CN117362963A - High-performance degradable plastic and preparation method thereof - Google Patents
High-performance degradable plastic and preparation method thereof Download PDFInfo
- Publication number
- CN117362963A CN117362963A CN202311584470.2A CN202311584470A CN117362963A CN 117362963 A CN117362963 A CN 117362963A CN 202311584470 A CN202311584470 A CN 202311584470A CN 117362963 A CN117362963 A CN 117362963A
- Authority
- CN
- China
- Prior art keywords
- weight
- parts
- cellulose
- degradable plastic
- brominated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920006238 degradable plastic Polymers 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000001913 cellulose Substances 0.000 claims abstract description 115
- 229920002678 cellulose Polymers 0.000 claims abstract description 115
- 239000000945 filler Substances 0.000 claims abstract description 29
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 26
- 239000004626 polylactic acid Substances 0.000 claims abstract description 26
- -1 polybutylene terephthalate-adipate Polymers 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000004014 plasticizer Substances 0.000 claims abstract description 8
- 239000002159 nanocrystal Substances 0.000 claims description 60
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 57
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 22
- 239000005457 ice water Substances 0.000 claims description 19
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 19
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 19
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical group CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 18
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims description 15
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 14
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 14
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical compound CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 229920006030 multiblock copolymer Polymers 0.000 claims description 2
- YLBPOJLDZXHVRR-UHFFFAOYSA-N n'-[3-[diethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CCO[Si](C)(OCC)CCCNCCN YLBPOJLDZXHVRR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 claims 1
- 229920003023 plastic Polymers 0.000 abstract description 37
- 239000004033 plastic Substances 0.000 abstract description 37
- 230000015556 catabolic process Effects 0.000 abstract description 15
- 238000006731 degradation reaction Methods 0.000 abstract description 15
- 230000006872 improvement Effects 0.000 abstract description 7
- 235000010980 cellulose Nutrition 0.000 description 93
- 229920000642 polymer Polymers 0.000 description 17
- 239000011159 matrix material Substances 0.000 description 11
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical group CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 5
- 238000005917 acylation reaction Methods 0.000 description 5
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 241000282414 Homo sapiens Species 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229920006392 biobased thermoplastic Polymers 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 238000009264 composting Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003141 primary amines Chemical group 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000006884 silylation reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 239000003000 extruded plastic Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- MMHWNKSVQDCUDE-UHFFFAOYSA-N hexanedioic acid;terephthalic acid Chemical compound OC(=O)CCCCC(O)=O.OC(=O)C1=CC=C(C(O)=O)C=C1 MMHWNKSVQDCUDE-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 238000005303 weighing Methods 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
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of plastics, in particular to a high-performance degradable plastic and a preparation method thereof. The high-performance degradable plastic disclosed by the invention is prepared from the following raw materials: polylactic acid, polybutylene terephthalate-adipate, filler, compatilizer and plasticizer, wherein cellulose nanocrystalline, brominated cellulose nanocrystalline and modified cellulose nanocrystalline are adopted as the filler, and the preparation method is simple, so that the mechanical property of the plastic can be improved, and the improvement of the degradation property of the plastic is promoted.
Description
Technical Field
The invention relates to the technical field of plastics, in particular to a high-performance degradable plastic and a preparation method thereof.
Background
With the development of industry and the rapid increase of world population, the demands of plastics for human life and industrial production are increasing, and the development of plastics industry is greatly accelerated. Plastics offer many advantages to human production and life, and have become an indispensable product in human production and life, and the world without plastic organic polymers seems to be inconceivable. However, the wide use of plastic products not only consumes a great amount of petroleum resources while bringing convenience to the daily life of human beings, but also causes a great amount of waste plastics to be piled up in the natural environment due to the degradation-resistant characteristic of the plastics, and to stay in the environment for a long time, thereby causing great damage to the ecological environment and causing a series of plastic pollution problems such as air pollution, water pollution, climate warming and the like. Moreover, most of the waste plastics remained in the environment are transferred from land to sea, so that the ecological environment of the sea is damaged, and the existence of marine organisms is seriously threatened. The growing problem of pollution of plastics in this series is a very serious problem, bringing serious environmental and ecological problems and being extremely disadvantageous for the development of economics, which has been attracting a great deal of attention worldwide.
