CN111286168A - Biodegradable polyester/cellulose composite blown film material and preparation method thereof - Google Patents
Biodegradable polyester/cellulose composite blown film material and preparation method thereof Download PDFInfo
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- CN111286168A CN111286168A CN202010301512.7A CN202010301512A CN111286168A CN 111286168 A CN111286168 A CN 111286168A CN 202010301512 A CN202010301512 A CN 202010301512A CN 111286168 A CN111286168 A CN 111286168A
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- 239000001913 cellulose Substances 0.000 title claims abstract description 61
- 229920002678 cellulose Polymers 0.000 title claims abstract description 61
- 239000000463 material Substances 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 229920000229 biodegradable polyester Polymers 0.000 title claims abstract description 37
- 239000004622 biodegradable polyester Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 229920002472 Starch Polymers 0.000 claims abstract description 32
- 239000008107 starch Substances 0.000 claims abstract description 32
- 235000019698 starch Nutrition 0.000 claims abstract description 32
- 239000003381 stabilizer Substances 0.000 claims abstract description 25
- 229920000379 polypropylene carbonate Polymers 0.000 claims abstract description 23
- 239000004626 polylactic acid Substances 0.000 claims abstract description 21
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims abstract description 16
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000004970 Chain extender Substances 0.000 claims abstract description 11
- 229920005862 polyol Polymers 0.000 claims abstract description 11
- 150000003077 polyols Chemical class 0.000 claims abstract description 11
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 27
- 229920001577 copolymer Polymers 0.000 claims description 24
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 18
- -1 polybutylene adipate Polymers 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 10
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 10
- 235000013539 calcium stearate Nutrition 0.000 claims description 10
- 239000008116 calcium stearate Substances 0.000 claims description 10
- 229940098697 zinc laurate Drugs 0.000 claims description 10
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 claims description 10
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 9
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical group OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 claims description 6
- 229960001173 oxybenzone Drugs 0.000 claims description 6
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 4
- LBSJFUFSEQQYFC-UHFFFAOYSA-N 8,8-diphenyloctyl dihydrogen phosphite Chemical compound C=1C=CC=CC=1C(CCCCCCCOP(O)O)C1=CC=CC=C1 LBSJFUFSEQQYFC-UHFFFAOYSA-N 0.000 claims description 2
- DTCPBBPYYOBKGN-UHFFFAOYSA-N N,N-dihydroxy-2,3-di(propan-2-yl)aniline Chemical compound ON(C1=C(C(=CC=C1)C(C)C)C(C)C)O DTCPBBPYYOBKGN-UHFFFAOYSA-N 0.000 claims description 2
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 238000006065 biodegradation reaction Methods 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000004631 polybutylene succinate Substances 0.000 description 2
- 229920002961 polybutylene succinate Polymers 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- JQYSLXZRCMVWSR-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione;terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.O=C1CCCCC(=O)OCCCCO1 JQYSLXZRCMVWSR-UHFFFAOYSA-N 0.000 description 1
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 1
- 229920008262 Thermoplastic starch Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PFNROQCAJVOSIR-UHFFFAOYSA-N oxiran-2-ylmethyl 2-methylprop-2-enoate;5-phenylpenta-2,4-dienenitrile Chemical group CC(=C)C(=O)OCC1CO1.N#CC=CC=CC1=CC=CC=C1 PFNROQCAJVOSIR-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004629 polybutylene adipate terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004628 starch-based polymer Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- 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
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
-
- 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
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
-
- 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
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
-
- 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
-
- 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
- C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the field of composite materials, and provides a biodegradable polyester/cellulose composite blown film material and a preparation method thereof aiming at the problems of poor starch plasticizing effect, low material comprehensive performance and the like, wherein the technical scheme is as follows: the material comprises the following raw materials in parts by weight: 35-50 parts of poly (butylene adipate/terephthalate), 10-15 parts of poly (propylene carbonate) polyol PPC, 0.01-0.03 part of chain extender, 8-15 parts of polylactic acid (PLA), 25-35 parts of starch, 20-25 parts of cellulose, 2-5 parts of compatilizer, 1-3 parts of stabilizer and 1-3 parts of anti-aging agent. The material has the advantages of simple formula, good compatibility and good mechanical property, improves the plasticity and strength of the composite material, has excellent degradation performance and does not pollute the environment.
