CN114989586A - Polyhydroxyalkanoate composition containing alcohol nucleating agent, polyhydroxyalkanoate molded body and preparation method thereof - Google Patents
Polyhydroxyalkanoate composition containing alcohol nucleating agent, polyhydroxyalkanoate molded body and preparation method thereof Download PDFInfo
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- CN114989586A CN114989586A CN202210626393.1A CN202210626393A CN114989586A CN 114989586 A CN114989586 A CN 114989586A CN 202210626393 A CN202210626393 A CN 202210626393A CN 114989586 A CN114989586 A CN 114989586A
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- polyhydroxyalkanoate
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- 239000005014 poly(hydroxyalkanoate) Substances 0.000 title claims abstract description 102
- 229920000903 polyhydroxyalkanoate Polymers 0.000 title claims abstract description 102
- 239000002667 nucleating agent Substances 0.000 title claims abstract description 49
- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title abstract description 5
- 238000002425 crystallisation Methods 0.000 claims abstract description 37
- 230000008025 crystallization Effects 0.000 claims abstract description 37
- 239000002994 raw material Substances 0.000 claims abstract description 10
- -1 alcohol compound Chemical class 0.000 claims abstract description 6
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 239000010408 film Substances 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 16
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 claims description 15
- 238000002844 melting Methods 0.000 claims description 15
- 230000008018 melting Effects 0.000 claims description 15
- IRHTZOCLLONTOC-UHFFFAOYSA-N hexacosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCO IRHTZOCLLONTOC-UHFFFAOYSA-N 0.000 claims description 10
- WHBMMWSBFZVSSR-UHFFFAOYSA-M 3-hydroxybutyrate Chemical compound CC(O)CC([O-])=O WHBMMWSBFZVSSR-UHFFFAOYSA-M 0.000 claims description 8
- WHBMMWSBFZVSSR-UHFFFAOYSA-N R3HBA Natural products CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 229920000739 poly(3-hydroxycarboxylic acid) polymer Polymers 0.000 claims description 8
- 229960000735 docosanol Drugs 0.000 claims description 7
- 230000009477 glass transition Effects 0.000 claims description 7
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims description 6
- BTFJIXJJCSYFAL-UHFFFAOYSA-N icosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCO BTFJIXJJCSYFAL-UHFFFAOYSA-N 0.000 claims description 6
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 claims description 6
- REZQBEBOWJAQKS-UHFFFAOYSA-N triacontan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO REZQBEBOWJAQKS-UHFFFAOYSA-N 0.000 claims description 6
- HPMGFDVTYHWBAG-UHFFFAOYSA-N 3-hydroxyhexanoic acid Chemical compound CCCC(O)CC(O)=O HPMGFDVTYHWBAG-UHFFFAOYSA-N 0.000 claims description 4
- REKYPYSUBKSCAT-UHFFFAOYSA-N 3-hydroxypentanoic acid Chemical compound CCC(O)CC(O)=O REKYPYSUBKSCAT-UHFFFAOYSA-N 0.000 claims description 4
- FARPMBPKLYEDIL-UHFFFAOYSA-N S-3-Hydroxyundecanoic acid Natural products CCCCCCCCC(O)CC(O)=O FARPMBPKLYEDIL-UHFFFAOYSA-N 0.000 claims description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 4
- GJBXIPOYHVMPQJ-UHFFFAOYSA-N hexadecane-1,16-diol Chemical compound OCCCCCCCCCCCCCCCCO GJBXIPOYHVMPQJ-UHFFFAOYSA-N 0.000 claims description 4
- SJZRECIVHVDYJC-UHFFFAOYSA-M 4-hydroxybutyrate Chemical compound OCCCC([O-])=O SJZRECIVHVDYJC-UHFFFAOYSA-M 0.000 claims description 3
- 229960000541 cetyl alcohol Drugs 0.000 claims description 3
- 239000010902 straw Substances 0.000 claims description 3
- XBUXARJOYUQNTC-UHFFFAOYSA-N ()-3-Hydroxynonanoic acid Chemical compound CCCCCCC(O)CC(O)=O XBUXARJOYUQNTC-UHFFFAOYSA-N 0.000 claims description 2
- FYSSBMZUBSBFJL-VIFPVBQESA-N (S)-3-hydroxydecanoic acid Chemical compound CCCCCCC[C@H](O)CC(O)=O FYSSBMZUBSBFJL-VIFPVBQESA-N 0.000 claims description 2
- OXSSIXNFGTZQMZ-UHFFFAOYSA-N 3-hydroxyheptanoic acid Chemical compound CCCCC(O)CC(O)=O OXSSIXNFGTZQMZ-UHFFFAOYSA-N 0.000 claims description 2
- NDPLAKGOSZHTPH-UHFFFAOYSA-N 3-hydroxyoctanoic acid Chemical compound CCCCCC(O)CC(O)=O NDPLAKGOSZHTPH-UHFFFAOYSA-N 0.000 claims description 2
- ALRHLSYJTWAHJZ-UHFFFAOYSA-M 3-hydroxypropionate Chemical compound OCCC([O-])=O ALRHLSYJTWAHJZ-UHFFFAOYSA-M 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 229940043348 myristyl alcohol Drugs 0.000 claims description 2
- 239000008188 pellet Substances 0.000 claims description 2
