CN113429759A - PBAT composite modified biodegradable material and preparation method thereof - Google Patents
PBAT composite modified biodegradable material and preparation method thereof Download PDFInfo
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- CN113429759A CN113429759A CN202110788780.0A CN202110788780A CN113429759A CN 113429759 A CN113429759 A CN 113429759A CN 202110788780 A CN202110788780 A CN 202110788780A CN 113429759 A CN113429759 A CN 113429759A
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- biodegradable material
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- 239000000463 material Substances 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 229920001896 polybutyrate Polymers 0.000 title claims abstract 18
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000010902 straw Substances 0.000 claims abstract description 56
- 241000209140 Triticum Species 0.000 claims abstract description 46
- 235000021307 Triticum Nutrition 0.000 claims abstract description 46
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000004970 Chain extender Substances 0.000 claims abstract description 9
- 239000004014 plasticizer Substances 0.000 claims abstract description 9
- 239000000314 lubricant Substances 0.000 claims abstract description 8
- 239000000945 filler Substances 0.000 claims abstract description 6
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 8
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 8
- -1 butyl p-diphenol Chemical compound 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 7
- WWXUGNUFCNYMFK-UHFFFAOYSA-N Acetyl citrate Chemical compound CC(=O)OC(=O)CC(O)(C(O)=O)CC(O)=O WWXUGNUFCNYMFK-UHFFFAOYSA-N 0.000 claims description 5
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 5
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- 235000012424 soybean oil Nutrition 0.000 claims description 5
- 239000003549 soybean oil Substances 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- 239000008117 stearic acid Substances 0.000 claims description 5
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 claims description 4
- PTPIRFSXRFIROJ-UHFFFAOYSA-N 2-(3-hydroxyphenoxy)ethane-1,1-diol Chemical compound OC(O)COC1=CC=CC(O)=C1 PTPIRFSXRFIROJ-UHFFFAOYSA-N 0.000 claims description 4
- CTNICFBTUIFPOE-UHFFFAOYSA-N 2-(4-hydroxyphenoxy)ethane-1,1-diol Chemical compound OC(O)COC1=CC=C(O)C=C1 CTNICFBTUIFPOE-UHFFFAOYSA-N 0.000 claims description 4
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 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 4
- 239000012188 paraffin wax Substances 0.000 claims description 4
- SXXILWLQSQDLDL-UHFFFAOYSA-N bis(8-methylnonyl) phenyl phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OC1=CC=CC=C1 SXXILWLQSQDLDL-UHFFFAOYSA-N 0.000 claims description 3
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 claims description 2
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 claims description 2
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 claims description 2
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 claims description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 125000005456 glyceride group Chemical group 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- 235000019198 oils Nutrition 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
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 2
- 229920000223 polyglycerol Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003063 flame retardant Substances 0.000 abstract description 4
- 239000000843 powder Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229920000704 biodegradable plastic Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229920006238 degradable plastic Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- 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
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/16—Inorganic impregnating agents
- B27K3/20—Compounds of alkali metals or ammonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
- B27K3/36—Aliphatic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
- B27K5/06—Softening or hardening of wood
-
- 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
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K2200/00—Wooden materials to be treated
- B27K2200/15—Pretreated particles or fibres
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Biological Depolymerization Polymers (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention belongs to the technical field of biodegradable materials, and particularly relates to a PBAT composite modified biodegradable material and a preparation method thereof. The PBAT composite modified biodegradable material comprises the following components in parts by weight: PBAT 50-70 parts, wheat straw 20-30 parts, PLA 4-10 parts, filler 2-6 parts, plasticizer 0.2-0.6 part, lubricant 2-8 parts, chain extender 0.1-0.5 part, and heat stabilizer 0.2-2.0 parts. The PBAT composite modified biodegradable material provided by the invention has the advantages of good extensibility and elongation at break, strong flame retardant property, low cost and contribution to market popularization; the invention also provides a preparation method of the composition.