Description
Technical Field
The invention relates to the field of composite materials, in particular to a biodegradable polyester/cellulose composite blown film material and a preparation method thereof.
Background
The biodegradable polyester is a high molecular material taking biological resources as raw materials, and can be degraded under the composting condition compared with petroleum-based polymers taking petrochemical resources as raw materials.
Generally, biodegradable composite materials such as biodegradable polyesters can be produced by mixing biodegradable polymers such as starch, Polycaprolactone (PLC), polybutylene succinate (PBS), polybutylene adipate terephthalate (PBAT), and the like, and a common process is to prepare a graft copolymer of starch and/or polyester, add the graft copolymer to a starch/polyester blending system, and compatibilize and modify the system by using the graft copolymer. In the prior art, the invention patent CN101805499B discloses a fully-degradable thermoplastic composite material prepared by using polylactic acid (PLA) and starch as base materials and using poly (butylene adipate terephthalate) (PBAT) and poly (propylene carbonate) (PCC), which saves a large amount of energy and reduces environmental pollution. Although the fully-degradable thermoplastic composite material prepared by the method can reduce the production cost, the modifier adopted in the preparation of the thermoplastic starch has higher molecular weight and poorer starch plasticizing effect, so that the method has room for improvement.
Disclosure of Invention
Aiming at the defects in the prior art, the first purpose of the invention is to provide a biodegradable polyester/cellulose composite blown film material.
In order to achieve the purpose, the invention provides the following technical scheme:
a biodegradable polyester/cellulose composite blown film material comprises the following raw materials in parts by weight: 35-50 parts of poly (butylene adipate/terephthalate), 10-15 parts of poly (propylene carbonate) polyol, 0.01-0.03 part of chain extender, 8-15 parts of polylactic acid, 25-35 parts of starch, 20-25 parts of cellulose, 2-5 parts of compatilizer, 1-3 parts of stabilizer and 1-3 parts of anti-aging agent.
The invention is further configured to: the material comprises the following raw materials in parts by weight: 45 parts of polybutylene adipate/terephthalate, 12 parts of polypropylene carbonate polyol, 0.03 part of a chain extender, 8 parts of polylactic acid, 30 parts of starch, 24 parts of cellulose, 4 parts of a compatilizer, 2 parts of a stabilizer and 1 part of an anti-aging agent.
The invention is further configured to: the compatilizer is maleic anhydride grafted vinyl acetate copolymer.
The invention is further configured to: the maleic anhydride grafted vinyl acetate copolymer is mainly prepared from the following raw materials in percentage by weight: 10-25% of maleic anhydride, 5-10% of ethylene glycol dimethacrylate and 30-40% of ethylene-vinyl acetate copolymer.
The invention is further configured to: the stabilizer is any two of calcium stearate, barium stearate, zinc laurate and diphenyl-octyl phosphite.
The invention is further configured to: the stabilizer is composed of calcium stearate and zinc laurate, and the calcium stearate and the zinc laurate are mixed according to the weight ratio of 1: 1.
The invention is further configured to: the anti-aging agent is benzophenone-3.
The invention is further configured to: the chain extender is any one of trimethylolpropane and N, N-dihydroxy (diisopropyl) aniline.
The inventor finds that when the maleic anhydride grafted vinyl acetate copolymer is added in the material processing process, the compatibility of PBAT, PPC, PLA, starch and cellulose can be improved, the dispersibility is improved, and under the condition that no plasticizer is added, the maleic anhydride grafted vinyl acetate copolymer can be used as a compatilizer to realize the complete compatibility of other components and perform the combined action with the rest components, so that the plasticizing effect can be exerted, the plasticity of the starch and the cellulose is increased, the strength of the composite material is not reduced, but the plasticity of the composite material and the strength of the composite material are improved.