- 229960001109 policosanol Drugs 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- HIBKFQRBONXURO-UHFFFAOYSA-N docosane-1,22-diol Chemical compound OCCCCCCCCCCCCCCCCCCCCCCO HIBKFQRBONXURO-UHFFFAOYSA-N 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 25
- 238000000034 method Methods 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 6
- 229920001169 thermoplastic Polymers 0.000 abstract description 4
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000005469 granulation Methods 0.000 description 16
- 230000003179 granulation Effects 0.000 description 16
- 239000002245 particle Substances 0.000 description 16
- 238000003825 pressing Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- 238000000465 moulding Methods 0.000 description 11
- 238000001125 extrusion Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 5
- 229910052582 BN Inorganic materials 0.000 description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920001020 poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XWAMHGPDZOVVND-UHFFFAOYSA-N 1,2-octadecanediol Chemical compound CCCCCCCCCCCCCCCCC(O)CO XWAMHGPDZOVVND-UHFFFAOYSA-N 0.000 description 3
- 229920006167 biodegradable resin Polymers 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 229920000520 poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ISAKRJDGNUQOIC-UHFFFAOYSA-N Uracil Chemical compound O=C1C=CNC(=O)N1 ISAKRJDGNUQOIC-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- CNNRPFQICPFDPO-UHFFFAOYSA-N octacosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCO CNNRPFQICPFDPO-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- RWQNBRDOKXIBIV-UHFFFAOYSA-N thymine Chemical compound CC1=CNC(=O)NC1=O RWQNBRDOKXIBIV-UHFFFAOYSA-N 0.000 description 2
- 229960002666 1-octacosanol Drugs 0.000 description 1
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229920013724 bio-based polymer Polymers 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940043356 mica Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001013 poly(3-hydroxybutyrate-co-4-hydroxybutyrate) Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920000070 poly-3-hydroxybutyrate Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229940113082 thymine Drugs 0.000 description 1
- 229940035893 uracil Drugs 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the field of high polymer materials, in particular to a polyhydroxyalkanoate composition containing an alcohol nucleating agent, a polyhydroxyalkanoate forming body and a preparation method thereof. The polyhydroxyalkanoate composition comprises polyhydroxyalkanoate and a nucleating agent, wherein the nucleating agent is an alcohol compound and comprises fatty alcohol, and particularly one or more of fatty alcohol with 5-30 carbon atoms. The nucleating agent in the polyhydroxyalkanoate composition is high in nucleating efficiency, and can improve the defects of slow crystallization speed, low processing efficiency and the like of polyhydroxyalkanoate in the process of preparing various molded bodies through thermoplastic processing. The nucleating agent provided by the invention has wide sources and lower product price, and reduces the raw material cost of various polyhydroxyalkanoate forming bodies; meanwhile, the nucleating agent provided by the invention is a biological source, does not influence the biological carbon ratio of the polyhydroxyalkanoate forming body, and can still reach 100% of biological source. The polyhydroxyalkanoate molded body obtained by the invention has the advantage of high transparency.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a polyhydroxyalkanoate composition containing an alcohol nucleating agent, a polyhydroxyalkanoate forming body and a preparation method thereof.
Background
Polyhydroxyalkanoates (PHAs) are intracellular polyhydroxyalkanoates synthesized by many microorganisms, and are natural high molecular biological materials. Most of monomers of the polyhydroxyalkanoate are 3-hydroxy fatty acid with the chain length of 3-14 carbon atoms, a side chain R of the polyhydroxyalkanoate is a highly variable saturated or unsaturated, straight chain or branched chain, aliphatic or aromatic group, and the diversity of the composition structure brings the diversity of performances, so that the polyhydroxyalkanoate has obvious advantages in application. Meanwhile, polyhydroxyalkanoate is a bio-based polymer which is biodegradable in a marine environment, can solve environmental problems caused by waste plastics, and has excellent biocompatibility and mechanical properties, so that polyhydroxyalkanoate can be processed into various molded bodies, such as films, straws, tableware and the like.
