CN114479021A - High-performance polyhydroxyalkanoate, preparation method and application thereof - Google Patents
High-performance polyhydroxyalkanoate, preparation method and application thereof Download PDFInfo
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- CN114479021A CN114479021A CN202011157757.3A CN202011157757A CN114479021A CN 114479021 A CN114479021 A CN 114479021A CN 202011157757 A CN202011157757 A CN 202011157757A CN 114479021 A CN114479021 A CN 114479021A
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- polyhydroxyalkanoate
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- 239000005014 poly(hydroxyalkanoate) Substances 0.000 title claims abstract description 139
- 229920000903 polyhydroxyalkanoate Polymers 0.000 title claims abstract description 136
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000004970 Chain extender Substances 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000000155 melt Substances 0.000 claims abstract description 15
- 229920005862 polyol Polymers 0.000 claims abstract description 7
- 150000003077 polyols Chemical group 0.000 claims abstract description 7
- 229920001634 Copolyester Polymers 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 55
- 238000001125 extrusion Methods 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 25
- 239000002667 nucleating agent Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 claims description 4
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- -1 aliphatic polyols Chemical class 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 238000010096 film blowing Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 229920000229 biodegradable polyester Polymers 0.000 claims description 3
- 239000004622 biodegradable polyester Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 3
- 239000004626 polylactic acid Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 2
- NBJODVYWAQLZOC-UHFFFAOYSA-L [dibutyl(octanoyloxy)stannyl] octanoate Chemical compound CCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCC NBJODVYWAQLZOC-UHFFFAOYSA-L 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 125000005313 fatty acid group Chemical group 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 claims description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 2
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 2
- 229920001020 poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) Polymers 0.000 claims description 2
- 229920000520 poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Polymers 0.000 claims description 2
- 229920001013 poly(3-hydroxybutyrate-co-4-hydroxybutyrate) Polymers 0.000 claims description 2
- 229920000070 poly-3-hydroxybutyrate Polymers 0.000 claims description 2
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical group CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims 1
- 230000000536 complexating effect Effects 0.000 claims 1
- 238000002347 injection Methods 0.000 claims 1
- 239000007924 injection Substances 0.000 claims 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims 1
- 229920000747 poly(lactic acid) Polymers 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 11
- 229920001896 polybutyrate Polymers 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 31
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- 239000000843 powder Substances 0.000 description 9
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
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- 150000005846 sugar alcohols Polymers 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
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- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
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- 229920000573 polyethylene Polymers 0.000 description 2
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- 230000009467 reduction Effects 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- 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
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
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- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
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- Biological Depolymerization Polymers (AREA)
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Abstract
The invention provides a high-performance polyhydroxyalkanoate, which comprises a polyhydroxyalkanoate chain segment and a copolyester chain segment of a first chain extender, wherein the first chain extender is selected from polyols. The preparation of the high-performance polyhydroxyalkanoate comprises the step of continuously reacting and extruding the components including the polyhydroxyalkanoate and the first chain extender to obtain the high-performance polyhydroxyalkanoate. The prepared high-performance polyhydroxyalkanoate, the compound polymer and other additives are further melted and mixed in a double-screw extruder to prepare blended particles and blow a film, the melt index of the PHA which is extruded and modified through continuous reaction is obviously reduced, the molecular weight is increased, and the mechanical property of the prepared modified PHA-PBAT film is improved.
Description
Technical Field
The invention belongs to the field of biological materials, and particularly relates to high-performance polyhydroxyalkanoate, a preparation method and application thereof.
Background
The commonly used biopolymer materials are mainly polylactic acid (PLA), Polycaprolactone (PCL), Polyhydroxyalkanoate (PHA), a copolymer of butylene adipate and butylene terephthalate (PBAT), and the like. The high molecular material formed by using renewable raw materials to obtain biological monomers through biological or chemical conversion and then further polymerizing belongs to the whole biological material. After the fully biodegradable material is used, the plastic is finally converted into water and carbon dioxide by composting or other degradation treatments through microorganisms, which is beneficial to environmental protection and conforms to the sustainable development direction. PHA is used as a full biodegradable material, is different from other synthetic polyesters (polymerized in a high-temperature reaction kettle), is prepared by microbial fermentation in a room-temperature aqueous solution, and is prepared by the steps of fermentation, precipitation, filtration, washing, centrifugal drying and the like.
