WO2022143914A1 - 一种聚羟基脂肪酸酯及其制备方法 - Google Patents
一种聚羟基脂肪酸酯及其制备方法 Download PDFInfo
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- WO2022143914A1 WO2022143914A1 PCT/CN2021/143143 CN2021143143W WO2022143914A1 WO 2022143914 A1 WO2022143914 A1 WO 2022143914A1 CN 2021143143 W CN2021143143 W CN 2021143143W WO 2022143914 A1 WO2022143914 A1 WO 2022143914A1
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- Prior art keywords
- polyhydroxyalkanoate
- propiolactone
- beta
- dimethylpropiolactone
- mol
- Prior art date
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- -1 fatty acid ester Chemical class 0.000 title abstract description 11
- 235000014113 dietary fatty acids Nutrition 0.000 title abstract description 6
- 229930195729 fatty acid Natural products 0.000 title abstract description 6
- 239000000194 fatty acid Substances 0.000 title abstract description 6
- 238000002360 preparation method Methods 0.000 title description 6
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229960000380 propiolactone Drugs 0.000 claims abstract description 27
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 86
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims description 85
- 238000000034 method Methods 0.000 claims description 50
- 239000000178 monomer Substances 0.000 claims description 44
- 229920001577 copolymer Polymers 0.000 claims description 38
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- RXDIFCRJKDATEB-UHFFFAOYSA-N 4-propan-2-yloxetan-2-one Chemical compound CC(C)C1CC(=O)O1 RXDIFCRJKDATEB-UHFFFAOYSA-N 0.000 claims description 21
- QTWLQDVFHKLZRA-UHFFFAOYSA-N 4-ethyloxetan-2-one Chemical compound CCC1CC(=O)O1 QTWLQDVFHKLZRA-UHFFFAOYSA-N 0.000 claims description 20
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 20
- 229920001519 homopolymer Polymers 0.000 claims description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 17
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- MRYQZMHVZZSQRT-UHFFFAOYSA-M tetramethylazanium;acetate Chemical compound CC([O-])=O.C[N+](C)(C)C MRYQZMHVZZSQRT-UHFFFAOYSA-M 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- VSCBATMPTLKTOV-UHFFFAOYSA-N 2-tert-butylimino-n,n-diethyl-1,3-dimethyl-1,3,2$l^{5}-diazaphosphinan-2-amine Chemical compound CCN(CC)P1(=NC(C)(C)C)N(C)CCCN1C VSCBATMPTLKTOV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002841 Lewis acid Substances 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 229940100198 alkylating agent Drugs 0.000 claims description 3
- 239000002168 alkylating agent Substances 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 150000007517 lewis acids Chemical class 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- GTCDARUMAMVCRO-UHFFFAOYSA-M tetraethylazanium;acetate Chemical compound CC([O-])=O.CC[N+](CC)(CC)CC GTCDARUMAMVCRO-UHFFFAOYSA-M 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- XTGSXZNTCQDKDF-UHFFFAOYSA-N 3-ethyloxetan-2-one Chemical compound CCC1COC1=O XTGSXZNTCQDKDF-UHFFFAOYSA-N 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 230000000704 physical effect Effects 0.000 abstract description 5
- 230000003287 optical effect Effects 0.000 abstract description 2
- 229920000070 poly-3-hydroxybutyrate Polymers 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000007334 copolymerization reaction Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 238000000113 differential scanning calorimetry Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- REKYPYSUBKSCAT-UHFFFAOYSA-N 3-hydroxypentanoic acid Chemical compound CCC(O)CC(O)=O REKYPYSUBKSCAT-UHFFFAOYSA-N 0.000 description 5
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical group OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012456 homogeneous solution Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- BOAHYOWLXYZJSN-UHFFFAOYSA-N 3-hydroxy-4-methylpentanoic acid Chemical group CC(C)C(O)CC(O)=O BOAHYOWLXYZJSN-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 150000001261 hydroxy acids Chemical class 0.000 description 3
- NSRBCQCXZAYQHF-UHFFFAOYSA-N n-[[tert-butylimino-bis[[tris(dimethylamino)-$l^{5}-phosphanylidene]amino]-$l^{5}-phosphanyl]imino-bis(dimethylamino)-$l^{5}-phosphanyl]-n-methylmethanamine Chemical compound CN(C)P(N(C)C)(N(C)C)=NP(=NC(C)(C)C)(N=P(N(C)C)(N(C)C)N(C)C)N=P(N(C)C)(N(C)C)N(C)C NSRBCQCXZAYQHF-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical group CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- AXFYFNCPONWUHW-UHFFFAOYSA-N 3-hydroxyisovaleric acid Chemical group CC(C)(O)CC(O)=O AXFYFNCPONWUHW-UHFFFAOYSA-N 0.000 description 1
- ALRHLSYJTWAHJZ-UHFFFAOYSA-M 3-hydroxypropionate Chemical compound OCCC([O-])=O ALRHLSYJTWAHJZ-UHFFFAOYSA-M 0.000 description 1
- SJZRECIVHVDYJC-UHFFFAOYSA-M 4-hydroxybutyrate Chemical compound OCCCC([O-])=O SJZRECIVHVDYJC-UHFFFAOYSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000001851 biosynthetic effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical class [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- VBBRYJMZLIYUJQ-UHFFFAOYSA-N cyclopropanone Chemical compound O=C1CC1 VBBRYJMZLIYUJQ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- IZSFVWCXDBEUQK-UHFFFAOYSA-N propan-2-ol;zinc Chemical compound [Zn].CC(C)O.CC(C)O IZSFVWCXDBEUQK-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
-
- 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
Definitions
- the invention relates to a polyhydroxy fatty acid ester and a preparation method thereof.
- Polyhydroxyalkanoates are a class of thermoplastic resins composed of hydroxyalkanoate units and having soil and marine biodegradability.
- PHA polyhydroxyalkanoate copolymers or homopolymers are mainly synthesized by microbial fermentation.
- PHA is a substance that microorganisms store as a carbon source and energy in the case of carbon and nitrogen nutritional imbalances.
- P3HB Biosynthetic poly-3-hydroxybutyrate
- PHBV poly-3-hydroxybutyrate/3-hydroxyvalerate
- PHBH poly-3-hydroxybutyrate/hexanoate
- P34HB polyhydroxyalkanoate homopolymers or copolymers such as acid/4-hydroxybutyrate
- the process flow and operating conditions of the biosynthesis method determine its long production cycle, low yield and high process cost, making its price far It is much higher than general-purpose plastics such as polyethylene and polypropylene, which limits its application range.