Chain extenders are added in the processing process, so that molecular chains of PBAT, PPC and PLA can be unfolded, and the molecular weight is increased; the addition of the stabilizer enables the PPC and PLA easily thermally degradable biological polyester to be more stable in the screw, and the addition of the anti-aging agent enables the composite material to be stable in performance and not easy to age in the daily transportation and use processes.
Aiming at the defects in the prior art, the second purpose of the invention is to provide a preparation method of a biodegradable polyester/cellulose composite blown film material, which comprises the following steps:
s1, putting starch and cellulose into a high-speed mixer, stirring at the rotating speed of 300rpm/min for 5-10min to uniformly mix the starch and the cellulose to form a premix;
s2, sequentially adding the premix prepared in the step S1, a chain extender, a compatilizer, a stabilizer and an anti-aging agent into a high-speed mixer, then adding the poly (butylene adipate/terephthalate), the poly (propylene carbonate) polyol and the polylactic acid into the high-speed mixer, rotating at 1000rpm/min for 20-30min, and uniformly stirring the materials to obtain a mixture;
s3, adding the mixture prepared in the step S2 into a double-screw granulator, wherein the die head temperature of the double-screw granulator is 120-.
Tests prove that the biodegradable polyester/cellulose composite blown film material prepared by the invention can be completely decomposed into carbon dioxide and water in 3 months in a natural environment after being used and discarded, cannot cause pollution to the environment, and is a completely biodegradable composite blown film material.
The preparation method of the compatilizer comprises the following steps: vacuumizing a 3L three-necked bottle after vacuum drying, baking and introducing nitrogen, inserting a stirrer into the neck in the middle of the 3L three-necked bottle, repeatedly adding 1kg of ethylene-vinyl acetate copolymer, 2.8kg of maleic anhydride, 0.25kg of ethylene glycol dimethacrylate and 300mL of toluene into the 3L three-necked bottle under the protection of nitrogen for 3 times, heating to 65 ℃ under the protection of nitrogen, stirring for 30min to completely dissolve the raw materials, heating to 85 ℃, dropwise adding ice methanol into reaction liquid after 8h to generate orange flocculent precipitate, performing suction filtration, washing with acetone, and vacuum drying to obtain a crude maleic anhydride grafted vinyl acetate copolymer.
Placing the crude maleic anhydride grafted vinyl acetate copolymer in a vacuum drying oven at 70 ℃, drying for 24h, scraping an oxidation film on the outer surface of the crude maleic anhydride grafted vinyl acetate copolymer, then pouring the dried graft into a solvent toluene, heating and refluxing, adding acetone to generate flocculent precipitate, filtering out the precipitate, and drying to obtain the refined maleic anhydride grafted vinyl acetate copolymer.
In conclusion, the invention has the following beneficial effects:
1. the biodegradable polyester/cellulose composite blown film material prepared by the invention has the advantages of excellent product performance, simple preparation method, better degradation performance and high content of bio-based materials.
2. The biodegradable polyester/cellulose composite blown film material prepared by the invention has simple components, is not added with a plasticizer, and obviously improves the plasticity of starch and cellulose only by matching the compatilizer with other components, thereby not only not reducing the strength of the composite material, but also obviously improving the strength of the composite material, reducing the environmental pollution and reducing the production cost.
Detailed Description
The following examples further illustrate the present invention in detail.
Example 1 Effect of different compatibilizer component content on Properties of biodegradable polyester/cellulose composite blown film Material
A biodegradable polyester/cellulose composite blown film material is prepared from the following components: 35 parts of poly (butylene adipate/terephthalate), 10 parts of PPC (polypropylene carbonate), 0.01 part of chain extender, 8 parts of PLA (polylactic acid), 25 parts of starch, 20 parts of cellulose, 2 parts of compatilizer, 1 part of stabilizer and 1 part of anti-aging agent; wherein, the components and the weight percentage of the compatilizer are shown in the table 1.
