12-25 | 青岛科技大学 | Preparation method of poly-6-hydroxyhexanoate |
| CN111995736A (en) * | 2020-08-24 | 2020-11-27 | 青岛科技大学 | Preparation method of polycaprolactone polyol |
| CN112142966A (en) * | 2020-08-26 | 2020-12-29 | 青岛科技大学 | Synthesis method of poly-6-hydroxyhexanoate |
| CN112142967A (en) * | 2020-08-27 | 2020-12-29 | 青岛科技大学 | Synthesis method of polycaprolactone polyol |
| CN115043727B (en) * | 2022-08-04 | 2024-04-26 | 东莞理工学院 | Method for preparing 3-bromobutyrate compounds and 3-hydroxybutyrate compounds by degrading poly (3-hydroxybutyrate) |
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