The control of the crystallization rate is an important factor in the processing rate of polyhydroxyalkanoate. However, the simple polyhydroxyalkanoate has the defects of slow crystallization speed, low crystallinity, low processing efficiency and the like in the process of preparing various molded bodies by hot processing. In the prior art, the crystallization speed of PHAs is often improved by adding auxiliary agents such as nucleating agents.
As disclosed in chinese patent application publication No. CN1503824A, patent document No. 1 discloses a composition processed with polyhydroxyalkanoate of a nucleating agent and a plasticizer, wherein the nucleating agent is a nucleating agent selected from the group consisting of talc, micronized mica, calcium carbonate, boron nitride, ammonium chloride, sodium salt, and carboxylates of metals of group I and group II of the periodic table of elements. Simultaneously, after extrusion, the mixture is crystallized by heat preservation at a certain temperature, for example, the temperature of a wire is 30-40 ℃, and the temperature of a film is 30-45 ℃.
Further, as disclosed in chinese patent application publication No. CN102906193A, patent document No. 2 discloses a toughened polylactic acid containing polyhydroxyalkanoate, and specifically discloses that the nucleating agent contained therein is selected from carbon black, cyanuric acid, uracil, thymine, mica talc, silica, boron nitride, barium nitride, clay, calcium carbonate, synthetic silicic acid and salts, metal salts of organic phosphoric acid, and kaolin or a combination thereof.
However, the nucleating agents are mainly inorganic substances or metal salts, and although the nucleating agents can improve the crystallization speed and the crystallinity of the conventional molded body prepared from polyhydroxyalkanoate to a certain extent, the improvement degree is limited; more importantly, the nucleating agent can affect the proportion of the biochar in the polyhydroxyalkanoate molded body, is difficult to degrade completely in the sea, and can cause the molded body to have color, reduce the transparency and influence the application.
Disclosure of Invention
The invention provides a polyhydroxyalkanoate composition, a polyhydroxyalkanoate molded body and a preparation method thereof, aiming at the problems in the prior art.
In a first aspect, the present invention provides a polyhydroxyalkanoate composition, which comprises polyhydroxyalkanoate and a nucleating agent, wherein the nucleating agent is one or more of alcohol compounds, and preferably, the nucleating agent is one or more of fatty alcohols.
Further, the nucleating agent is one or more of fatty alcohols with 5-30 carbon atoms.
The research of the invention finds that the alcohol compound as the nucleating agent comprises an aliphatic alcohol compound, for example, aliphatic alcohol with 5-30 carbon atoms can be used as the nucleating agent in the preparation of polyhydroxyalkanoate molded bodies, can obviously improve the crystallization speed and the crystallinity of the polyhydroxyalkanoate in the preparation of the molded bodies, has the advantages of high nucleating efficiency and simpler processing mode, and simultaneously can ensure that the prepared polyhydroxyalkanoate molded bodies have the advantage of high transparency, thereby having wider application scenes.
From the point of view of saturation, the nucleating agent of the present invention is preferably a saturated aliphatic alcohol. The nucleating agent may be a monohydric alcohol or a polyhydric alcohol in view of the number of hydroxyl groups.
Further preferably, the nucleating agent is one or more of 1, 16-hexadecanediol, 1, 22-docosanol, stearyl glycol (1, 2-octadecanediol), behenyl alcohol (behenyl alcohol), arachidyl alcohol (arachidyl alcohol), palmityl alcohol (cetyl alcohol), ceryl alcohol (ceryl alcohol), policosanol (octacosanol), melissyl alcohol (triacontanol), ceryl alcohol, myristyl alcohol (tetradecanol), and lauryl alcohol (dodecanol). Still more preferably, the nucleating agent is behenyl alcohol (behenyl alcohol).
Further, the addition amount of the nucleating agent is 0.01-20% of the mass of the polyhydroxyalkanoate; preferably 0.1% to 5%.
Studies have shown that by controlling the addition ratio of the nucleating agent within this preferred range, better crystallization results can be achieved and the molded articles produced can be processed better. In the course of the study, it was found that in the above preferred ranges, typically, but not limited to, for example, 0.1%, 1%, 2%, 2.5%, 3%, 4%, 5% are possible.
The polyhydroxyalkanoate of the present invention may be a single polymer, or may be a composition of two or more polymers. Wherein the polymerized monomer of each polymer may be one or more (i.e., the structural unit in the polymer is one or more).