- the chemical synthesis method has the advantages of low cost, short cycle and simple process flow, and can also control the structure of PHA, which is the best synthetic method for its wide application.
- the chemical synthesis methods of polyhydroxyalkanoates include direct polycondensation of hydroxy acids and ring-opening polymerization of lactones.
- the method for the direct polycondensation of hydroxy acids is simple, the hydroxy acids are unstable and can be easily hydrolyzed to remove hydroxyl groups.
- the reaction by-products are difficult to remove in the viscous melt, and it is difficult to ensure that the reaction proceeds in the positive direction.
- the molecular weight of the obtained polymer is generally low.
- the polymerization temperature is high, which often leads to the color of the product. Therefore, currently, the ring-opening polymerization method is mainly used to synthesize polyhydroxyalkanoate.
- Poly3-hydroxypropionate (P3HP) homopolymer has excellent biodegradability due to its simple carbon skeleton, but its application range is limited due to its low processing temperature.
- Poly-3-hydroxybutyrate (P3HB) homopolymer has high crystallinity, slow crystallization speed, easy to form spherulites, and poor thermal stability, all of which limit the performance of poly-3-hydroxybutyrate (P3HB) homopolymer. application.
- the present invention relates to polyhydroxyalkanoates from beta-propiolactone homologues.
- the polyhydroxyalkanoate has the characteristics of high molecular weight, excellent physical properties, optical activity and biodegradability.
- a polyhydroxyalkanoate wherein the polyhydroxyalkanoate comprises the following structural formula:
- R 1 and R 2 are independently of each other selected from H, methyl, ethyl and isopropyl or combinations thereof, and n is 10-3500, preferably 50-2500, more preferably 100-1000.
- polyhydroxyalkanoate according to scheme 1 or 2, wherein the polyhydroxyalkanoate is a homopolymer of the following monomers or a copolymer comprising two or more of the monomers Substances: ⁇ -propiolactone, ⁇ -methylpropiolactone, ⁇ -dimethylpropiolactone, ⁇ -ethylpropiolactone or ⁇ -isopropylpropiolactone.
- polyhydroxyalkanoate according to any one of schemes 1-3, wherein the polyhydroxyalkanoate is a homopolymer of the following monomers: ⁇ -dimethylpropiolactone, ⁇ -Ethyl propiolactone or beta-isopropyl propiolactone.
- polyhydroxyalkanoate according to any one of schemes 1-3, wherein the polyhydroxyalkanoate is a homopolymer of the following monomers: ⁇ -dimethylpropiolactone or ⁇ - isopropyl propiolactone.
- polyhydroxyalkanoate according to any one of schemes 1-3, wherein the polyhydroxyalkanoate is a copolymer of two of the following monomers: ⁇ -propiolactone, ⁇ -propiolactone Methylpropiolactone, ⁇ -dimethylpropiolactone, ⁇ -ethylpropiolactone or ⁇ -isopropylpropiolactone, and the molar ratio of the two monomer units in the copolymer is 1:99 ⁇ 99:1, preferably 5:95 to 99:5, more preferably 10:90 to 90:10.
- polyhydroxyalkanoate according to scheme 6, wherein the polyhydroxyalkanoate is a copolymer of ⁇ -propiolactone and ⁇ -dimethylpropiolactone; ⁇ -propiolactone and Copolymer of ⁇ -ethylpropiolactone; Copolymer of ⁇ -methylpropiolactone and ⁇ -dimethylpropiolactone; Copolymer of ⁇ -dimethylpropiolactone and ⁇ -ethylpropiolactone ; or a copolymer of ⁇ -dimethylpropiolactone and ⁇ -isopropylpropiolactone.
- polyhydroxyalkanoate according to any one of schemes 1 to 8, wherein the polyhydroxyalkanoate has a weight-average molecular weight ranging from 8,000 Da to 9.8 ⁇ 10 5 Da, preferably 3.5 ⁇ 10 4 Da to 6.0 ⁇ 10 5 Da, more preferably 5.0 ⁇ 10 4 Da to 4.0 ⁇ 10 5 Da; polydispersity is 0.5 to 7.0, preferably 1.0 to 5.0, more preferably 1.2 to 4.0.
- polyhydroxyalkanoate according to any one of claims 1 to 9, wherein the polyhydroxyalkanoate has a tensile strength in the range of 1 MPa to 60 MPa, preferably 1.5 MPa to 50 MPa, more preferably 2MPa ⁇ 40MPa, the elongation at break ranges from 5% ⁇ 800%, preferably 10% ⁇ 700%, more preferably 15% ⁇ 650%, and the elastic modulus ranges from 100MPa ⁇ 8000MPa, preferably 600MPa ⁇ 3000MPa, more preferably 650MPa ⁇ 3000MPa.
- the method further comprises synthesizing a monomer for preparing polyhydroxyalkanoate under the action of a catalyst, and the raw material for the synthesis comprises ethylene Ketone and aldehyde or acetone;
- the catalyst includes one or more of BF 3 ⁇ Et 2 O, aluminum chloride, zinc chloride, Y-type zeolite;
- the synthetic solvent includes tetrahydrofuran, ethyl acetate, acetone One or more of ; the synthesis is carried out at a temperature of -10°C to 50°C for a period of 0.1 to 72 hours.
- the polyhydroxyalkanoate involved in the present invention has the advantages of high molecular weight, diverse physical properties, biodegradability and the like.
- polyhydroxyalkanoate characterized in that the polyhydroxyalkanoate comprises the following structural formula:
- R 1 and R 2 are independently of each other selected from H, methyl, ethyl and isopropyl or combinations thereof, and n is 10-3500, preferably 50-2500, more preferably 100-1000.
- n can be, for example, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900 , 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, or within a range between any two of these values.
- the polyhydroxyalkanoate comprises the following structural formula:
- the polyhydroxyalkanoate is a homopolymer or a copolymer comprising two or more of the following monomers: ⁇ -propiolactone, ⁇ - Methylpropiolactone, beta-dimethylpropiolactone, beta-ethylpropiolactone or beta-isopropylpropiolactone.
- the polyhydroxyalkanoate is a homopolymer of the following monomers: ⁇ -dimethylpropiolactone, ⁇ -ethylpropiolactone or ⁇ -isopropylpropiolactone ester.
- the polyhydroxyalkanoate is a homopolymer of the following monomers: ⁇ -dimethylpropiolactone or ⁇ -isopropylpropiolactone.
- the segments of the homopolymer may assume a stereo or random state.