TABLE 1 different constituents of the compatibilizers and their percentages by weight
The properties of the resulting materials were determined with reference to GB/T1040.3, QB/T2538, GB/T1038 and GB/T2679.3, and the results are shown in Table 2.
TABLE 2 Material Performance test results for different Components of the compatibilizer
| Item | 1 | 2 | 3 | 4 | 5 |
| Tensile strength (Mpa) | 16.1 | 16.4 | 17.2 | 17.0 | 16.5 |
| Elongation at Break (%) | 500 | 542 | 614 | 560 | 556 |
| Sealing strength/(N/15 mm) | 40 | 43.4 | 49.2 | 48.7 | 48.8 |
| Oxygen permeability (%) | 1.0 | 0.8 | 0.61 | 0.62 | 0.65 |
| stiffness/mN.m | 10.5 | 10.9 | 15.6 | 15.4 | 14.9 |
| Water content (%) | 0.5 | 0.45 | 0.32 | 0.35 | 0.40 |
| Melt index (g/10min) | 5.2 | 6.4 | 8.3 | 8.2 | 8.0 |
| Biobased content (%) | 45 | 47 | 51 | 49 | 48 |
As shown in Table 2, when the maleic anhydride MAH is 10-18%, the ethylene glycol dimethacrylate is 5-8%, and the ethylene-vinyl acetate copolymer EVA is 30-35%, the mechanical properties of the prepared composite material are good, the water content is low, the tensile strength and the stiffness are high, the bio-based content is high, the melt index is high, and particularly, the material prepared by the number 3 has good properties, and when the raw material exceeds the range, the tensile strength and the stiffness of the prepared composite material are reduced, the bio-based content and the melt index are reduced, and the water content and the oxygen permeability are increased.
Example 2 biodegradable polyester/cellulose composite blown film material and preparation method thereof
The formula is as follows: 40 parts of polybutylene adipate/terephthalate, 12 parts of polypropylene carbonate polyol, 0.02 part of trimethylolpropane, 10 parts of polylactic acid (PLA), 30 parts of starch, 21 parts of cellulose, 3 parts of maleic anhydride grafted vinyl acetate copolymer, 2 parts of stabilizer (formed by mixing calcium stearate and zinc laurate according to the weight ratio of 1: 1) and 31.5 parts of benzophenone.
Wherein the compatilizer maleic anhydride grafted vinyl acetate copolymer is polymerized by the following raw materials in percentage by weight: 18% of maleic anhydride, 8% of benzoyl peroxide and 35% of ethylene-vinyl acetate copolymer.
The preparation method comprises the following steps:
s1, putting starch and cellulose into a high-speed mixer, stirring at the rotating speed of 300rpm/min for 5min to uniformly mix the starch and the cellulose to form a premix;
s2, compounding a stabilizer and an anti-aging agent according to a volume ratio of 1:1 for thermal degradation, then sequentially adding the premix prepared in the step S1, trimethylolpropane, a maleic anhydride grafted vinyl acetate copolymer, the stabilizer and benzophenone-3 into a high-speed mixer, then adding the poly (butylene adipate/terephthalate), the poly (propylene carbonate) and the polylactic acid into the high-speed mixer, rotating at 1000rpm/min for 20min, and uniformly stirring the materials to obtain a mixture;
and S3, adding the mixture prepared in the step S2 into a double-screw granulator, starting a motor when the die head temperature of the double-screw granulator is 120 ℃ and the screw rotating speed is 400rpm/min, and melting, extruding and granulating the mixture to obtain the biodegradable polyester/cellulose composite blown film material, wherein the vacuum degree of the mixture at the die head is 0.04 MPa.