Specifically, any of the polymers contains a structural unit represented by the following general formula (1):
[CHR(CH 2 ) m COO](1)
in the general formula (1), R represents C p H 2p+1 The alkyl group p represents an integer of 1 to 15, preferably an integer of 1 to 10, and more preferably an integer of 1 to 8. Examples of R include: a straight-chain or branched alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, and a hexyl group.
When m is 1,2 or 3, the general formula (1) represents a 3-hydroxyalkanoate structural unit, when m is 1, the general formula (1) represents a 4-hydroxyalkanoate structural unit, and when m is 3, the general formula (1) represents a 5-hydroxyalkanoate structural unit. Among these, 3-hydroxyalkanoate structural units and 4-hydroxyalkanoate structural units are common, and examples thereof include a 3-hydroxybutyrate structural unit (hereinafter, may be referred to as 3HB) and a 4-hydroxybutyrate structural unit (hereinafter, may be referred to as 4 HB).
Preferably, the polyhydroxyalkanoates of the present invention comprise at least one poly (3-hydroxyalkanoate).
Further, the poly (3-hydroxyalkanoate) comprises only 3-hydroxybutyrate structural units, or comprises 3-hydroxybutyrate structural units and other hydroxyalkanoate structural units.
The method for producing the polyhydroxyalkanoate of the present invention is not particularly limited, and may be a method for producing the polyhydroxyalkanoate by chemical synthesis, or a method for producing the polyhydroxyalkanoate by a microorganism.
Studies have shown that, overall, an accelerated crystallization is achieved with the nucleating agents of the invention, independently of the proportion of structural monomers in the polyhydroxyalkanoates in the composition. The polyhydroxyalkanoates described in the present invention are particularly preferably polyhydroxyalkanoates produced by microorganisms in which all of the 3-hydroxyalkanoate structural units are contained in the form of (R) 3-hydroxyalkanoate structural units. Wherein the poly (3-hydroxyalkanoate) comprises a copolymer of a 3-hydroxybutyrate structural unit and other structural units, and the average content ratio of the 3-hydroxybutyrate structural unit to the other structural units in the poly (3-hydroxyalkanoate) is 50/50 to 99/1 (mol%/mol%); the nucleating agent disclosed by the invention has a more obvious crystallization promoting effect on the preferable materials of 80/20-94/6 (mol%/mol%); when the starting material of the polyhydroxyalkanoate is a mixture of two or more polyhydroxyalkanoates, the average content ratio refers to the molar ratio of the monomers contained in the entire mixture. Within the preferable range, the secondary molding difficulty and the processing efficiency can be both considered.
Further, the other hydroxyalkanoate structural units include: one or more of 3-hydroxypropionate, 3-hydroxyvalerate, 3-hydroxyhexanoate, 3-hydroxyheptanoate, 3-hydroxyoctanoate, 3-hydroxynonanoate, 3-hydroxydecanoate, 3-hydroxyundecanoate, or 4-hydroxybutyrate; 3-hydroxycaproic acid esters are preferred.
Specific examples of the poly (3-hydroxyalkanoate) include, for example: poly (3-hydroxybutyrate), poly (3-hydroxybutyrate-co-3-hydroxypropionate), poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (abbreviated as P3HB3HV), poly (3-hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate), poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) (abbreviated as P3HB3HH), poly (3-hydroxybutyrate-co-3-hydroxyheptanoate), poly (3-hydroxybutyrate-co-3-hydroxyoctanoate), poly (3-hydroxybutyrate-co-3-hydroxynonanoate), poly (3-hydroxybutyrate-co-3-hydroxydecanoate), Poly (3-hydroxybutyrate-co-3-hydroxyundecanoate), poly (3-hydroxybutyrate-co-4-hydroxybutyrate) (abbreviated as P3HB4HB), and the like. In particular, poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) is preferable from the viewpoints of processability, mechanical properties, and the like.
Further, the weight average molecular weight of the polyhydroxyalkanoate is 10 to 100 ten thousand; preferably 20 to 90 ten thousand; more preferably 30 to 80 ten thousand. When the weight average molecular weight is less than 10 ten thousand, the mechanical properties of the obtained molded polyhydroxyalkanoate resin tend to be low. On the other hand, when the weight average molecular weight exceeds 100 ten thousand, the load on the machine during melt processing tends to be high, and the productivity tends to be low.
In a second aspect, the present invention provides a polyhydroxyalkanoate molded body prepared from a raw material including the polyhydroxyalkanoate composition. The polyhydroxyalkanoate forming body obtained by the invention has the advantages of high transparency and good mechanical property, thereby having wider application scenes.