- the polyhydroxy fatty acid ester is a copolymer of two of the following monomers: ⁇ -propiolactone, ⁇ -methylpropiolactone, ⁇ -dimethylpropiolactone ester, ⁇ -ethyl propiolactone or ⁇ -isopropyl propiolactone, and the molar ratio of the two monomer units in the copolymer is 1:99-99:1, preferably 5:95-99:5 , more preferably 10:90 to 90:10.
- the molar ratio of the two monomer units in the copolymer can be, for example, 1:99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70: 30, 80:20, 90:10, 95:5, 99:1, or a range between any of these values.
- the segments of the copolymer may exhibit a stereo or random state.
- the polyhydroxyalkanoate is a copolymer of ⁇ -propiolactone and ⁇ -dimethylpropiolactone; a copolymer of ⁇ -propiolactone and ⁇ -ethylpropiolactone Copolymers; copolymers of ⁇ -methylpropiolactone and ⁇ -dimethylpropiolactone; copolymers of ⁇ -dimethylpropiolactone and ⁇ -ethylpropiolactone; or ⁇ -dimethylpropiolactone Copolymer of lactone and beta-isopropylpropiolactone.
- the polyhydroxyalkanoate comprises monomeric units of R and/or S configuration.
- the polyhydroxyalkanoate has a weight average molecular weight ranging from 8,000 Da to 9.8 ⁇ 10 5 Da, preferably 3.5 ⁇ 10 4 Da to 6.0 ⁇ 10 5 Da, more preferably 5.0 ⁇ 10 4 Da to 4.0 ⁇ 10 5 Da; the polydispersity is 0.5 to 7.0, preferably 1.0 to 5.0, more preferably 1.2 to 4.0.
- the polyhydroxyalkanoate has a tensile strength ranging from 1 MPa to 60 MPa, preferably 1.5 MPa to 50 MPa, more preferably 2 MPa to 40 MPa, and an elongation at break ranging from 5% to 800 %, preferably 10% to 700%, more preferably 15% to 650%, and the elastic modulus ranges from 100MPa to 8000MPa, preferably 600MPa to 3000MPa, more preferably 650MPa to 3000MPa.
- a method for preparing the polyhydroxyalkanoate according to the present invention wherein the method is a ring-opening polymerization method.
- the polyhydroxyalkanoate is obtained by homopolymerization of the following monomers or copolymerization comprising two or more of the monomers: ⁇ -propiolactone, ⁇ -methyl Propiolactone, beta-dimethylpropiolactone, beta-ethylpropiolactone or beta-isopropylpropiolactone.
- the polyhydroxyalkanoate is obtained by homopolymerization of the following monomers: ⁇ -dimethylpropiolactone, ⁇ -ethylpropiolactone or ⁇ -isopropylpropiolactone ester.
- the polyhydroxyalkanoate is obtained by homopolymerization of the following monomers: ⁇ -dimethylpropiolactone or ⁇ -isopropylpropiolactone.
- the polyhydroxyalkanoate is obtained by copolymerization of two of the following monomers: ⁇ -propiolactone, ⁇ -methylpropiolactone, ⁇ -dimethylpropiolactone ester, ⁇ -ethyl propiolactone or ⁇ -isopropyl propiolactone, and the feeding ratio of the two monomers should be such that the molar ratio of the two monomer units in the copolymer is 1:99 to 99 : 1, preferably 5:95 ⁇ 99:5, more preferably 10:90 ⁇ 90:10, the feeding ratio of the two monomers should be such that the molar ratio of the two monomer units in the copolymer can be, for example, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10, 95:5, 99:1 or within a range between any two of these values.
- the polyhydroxy fatty acid ester is obtained by copolymerization of ⁇ -propiolactone and ⁇ -dimethylpropiolactone; or by ⁇ -propiolactone and ⁇ -ethylpropiolactone Obtained by copolymerization of ⁇ -methylpropiolactone; or obtained by copolymerization of ⁇ -methylpropiolactone and ⁇ -dimethylpropiolactone; or obtained by copolymerization of ⁇ -dimethylpropiolactone and ⁇ -ethylpropiolactone; or Obtained by copolymerization of ⁇ -dimethylpropiolactone and ⁇ -isopropylpropiolactone.
- the method is carried out at a temperature of 25°C to 200°C, preferably 40°C to 160°C, more preferably 50°C to 100°C.
- the method is carried out for a period of 0.1 to 72 hours, preferably 1 to 30 hours, more preferably 3 to 15 hours.
- the method is carried out in the presence of a catalyst comprising one or more of an alkylating agent, a protonic acid, a Lewis acid, the amount of which is added based on the total amount of monomers used It is 0.01-5 mol%, preferably 0.05-2 mol%, more preferably 0.01-0.5 mol%.
- the method is carried out in the presence of an initiator, the initiator includes one or more of strong basic initiators, preferably TBD, BEMP, P2, P4 as shown below
- the initiator includes one or more of strong basic initiators, preferably TBD, BEMP, P2, P4 as shown below
- One or more of the initiators in an amount of 0.1-10 mol %, preferably 1.0-5 mol %, more preferably 2.5-4 mol %, based on the total amount of monomers used:
- the method is carried out in the presence of a solvent including one or more of toluene, chloroform, dichloroethane, tetrahydrofuran, hexane, and ethyl acetate.
- a solvent including one or more of toluene, chloroform, dichloroethane, tetrahydrofuran, hexane, and ethyl acetate.
- the method may further comprise synthesizing a monomer for preparing the polyhydroxyalkanoate under the action of a catalyst.
- the chemical reaction of the monomer for preparing the polyhydroxyalkanoate mainly includes the following:
- group R is selected from H, CH3 , CH2CH3 , CH( CH3 ) 2 ;
- the catalyst may include one or more of BF 3 ⁇ Et 2 O, aluminum chloride, zinc chloride, and Y-type zeolite.
- the synthesis can be carried out in the presence of a solvent, and the solvent includes one or more of tetrahydrofuran, ethyl acetate, and acetone.
- the synthesis can be carried out at a temperature of -10°C to 50°C.
- the synthesis can be carried out for a period of 0.1 to 72 hours.
- the molar ratio of ketene to aldehyde (formula (1)) or acetone (formula (2)) is 0.7 to 2.0 eq.
- the catalyst equivalent weight (based on aldehyde or acetone) is 0.1% to 10% eq.
- the yield of the prepared monomer is 50% to 93%.
- the polyhydroxyalkanoate involved in the present invention has the advantages of high molecular weight, diverse physical properties, biodegradability and the like.