Based on serious environmental pollution caused by plastics, finding an effective treatment mode for waste plastic pollution becomes a current research hot spot. There are two common ways of disposing of waste plastic contamination: (1) Recycling waste plastics, and converting the waste plastics into products with economic value through a physical or chemical method; (2) Develop and apply novel degradable green environment-friendly plastic to replace the traditional chemical inert plastic. The first method can improve the use value of plastics, but has high requirements on investment, technology, environment and the like. Thus, the search for strategies to effectively degrade plastics and further convert them into economically valuable products without causing additional pollution and the synthesis and development of entirely new readily degradable plastics to replace traditional chemically inert plastics has become a current hot spot for a vast number of researchers.
The invention patent with application number 201110067919.9 discloses a high-performance degradable plastic and a manufacturing method thereof, wherein the high-performance degradable plastic comprises the following raw materials: polylactic acid, polycarbonate, short glass fiber, heat-resistant modifier, compatilizer, anti-floating fiber agent, coupling agent and toughening agent. The plastic has the characteristics of high mechanical strength, good toughness, high heat resistance and the like, but has poor degradation performance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a high-performance degradable plastic and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
a high-performance degradable plastic consists of the following raw materials in parts by weight:
50-70 parts of polylactic acid, 20-40 parts of polybutylene terephthalate-adipate, 10-20 parts of filler, 1-3 parts of compatilizer and 2-5 parts of plasticizer.
The compatilizer is any one of maleic anhydride, maleic anhydride grafted polypropylene and ethylene-propylene multiblock copolymer.
The plasticizer is any one of ethylene glycol, citric acid ester, dioctyl phthalate and glycerin.
The filler is any one of cellulose nanocrystalline, brominated cellulose nanocrystalline and modified cellulose nanocrystalline.
Polylactic acid is a biodegradable and biocompatible commercial polymer derived from renewable natural resources such as corn starch and sugarcane, and as a thermoplastic, has the advantages of high mechanical strength, environmental friendliness, easiness in processing, price advantage and the like, but has limited its further application due to its brittleness, low crystallization kinetics, poor heat resistance and low impact toughness. To solve the above problems, bio-based thermoplastic polymer-polybutylene terephthalate-adipate having excellent ductility and toughness is added to compensate for the intrinsic defect of polylactic acid, but the incorporation of polybutylene terephthalate-adipate may greatly sacrifice the mechanical properties of the blend. In order to balance the properties of the blend and improve the degradation properties of the blend, nano fillers with degradation properties are generally used as reinforcing materials, which can effectively enhance the crystal nucleation and promote crystallization of polylactic acid, greatly improve the mechanical properties of plastics and improve the degradation properties.
The cellulose nanocrystalline is a one-dimensional nanomaterial extracted from natural cellulose or microcrystalline cellulose, has the excellent properties of low density, high aspect ratio, large specific surface area, high strength, complete biodegradation, good biocompatibility and the like, and becomes an excellent substitute for the traditional inorganic nanoparticle reinforcing material. Because the surface of the cellulose nanocrystalline has abundant hydroxyl groups, the cellulose nanocrystalline is easy to aggregate into a highly ordered structure, so that the cellulose nanocrystalline has higher polarity, has poor compatibility with most organic media, is easy to self-agglomerate in a polymer matrix, weakens interface interaction, and influences the mechanical properties of plastics. Therefore, the cellulose nanocrystals are subjected to surface modification to realize the dispersibility of the cellulose nanocrystals in a polymer matrix, so that the mechanical property and the degradation property of the plastic are improved.
The preparation method of the brominated cellulose nanocrystalline comprises the following steps:
adding 1-3 parts by weight of cellulose nanocrystalline into 40-60 parts by weight of N, N-dimethylformamide, performing ultrasonic dispersion in an ice-water bath for 20-40min, wherein the ultrasonic power is 250-400W, the ultrasonic frequency is 20-40kHz, then adding 5-6 parts by weight of triethylamine, continuing ultrasonic treatment for 10-30min to obtain a mixed solution, adding 4-6 parts by weight of alpha-bromoisobutyryl bromide into the mixed solution, stirring and reacting for 18-30h at a rotating speed of 600-1000rpm under the conditions of room temperature and nitrogen atmosphere, centrifuging, washing and drying after the completion to obtain the brominated cellulose nanocrystalline.