Example 3 biodegradable polyester/cellulose composite blown film Material and method for producing the same
The formula is as follows: 45 parts of polybutylene adipate/terephthalate, 14 parts of polypropylene carbonate polyol, 0.025 part of trimethylolpropane, 12 parts of polylactic acid, 33 parts of starch, 23 parts of cellulose, 4 parts of maleic anhydride grafted vinyl acetate copolymer, 2.5 parts of stabilizer (formed by mixing calcium stearate and zinc laurate according to the weight ratio of 1: 1) and 32 parts of benzophenone.
Wherein the compatilizer maleic anhydride grafted vinyl acetate copolymer is polymerized by the following raw materials in percentage by weight: 15% of maleic anhydride, 7% of benzoyl peroxide and 33% of ethylene-vinyl acetate copolymer.
The preparation method comprises the following steps:
s1, putting starch and cellulose into a high-speed mixer, stirring at the rotating speed of 300rpm/min for 7min to uniformly mix the starch and the cellulose to form a premix;
s2, compounding a stabilizer and an anti-aging agent according to a volume ratio of 1:1 for thermal degradation, then sequentially adding the premix prepared in the step S1, trimethylolpropane, a maleic anhydride grafted vinyl acetate copolymer, the stabilizer and benzophenone-3 into a high-speed mixer, then adding the poly (butylene adipate/terephthalate), the poly (propylene carbonate) and the polylactic acid into the high-speed mixer, rotating at 1000rpm/min for 25min, and uniformly stirring the materials to obtain a mixture;
and S3, adding the mixture prepared in the step S2 into a double-screw granulator, starting a motor when the die head temperature of the double-screw granulator is 140 ℃ and the screw rotating speed is 400rpm/min, and melting, extruding and granulating the mixture to obtain the biodegradable polyester/cellulose composite blown film material, wherein the vacuum degree of the mixture at the die head is 0.04 MPa.
Example 4 biodegradable polyester/cellulose composite blown film Material and method for producing the same
The formula is as follows: 50 parts of polybutylene adipate/terephthalate, 15 parts of polypropylene carbonate polyol, 0.03 part of trimethylolpropane, 15 parts of polylactic acid, 35 parts of starch, 25 parts of cellulose, 5 parts of maleic anhydride grafted vinyl acetate copolymer, 3 parts of stabilizer (formed by mixing calcium stearate and zinc laurate according to the weight ratio of 1: 1) and 33 parts of benzophenone.
Wherein the compatilizer maleic anhydride grafted vinyl acetate copolymer is polymerized by the following raw materials in percentage by weight: 10% of maleic anhydride, 5% of benzoyl peroxide and 30% of ethylene-vinyl acetate copolymer.
The preparation method comprises the following steps:
s1, putting starch and cellulose into a high-speed mixer, stirring at the rotating speed of 300rpm/min for 10min to uniformly mix the starch and the cellulose to form a premix;
s2, compounding a stabilizer and an anti-aging agent according to a volume ratio of 1:1 for thermal degradation, then sequentially adding the premix prepared in the step S1, trimethylolpropane, a maleic anhydride grafted vinyl acetate copolymer, the stabilizer and benzophenone-3 into a high-speed mixer, then adding the poly (butylene adipate/terephthalate), the poly (propylene carbonate) and the polylactic acid into the high-speed mixer, rotating at 1000rpm/min for 30min, and uniformly stirring the materials to obtain a mixture;
and S3, adding the mixture prepared in the step S2 into a double-screw granulator, starting a motor when the die head temperature of the double-screw granulator is 180 ℃ and the rotating speed of a screw is 400rpm/min, and melting, extruding and granulating the mixture to obtain the biodegradable polyester/cellulose composite blown film material, wherein the vacuum degree of the mixture at the die head is 0.05 MPa.
Example 5 biodegradable polyester/cellulose composite blown film Material and method for producing the same
The formula is as follows: 45 parts of polybutylene adipate/terephthalate, 12 parts of polypropylene carbonate polyol, 0.03 part of trimethylolpropane, 8 parts of polylactic acid, 30 parts of starch, 24 parts of cellulose, 4 parts of maleic anhydride grafted vinyl acetate copolymer, 2 parts of stabilizer (formed by mixing calcium stearate and zinc laurate according to the weight ratio of 1: 1) and 31 parts of benzophenone.