Because PHA can be produced by bacterial fermentation of corn steep liquor powder and sodium chloride, PHA low-cost production is expected to be realized by subsequent optimization of process conditions, and PHA has a certain competitive potential compared with non-renewable petroleum-based plastics. Meanwhile, PHA can be completely decomposed by microorganisms in soil in the using process, and has wide application prospect in the field of agricultural mulching films (Brandi H et al, Degradation and applications of polyhydroxyakohoates. Can.J.Microbiol,1995,41: 143-. Compare in traditional plastic film, can effectively solve current difficult to retrieve of non-degradable Polyethylene (PE) plastic film, cause environmental pollution's problem. However, compared with the traditional polyester material, the PHA material has different preparation modes, and because the PHA material has different chemical structures and does not have the processes of high-temperature melt chain extension and the like of the traditional polyester in a reaction kettle, the melt strength of the prepared polymer is often lower, the processing performance of the produced film is poor, and the PHA material generally has the defects of weaker mechanical property, lower crystallinity, longer crystallization period, easiness in secondary crystallization and the like; and the mechanical properties of the molding material are further influenced by thermal degradation due to ester bond fracture caused by high temperature and screw shearing in the process of processing and molding (SCL-PHA) Polymers 2016; 8: 273).
Disclosure of Invention
In order to solve the problems, the PHA (polyhydroxyalkanoate) is modified by adopting a continuous reaction extrusion method, and the polyol is added to carry out chain extension on the PHA under the action of a high-efficiency esterification catalyst, so that the processing performance and the mechanical property of the polyester are improved.
The invention aims to provide a high-performance polyhydroxyalkanoate, which comprises a polyhydroxyalkanoate chain segment and a copolyester chain segment of a first chain extender, wherein the first chain extender is selected from polyols.
In the high-performance polyhydroxyalkanoate, the first chain extender is selected from aliphatic polyhydric alcohols, preferably selected from aliphatic dihydric alcohols with 2-10 carbon atoms, and more preferably selected from at least one of ethylene glycol, propylene glycol, butanediol and pentanediol;
the polyhydroxyalkanoate has a structure shown in a formula (I):
wherein R is an alkyl group having a carbon chain length of 1 to 15,
the polyhydroxyalkanoate is selected from homopolymers or copolymers of hydroxy fatty acids with 4-18 carbon atoms, and preferably is at least one selected from poly (3-hydroxybutyrate), poly (3-hydroxybutyrate-co-4-hydroxybutyrate), poly (3-hydroxybutyrate-co-3-hydroxyvalerate) and poly (3-hydroxybutyrate-co-3-hydroxyhexanoate); the weight average molecular weight M of the polyhydroxyalkanoatew50000g/mol or more, preferably Mw100000g/mol or more.
In the high-performance polyhydroxyalkanoate, the first chain extender is used in an amount of 0.05 to 10 parts by mass, preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the polyhydroxyalkanoate.
The second object of the present invention is to provide a method for preparing the high-performance polyhydroxyalkanoate, which comprises reacting the components including the polyhydroxyalkanoate and the first chain extender to obtain the high-performance polyhydroxyalkanoate, and specifically comprises the following steps:
step 1, premixing a first chain extender and a catalyst;
and 2, carrying out melt reaction on the mixture obtained in the step 1 and polyhydroxyalkanoate, and extruding to obtain the high-performance polyhydroxyalkanoate.
In the preparation method, the first chain extender is used in an amount of 0.05 to 10 parts by mass, preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the polyhydroxyalkanoate; the dosage of the catalyst is 0.001-0.2 part, preferably 0.001-0.2 part;
the extrusion temperature is 100-250 ℃, and preferably 100-180 ℃;
the melt reaction extrusion is carried out in a double-screw extruder which can be a co-rotating or counter-rotating double screw, and the rotating speed of the screw is 0-500 rpm, preferably 20-250 rpm. Twin screw extruders useful in the present invention include, but are not limited to: a Micro 27 twin-screw extruder manufactured by Leistritz, germany, which has a function of switching between a co-rotation direction and a counter-rotation direction; a co-rotating twin screw extruder of model PolyLab, EuroLab, etc. manufactured by Thermo Fisher Scientific, USA; a ZSK 30 co-rotating parallel twin-screw extruder manufactured by Coperion corporation, Germany, and the like;
the catalyst is selected from metal salts or oxides of IVB group and IVA group, preferably at least one selected from titanate catalyst and metal alkoxide, more preferably at least one selected from tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetrabutyl zirconate, titanium glycol, antimony glycol and dibutyltin dioctoate, and most preferably at least one selected from tetrabutyl titanate, titanium glycol and antimony glycol.
The invention also aims to provide a high-performance polyhydroxyalkanoate film, which contains the high-performance polyhydroxyalkanoate or the high-performance polyhydroxyalkanoate prepared by the preparation method.