In addition, without inhibiting the effect of the present invention, additives and other additives may be added to the composition to prepare the composition according to the production requirements of the molded article. The additives may include organic or inorganic materials such as plasticizers, crosslinking agents, chain extenders, lubricants, and the like. The organic or inorganic materials may be used alone or in combination of two or more. The amount of the additive may be adjusted according to production requirements, and the present invention is not particularly limited thereto.
The shaped bodies according to the invention can comprise various forms, such as films, fibers, straws, plates, pellets and the like.
In a third aspect, the present invention provides a method for producing the above-mentioned polyhydroxyalkanoate molded product.
The polyhydroxyalkanoate molded product of the present invention can be produced by various thermal processing methods such as extrusion molding, injection molding, calender molding, tape casting, blow molding, biaxial stretching molding, etc., or can be produced by non-thermal processing methods such as solution casting. The preparation is preferably carried out by a hot working forming method.
The hot-working forming preparation method of the polyhydroxyalkanoate forming body provided by the invention comprises the following steps:
heating and melting the polyhydroxyalkanoate composition at a temperature above the melting temperature; cooling and forming at a temperature between the glass transition temperature and the melting temperature.
Further, when the molded body is a thin film, the production method comprises:
heating and melting the polyhydroxyalkanoate composition at a temperature 10-60 ℃ above the melting temperature (corresponding to a first temperature); performing an extension of 50% or more at a temperature between the glass transition temperature and the cold crystallization temperature (corresponding to the second temperature); the molding is cooled at a temperature between the glass transition temperature and the melting temperature (corresponding to a third temperature).
Among them, more preferable are:
considering that the smaller the enthalpy of crystallization, the better the formability of the formed body at the second temperature (stretch forming) and the more favorable the secondary forming, i.e., the higher the elongation at the secondary temperature can be. In view of easy processing at the second temperature (stretch molding), the enthalpy of crystallization is preferably 12.5J/g or less, more preferably 7.5J/g or less, and still more preferably 2J/g or less.
The smaller the data of the half-peak width of the secondary heating cold crystallization is, the more easily the formed body is crystallized and hardened in the processing process, and the processing and forming are more facilitated. In view of improving the processing efficiency, the cold crystallization half-value width is preferably 15 ℃ or less, more preferably 10 ℃ or less, and still more preferably 8 ℃ or less.
During the processing of the polyhydroxyalkanoate molded body, the molded product is easy to be adhered, and the quality of the molded product is reduced. Therefore, it is well known to those skilled in the art that the blocking of the molded article can be reduced by extending the processing time, but the processing efficiency is greatly reduced.
Therefore, the present inventors have found in their studies that, in the production of a polyhydroxyalkanoate molded product, the first temperature is not particularly limited in consideration of the uniformity of mixing, but is preferably not lower than the melting temperature of the polyhydroxyalkanoate, more preferably not lower than 10 ℃ lower than the melting temperature of the polyhydroxyalkanoate, and still more preferably not lower than 20 ℃ lower than the melting temperature of the polyhydroxyalkanoate. When the second temperature is selected to be too low or too high, the maximum drawability of the polyhydroxyalkanoate molded article is lowered, and the transparency is lowered. Therefore, it is preferable that, for example, when a molded article of a polyhydroxyalkanoate film is produced, the temperature is lowered from a first temperature to a second temperature in a primary molding process, and secondary molding is performed by stretching at the second temperature. Preferably, the second temperature is more than 20 ℃ and less than the cold crystallization temperature of the polyhydroxyalkanoate; more preferably 30 ℃ or higher and the cold crystallization temperature of polyhydroxyalkanoate or lower; during the study it was found that in the preferred range mentioned above, typically, but not limitatively, for example 40 ℃ is possible. And crystallization and shaping are carried out at a third temperature, so that the polyhydroxyalkanoate forming body is better formed and has high stable physical property. The third temperature is preferably not lower than the glass transition temperature but not higher than the melting temperature of the polyhydroxyalkanoate.
The transparency of the polyhydroxyalkanoate molded body prepared from the raw materials including the above composition is greatly improved. In the art, the greater the light transmittance, the lower the haze, and the better the transparency of the film sample. The molded article obtained by the present invention has a linear light transmittance of 80% or more and a haze of 50% or less. In particular, in the examples, a fully biodegradable resin film product having a total light transmittance of 90% or more and a haze of 40% or less and a total light transmittance of 90% or more and a haze of 30% or less was obtained.
Compared with the prior art, the invention at least comprises the following advantages:
1. the nucleating agent for polyhydroxyalkanoate provided by the invention has high nucleating efficiency, and can improve the defects of slow crystallization speed, low processing efficiency and the like of polyhydroxyalkanoate in the process of preparing various molded bodies by thermoplastic processing.