Description
Technical Field
The invention belongs to the technical field of biodegradable materials, and particularly relates to a PBAT composite modified biodegradable material and a preparation method thereof.
Background
PBAT (a copolymer of butylene adipate and butylene terephthalate), which belongs to thermoplastic biodegradable plastics, has the characteristics of PBA and PBT, and has better ductility, elongation at break, heat resistance and impact performance; in addition, the biodegradable plastic has excellent biodegradability, and is one of the best degradable materials for active research and market application of biodegradable plastics. But the product is single, the price is high, the cost of the degradable plastic product is high, the cost of the raw material of one plastic bag is nearly one yuan, the number of accepted people is small, the modified PBAT products in the market are uneven and have different quality, and the market popularization of the degradable plastic is not facilitated.
CN201910485627.3 discloses a straw powder/PLA/PBAT biomass full-degradable plastic and a preparation method thereof, comprising 15-30 parts of straw powder, 35-50 parts of PLA, 35-50 parts of PBAT, 2-4 parts of plasticizer, 1-3 parts of coupling agent, 1-3 parts of chain extender, 1-3 parts of lubricant, 1-3 parts of heat stabilizer and 0.1-0.3 part of antioxidant, the straw powder is subjected to alkaline hydrolysis, sulfuric acid swelling and ultrasonic wall breaking treatment, then the double-screw extrusion granulation preparation method by mixing with other additives reduces the cost and obtains better performance, but the straw powder treatment method is complex and has more process steps, other auxiliary agents are single, the formula is single, the applicability is not wide, meanwhile, the proportion of PLA is large, the proportion of PLA is the same as that of PBAT, the proportion of straw powder is small, the PLA price is high, and the cost is still high.
CN201611193435.8 discloses a preparation method of lignin-modified full-bio-based PBAT biodegradable plastic, which comprises the following raw materials of 60-80 parts of bio-based PBAT, 20-40 parts of lignin, 0.1-0.3 part of antioxidant, 0.5-1.5 parts of chain extender, 0.1-0.3 part of plasticizer, 0.2-0.4 part of heat stabilizer and 0.4-0.6 part of lubricant; the lignin-modified PBAT biodegradable plastic is obtained by mixing, extruding, granulating and film blowing, the mechanical property of the bio-based PBAT resin is enhanced, the cost of the plastic is reduced, but the elongation at break and the extensibility of the lignin-modified PBAT are still poor.
CN201510380483.7 discloses a method for preparing a PLA/PBAT/PPC composite modified material by reactive extrusion, which comprises the following steps of preparing raw materials of PLA5-35 parts, PBAT30-55 parts, PPC5-15 parts, plasticizer 0.5-2 parts, initiator 0.01-0.08 part, auxiliary reactant 0.01-0.05 part, grafting monomer 1-3 parts and anti-aging auxiliary agent 0.5-1.5 parts, and granulating by a double-screw extruder after mixing in subareas, thus the preparation cost is low, the degradation performance is good, and the mechanical property is excellent.
Disclosure of Invention
The invention aims to solve the technical problem of providing a PBAT composite modified biodegradable material which has better extensibility and elongation at break, strong flame retardant property, low cost and contribution to market popularization; the invention also provides a preparation method of the composition.
The PBAT composite modified biodegradable material comprises the following components in parts by weight:
the filler is one or more of starch, calcium carbonate, pottery clay, silicate and talcum powder.
The plasticizer is one or more of glycerol, polyglycerol, PEG-400, PEG-600, PEG-800, epoxidized soybean oil, citrate, acetyl citrate, triacetyl glyceride, and dioctyl adipate.
The lubricant is one or more of stearic acid, stearate, polyvinyl chloride wax, white oil, paraffin, oleamide and erucamide.
The chain extender is one or more of isocyanate, hydroquinone dihydroxyethyl ether, resorcinol dihydroxyethyl ether, bisphenol A, ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol and monoethylene glycol.
The anti-stabilizer is one or more of butyl hydroxy anisole, dibutyl hydroxy toluene, butyl p-diphenol, phenyl diisodecyl phosphite, pentaerythritol diphosphite and tri (2, 4-di-tert-butylphenyl) phosphite.