The preparation method of the modified cellulose nanocrystalline comprises the following steps:
s1, adding 1-3 parts by weight of cellulose nanocrystals into 40-60 parts by weight of N, N-dimethylformamide, performing ultrasonic dispersion in an ice-water bath for 20-40min, wherein the ultrasonic power is 250-400W, the ultrasonic frequency is 20-40kHz, then adding 5-6 parts by weight of triethylamine, continuing ultrasonic treatment for 10-30min to obtain a mixed solution, adding 4-6 parts by weight of alpha-bromoisobutyryl bromide into the mixed solution, stirring and reacting for 18-30h at a rotating speed of 600-1000rpm under the conditions of room temperature and nitrogen atmosphere, and centrifuging, washing and drying after the completion to obtain brominated cellulose nanocrystals;
s2, adding 0.5-1.5 parts by weight of the brominated cellulose nanocrystalline obtained in the step S1 into 40-60 parts by weight of N, N-dimethylformamide, performing ultrasonic dispersion in an ice-water bath for 20-40min, wherein the ultrasonic power is 250-400W, the ultrasonic frequency is 20-40kHz, then adding 1-2 parts by weight of an auxiliary agent and 5-6 parts by weight of a monomer, adding 0.4-0.8 part by weight of a catalyst in a nitrogen atmosphere at room temperature, heating to 35-45 ℃, stirring and reacting for 3-5h at a rotating speed of 800-1200rpm under the protection of nitrogen, and centrifuging, washing and drying after the completion to obtain the modified cellulose nanocrystalline.
The effective improvement in properties of the brominated cellulose nanocrystals compared to the cellulose nanocrystals may be due to the poor interfacial adhesion between the cellulose nanocrystals and the polymer matrix, which is difficult to disperse in the polymer matrix, due to the hydrophilicity of the cellulose nanocrystals. The surface of the cellulose nanocrystalline after further modification is grafted with a macromolecular polymer, so that the cellulose nanocrystalline possibly has stronger attraction with a polylactic acid chain, and contains a large amount of hydrophobic groups, so that the surface hydrophobicity is greatly increased, the interfacial adhesion between the modified cellulose nanocrystalline and a polymer matrix is obviously improved, and the improvement of the mechanical property of plastics is facilitated.
Further, the preparation method of the modified cellulose nanocrystalline comprises the following steps:
s1, adding 2-5 parts by weight of cellulose nanocrystals into 180-220 parts by weight of 40-60wt% ethanol water solution, stirring for 2-5 hours at room temperature at a rotating speed of 500-800rpm, then adding 5-7 parts by weight of silane coupling agent, continuously stirring for 15-30 minutes, then heating to 70-90 ℃, continuously stirring for reacting for 3-4 hours, and centrifuging, washing and drying after the completion of the reaction to obtain the aminated cellulose nanocrystals;
s2, adding 1-3 parts by weight of the aminated cellulose nanocrystal obtained in the step S1 into 40-60 parts by weight of N, N-dimethylformamide, performing ultrasonic dispersion in an ice-water bath for 20-40min, wherein the ultrasonic power is 250-400W, the ultrasonic frequency is 20-40kHz, then adding 5-6 parts by weight of triethylamine, continuing ultrasonic treatment for 10-30min to obtain a mixed solution, adding 4-6 parts by weight of alpha-bromoisobutyryl bromide into the mixed solution, stirring at a rotating speed of 600-1000rpm under the conditions of room temperature and nitrogen atmosphere, reacting for 18-30h, and centrifuging, washing and drying after the completion to obtain the brominated cellulose nanocrystal;
s3, adding 0.5-1.5 parts by weight of the brominated cellulose nanocrystalline obtained in the step S2 into 40-60 parts by weight of N, N-dimethylformamide, performing ultrasonic dispersion in an ice-water bath for 20-40min, wherein the ultrasonic power is 250-400W, the ultrasonic frequency is 20-40kHz, then adding 1-2 parts by weight of an auxiliary agent and 5-6 parts by weight of a monomer, adding 0.4-0.8 part by weight of a catalyst in a nitrogen atmosphere at room temperature, heating to 35-45 ℃, stirring and reacting for 3-5h at a rotating speed of 800-1200rpm under the protection of nitrogen, and centrifuging, washing and drying after the completion to obtain the modified cellulose nanocrystalline.
The surface of the cellulose nanocrystal contains more hydroxyl groups, so that the acylation reaction can be carried out, but the density of acylated grafting bromo groups can be greatly reduced due to the large density of hydroxyl groups on the surface of the cellulose nanocrystal and the influence of steric hindrance, so that a silane layer with primary amine groups outside is formed on the surface of the original cellulose nanocrystal through the silylation reaction, the acylation reaction is facilitated, and an initiator is fixed on the surface of the cellulose nanocrystal. In addition, in the atom transfer radical polymerization reaction performed in the step S3, the brominated cellulose nanocrystal obtained in the step S2 can serve as an initiator of the polymerization reaction and also can serve as a crosslinking agent.
The silane coupling agent is any one of 3-aminopropyl triethoxy silane, 3-aminopropyl methyl dimethoxy silane and N-2-aminoethyl-3-aminopropyl methyl diethoxy silane.