2. The nucleating agent provided by the invention has wide sources and lower product price, and reduces the raw material cost of various polyhydroxyalkanoate forming bodies; meanwhile, the nucleating agent provided by the invention is a biological source, does not influence the biological carbon ratio of the polyhydroxyalkanoate forming body, and can still reach 100% of biological source.
3. Compared with other conventional nucleating agents, various polyhydroxyalkanoate molded bodies prepared by using the nucleating agent provided by the invention have higher transparency, and the color of various molded bodies cannot be influenced.
4. The formed body provided by the invention is convenient for secondary processing and forming at the second temperature lower than the melting temperature, and still keeps good transparency after secondary processing and forming.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation. The present invention will be described in detail below by way of examples. In the following examples, each material used was commercially available unless otherwise specified, and the method used was a conventional method in the art unless otherwise specified.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The present invention is described in more detail by the following examples, which are not intended to limit the present invention. All the raw materials used in the following examples and comparative examples were commercially available except for the specific ones.
The method comprises the following steps:
PHBH-350: poly (3-hydroxybutyrate-co-3-hydroxyhexanoate), self-made (BP 350).
PHBH-330: poly (3-hydroxybutyrate-co-3-hydroxyhexanoate), self-made (BP 330).
PHBV: poly (3-hydroxybutyrate-co-3-hydroxyvalerate), self-made.
The adopted equipment comprises the following steps:
material mixing equipment: blending in a high-speed mixer at room temperature.
Granulation equipment: the common extrusion granulation equipment in the field such as a parallel co-rotating twin-screw extruder, a parallel counter-rotating twin-screw extruder, a conical twin-screw extruder and a single-screw extruder with different length-diameter ratios can be used; placing the composition in a discharge hopper or a weightless scale of a double-screw extruder; the temperature of the extrusion granulation equipment is set within the range of 50-180 ℃, the rotating speed of a main machine is 50-500r/min, and the feeding amount or the productivity is adjusted according to the actual production state; subsequently, granulation can be carried out in the granulation modes of air cooling bracing granulation, water bath bracing granulation, grinding surface hot cutting, water ring cutting, underwater granulation and the like, and the water bath condition of 25-65 ℃ is kept in the production and processing process; the prepared particles are dried by using an air-blast drying oven, the influence of moisture on the particle performance is eliminated, and the particles are completely crystallized.
Film making equipment: and (2) performing mould pressing on the biodegradable resin at a low temperature by using a mould pressing machine (manufactured by Jiangsu Tianyuan company), preparing a mould pressing product, then putting the mould pressing product into water at a second temperature, stretching two ends of the mould pressing film by hand at a certain multiplying power, and finally putting the mould pressing film into an oven to heat at a third temperature.
Example 1 composition
This example provides 12 sets of polyhydroxyalkanoate compositions, including polyhydroxyalkanoates and nucleating agents, having the specific compositions shown in table 1.
TABLE 1
EXAMPLE 2 granulation
Preparing a particle forming body, and extruding and granulating by adopting a double screw; the raw materials are respectively compositions 1-12 in the table 1.
The manufacturing steps are as follows:
step 1, mixing materials: putting polyhydroxyalkanoate powder and a nucleating agent into a high-speed mixer, mixing at room temperature at a mixing speed of 200(r/min) for 5 (min); after mixing, placing the mixed material in a discharge hopper of a double-screw extruder;
step 2, extrusion: setting the conditions of extrusion granulation equipment, and extruding at the melt temperature of about 165 ℃;
step 3, granulation and cooling: granulation was performed by strand granulation in a water bath, wherein the heating temperature and heating time in the water bath are shown in Table 2.
The performance parameters (enthalpy of crystallization at reduced temperature and half-width of cold crystallization at second temperature increase) of each particle molded body are shown in table 2.
TABLE 2
Comparative example 1
The particle forming body is prepared by using PHBH-350100 parts by weight as a raw material and adding no nucleating agent.
The manufacturing steps are as follows: directly carrying out melt extrusion on the raw materials: setting the conditions of extrusion granulation equipment, and extruding at the melt temperature of about 165 ℃; then granulating and cooling: granulating by water bath bracing and granulating, wherein the water bath temperature is set to 55 deg.C, and the heating time is 3 min.
As a result, the enthalpy of crystallization at a reduced temperature of the particle molded body was 0J/g, and the half width of cold crystallization at a secondary temperature rise was 27 ℃.
Comparative example 2
Preparing a particle forming body, and extruding and granulating by adopting a double screw; the raw material adopts PHBH-350100 weight portions and nucleating agent boron nitride 1 weight portion.