The preparation method of the PBAT composite modified biodegradable material comprises the following steps:
(1) drying PBAT, PLA and wheat straw at 70-100 deg.C for 8-16 hr;
(2) pretreatment of wheat straws: crushing the dried wheat straws, and softening;
(3) adding the pretreated wheat straw, PBAT, PLA, a filler, a plasticizer, a lubricant, a chain extender and a heat stabilizer into a high-speed mixer according to the formula amount, and stirring to obtain a mixture;
(4) and adding the mixture into a double-screw extruder, and melting, extruding and granulating to obtain the PBAT composite modified biodegradable material.
The wheat straw pretreatment steps are as follows: firstly, crushing the wheat straws to be less than 3mm, then mixing the wheat straws, ammonium sulfate and glycerol according to the mass ratio of 8:1:1, stirring and softening, wherein the softening temperature is 90-100 ℃, and the softening time is 10-20 min.
In the step (3), the rotating speed of the high-speed mixer is 600-1000 r/min, the mixing time is 5-10 min, and the mixing temperature is 60-90 ℃.
The temperature of the twin-screw extruder in the step (4) is respectively as follows: the temperature of the first zone is 120-150 ℃, the temperature of the second zone is 140-170 ℃, the temperature of the third zone is 160-180 ℃, the temperature of the fourth zone is 160-180 ℃, the temperature of the fifth zone is 170-185 ℃, and the temperature of the sixth zone is 175-185 ℃.
Specifically, the preparation method of the PBAT composite modified biodegradable material comprises the following steps:
(1) drying PBAT, PLA and wheat straw at 70-100 deg.C for 8-16 hr;
(2) pretreatment of wheat straws: firstly, crushing wheat straws to be less than 3mm, then mixing the wheat straws, ammonium sulfate and glycerol according to the mass ratio of 8:1:1, stirring and softening, wherein the softening temperature is 90-100 ℃, and the softening time is 10-20 min;
(3) adding 20-30 parts of pretreated wheat straw, 50-70 parts of PBAT, 4-10 parts of PLA, 2-6 parts of filler, 0.2-0.6 part of plasticizer, 2-8 parts of lubricant, 0.1-0.5 part of chain extender and 0.2-2.0 parts of heat stabilizer into a high-speed mixer for stirring, wherein the rotating speed of the high-speed mixer is 600-1000 r/min, the mixing time is 5-10 min, and the mixing temperature is 60-90 ℃ to obtain a mixture;
(4) adding the mixture into a double-screw extruder, wherein the temperature of the double-screw extruder is respectively as follows: and melting, extruding and granulating the PBAT composite modified biodegradable material at the temperature of 120-150 ℃ in the first area, 140-170 ℃ in the second area, 160-180 ℃ in the third area, 160-180 ℃ in the fourth area, 170-185 ℃ in the fifth area and 175-185 ℃ in the sixth area to obtain the PBAT composite modified biodegradable material.
The preparation method of the PBAT composite modified biodegradable material achieves uniform dispersion in a system by softening wheat straws, ensures the environmental protection and degradability of the product by using less additive than other products, and adopts different additives to better fuse the wheat straws and the PBAT in different proportions.