- the mechanical properties (tensile strength, elongation at break, elastic modulus, etc.) of the polyhydroxyalkanoate are tested, and the instrument used is the precision electronic universal material testing machine AGX-V of Shimadzu Corporation ,
- the test specimens for mechanical properties were prepared according to the test method requirements of ASTM D638, and the experiments were carried out at room temperature.
- DSC Differential scanning calorimetry
- the molecular weight (number average molecular weight, weight average molecular weight, molecular weight distribution) of the polyhydroxyalkanoate was tested by GPC, the instrument used was Tosoh HLC-8329GPC, polystyrene was used as a standard sample, and the polyhydroxyalkanoate was The samples were dissolved in chloroform, and the test sample concentration was 0.2 wt/vol%. The temperature of the chromatographic column was set at 40°C and the flow rate was set at 1.0 ml/min.
- the molecular structure of the polyhydroxyalkanoate was characterized by hydrogen nuclear magnetic resonance spectroscopy ( 1 H-NMR), and the instrument used was a JEOL AL-400 nuclear magnetic resonance spectrometer, and the sample of the polyhydroxyalkanoate was dissolved in chloroform , the test sample concentration is 30mg/0.8ml.
- the physical properties of the homopolymers and copolymers of each polyhydroxyalkanoate prepared according to the present invention are shown in Table 1 below.
- the homopolymers P(3H3MB) and P(3HV) were prepared analogously to Example 3, except that the monomers were changed. Except for the copolymers in Examples 1 and 2, other copolymers were prepared similarly to Example 4, except that the monomers and amounts were changed.
- poly-3-hydroxy-4-methylvalerate homopolymer exhibits high elongation at break, and the material itself exhibits the characteristics of high toughness; poly-3-hydroxypropionic acid/3- Hydroxyvalerate copolymer (P(3HP-co-3HV)) not only exhibits higher tensile strength and modulus, but also exhibits superior toughness.
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Abstract
本发明提供一种来自β-丙内酯同系物的聚羟基脂肪酸酯。该类聚羟基脂肪酸酯具有高分子量、优异的物理性能、旋光性和生物降解性等特点。
Description
本发明涉及一种聚羟基脂肪酸酯及其制备方法。
聚羟基脂肪酸酯是一类由羟基脂肪酸酯单元所组成且具有土壤和海洋性生物降解性的热塑性树脂。
目前主要通过微生物发酵的方法合成聚羟基脂肪酸酯(PHA)共聚物或均聚物。PHA是微生物为了在碳、氮营养失衡的情况下,作为碳源和能量而储存的物质。截止2019年,在众多的PHA合成菌株中,已发现150种不同的PHA单体。生物合成的聚3-羟基丁酸酯(P3HB)、聚3-羟基丁酸/3-羟基戊酸酯(PHBV)、聚3-羟基丁酸/己酸酯(PHBH)、聚3-羟基丁酸/4-羟基丁酸酯(P34HB)等聚羟基脂肪酸酯均聚物或共聚物均已得到产业化。
虽然已经在生物合成聚羟基脂肪酸酯领域取得了很多喜人的成就,然而,生物合成法本身的工艺流程和操作条件,决定了其生产周期长、产率低、工艺成本高,使得其价格远远高于聚乙烯、聚丙烯等通用塑料,限制了其应用范围。与生物合成法相比,化学合成法成本低、周期短、工艺流程较简单,也能实现对PHA的结构进行控制,是使其得到广泛应用的最佳合成途径。
聚羟基脂肪酸酯的化学合成方法有羟基酸直接缩聚法和内酯开环聚合法。