Wherein the compatilizer maleic anhydride grafted vinyl acetate copolymer is polymerized by the following raw materials in percentage by weight: 18% of maleic anhydride, 8% of benzoyl peroxide and 35% of ethylene-vinyl acetate copolymer.
The preparation method comprises the following steps:
s1, putting starch and cellulose into a high-speed mixer, stirring at the rotating speed of 300rpm/min for 10min to uniformly mix the starch and the cellulose to form a premix;
s2, compounding a stabilizer and an anti-aging agent according to a volume ratio of 1:1 for thermal degradation, then sequentially adding the premix prepared in the step S1, trimethylolpropane, a maleic anhydride grafted vinyl acetate copolymer, the stabilizer and benzophenone-3 into a high-speed mixer, then adding the poly (butylene adipate/terephthalate), the poly (propylene carbonate) and the polylactic acid into the high-speed mixer, rotating at 1000rpm/min for 30min, and uniformly stirring the materials to obtain a mixture;
and S3, adding the mixture prepared in the step S2 into a double-screw granulator, starting a motor when the die head temperature of the double-screw granulator is 180 ℃ and the rotating speed of a screw is 400rpm/min, and melting, extruding and granulating the mixture to obtain the biodegradable polyester/cellulose composite blown film material, wherein the vacuum degree of the mixture at the die head is 0.05 MPa.
Comparative example 1 biodegradable polyester/cellulose composite blown film material and preparation method thereof
Except for the difference from example 5 in that the compatibilizer of comparative example 1 was replaced with an ethylene-methyl acrylate-glycidyl methacrylate copolymer, and the remaining components and preparation method were referenced to example 5.
Comparative example 2 biodegradable polyester/cellulose composite blown film material and preparation method thereof
Except for the difference from example 5 in that the compatibilizer of comparative example 2 was replaced with styrene-acrylonitrile-glycidyl methacrylate, and the remaining components and preparation method were according to example 5.
Comparative example 3 biodegradable polyester/cellulose composite blown film material and preparation method thereof
The difference from the example 5 is that instead of adding ethylene-methyl acrylate-glycidyl methacrylate copolymer as the compatibilizer in the formulation, the plasticizer components of ethylene glycol and epoxidized soybean oil were added, and the ethylene glycol and the epoxidized soybean oil were mixed according to a ratio of 1:1, and the rest of the components and the preparation method were referred to the example 5.
Test example I, Performance test
The biodegradable polyester/cellulose composite blown film materials prepared in example 5 and comparative examples 1 to 3 were subjected to performance tests with reference to GB/T1040.3, QB/T2538, GB/T1038 and GB/T2679.3, and the results obtained are shown in Table 3.
TABLE 3 biodegradable polyester/cellulose composite blown film Material Performance test results
| Item | Example 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Tensile strength (Mpa) | 18.8 | 14.9 | 15.2 | 16.9 |
| Elongation at Break (%) | 650 | 434 | 464 | 499 |
| Sealing strength/(N/15 mm) | 51.9 | 40.9 | 41.2 | 47.9 |
| Oxygen permeability (%) | 0.56 | 0.63 | 0.61 | 0.59 |
| stiffness/mN.m | 16.3 | 14.5 | 14.6 | 15.4 |
| Water content (%) | 0.32 | 1.0 | 0.9 | 0.68 |
| Melt index (g/10min) | 8.5 | 5.3 | 5.0 | 7.8 |
| Biobased content (%) | 53 | 25 | 29 | 42 |
| Biodegradation Rate (%) | 99 | 75 | 78 | 76 |
As can be seen from table 3, the biodegradable polyester/cellulose composite blown film materials prepared in example 5 and comparative examples 1 to 3 of the present invention have good mechanical properties such as tensile strength, elongation at break, and sealing strength, which indicates that the compatibility between PBAT/PPC/PLA and starch/cellulose is good, but the biodegradation rate of the material prepared in example 5 is high, and the content of the bio-based is high, and the comparative examples 1 to 2 do not add a plasticizer, and the oxygen permeability, melt index, bio-based content, and biodegradation rate of the prepared material are low, and compared with example 5, the prepared material has a biodegradation rate difference of 22%, a bio-based content difference of more than 11%, a melt index difference of 3.5(g/10min) at the maximum, and the like, and is easy to pollute the environment.