Compared with the prior art, the invention has the following beneficial effects:
(1) the PBAT composite modified biodegradable material has high breaking strength, good ductility and elongation at break, good heat resistance and impact resistance and good flame retardant property;
(2) in the PBAT composite modified biodegradable material, the wheat straw acquisition cost is low, the production cost of the degradable plastic product is reduced, and the market popularization is facilitated;
(3) in the preparation method of the PBAT composite modified biodegradable material, various raw materials are uniformly dispersed, completely melted and stably produced.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
The PBAT composite modified biodegradable material is prepared from the following components in parts by weight in the following table 1:
table 1 raw material component recipe
The preparation method of the PBAT composite modified biodegradable material comprises the following steps:
(1) drying PBAT, PLA and wheat straw for 8 hours at 80 ℃;
(2) pretreatment of wheat straws: firstly, crushing wheat straws to be less than 3mm, then mixing the wheat straws, ammonium sulfate and glycerol according to the mass ratio of 8:1:1, stirring and softening, wherein the softening temperature is 90 ℃, and the softening time is 20 min;
(3) adding the pretreated wheat straw, PBAT, PLA, starch, acetyl citrate, erucamide, isocyanate and tris (2, 4-di-tert-butylphenyl) phosphite into a high-speed mixer according to the formula amount shown in Table 1, and stirring, wherein the rotating speed of the high-speed mixer is 1000r/min, the mixing time is 10min, and the mixing temperature is 70 ℃, so as to obtain a mixture;
(4) adding the mixture into a double-screw extruder, wherein the temperature of the double-screw extruder is respectively as follows: melting, extruding and granulating the PBAT composite modified biodegradable material at the temperature of 120 ℃ in the first area, 140 ℃ in the second area, 160 ℃ in the third area, 175 ℃ in the fourth area, 180 ℃ in the fifth area and 185 ℃ in the sixth area.
Example 2
The PBAT composite modified biodegradable material is prepared from the following components in parts by weight in the following table 2:
table 2 raw material component recipe
| Species of | Parts by weight/parts |
| PBAT | 55 |
| PLA | 10 |
| Wheat straw | 25 |
| Calcium carbonate | 4.5 |
| PEG-400 | 0.3 |
| Paraffin wax | 4 |
| Resorcinol dihydroxyethyl ether | 0.2 |
| Pentaerythritol diphosphite | 1.0 |
The preparation method of the PBAT composite modified biodegradable material comprises the following steps:
(1) drying PBAT, PLA and wheat straw for 10 hours at 90 ℃;
(2) pretreatment of wheat straws: firstly, crushing wheat straws to be less than 3mm, then mixing the wheat straws, ammonium sulfate and glycerol according to the mass ratio of 8:1:1, stirring and softening, wherein the softening temperature is 95 ℃, and the softening time is 15 min;
(3) adding the pretreated wheat straws, PBAT, PLA, calcium carbonate, PEG-400, paraffin, resorcinol dihydroxyethyl ether and pentaerythritol diphosphite into a high-speed mixer according to the formula amount shown in Table 2, and stirring, wherein the rotating speed of the high-speed mixer is 800r/min, the mixing time is 10min, and the mixing temperature is 80 ℃, so as to obtain a mixture;
(4) adding the mixture into a double-screw extruder, wherein the temperature of the double-screw extruder is respectively as follows: melting, extruding and granulating the PBAT composite modified biodegradable material at the temperature of 120 ℃ in the first area, 140 ℃ in the second area, 160 ℃ in the third area, 175 ℃ in the fourth area, 180 ℃ in the fifth area and 185 ℃ in the sixth area.
Example 3
The PBAT composite modified biodegradable material is prepared from the following components in parts by weight in the following table 3:
table 3 raw material composition formula
| Species of | Parts by weight/parts |
| PBAT | 60 |
| PLA | 8 |
| Wheat straw | 20 |
| Talcum powder | 6.0 |
| Epoxidized soybean oil | 0.5 |
| Stearic acid | 3 |
| Hydroquinone bis hydroxyethyl ether | 0.3 |
| Phosphorous acid diisodecyl benzene ester | 1.7 |
The preparation method of the PBAT composite modified biodegradable material comprises the following steps:
(1) drying PBAT, PLA and wheat straw at 80 ℃ for 12 hours;
(2) pretreatment of wheat straws: firstly, crushing wheat straws to be less than 3mm, then mixing the wheat straws, ammonium sulfate and glycerol according to the mass ratio of 8:1:1, stirring and softening, wherein the softening temperature is 95 ℃, and the softening time is 20 min;
(3) adding the pretreated wheat straws, PBAT, PLA, talcum powder, epoxidized soybean oil, stearic acid, hydroquinone dihydroxyethyl ether and phenyl diisodecyl phosphite into a high-speed mixer according to the formula amount shown in the table 3, and stirring, wherein the rotating speed of the high-speed mixer is 900r/min, the mixing time is 8min, and the mixing temperature is 70 ℃, so as to obtain a mixture;
(4) adding the mixture into a double-screw extruder, wherein the temperature of the double-screw extruder is respectively as follows: melting, extruding and granulating the PBAT composite modified biodegradable material at the temperature of 120 ℃ in the first area, 140 ℃ in the second area, 160 ℃ in the third area, 175 ℃ in the fourth area, 180 ℃ in the fifth area and 185 ℃ in the sixth area.