羟基酸直接缩聚的方法虽然简单,但是羟基酸不稳定,很容易水解脱掉羟基,反应副产物在粘性熔融物中难以去除,很难保证反应向正方向进行,所得聚合物分子量一般较低,而且聚合温度较高,常会导致产物带色。因此,目前主要使用开环聚合法来合成聚羟基脂肪酸酯。Lee等(J.Am.Chem.Soc.2002,124,51,15239–15248)使用以亚胺作配体的异丙醇锌作为催化剂,在温和条件下它可以快速催化无定形β-甲基丙内酯聚合,得到分子量分布很均一的无规立构聚3-羟基丁酸酯。Rieger等(ChemCatChem 2015,7,3963–3971)使用一类高活性的手性Cr(Ⅲ)络合物引发β-甲基丙内酯聚合,在100℃下得到了全同立构的高分子量聚 3-羟基丁酸酯。Dunn等(ACS Catal.2016,6,8219-8223)报导了聚3-羟基丙酸酯(P3HP)的合成。这些反应虽然可以得到高分子量、有结构选择性的聚羟基脂肪酸酯,但是所得到的几乎都是聚3-羟基丙酸酯(P3HP)与聚3-羟基丁酸酯(P3HB)的均聚物。
聚3-羟基丙酸酯(P3HP)均聚物由于碳骨架简单,具备优良的生物降解能力,但是因为其加工温度较低,限制了其应用范围。聚3-羟基丁酸酯(P3HB)均聚物结晶度高、结晶速度慢、易成球晶、热稳定性比较差,这些都限制了聚3-羟基丁酸酯(P3HB)均聚物的应用。
为了降低聚羟基脂肪酸酯生产成本,扩大聚羟基脂肪酸酯的应用范围,还需要使用化学合成方法开发其他类聚羟基脂肪酸酯。
发明内容
本发明涉及来自β-丙内酯同系物的聚羟基脂肪酸酯。该类聚羟基脂肪酸酯具有高分子量、优异的物理性能、旋光性和生物降解性等特点。
为了实现上述的发明,本发明的技术方案如下:
1.一种聚羟基脂肪酸酯,其特征在于,所述聚羟基脂肪酸酯包含如下的结构式:
其中基团R
1和R
2彼此独立地选自H、甲基、乙基和异丙基或其组合,并且n为10~3500,优选50~2500,更优选100~1000。
2.根据方案1所述的聚羟基脂肪酸酯,其特征在于,所述聚羟基脂肪酸酯包含如下的结构式:
其中基团R
1a、R
2a、R
1b和R
2b彼此独立地选自H、甲基、乙基和异丙基或其组合且可以相同或不同,且n
a:n
b=(0.01~0.99):(0.99~0.01)。
3.根据方案1或2所述的聚羟基脂肪酸酯,其特征在于,所述聚羟基脂肪酸酯为如下单体的均聚物或包含所述单体中两种或更多种的共聚物:β-丙内酯、β-甲基丙内酯、β-二甲基丙内酯、β-乙基丙内酯或β-异丙基丙内酯。
4.根据方案1-3中任一项所述的聚羟基脂肪酸酯,其特征在于,所述聚羟基脂肪酸酯为如下单体的均聚物:β-二甲基丙内酯、β-乙基丙内酯或β-异丙基丙内酯。
5.根据方案1-3中任一项所述的聚羟基脂肪酸酯,其特征在于,所述聚羟基脂肪酸酯为如下单体的均聚物:β-二甲基丙内酯或β-异丙基丙内酯。
6.根据方案1-3中任一项所述的聚羟基脂肪酸酯,其特征在于,所述聚羟基脂肪酸酯为如下单体中两种的共聚物:β-丙内酯、β-甲基丙内酯、β-二甲基丙内酯、β-乙基丙内酯或β-异丙基丙内酯,并且所述共聚物中两种单体单元的摩尔比为1:99~99:1,优选5:95~99:5,更优选10:90~90:10。
7.根据方案6所述的聚羟基脂肪酸酯,其特征在于,所述聚羟基脂肪酸酯为β-丙内酯和β-二甲基丙内酯的共聚物;β-丙内酯和β-乙基丙内酯的共聚物;β-甲基丙内酯和β-二甲基丙内酯的共聚物;β-二甲基丙内酯和β-乙基丙内酯的共聚物;或β-二甲基丙内酯和β-异丙基丙内酯的共聚物。
8.根据方案1-7中任一项所述的聚羟基脂肪酸酯,其特征在于,所述聚羟基脂肪酸酯包含R和/或S构型的单体单元。
9.根据方案1-8中任一项所述的聚羟基脂肪酸酯,其特征在于,所述聚羟基脂肪酸酯具有的重均分子量范围为8,000Da~9.8×10
5Da,优选3.5×10
4Da~6.0×10
5Da,更优选5.0×10
4Da~4.0×10
5Da;多分散性为0.5~7.0,优选1.0~5.0,更优选1.2~4.0。
10.根据方案1-9中任一项所述的聚羟基脂肪酸酯,其特征在于,所述聚羟基脂肪酸酯具有的拉伸强度范围为1MPa~60MPa,优选1.5MPa~50MPa,更优选2MPa~40MPa,断裂伸长率范围为5%~800%,优选10%~700%,更优选15%~650%,和弹性模量范围为100MPa~8000MPa,优选600MPa~3000MPa,更优选650MPa~3000MPa。
11.一种制备根据方案1-10中任一项所述的聚羟基脂肪酸酯的方法,其特征在于,所述方法为开环聚合法。
12.根据方案11所述的方法,其特征在于,所述方法在25℃~200℃,优选40℃~160℃,更优选50℃~100℃的温度下进行。
13.根据方案11或12所述的方法,其特征在于,所述方法进行0.1~72小时,优选1~30小时,更优选3~15小时的时间。
14.根据方案11-13中任一项所述的方法,其特征在于,所述方法在催化剂存在下进行,所述催化剂包括烷基化试剂、质子酸、路易斯酸中的一种或多种,优选四甲基醋酸铵(Me
4NOAc)、四乙基醋酸铵(Et
4NOAc)、[Ph
3P=N=PPh
3][OAc]、Y(Oi-Pr)
3、醋酸钾(AcOK)中的一种或多种,其添加量基于所用单体总量为0.01-5mol%,优选0.05-2mol%,更优选0.01-0.5mol%。
15.根据方案11-14中任一项所述的方法,其特征在于,所述方法在引发剂存在下进行,所述引发剂包括强碱性引发剂中的一种或多种,优选如下所示的TBD、BEMP、P2、P4引发剂中的一种或多种,其添加量基于所用单体总量为0.1-10mol%,优选1.0-5mol%,更优选2.5-4mol%:
16.根据方案11-15中任一项所述的方法,其特征在于,所述方法在溶剂存在下进行,所述溶剂包括甲苯、氯仿、二氯乙烷、四氢呋喃、己烷、醋酸乙酯中的一种或多种。
17.根据方案11-16中任一项所述的方法,其特征在于,所述方法进一步包括 在催化剂的作用下合成用于制备聚羟基脂肪酸酯的单体,所述合成的原料包括乙烯酮与醛或丙酮;所述催化剂包括BF
3·Et
2O、氯化铝、氯化锌、Y型沸石中的一种或多种;所述合成的溶剂包括四氢呋喃、醋酸乙酯、丙酮中的一种或多种;所述合成在-10℃~50℃的温度下进行0.1~72小时的时间。
本发明的这些和其它目的、特征和优点在结合下文考虑本发明后,将易于为普通技术人员所明白。
本发明所涉及的聚羟基脂肪酸酯具有高分子量、物性多样、可生物降解等优点。
根据本发明的一个方面,提供了一种聚羟基脂肪酸酯,其特征在于,所述聚羟基脂肪酸酯包含如下的结构式:
其中基团R
1和R
2彼此独立地选自H、甲基、乙基和异丙基或其组合,并且n为10~3500,优选50~2500,更优选100~1000。
在式(I)中,n可以为例如50、100、200、300、400、500、600、700、800、900、1000、1100、1200、1300、1400、1500、1600、1700、1800、1900、2000、2100、2200、2300、2400、2500、2600、2700、2800、2900、3000、3100、3200、3300、3400、3500或者在这些数值任意两者之间的范围内。
在本发明的一个实施方案中,所述聚羟基脂肪酸酯包含如下的结构式:
其中基团R
1a、R
2a、R
1b和R
2b彼此独立地选自H、甲基、乙基和异丙基或其组合且可以相同或不同,且n
a:n
b=(0.01~0.99):(0.99~0.01)。
在本发明的另一个实施方案中,所述聚羟基脂肪酸酯为如下单体的均聚物或包含所述单体中两种或更多种的共聚物:β-丙内酯、β-甲基丙内酯、β-二甲基丙内酯、β-乙基丙内酯或β-异丙基丙内酯。
所述单体的结构式如下所示:
在本发明的一个优选实施方案中,所述聚羟基脂肪酸酯为如下单体的均聚物:β-二甲基丙内酯、β-乙基丙内酯或β-异丙基丙内酯。优选地,所述聚羟基脂肪酸酯为如下单体的均聚物:β-二甲基丙内酯或β-异丙基丙内酯。所述均聚物的链段可呈现立构或无规的状态。
在本发明的另一个优选实施方案中,所述聚羟基脂肪酸酯为如下单体中两种的共聚物:β-丙内酯、β-甲基丙内酯、β-二甲基丙内酯、β-乙基丙内酯或β-异丙基丙内酯,并且所述共聚物中两种单体单元的摩尔比为1:99~99:1,优选5:95~99:5,更优选10:90~90:10。所述共聚物中两种单体单元的摩尔比可以为例如1:99、5:95、10:90、20:80、30:70、40:60、50:50、60:40、70:30、80:20、90:10、95:5、99:1或者在这些数值任意两者之间的范围内。所述共聚物的链段可呈现立构或无规的状态。
在本发明的更优选实施方案中,所述聚羟基脂肪酸酯为β-丙内酯和β-二甲基丙内酯的共聚物;β-丙内酯和β-乙基丙内酯的共聚物;β-甲基丙内酯和β-二甲基丙内酯的共聚物;β-二甲基丙内酯和β-乙基丙内酯的共聚物;或β-二甲基丙内酯和β-异丙基丙内酯的共聚物。
在本发明的一个实施方案中,所述聚羟基脂肪酸酯包含R和/或S构型的单 体单元。
在本发明的另一个实施方案中,所述聚羟基脂肪酸酯具有的重均分子量范围为8,000Da~9.8×10
5Da,优选3.5×10
4Da~6.0×10
5Da,更优选5.0×10
4Da~4.0×10
5Da;多分散性为0.5~7.0,优选1.0~5.0,更优选1.2~4.0。
在本发明的再一个实施方案中,所述聚羟基脂肪酸酯具有的拉伸强度范围为1MPa~60MPa,优选1.5MPa~50MPa,更优选2MPa~40MPa,断裂伸长率范围为5%~800%,优选10%~700%,更优选15%~650%,和弹性模量范围为100MPa~8000MPa,优选600MPa~3000MPa,更优选650MPa~3000MPa。
根据本发明的另一个方面,提供了一种制备根据本发明的聚羟基脂肪酸酯的方法,其中所述方法为开环聚合法。
在本发明的一个实施方案中,所述聚羟基脂肪酸酯通过如下单体的均聚或包含所述单体中两种或更多种的共聚获得:β-丙内酯、β-甲基丙内酯、β-二甲基丙内酯、β-乙基丙内酯或β-异丙基丙内酯。
在本发明的一个优选实施方案中,所述聚羟基脂肪酸酯通过如下单体的均聚获得:β-二甲基丙内酯、β-乙基丙内酯或β-异丙基丙内酯。优选地,所述聚羟基脂肪酸酯通过如下单体的均聚获得:β-二甲基丙内酯或β-异丙基丙内酯。
在本发明的另一个优选实施方案中,所述聚羟基脂肪酸酯通过如下单体中两种的共聚获得:β-丙内酯、β-甲基丙内酯、β-二甲基丙内酯、β-乙基丙内酯或β-异丙基丙内酯,并且所述两种单体的投料比应使得所述共聚物中两种单体单元的摩尔比为1:99~99:1,优选5:95~99:5,更优选10:90~90:10,所述两种单体的投料比应使得所述共聚物中两种单体单元的摩尔比可以为例如1:99、5:95、10:90、20:80、30:70、40:60、50:50、60:40、70:30、80:20、90:10、95:5、99:1或者在这些数值任意两者之间的范围内。
在本发明的更优选实施方案中,所述聚羟基脂肪酸酯通过β-丙内酯和β-二甲基丙内酯的共聚获得;或者通过β-丙内酯和β-乙基丙内酯的共聚获得;或者通过β-甲基丙内酯和β-二甲基丙内酯的共聚获得;或者通过β-二甲基丙内酯和β-乙基丙内酯的共聚获得;或者通过β-二甲基丙内酯和β-异丙基丙内酯的共聚获得。
在本发明的一个实施方案中,所述方法在25℃~200℃,优选40℃~160℃,更优选50℃~100℃的温度下进行。
在本发明的另一个实施方案中,所述方法进行0.1~72小时,优选1~30小时,更优选3~15小时的时间。
在本发明的又一个实施方案中,所述方法在催化剂存在下进行,所述催化剂包括烷基化试剂、质子酸、路易斯酸中的一种或多种,其添加量基于所用单体总量为0.01~5mol%,优选0.05-2mol%,更优选0.01-0.5mol%。优选地,所述催化剂包括四甲基醋酸铵(Me
4NOAc)、四乙基醋酸铵(Et
4NOAc)、[Ph
3P=N=PPh
3][OAc]、Y(Oi-Pr)
3、醋酸钾(AcOK)中的一种或多种。
在本发明的再一个实施方案中,所述方法在引发剂存在下进行,所述引发剂包括强碱性引发剂中的一种或多种,优选如下所示的TBD、BEMP、P2、P4引发剂中的一种或多种,其添加量基于所用单体总量为0.1-10mol%,优选1.0-5mol%,更优选2.5-4mol%:
在本发明的还一个实施方案中,所述方法在溶剂存在下进行,所述溶剂包括甲苯、氯仿、二氯乙烷、四氢呋喃、己烷、醋酸乙酯中的一种或多种。
在本发明的一个优选实施方案中,所述方法可进一步包括在催化剂的作用下合成用于制备聚羟基脂肪酸酯的单体。
制备聚羟基脂肪酸酯的单体的化学反应主要包括如下:
其中基团R选自H、CH
3、CH
2CH
3、CH(CH
3)
2;
或者
所述催化剂可包括BF
3·Et
2O、氯化铝、氯化锌、Y型沸石中的一种或多种。
所述合成可在溶剂存在下进行,所述溶剂包括四氢呋喃、醋酸乙酯、丙酮中的一种或多种。
所述合成可在-10℃~50℃的温度下进行。
所述合成可进行0.1~72小时的时间。
在所述合成中,乙烯酮与醛(式(1))或丙酮(式(2))的摩尔比为0.7~2.0eq。
在所述合成中,催化剂当量(基于醛或丙酮)为0.1%~10%eq。
在所述合成中,所制备的单体的产率为50%~93%。
本发明所涉及的聚羟基脂肪酸酯具有高分子量、物性多样、可生物降解等优点。
实施例
下面的实施例将对本发明予以进一步说明,但本发明并不局限于以下的实施例中。
使用如下缩写:
3-羟基丙酸单元:3HP
3-羟基丁酸单元:3HB
3-羟基戊酸单元:3HV
3-羟基-3-甲基丁酸单元:3H3MB
3-羟基-4-甲基戊酸单元:3H4MV
测试方法:
根据ASTM D638的测试方法测试所述聚羟基脂肪酸酯的力学性能(拉伸强度,断裂伸长率,弹性模量等),所用仪器为岛津制作所的精密电子万能材料试验机AGX-V,力学性能测试样条根据ASTM D638的测试方法要求进行制备,实验在室温条件下进行。