The high-performance polyhydroxyalkanoate film provided by the invention contains at least one of a compound polymer, a nucleating agent, a second chain extender and an opening agent besides the high-performance polyhydroxyalkanoate.
In the high-performance polyhydroxyalkanoate film, the total amount of the high-performance polyhydroxyalkanoate and the compound polymer is 100 parts by mass, the using amount of the compound polymer is 0-99 parts, the using amount of the nucleating agent is 0.02-30 parts, the using amount of the second chain extender is 0.01-6 parts, and the using amount of the opening agent is 0.02-10 parts; preferably, the amount of the compound polymer is 50-99 parts, the amount of the nucleating agent is 1-20 parts, the amount of the second chain extender is 0.05-2 parts, and the amount of the opening agent is 0.05-5 parts.
In the high-performance polyhydroxyalkanoate film, the compound polymer is selected from biodegradable polyester compounds, preferably at least one selected from polylactic acid (PLA), poly (butylene adipate/butylene terephthalate) (PBAT), poly (butylene succinate/butylene terephthalate) (PBST), and poly (butylene succinate/butylene adipate) (PBSA); the compound polymer is not limited to the above polymer types, and other common biodegradable polyester compounds can be selected;
the nucleating agent is selected from inorganic nucleating agents, preferably at least one selected from nano-crystalline cellulose, talcum powder, silicon dioxide and flaky calcium carbonate; the nucleating agent in the invention is not limited to the compounds, and other commonly used nucleating agents in polymerization reaction can be selected;
the second chain extender is selected from at least one of polycarbodiimide, epoxy ethylene glycol, toluene diisocyanate and antimony trioxide;
the opening agent is selected from fatty acid amide compounds, preferably at least one selected from oleic acid amide, erucic acid amide and stearic acid amide.
The fourth purpose of the present invention is to provide a preparation method of the high-performance polyhydroxyalkanoate film, which comprises the step of mixing the components including the high-performance polyhydroxyalkanoate, the compound polymer, the nucleating agent, the second chain extender and the opening agent to obtain the high-performance polyhydroxyalkanoate film, and specifically comprises the following steps:
mixing the high-performance polyhydroxyalkanoate and a compound polymer, adding a nucleating agent, a second chain extender and a mouth-opening agent, and mixing, melting and reacting in a double-screw extruder; adding the obtained reaction product into a single-screw extruder for melting, extruding and film blowing, and cooling to obtain the high-performance polyhydroxyalkanoate film.
In the preparation method of the high-performance polyhydroxyalkanoate film, the extrusion temperature of the double-screw extruder is 50-300 ℃, and preferably 100-200 ℃; the screw rotating speed of the double-screw extruder is 0-500 rpm, preferably 50-300 rpm, and more preferably 100-220 rpm; the extrusion temperature of the single-screw extruder is 50-300 ℃, and preferably 100-200 ℃; the screw rotation speed of the single screw extruder is 0-150 rpm, preferably 10-100 rpm.
The invention adopts the polyalcohol chain extender to chain the polyhydroxyalkanoate, and the melt index of the chain-extended high-performance polyhydroxyalkanoate is obviously reduced through the double-screw continuous extrusion reaction under the action of the high-efficiency esterification catalyst, so that the polyhydroxyalkanoate has more excellent thermal stability, processability and mechanical property, and the mechanical property of the film material prepared by adopting the high-performance polyhydroxyalkanoate is also improved. According to some embodiments of the invention, the thickness of the continuous reaction extrusion modified PHA film is less than 50 μm, even less than 25 μm, the elongation at break is not less than 300%, even more than 400%, and the breaking strength is greater than 15MPa, up to 20MPa or more.
Compared with the prior art, the invention has the following beneficial effects:
1. after the polyol is adopted to carry out chain extension on the polyhydroxyalkanoate, the melt index can be obviously reduced, so that the polyhydroxyalkanoate has excellent thermal stability and processability;
2. the modified high-performance polyhydroxyalkanoate is used as a raw material, chain extension modification is carried out through a double-screw continuous extrusion process, and then a film material prepared by single-screw film blowing has excellent mechanical properties;
3. the preparation method provided by the invention is simple and feasible, can be used for continuous production, is green and environment-friendly, and is easy to realize industrialization.