The manufacturing steps are as follows:
step 1, mixing materials: putting the PHBH-350 powder and a nucleating agent boron nitride into a high-speed mixer, and mixing at room temperature at a mixing speed of 200(r/min) for 5 (min); after mixing, placing the mixed material in a discharge hopper of a double-screw extruder;
step 2, extrusion: setting the conditions of extrusion granulation equipment, and extruding at the melt temperature of about 165 ℃;
step 3, granulation and cooling: granulating by water bath bracing and granulating at 55 deg.C for 0.5 min.
As a result, the enthalpy of crystallization at a reduced temperature of the particle molded body was 17.2J/g, and the half width of cold crystallization at a secondary temperature rise was 21 ℃.
From the above results, it is understood that the data of the peak widths at half maximum of the secondary heating cold crystallization of the particle molded articles 1 to 5 and 11 to 12 of the present example are smaller than those of the comparative examples 1 and 2, indicating that the processing and molding are more favorable; moreover, their lower temperature crystallization enthalpy is also smaller, indicating that secondary molding is more favored. Namely, the particle forming body prepared by the nucleating agent provided by the invention has relatively lower thermoplastic processing difficulty, can be continuously and stably processed, and has better quality. Among them, the particle-shaped articles 6 to 10 had unsatisfactory results, and were mainly affected by the heating temperature in a water bath of 25 ℃. The molded articles 1 to 5 and 11 to 12 were excellent in molding effect, and the molded articles 6 to 10 were not preferable, and it was found that the water bath heating temperature was preferably set to 40 to 90 ℃.
Example 3 preparation of a film
The particles 1 to 12 of example 2 and the particles of comparative examples 1 to 2 were used to prepare films by secondary processing. It is noted here, of course, that it is also possible to directly prepare films using the starting materials for particles 1-12 (i.e., compositions 1-12) and are intended to be within the scope of the present invention.
At the same time, 4 sets of experiments were added, using particle 3, and the elongation was set as: 100 (not extended), 150, 250, 300;
the heating time was extended to 3(min) by adding 1 set of comparative experiments and using the particles of comparative example 1.
The manufacturing steps are as follows: and (2) performing mould pressing on the biodegradable resin at a first temperature (melt temperature) by using a mould pressing machine to prepare a mould pressing product with the thickness of 200 mu m, then putting the mould pressing product into water at a second temperature (extension temperature) to stretch two ends of the mould pressing film by hand at a certain multiplying power, and finally putting the mould pressing film into an oven at a third temperature (heating temperature) to heat so as to prepare a film sample. Specific process parameters are shown in table 3. The performance parameters of each of the film molded articles obtained are shown in Table 4.
TABLE 3
TABLE 4
From the above results, it is clear that the molded film obtained from the composition of the nucleating agent of the present invention and polyhydroxyalkanoate has relatively low thermoplastic processability, can be continuously and stably processed into a film, and has good quality of molded articles, particularly good transparency.
The performance parameters are evaluated by the following performance evaluation mode of the polyhydroxyalkanoate molded body, and the polyhydroxyalkanoate molded body is made into a test piece required by the corresponding standard through an injection molding machine and is evaluated after measurement.
Evaluation of the properties of the molded polyhydroxyalkanoate products:
cooling and crystallizing enthalpy:
2-10mg of the molded polyhydroxyalkanoate was measured by a differential scanning calorimeter (DSC 25, TA Instrument Co., Ltd.), the temperature was once raised from 25 ℃ to 180 ℃ at a temperature raising rate of 10 ℃/min, the temperature was lowered from 180 ℃ to-50 ℃ at a temperature lowering rate of 10 ℃/min to obtain a temperature lowering curve, and enthalpy of crystallization was obtained from the temperature lowering curve.
The smaller the enthalpy of crystallization, the better the formability of the shaped body at the second temperature, which is more favorable for secondary forming, i.e. the higher the elongation at the secondary temperature can be. In view of easy processing at the second temperature, the enthalpy of crystallization is preferably 12.5J/g or less (film 5), more preferably 7.5J/g or less (film 4), and still more preferably 2J/g or less (films 1 to 3, 11, 13 to 16). Although the enthalpy of crystallization is low in comparative examples 17 and 19, the half width of cold crystallization at the second temperature rise is large, and the molding efficiency is low.