使用差示扫描量热法(DSC)测试所述聚羟基脂肪酸酯的各项热力学参数(熔点、玻璃化转变温度等),所用仪器为日立X-DSC7000型DSC测试机,在氮气气氛下进行测试(40ml/min),测试样品量约为5mg,测试温度范围为-50℃到200℃。
使用GPC测试所述聚羟基脂肪酸酯的分子量(数均分子量,重均分子量,分子量分布),所用仪器为东曹HLC-8329GPC,使用聚苯乙烯作为标样,将所述聚羟基脂肪酸酯的样品溶于氯仿中,测试样品浓度为0.2wt/vol%。色谱柱的温度设置为40℃,流速设置为1.0ml/min。
使用核磁共振氢谱(
1H-NMR)表征所述聚羟基脂肪酸酯的分子结构,所用仪器为日本电子AL-400型核磁共振波谱仪,将所述聚羟基脂肪酸酯的样品溶于氯仿中,测试样品浓度为30mg/0.8ml。
实施例1:聚3-羟基丙酸/3-羟基丁酸酯共聚物(P(3HB-co-3HP))的制备
在20ml烧瓶中称取β-甲基丙内酯(纯度99.3%)1.0998g(12.8mmol),用四氢呋喃(THF)2ml溶解。向其中加入0.3304g磷腈碱P4-t-Bu己烷溶液(0.93mmol/g,Aldrich公司制造),并在氮气气氛中搅拌。从室温开始逐渐加温,在60℃下搅拌3小时后冷却至25℃。向其中加入1.3942g(19.0mmol)的β-丙内酯(纯度98.7%),搅拌,再次逐渐加热,在60℃下反应4小时。冷却至25℃后,加入3ml氯仿,制成均相溶液,在搅拌下加入100ml甲醇中,使聚合物沉淀。将得到的聚合物进行抽吸过滤,然后真空干燥,得到2.1135g白色固体。产率为86%。
根据GPC分析的结果,数均分子量=50,000Da、重均分子量=75,000Da、多分散性=1.5。根据DSC分析,熔点为63℃。使用
1H-NMR表征上述聚合物的结 构,如下表所示,通过计算各共聚单元的氢化学位移峰面积,β-丙内酯与β-丁内酯的共聚比为76:24(mol/mol)。
实施例2:聚3-羟基丙酸/3-羟基-4-甲基戊酸酯共聚物(P(3HP-co-3H4MV))的制备
在20ml烧瓶中称取β-异丙基丙内酯(纯度95.2%)1.4027g(12.2mmol),用THF 2ml溶解。向其中加入0.93g磷腈碱P4-t-Bu己烷溶液(0.93mmol/g,Aldrich公司制造),并在氮气气氛中搅拌。从室温开始逐渐加温,在60℃下搅拌3小时后冷却至25℃。向其中加入1.3443g(18.3mmol)的β-丙内酯(纯度98.7%),搅拌,再次逐渐加热,在60℃下反应2小时。冷却至25℃后,加入3ml氯仿,制成均相溶液,在搅拌下加入100ml甲醇中,使聚合物沉淀。将得到的聚合物进行抽吸过滤,然后真空干燥,得到2.637g白色固体。产率为96%。
根据GPC分析的结果,数均分子量=28,000Da、重均分子量=78,000Da、多分散性=2.8。根据DSC分析,熔点为56℃。使用
1H-NMR表征上述聚合物的结构,如下表所示,通过计算各共聚单元的氢化学位移峰面积,β-丙内酯与β-异丙基丙内酯的共聚比为61:39(mol/mol)。
实施例3:聚3-羟基-4-甲基戊酸酯均聚物(P(3H4MV))的制备
在20ml烧瓶中称取β-异丙基丙内酯(纯度95.2%)1.7550g(15.60mmol),用THF 2ml溶解。向其中加入0.98g磷腈碱P4-t-Bu己烷溶液(0.98mmol/g,Aldrich公司制造),并在氮气气氛中搅拌。从室温开始逐渐加温,在60℃下搅拌3小时后冷却至25℃,搅拌,再次逐渐加热,在100℃下反应6小时。冷却至25℃后,加入3ml氯仿,制成均相溶液,在搅拌下加入100ml甲醇中,使聚合物沉淀。将得到的聚合物进行抽吸过滤,然后真空干燥,得到1.703g白色固体。产率为97%。
根据GPC分析的结果,数均分子量=50,000Da、重均分子量=70,000Da、多分散性=1.4。根据DSC分析,熔点为53℃。使用
1H-NMR表征上述聚合物的结构,如下表所示。
实施例4:聚3-羟基丙酸/3-羟基戊酸酯共聚物(P(3HP-co-3HV))的制备
在20ml烧瓶中称取β-乙基丙内酯(纯度99.3%)1.6510g(20.9mmol),用THF 2ml溶解。向其中加入0.0989g四甲基醋酸铵(Me
4NOAc)氯仿溶液(0.05mmol/g,Aldrich公司制造),并在氮气气氛中搅拌。从室温开始逐渐加温,在65℃下搅拌3小时后冷却至25℃。向其中加入1.8139g(24.8mmol)的β-丙内酯(纯度98.7%), 搅拌,再次逐渐加热,在65℃下反应9小时。冷却至25℃后,加入3ml氯仿,制成均相溶液,在搅拌下加入100ml甲醇中,使聚合物沉淀。将得到的聚合物进行抽吸过滤,然后真空干燥,得到3.0838g白色固体。产率为89%。
根据GPC分析的结果,数均分子量=68,000Da、重均分子量=176,000Da、多分散性=2.6。根据DSC分析,熔点为76℃。使用
1H-NMR表征上述聚合物的结构,如下表所示,通过计算各共聚单元的氢化学位移峰面积,β-丙内酯与β-乙基丙内酯的共聚比为90:10(mol/mol)。
根据本发明制备的各聚羟基脂肪酸酯的均聚物与共聚物的物理性能示于下表1中。均聚物P(3H3MB)和P(3HV)的制备类似于实施例3,不同之处在于单体改变。除实施例1和实施例2中共聚物外,其它共聚物的制备类似于实施例4,不同之处在于单体和用量改变。
从上表1可以看出,聚3-羟基-4-甲基戊酸酯均聚物呈现较高的断裂伸长率,材料本身表现出高韧性的特点;聚3-羟基丙酸/3-羟基戊酸酯共聚物(P(3HP-co-3HV))不仅呈现较高的拉伸强度和模量,还呈现更优越的韧性。
以上所述仅仅为本发明的优选实施方式,需要指出的是,对于本领域的技术人员来说,在本发明原理的范围内,所作出的若干改进和修饰,这些改进和修饰也应被同样视为本发明的保护范围。
Claims (17)
- 根据权利要求1或2所述的聚羟基脂肪酸酯,其特征在于,所述聚羟基脂肪酸酯为如下单体的均聚物或包含所述单体中两种或更多种的共聚物:β-丙内酯、β-甲基丙内酯、β-二甲基丙内酯、β-乙基丙内酯或β-异丙基丙内酯。
- 根据权利要求1-3中任一项所述的聚羟基脂肪酸酯,其特征在于,所述聚羟基脂肪酸酯为如下单体的均聚物:β-二甲基丙内酯、β-乙基丙内酯或β-异丙基丙内酯。
- 根据权利要求1-3中任一项所述的聚羟基脂肪酸酯,其特征在于,所述聚羟基脂肪酸酯为如下单体的均聚物:β-二甲基丙内酯或β-异丙基丙内酯。
- 根据权利要求1-3中任一项所述的聚羟基脂肪酸酯,其特征在于,所述聚羟基脂肪酸酯为如下单体中两种的共聚物:β-丙内酯、β-甲基丙内酯、β-二甲基丙内酯、β-乙基丙内酯或β-异丙基丙内酯,并且所述共聚物中两种单体单元的 摩尔比为1:99~99:1,优选5:95~99:5,更优选10:90~90:10。