Drawings
FIG. 1 is a second temperature-rise curve of PHA powder before and after extrusion processing at different rotation speeds and at different temperatures, wherein curves a and B in FIG. 1-A are the second temperature-rise curves of PHA obtained in comparative example 1 and comparative example 4, respectively, curves a and B in FIG. 1-B are the second temperature-rise curves of high-performance polyhydroxyalkanoate (modified PHA) obtained in example 2 and example 1 at different rotation speeds, respectively, and curves a and B in FIG. 1-C are the second temperature-rise curves of modified PHA obtained in example 3 and example 1 at different temperatures, respectively;
FIG. 2 is a graph showing elongation at break in parallel to the direction of stretching (MD) after blowing films of PHA obtained in examples 1 to 3 and comparative examples 1 to 6;
FIG. 3 shows MD fracture strength after blowing PHA films obtained in examples 1 to 3 and comparative examples 1 to 6.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The test instruments and test conditions used in the examples were as follows:
melt index (MFR) determination method: according to ISO 1133 standard, the melt index instrument is adopted to measure, the cylinder temperature is 150 ℃, the mass load is 2.16kg, the diameter of a die is 2.095 mm, the length is 8mm, the preheating time is 4min, samples are automatically cut at set time intervals, 5 times of averaging is carried out, and the measurement result is expressed by grams per 10 minutes (g/10 min).
Thermal performance analysis (DSC): the tests were carried out on a Discovery series Differential Scanning Calorimeter (DSC) manufactured by TAInstructions Inc., with the processing software TAInstructions Trios version 3.1.5, equipped with a calibrated cooking System 90 mechanical refrigeration accessory. The testing atmosphere is 50mL/min of nitrogen, and the amount of the sample required by the test is 5-10 mg. The test procedure was as follows: the temperature is stabilized at 40 ℃, then the temperature is raised to 220 ℃ at 10 ℃/min and kept constant for 1min to remove the thermal history, then the temperature is lowered to-50 ℃ at 10 ℃/min and kept constant for 1min, and then the temperature is raised to 220 ℃ at 10 ℃/min. And recording the temperature reduction process and the second temperature rise process to research the thermal performance of the sample. By DSC measurement, software can be used to directly derive the crystallization temperature ("T") of a samplec"), melting temperature (" T ")m"), glass transition (" T ")g"), enthalpy change (" H "), etc.
Film tensile test: the test was carried out according to ISO 527-3 using a model 3344 materials tester from Instron with the processing software Bluehill version 2.31. The film was cut into Type 5 according to ISO 527-3 in a direction parallel to the stretching direction (MD) and a direction perpendicular to the stretching direction (CD), and the cut film was allowed to stand in a Bluepard BPS-100 CB constant temperature and humidity cabinet (temperature 23 ℃ C., relative humidity 50%) of Shanghai-Hengscience instruments Co., Ltd for 24 hours. During testing, the initial clamp spacing was 75mm, the test pull rate was 100mm/min, and each sample was tested at least 5 times, and the average was taken.
[ example 1 ] preparation of high Performance polyhydroxyalkanoate
The catalyst tetraethyl titanate used in the invention is selected from Shanghai leaf Co., Ltd, and the ethylene glycol is selected from the national drug company, polyhydroxyalkanoate (PHA, M)w300000g/mol) from Tianjin chlorophyll.
In example 1, PolyLab HAAKE from Thermo Fisher science and technology, USA, was selectedTMRheomex OS PTW16 co-rotating twin screw extruder (screw diameter 16mm, L/D40) modified PHA. 100 parts of PHA powder, 0.01 part of catalyst and 0.5 part of ethylene glycol are premixed by mass, and the premixed PHA is plasticized, reacted and extruded, wherein the feeding speed of the premixed PHA is 3 kg/h.
The extruder has a total of 11 sections from the feeding port to the die, which are numbered as 1-11, wherein the section 1 only plays a role of feeding and is not heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 140 ℃,140 ℃,150 ℃,150 ℃,150 ℃,150 ℃ and 150 ℃, and the screw rotation speed is set at 50 rpm. Feeding PHA mixture to the 1 st section of the double-screw extruder by using a weightless feeder of the extruder, wherein the feeding speed is as follows: 3 kg/h. After the operation is stable, the pressure of the twin-screw extrusion is 20-30 bar, and the torque is about 46%. The extruder is provided with two circular outlets with the diameter of 4mm on a neck ring mold, a sample strip is extruded from the neck ring mold, passes through a water bath cooling tank, is cut into cylindrical particles with the length of about 5mm by a granulator, and is collected and packaged for later use after being vacuumized for 4 hours (h) in a vacuum drying box at the temperature of 70 ℃.