The embodiments of the present invention are preferred embodiments of the present invention, and the scope of the present invention is not limited by these embodiments, so: all equivalent changes made according to the structure, shape and principle of the invention are covered by the protection scope of the invention.
Claims (9)
1. A biodegradable polyester/cellulose composite blown film material is characterized in that: the material comprises the following raw materials in parts by weight: 35-50 parts of poly (butylene adipate/terephthalate), 10-15 parts of poly (propylene carbonate) polyol, 0.01-0.03 part of chain extender, 8-15 parts of polylactic acid, 25-35 parts of starch, 20-25 parts of cellulose, 2-5 parts of compatilizer, 1-3 parts of stabilizer and 1-3 parts of anti-aging agent.
2. The biodegradable polyester/cellulose composite blown film material as set forth in claim 1, wherein: the material comprises the following raw materials in parts by weight: 45 parts of polybutylene adipate/terephthalate, 12 parts of polypropylene carbonate polyol, 0.03 part of a chain extender, 8 parts of polylactic acid, 30 parts of starch, 24 parts of cellulose, 4 parts of a compatilizer, 2 parts of a stabilizer and 1 part of an anti-aging agent.
3. The biodegradable polyester/cellulose composite blown film material according to claim 1 or 2, characterized in that: the compatilizer is maleic anhydride grafted vinyl acetate copolymer.
4. The biodegradable polyester/cellulose composite blown film material according to claim 3, characterized in that: the maleic anhydride grafted vinyl acetate copolymer is mainly prepared from the following raw materials in percentage by weight: 10-25% of maleic anhydride, 5-10% of ethylene glycol dimethacrylate and 30-40% of ethylene-vinyl acetate copolymer.
5. The biodegradable polyester/cellulose composite blown film material according to claim 1 or 2, characterized in that: the stabilizer is any two of calcium stearate, barium stearate, zinc laurate and diphenyl-octyl phosphite.
6. The biodegradable polyester/cellulose composite blown film material according to claim 5, characterized in that: the stabilizer is composed of calcium stearate and zinc laurate, and the calcium stearate and the zinc laurate are mixed according to the weight ratio of 1: 1.
7. The biodegradable polyester/cellulose composite blown film material according to claim 1 or 2, characterized in that: the anti-aging agent is benzophenone-3.
8. The biodegradable polyester/cellulose composite blown film material according to claim 1 or 2, characterized in that: the chain extender is any one of trimethylolpropane and N, N-dihydroxy (diisopropyl) aniline.
9. The method for preparing biodegradable polyester/cellulose composite blown film material according to any one of claims 1-2, characterized in that: the method comprises the following steps:
s1, putting starch and cellulose into a high-speed mixer, stirring at the rotating speed of 300rpm/min for 5-10min to uniformly mix the starch and the cellulose to form a premix;
s2, sequentially adding the premix prepared in the step S1, a chain extender, a compatilizer, a stabilizer and an anti-aging agent into a high-speed mixer, then adding the poly (butylene adipate/terephthalate), the poly (propylene carbonate) polyol and the polylactic acid into the high-speed mixer, rotating at 1000rpm/min for 20-30min, and uniformly stirring the materials to obtain a mixture;
s3, adding the mixture prepared in the step S2 into a double-screw granulator, wherein the die head temperature of the double-screw granulator is 120-.
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