Comparative example 1
The detection of relevant parameters is performed only on PBAT feedstock.
Comparative example 2
The degradable material is prepared according to the formula proportion disclosed in example 1 of CN 201910485627.3.
A preparation method of straw powder/PLA/PBAT biodegradable material comprises the following steps:
(1) pretreatment of straw powder: firstly, mixing straw powder, ammonium sulfate and glycerol according to a mass ratio of 8:1:1, stirring and softening, wherein the softening temperature is 90 ℃, and the softening time is 20 min;
(2) adding 40 parts of treated straw powder, 50 parts of PBAT, 50 parts of PLA, 3 parts of silane coupling agent KH560, 3 parts of BASF chain extender ADR, 3 parts of stearic acid, 4 parts of acetyl tributyl citrate ATBC, 0.3 part of BASF antioxidant 1010 and 3 parts of epoxidized soybean oil into a high-speed mixer, stirring at the rotating speed of 1000r/min for 10min and at the mixing temperature of 70 ℃ to obtain a mixture;
(3) adding the mixture into a double-screw extruder, wherein the temperature of the double-screw extruder is respectively as follows: melting, extruding and granulating the straw powder/PLA/PBAT biodegradable material in a first area at 120 ℃, a second area at 140 ℃, a third area at 160 ℃, a fourth area at 175 ℃, a fifth area at 180 ℃ and a sixth area at 185 ℃.
Comparative example 3
A composite modified biodegradable material comprises the following components in parts by weight in Table 4:
table 4 raw material component recipe
| Species of | Parts by weight/parts |
| PBAT | 30 |
| PLA | 10 |
| Wheat straw | 50 |
| Starch | 4 |
| Acetyl citrate esters | 0.4 |
| Erucamide | 4 |
| Isocyanates | 0.3 |
| Phosphorous acid tris (2, 4-di-tert-butylphenyl) ester | 1.3 |
A preparation method of a composite modified biodegradable material comprises the following steps:
(1) drying PBAT, PLA and wheat straw for 8 hours at 80 ℃;
(2) pretreatment of wheat straws: firstly, crushing wheat straws to be less than 3mm, then mixing the wheat straws, ammonium sulfate and glycerol according to the mass ratio of 8:1:1, stirring and softening, wherein the softening temperature is 90 ℃, and the softening time is 20 min;
(3) adding the pretreated wheat straw, PBAT, PLA, starch, acetyl citrate, erucamide, isocyanate and tris (2, 4-di-tert-butylphenyl) phosphite into a high-speed mixer according to the formula amount shown in Table 1, and stirring, wherein the rotating speed of the high-speed mixer is 1000r/min, the mixing time is 10min, and the mixing temperature is 70 ℃, so as to obtain a mixture;
(4) adding the mixture into a double-screw extruder, wherein the temperature of the double-screw extruder is respectively as follows: melting, extruding and granulating the PBAT composite modified biodegradable material at the temperature of 120 ℃ in the first area, 140 ℃ in the second area, 160 ℃ in the third area, 175 ℃ in the fourth area, 180 ℃ in the fifth area and 185 ℃ in the sixth area.