[ example 2 ] preparation of high Performance polyhydroxyalkanoates
In example 2, the effect of different screw speeds on the continuous reaction and extrusion of PHA was examined by selecting PolyLab HAAKE from Thermo Fisher science and technology, USATMRheomex OS PTW16 co-rotating twin screw extruder (screw diameter 16mm, L/D40) modified PHA. 100 parts of PHA powder, 0.01 part of catalyst and 0.5 part of ethylene glycol are premixed by mass, and the premixed PHA is plasticized, reacted and extruded, wherein the feeding speed of the premixed PHA is 3 kg/h. The screw rotation speed was changed to 150rpm, and other conditions were controlled in the same manner as in example 1.
[ example 3 ] preparation of high Performance polyhydroxyalkanoates
Example 3 examines the continuous reactive extrusion of PHA at a higher bulk reactive extrusion temperature of 160 ℃ using PolyLab HAAKE from Thermo Fisher science, USATMRheomex OS PTW16 co-rotating twin screw extruder (screw diameter 16mm, L/D40) modified PHA. 100 parts of PHA powder, 0.01 part of catalyst and 0.5 part of ethylene glycol are premixed by mass, and the premixed PHA is plasticized, reacted and extruded, wherein the feeding speed of the premixed PHA is 3 kg/h. The reaction temperature of the main body of the extruder is changed to 160 ℃, and the rotating speed of the screw is 50 rpm.
The extruder has a total of 11 sections from the feed port to the die, numbered 1-11, wherein section 1 serves only as a feed and is not heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 150 ℃,150 ℃,160 ℃,160 ℃,160 ℃,160 ℃ and 160 ℃, and the screw rotation speed is set at 50 rpm. Feeding PHA mixture to the 1 st section of the double-screw extruder by using a weightless feeder of the extruder, wherein the feeding speed is as follows: 3 kg/h. After the operation is stable, the pressure of the twin-screw extrusion is 20-30 bar, and the torque is about 36%. The extruder is provided with two circular outlets with the diameter of 4mm on the neck mold, a sample strip is extruded from the neck mold, and is cut into cylindrical particles with the length of about 5mm by a granulator through a water bath cooling tank, and the cylindrical particles are collected and packaged for later use after being vacuumized for 4 hours in a vacuum drying box at 70 ℃.
[ COMPARATIVE EXAMPLES 1 to 3 ] preparation of polyhydroxyalkanoate
In comparative examples 1-3, in which the addition of ethylene glycol and catalyst was not considered, PHA was extruded using a PolyLab HAAKETM Rheomex OS PTW16 co-rotating twin screw extruder (screw diameter 16mm, L/D40) from Thermo Fisher technologies, USA. Wherein, the comparative examples 1 to 3 are prepared by adding only PHA powder into a double screw without adding ethylene glycol and a catalyst, plasticizing, reacting and extruding, and controlling other conditions to be respectively the same as the corresponding examples 1 to 3. Wherein, PHA powder without screw modification was selected as comparative example 4.
[ example 4 ] melt index test
The PHA particles obtained in examples 1 to 3 and comparative examples 1 to 3 were subjected to the melt index test, which was performed as described above, at a temperature of 150 ℃ and a mass of 2.16kg, and the melt indices of the PHA particles obtained in examples 1 to 3 and comparative examples 1 to 3 were measured, and are shown in Table 1. Wherein comparative example 4 is PHA powder without any extrusion modification reaction.
TABLE 1150 ℃ melt index of 2.16kg melt index of examples 1 to 3 and comparative examples 1 to 4
The melt indices of comparative examples 1-4 were 0.25-0.47g/10min, with little change. Comparing examples 1-3 with comparative examples 1-4, the melt index of PHA was reduced to some extent and the molecular weight was increased after adding the catalyst and ethylene glycol, which indicates that the catalyst and ethylene glycol can significantly promote the chain extension of PHA, resulting in a reduction in melt index.
The effect of the rotational speed on the melt index was remarkable, and the melt index was remarkably decreased at 150 ℃ and 100rpm (example 2) compared to 150 ℃ and 30rpm (example 1) under the same conditions, and it is presumed that the chain extension effect was superior by the melt index. The temperature influence was small, and the melt index change was also insignificant at 160 ℃ and 30rpm (example 3) compared to 150 ℃ and 30rpm (example 1).
[ example 5 ] Differential Scanning Calorimetry (DSC) test
All of the above particles, including examples 1-3 and comparative examples 1-4, were subjected to Differential Scanning Calorimetry (DSC) testing according to the procedure described above, and their second melting temperatures (T;)m) Enthalpy of fusion (. DELTA.H)m) Glass transition temperature TgWith recrystallization enthalpy Δ HcThe values are shown in Table 2.