- 根据权利要求6所述的聚羟基脂肪酸酯,其特征在于,所述聚羟基脂肪酸酯为β-丙内酯和β-二甲基丙内酯的共聚物;β-丙内酯和β-乙基丙内酯的共聚物;β-甲基丙内酯和β-二甲基丙内酯的共聚物;β-二甲基丙内酯和β-乙基丙内酯的共聚物;或β-二甲基丙内酯和β-异丙基丙内酯的共聚物。
- 根据权利要求1-7中任一项所述的聚羟基脂肪酸酯,其特征在于,所述聚羟基脂肪酸酯包含R和/或S构型的单体单元。
- 根据权利要求1-8中任一项所述的聚羟基脂肪酸酯,其特征在于,所述聚羟基脂肪酸酯具有的重均分子量范围为8,000Da~9.8×10 5Da,优选3.5×10 4Da~6.0×10 5Da,更优选5.0×10 4Da~4.0×10 5Da;多分散性为0.5~7.0,优选1.0~5.0,更优选1.2~4.0。
- 根据权利要求1-9中任一项所述的聚羟基脂肪酸酯,其特征在于,所述聚羟基脂肪酸酯具有的拉伸强度范围为1MPa~60MPa,优选1.5MPa~50MPa,更优选2MPa~40MPa,断裂伸长率范围为5%~800%,优选10%~700%,更优选15%~650%,和弹性模量范围为100MPa~8000MPa,优选600MPa~3000MPa,更优选650MPa~3000MPa。
- 一种制备根据权利要求1-10中任一项所述的聚羟基脂肪酸酯的方法,其特征在于,所述方法为开环聚合法。
- 根据权利要求11所述的方法,其特征在于,所述方法在25℃~200℃,优选40℃~160℃,更优选50℃~100℃的温度下进行。
- 根据权利要求11或12所述的方法,其特征在于,所述方法进行0.1~72小时,优选1~30小时,更优选3~15小时的时间。
- 根据权利要求11-13中任一项所述的方法,其特征在于,所述方法在催化剂存在下进行,所述催化剂包括烷基化试剂、质子酸、路易斯酸中的一种或多种,优选四甲基醋酸铵(Me 4NOAc)、四乙基醋酸铵(Et 4NOAc)、[Ph 3P=N=PPh 3][OAc]、Y(Oi-Pr) 3、醋酸钾(AcOK)中的一种或多种,其添加量基于所用单体总量为0.01-5mol%,优选0.05-2mol%,更优选0.01-0.5mol%。
- 根据权利要求11-15中任一项所述的方法,其特征在于,所述方法在溶剂存在下进行,所述溶剂包括甲苯、氯仿、二氯乙烷、四氢呋喃、己烷、醋酸乙酯中的一种或多种。
- 根据权利要求11-16中任一项所述的方法,其特征在于,所述方法进一步包括在催化剂的作用下合成用于制备聚羟基脂肪酸酯的单体,所述合成的原料包括乙烯酮与醛或丙酮;所述催化剂包括BF 3·Et 2O、氯化铝、氯化锌、Y型沸石中的一种或多种;所述合成的溶剂包括四氢呋喃、醋酸乙酯、丙酮中的一种或多种;所述合成在-10℃~50℃的温度下进行0.1~72小时的时间。
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WO2023009773A1 (en) * | 2021-07-29 | 2023-02-02 | Meredian, Inc. | Biopolymer compositions incorporating poly(3-hydroxypropionate) |
WO2024026140A1 (en) * | 2022-07-29 | 2024-02-01 | Danimer Ipco, Llc | Aqueous mixtures of novel poly(hydroxyalkanoates) |
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US3522219A (en) * | 1966-01-21 | 1970-07-28 | Montedison Spa | Process for the suspension polymerization of beta-substituted-beta-lactones |
US5440007A (en) * | 1992-10-22 | 1995-08-08 | University Of Massachusetts Lowell | Composition of and method for forming high molecular weight predominantly syndiotactic substituted-poly (β-propioesters) |
CN1139937A (zh) * | 1994-01-28 | 1997-01-08 | 普罗克特和甘保尔公司 | 由烷氧基烷基锌引发的β-取代的β-丙内酯的聚合方法 |
CN108026013A (zh) * | 2015-07-31 | 2018-05-11 | 诺沃梅尔公司 | 用于丙烯酸及其前体的生产系统/生产方法 |
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US5440007A (en) * | 1992-10-22 | 1995-08-08 | University Of Massachusetts Lowell | Composition of and method for forming high molecular weight predominantly syndiotactic substituted-poly (β-propioesters) |
CN1139937A (zh) * | 1994-01-28 | 1997-01-08 | 普罗克特和甘保尔公司 | 由烷氧基烷基锌引发的β-取代的β-丙内酯的聚合方法 |
CN108026013A (zh) * | 2015-07-31 | 2018-05-11 | 诺沃梅尔公司 | 用于丙烯酸及其前体的生产系统/生产方法 |
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WO2023009773A1 (en) * | 2021-07-29 | 2023-02-02 | Meredian, Inc. | Biopolymer compositions incorporating poly(3-hydroxypropionate) |
WO2024026140A1 (en) * | 2022-07-29 | 2024-02-01 | Danimer Ipco, Llc | Aqueous mixtures of novel poly(hydroxyalkanoates) |
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