The degraded materials prepared in examples 1-3 and comparative examples 1-3 were tested for melt Mass Flow Rate (MFR) g/10min according to method A in GB/T3682-2000 under test conditions D (temperature: 190 ℃ C., load: 2.16 KG); the method is characterized in that the tensile strength at break MPa and the tensile strain at break are detected according to 4.10 in GB/T32366-2015, the flame retardance is shown according to the oxygen index detected by GB/T2406.2-2009, the high oxygen index indicates that the material is not easy to burn, the low oxygen index indicates that the material is easy to burn, the oxygen index is less than 22 and belongs to a combustible material, the oxygen index is between 22 and 27 and belongs to a flame-retardant material, and the oxygen index is more than 27. The results are shown in table 4:
TABLE 4 test results
Of course, the foregoing is only a preferred embodiment of the invention and should not be taken as limiting the scope of the embodiments of the invention. The present invention is not limited to the above examples, and equivalent changes and modifications made by those skilled in the art within the spirit and scope of the present invention should be construed as being included in the scope of the present invention.
Claims (10)
1. A PBAT composite modified biodegradable material is characterized in that: the paint comprises the following components in parts by weight:
2. the PBAT composite modified biodegradable material of claim 1, characterized in that: the filler is one or more of starch, calcium carbonate, pottery clay, silicate and talcum powder.
3. The PBAT composite modified biodegradable material of claim 1, characterized in that: the plasticizer is one or more of glycerol, polyglycerol, PEG-400, PEG-600, PEG-800, epoxidized soybean oil, citrate, acetyl citrate, triacetyl glyceride, and dioctyl adipate.
4. The PBAT composite modified biodegradable material of claim 1, characterized in that: the lubricant is one or more of stearic acid, stearate, polyvinyl chloride wax, white oil, paraffin, oleamide and erucamide.
5. The PBAT composite modified biodegradable material of claim 1, characterized in that: the chain extender is one or more of isocyanate, hydroquinone dihydroxyethyl ether, resorcinol dihydroxyethyl ether, bisphenol A, ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol and monoethylene glycol.
6. The PBAT composite modified biodegradable material of claim 1, characterized in that: the anti-stabilizer is one or more of butyl hydroxy anisole, dibutyl hydroxy toluene, butyl p-diphenol, phenyl diisodecyl phosphite, pentaerythritol diphosphite and tri (2, 4-di-tert-butylphenyl) phosphite.
7. A method for preparing the PBAT composite modified biodegradable material of any one of claims 1-6, which is characterized in that: the method comprises the following steps:
(1) drying PBAT, PLA and wheat straw at 70-100 deg.C for 8-16 hr;
(2) pretreatment of wheat straws: crushing the dried wheat straws, and softening;
(3) adding the pretreated wheat straw, PBAT, PLA, a filler, a plasticizer, a lubricant, a chain extender and a heat stabilizer into a high-speed mixer according to the formula amount, and stirring to obtain a mixture;
(4) and adding the mixture into a double-screw extruder, and melting, extruding and granulating to obtain the PBAT composite modified biodegradable material.
8. The method for preparing the PBAT composite modified biodegradable material according to claim 7, characterized in that: the wheat straw pretreatment steps are as follows: firstly, crushing the wheat straws to be less than 3mm, then mixing the wheat straws, ammonium sulfate and glycerol according to the mass ratio of 8:1:1, stirring and softening, wherein the softening temperature is 90-100 ℃, and the softening time is 10-20 min.
9. The method for preparing the PBAT composite modified biodegradable material according to claim 7, characterized in that: in the step (3), the rotating speed of the high-speed mixer is 600-1000 r/min, the mixing time is 5-10 min, and the mixing temperature is 60-90 ℃.
10. The method for preparing the PBAT composite modified biodegradable material according to claim 7, characterized in that: the temperature of the twin-screw extruder in the step (4) is respectively as follows: the temperature of the first zone is 120-150 ℃, the temperature of the second zone is 140-170 ℃, the temperature of the third zone is 160-180 ℃, the temperature of the fourth zone is 160-180 ℃, the temperature of the fifth zone is 170-185 ℃, and the temperature of the sixth zone is 175-185 ℃.
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