TABLE 2 DSC results of examples 1 to 3 and comparative examples 1 to 4
The second temperature rise curve of the high performance polyhydroxyalkanoate at different temperatures and rotation speeds is shown in fig. 1, and as shown in fig. 1-a, the melting curve of the PHA extruded only without the catalyst and the chain extender (comparative example 1) is almost unchanged, which indicates that the single extrusion reaction has little influence on the thermodynamic properties of the PHA. As for the rotation speed, it can be seen from FIG. 1-B that the melting peak of the high-performance polyhydroxyalkanoate obtained in example 2 is not significantly changed when the rotation speed is 100rpm compared with 30rpm (example 2 and example 1), the recrystallization peak is shifted to the left, and Δ HcDecrease, indicating high speedThe crystal structure is changed, and the crystal structure is damaged and the crystallinity is reduced due to the shear enhancement of high rotating speed. Similarly, in FIG. 1-C, the enthalpy of recrystallization is reduced and the crystallinity of the high-performance polyhydroxyalkanoate obtained in example 3 is reduced at a high temperature, as compared with example 1 in example 3, which indicates that the high temperature is not favorable for crystallization.
Compared with the comparative examples 1 to 4 and the examples 1 to 3, after the polyol chain extender and the catalyst are added to chain extend the PHA, the enthalpy of crystallization and melting is not changed obviously, and the T isgThere is a certain reduction, indicating an increased mobility of the polymer chains of the material.
[ COMPARATIVE EXAMPLES 5 to 6 ]
Comparative examples 5 to 6 modification of PHA with Monool
PolyLab HAAKE from Thermo Fisher science and technology of America is selectedTMRheomex OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D40). 100 parts of PHA powder, 0.01 part of catalyst and different amounts of n-butanol (national drug company) are premixed according to the mass parts, and the premixed PHA is plasticized, reacted and extruded, wherein the feeding speed is 3 kg/h. Wherein the amount of n-butanol added in comparative example 5 was 0.1 part, and the amount of n-butanol added in comparative example 6 was 1 part, and the other conditions were controlled to be the same as in example 1.
Example 6 preparation of high Performance PHA-PBAT films
All of the PHA particles above, including examples 1-3 and comparative examples 1-6, were PolyLab HAAKE from Thermo Fisher technologies, USATMIn a Rheomex OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D is 40), melt blending modification is carried out with PBAT, and PHA-PBAT blending particles are prepared. The preparation method comprises the following steps of blending 10 parts by mass of high-performance polyhydroxyalkanoate, 90 parts of PBAT (from BASF, brand FBlendC1200), 0.5 part of epoxy chain extender ADR (BASF), 0.5 part of opening agent erucamide (Jiangxi Zhi combined plastication science and technology Co., Ltd.), and 5 parts of nucleating agent talcum powder (Kay chemical industry), plasticizing, reacting and extruding.
The extruder has a total of 11 sections from the feed port to the die, numbered 1-11, wherein section 1 serves only as a feed and is not heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 140 ℃,140 ℃,150 ℃,150 ℃,150 ℃,150 ℃ and 150 ℃, and the screw speed is set at 200 rpm. Feeding PHA mixture to the 1 st section of the double-screw extruder by using a weightless feeder of the extruder, wherein the feeding speed is as follows: 6 kg/hr. After the operation is stable, the pressure of the twin-screw extrusion is 20-30 bar, and the torque is about 46%. The extruder is provided with two circular outlets with the diameter of 4mm on a neck ring mold, a sample strip is extruded from the neck ring mold, passes through a water bath cooling tank, is cut into cylindrical particles with the length of about 5mm by a granulator, and is collected and packaged for later use after being vacuumized for 4 hours in a vacuum drying box at the temperature of 70 ℃.
All of the PHA-PBAT blend pellets, including examples 1-3 and comparative examples 1-4, were blown on a HAAKETM Rheomex OS single screw extruder, manufactured by Thermo Fisher Scientific Inc., USA, having a screw diameter of 19mm and a length to diameter ratio of 25, equipped with a 3:1 standard metering screw, from HAAKETM PolyLabTMOS torque rheometer platform control. The extruder is provided with four heating sections, the number of the heating sections is 1-4 from a feed inlet to an outlet, a film blowing die with the heating function and a die diameter of 19.5mm and a die gap of 0.5mm is configured, the rotating speed of a screw is set to be 50rpm, and the temperature of each section is respectively set as: cooling at 50 deg.C, 135 deg.C, 145 deg.C and 145 deg.C, shaping, drafting, and rolling to obtain film with thickness of about 15 μm.