Cold crystallization half-peak width at secondary temperature rise:
2-10mg of the molded polyhydroxyalkanoate was measured by a differential scanning calorimeter (DSC 25, manufactured by TA Instrument Co., Ltd.), the temperature was once raised from 25 ℃ to 180 ℃ at a temperature raising rate of 10 ℃/min, the temperature was maintained at 180 ℃ for 3min, the temperature was lowered from 180 ℃ to-50 ℃ at a temperature lowering rate of 10 ℃/min, and the temperature was twice raised from 50 ℃ to 180 ℃ at a temperature raising rate of 10 ℃/min to obtain a DSC curve of the second temperature rise. And obtaining a secondary heating curve, and obtaining the half-peak width of the cold crystallization from the secondary heating curve under the condition that the secondary heating curve has a cold crystallization peak.
The smaller the data of the half-peak width of the secondary heating and cold crystallization is, the more easily the formed body is crystallized and hardened in the processing process, and the more easily the formed body is processed and formed. In view of improving the processing efficiency, the cold crystallization half-value width is preferably 15 ℃ or less (film 1), more preferably 10 ℃ or less (films 11 and 12), and still more preferably 8 ℃ or less (e.g., films 2 to 5 and 13 to 16).
Light transmittance and haze:
a sample of 5 cm. times.5 cm was subjected to haze measurement and light transmittance measurement using a Japanese SUGA haze meter HZ-V3 with D65 as a light source.
The greater the light transmittance, the lower the haze, and the better the transparency of the film sample.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The polyhydroxyalkanoate composition is characterized by comprising polyhydroxyalkanoate and a nucleating agent, wherein the nucleating agent is one or more of alcohol compounds.
2. The polyhydroxyalkanoate composition of claim 1, wherein the nucleating agent is one or more of a fatty alcohol; preferably, the fatty alcohol has 5 to 30 carbon atoms.
3. The polyhydroxyalkanoate composition of claim 2, wherein the nucleating agent is one or more of 1, 16-hexadecanediol, 1, 22-docosandiol, stearinediol, behenyl alcohol, arachidyl alcohol, palmityl alcohol, ceryl alcohol, policosanol, melissyl alcohol, ceryl alcohol, myristyl alcohol, lauryl alcohol; the addition amount of the nucleating agent is 0.01-20% of the mass of the polyhydroxyalkanoate.
4. The polyhydroxyalkanoate composition of claim 3, wherein the nucleating agent is behenyl alcohol, and the amount of behenyl alcohol added is 0.1% -5% of the polyhydroxyalkanoate by mass.
5. The polyhydroxyalkanoate composition of any one of claims 1-4, wherein the polyhydroxyalkanoate comprises at least one poly (3-hydroxyalkanoate).
6. The polyhydroxyalkanoate composition of claim 5, wherein the poly (3-hydroxyalkanoate) comprises only 3-hydroxybutyrate structural units, or comprises 3-hydroxybutyrate structural units and other hydroxyalkanoate structural units.
7. The polyhydroxyalkanoate composition of claim 6, wherein the poly (3-hydroxyalkanoate) comprises a copolymer of at least one 3-hydroxybutyrate structural unit and other hydroxyalkanoate structural units.
8. The polyhydroxyalkanoate composition of claim 6 or 7, wherein the other hydroxyalkanoate structural units comprise: one or more of 3-hydroxypropionate, 3-hydroxyvalerate, 3-hydroxyhexanoate, 3-hydroxyheptanoate, 3-hydroxyoctanoate, 3-hydroxynonanoate, 3-hydroxydecanoate, 3-hydroxyundecanoate, or 4-hydroxybutyrate;
3-hydroxycaproic acid esters are preferred.
9. A polyhydroxyalkanoate molded body, characterized by being produced from a raw material comprising the polyhydroxyalkanoate composition according to any one of claims 1 to 8; the shaped bodies include films, fibers, straws, plates or pellets.
10. A method for producing a polyhydroxyalkanoate molded body, comprising:
heating to melt the polyhydroxyalkanoate composition of any one of claims 1-8 at a temperature above the melting temperature; cooling and forming at a temperature between the glass transition temperature and the melting temperature;
preferably, in the production of the polyhydroxyalkanoate molded article, the polyhydroxyalkanoate composition according to any one of claims 1 to 8 is heated and melted at a temperature of 10 ℃ to 60 ℃ above the melting temperature; performing an elongation of more than 50% at a temperature between the glass transition temperature and the cold crystallization temperature; cooling and forming at a temperature between the glass transition temperature and the melting temperature.
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| PCT/CN2023/093386 WO2023231732A1 (en) | 2022-06-02 | 2023-05-11 | Polyhydroxyalkanoate composition containing alcohol nucleating agent, polyhydroxyalkanoate molded body and preparation method therefor |
| TW112120298A TWI861913B (en) | 2022-06-02 | 2023-05-31 | Polyhydroxyalkanoate composition containing alcohol nucleating agent, polyhydroxyalkanoate molded body and preparation method thereof |
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