[ example 7 ]
The above films of all 9 kinds of particles were subjected to the tensile property test of film strips parallel to the stretching direction (MD) in accordance with the procedure described above, and the results are shown in FIGS. 2 and 3.
As can be seen in FIG. 2, the elongation at break of the film sample strip is 416% compared to comparative example 4 containing no modification, and comparative examples 1 to 3, which were continuously reaction-extruded only by reaction extrusion, showed a decrease in elongation at break of the corresponding film sample strip of about 330%. After the PHA is subjected to chain extension by adding ethylene glycol and a catalyst, the elongation at break of the film sample strips corresponding to the film samples in examples 1-3 is obviously increased on the whole and is about 540%. Therefore, the mechanical extensibility of the PHA film is obviously improved after the extrusion chain extension through the polyol reaction. Compared with the film sample strips corresponding to comparative examples 5-6 containing example 1, the mechanical elongation of the PHA film is reduced from 416% to 337% after the modification with 0.1% of the mono-alcohol (comparative example 5), and the elongation is further reduced after the addition of 1% of the mono-alcohol (comparative example 6), which shows that the introduction of the mono-alcohol reduces the elongation of the film sample strips, and the chain scission caused by the ester exchange reaction occurs after the addition of the mono-alcohol, thereby reducing the elongation of the film. In the rupture strength of fig. 3, compared with comparative examples 1-3, the rupture strength of the film containing the dihydric alcohol and the catalyst in examples 2 and 3 is obviously improved, and is also superior to the film containing comparative example 4 without any modification, which shows that after the continuous reaction extrusion chain extension of the polyhydric alcohol, the rupture strength of the modified high-performance PHA-PBAT film is obviously improved, and simultaneously, the mechanical property of the PHA-PBAT film can be effectively improved by utilizing the continuous reaction extrusion.
Claims (17)
1. A high-performance polyhydroxyalkanoate comprises a polyhydroxyalkanoate chain segment and a copolyester chain segment of a first chain extender, wherein the first chain extender is selected from polyols.
2. The high-performance polyhydroxyalkanoate according to claim 1,
the first chain extender is selected from aliphatic polyols; and/or the presence of a gas in the atmosphere,
the polyhydroxyalkanoate has a structure shown in a formula (I):
wherein R is an alkyl group with a carbon chain length of 1-15.
3. The high-performance polyhydroxyalkanoate according to claim 2,
the first chain extender is selected from aliphatic diol with 2-10 carbon atoms; and/or the presence of a gas in the gas,
the polyhydroxyalkanoate is selected from homopolymers or copolymers of hydroxy fatty acid with 4-18 carbon atoms; and/or the presence of a gas in the gas,
the weight average molecular weight M of the polyhydroxyalkanoatew50000g/mol or more, preferably Mw100000g/mol or more.
4. The high-performance polyhydroxyalkanoate according to claim 3,
the first chain extender is at least one selected from ethylene glycol, propylene glycol, butanediol and pentanediol; and/or the presence of a gas in the gas,
the polyhydroxyalkanoate is selected from at least one of poly (3-hydroxybutyrate), poly (3-hydroxybutyrate-co-4-hydroxybutyrate), poly (3-hydroxybutyrate-co-3-hydroxyvalerate) and poly (3-hydroxybutyrate-co-3-hydroxyhexanoate).
5. The high-performance polyhydroxyalkanoate according to claim 1, wherein the first chain extender is used in an amount of 0.05 to 10 parts by mass, preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the polyhydroxyalkanoate.
6. A method for preparing the high-performance polyhydroxyalkanoate according to any one of claims 1 to 5, comprising the step of reacting components including the polyhydroxyalkanoate and a first chain extender to obtain the high-performance polyhydroxyalkanoate.
7. The preparation method according to claim 6, wherein the preparation method specifically comprises the following steps:
step 1, premixing a first chain extender and a catalyst;
and 2, blending the obtained mixed solution and 100 parts of polyhydroxyalkanoate, adding the blended solution and the polyhydroxyalkanoate into a first double-screw extruder, or adding the mixed solution and the polyhydroxyalkanoate into the extruder through an injection pump in a second section separately, mixing, melting, reacting, grafting and extruding, cooling and granulating.
8. The production method according to claim 7,
the amount of the first chain extender is 0.05-10 parts and the amount of the catalyst is 0.001-1 part based on 100 parts by mass of the polyhydroxyalkanoate; and/or the presence of a gas in the atmosphere,
the extrusion temperature is 100-250 ℃; and/or the presence of a gas in the gas,
the melt reaction extrusion is carried out in a double-screw extruder; and/or the presence of a gas in the gas,
the catalyst is selected from metal salts or oxides of IVB group and IVA group, preferably at least one of titanate catalyst and metal alkoxide.
9. The method according to claim 8,
the amount of the first chain extender is 0.1-5 parts and the amount of the catalyst is 0.001-0.2 part based on 100 parts by mass of the polyhydroxyalkanoate; and/or the presence of a gas in the gas,
the extrusion temperature is 100-180 ℃; and/or the presence of a gas in the atmosphere,
the screw rotating speed of the double-screw extruder is 5-1200 rpm, preferably 20-250 rpm; and/or the presence of a gas in the gas,
the catalyst is at least one selected from the group consisting of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetrabutyl zirconate, titanium glycol, antimony glycol and dibutyltin dioctoate, and preferably at least one selected from the group consisting of tetrabutyl titanate, titanium glycol and antimony glycol.
10. A high-performance polyhydroxyalkanoate film comprising the high-performance polyhydroxyalkanoate of any one of claims 1 to 5 or the high-performance polyhydroxyalkanoate prepared by the preparation method of any one of claims 6 to 9.
11. The film of claim 10, further comprising at least one of a complexing polymer, a nucleating agent, a second chain extender, and an opening agent.
12. The film of claim 11,
the total amount of the high-performance polyhydroxyalkanoate and the compound polymer is 100 parts by mass, the amount of the compound polymer is 0-99 parts, the amount of the nucleating agent is 0.02-30 parts, the amount of the second chain extender is 0.01-6 parts, and the amount of the opening agent is 0.02-10 parts;
preferably, the using amount of the compound polymer is 50-99 parts, the using amount of the nucleating agent is 1-20 parts, the using amount of the second chain extender is 0.05-2 parts, and the using amount of the opening agent is 0.05-5 parts.
13. The film of claim 11,
the compound polymer is selected from biodegradable polyester compounds; and/or the presence of a gas in the gas,
the nucleating agent is selected from inorganic nucleating agents; and/or the presence of a gas in the gas,
the second chain extender is selected from at least one of polycarbodiimide, epoxy ethylene glycol, toluene diisocyanate and antimony trioxide; and/or the presence of a gas in the gas,
the opening agent is selected from fatty acid amide compounds.
14. The film of claim 13,
the compound polymer is selected from at least one of polylactic acid, poly (butylene adipate/terephthalate), poly (butylene succinate/terephthalate) and poly (butylene succinate/adipate); and/or the presence of a gas in the atmosphere,
the nucleating agent is selected from at least one of nano-crystalline cellulose, talcum powder, silicon dioxide and flaky calcium carbonate; and/or the presence of a gas in the gas,
the opening agent is selected from at least one of oleamide, erucamide and stearic acid amide.
15. A preparation method of the high-performance polyhydroxyalkanoate film of any one of claims 10 to 14, comprising the step of mixing the components including the high-performance polyhydroxyalkanoate, the compound polymer, the nucleating agent, the second chain extender and the opening agent to obtain the high-performance polyhydroxyalkanoate film.
16. The method according to claim 15, wherein the method comprises the steps of:
mixing the high-performance polyhydroxyalkanoate and a compound polymer, adding a nucleating agent, a second chain extender and an opening agent, and mixing, melting and reacting in a double-screw extruder; adding the obtained reaction product compound into a single-screw extruder for melting, extruding and film blowing, and cooling to obtain the high-performance polyhydroxyalkanoate film.
17. The method of claim 16,
the extrusion temperature of the double-screw extruder is 50-300 ℃, and preferably 100-200 ℃; and/or the presence of a gas in the gas,
the screw rotating speed of the double-screw extruder is 5-1200 rpm, preferably 50-300 rpm, and more preferably 100-220 rpm; and/or the presence of a gas in the gas,
the extrusion temperature of the single-screw extruder is 50-300 ℃, and preferably 50-200 ℃; and/or the presence of a gas in the gas,
the screw rotating speed of the single-screw extruder is 5-150 rpm, preferably 10-100 rpm.
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| CN116836531A (en) * | 2023-09-04 | 2023-10-03 | 北京蓝晶微生物科技有限公司 | Polyol-containing polyhydroxyalkanoate composition with high fluidity, molded body and preparation method thereof |
| WO2024183156A1 (en) | 2023-03-09 | 2024-09-12 | 上海蓝晶微生物科技有限公司 | Granulation processing method for low-melt-index degradable material, and shaped body prepared thereby |
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