The auxiliary agent is pentamethyldiethylenetriamine.
The catalyst is one or more of cuprous bromide, trimethyl phosphite and 2, 2-bipyridine.
The monomer is glycidyl methacrylate and/or benzyl methacrylate.
Preferably, the monomer is a mixture of glycidyl methacrylate and benzyl methacrylate, wherein the mass ratio of the glycidyl methacrylate to the benzyl methacrylate is 1 (1-3).
The invention adopts glycidyl methacrylate and benzyl methacrylate as monomers together, and mainly probably because the glycidyl methacrylate and the benzyl methacrylate can both form a macromolecular polymer through free radical polymerization reaction, meanwhile, the glycidyl methacrylate contains epoxy groups, and the benzyl methacrylate contains hydrophobic benzene rings, and the glycidyl methacrylate and the benzyl methacrylate act together, so that the oxygen content in modified cellulose nanocrystals is increased, the hydrophobicity of the modified cellulose nanocrystals is improved, the interfacial compatibility between the modified cellulose nanocrystals and a polymer matrix is greatly improved, and the improvement of the comprehensive performance of plastics is facilitated.
The invention also provides a preparation method of the high-performance degradable plastic, which comprises the following steps:
firstly, adding polylactic acid, polybutylene terephthalate-adipate, a filler compatilizer and a plasticizer into a high-speed mixer according to parts by weight, and mixing for 20-40min at a rotating speed of 500-800rpm to obtain a mixture; and then the mixture is put into a double-screw extruder, extruded and granulated, and the high-performance degradable plastic is obtained.
The invention has the beneficial effects that: the invention takes polylactic acid, polybutylene terephthalate-adipate, filler, compatilizer and plasticizer as raw materials, wherein cellulose nanocrystalline, brominated cellulose nanocrystalline and modified cellulose nanocrystalline are adopted as the filler, the dispersibility in a polymer matrix is good, the compatibility is high, and the prepared plastic has excellent mechanical property and good degradability.
Detailed Description
The above summary of the present invention is described in further detail below in conjunction with the detailed description, but it should not be understood that the scope of the above-described subject matter of the present invention is limited to the following examples.
Introduction of some of the raw materials in this application:
polylactic acid, density: 1.25g/cm 3 Brand: REVODE 213TR is provided by Zhejiang Zheng Juan Living being.
Polybutylene terephthalate-adipate, density: 1.25-1.35g/cm 3 Brand: THJS-8801 is provided by Xinjiang blue mountain Tun river.
Maleic anhydride grafted polypropylene, grafting ratio: 1%, brand: b1, available from America, inc.
Cellulose nanocrystals, diameter: 5-30nm, length: 50-300nm, obtained in spray dried form, supplied by the green nanomaterials company, inc. of Zhejiang Jin Jiahao.
α -bromoisobutyryl bromide, CAS number: 20769-85-1.
Pentamethyldiethylenetriamine, CAS number: 3030-47-5.
Glycidyl methacrylate, CAS number: 106-91-2.
Benzyl methacrylate, CAS number: 2495-37-6.
Example 1
A high-performance degradable plastic consists of the following raw materials in parts by weight:
60 parts by weight of polylactic acid, 30 parts by weight of polybutylene terephthalate-adipate, 15 parts by weight of filler, 2 parts by weight of maleic anhydride-grafted polypropylene and 3 parts by weight of dioctyl phthalate.
The filler is cellulose nanocrystalline.
A preparation method of high-performance degradable plastic comprises the following steps:
firstly, adding polylactic acid, polybutylene terephthalate-adipate, filler, maleic anhydride grafted polypropylene and dioctyl phthalate into a high-speed mixer according to parts by weight, and mixing for 30 minutes at a rotating speed of 600rpm to obtain a mixture; and then the mixture is put into a double-screw extruder, extruded and granulated, and the high-performance degradable plastic is obtained.
Example 2
A high-performance degradable plastic consists of the following raw materials in parts by weight:
60 parts by weight of polylactic acid, 30 parts by weight of polybutylene terephthalate-adipate, 15 parts by weight of filler, 2 parts by weight of maleic anhydride-grafted polypropylene and 3 parts by weight of dioctyl phthalate.
The filler is brominated cellulose nanocrystalline.
The preparation method of the brominated cellulose nanocrystalline comprises the following steps:
adding 2 parts by weight of cellulose nanocrystals into 50 parts by weight of N, N-dimethylformamide, performing ultrasonic dispersion in an ice-water bath for 30min, wherein the ultrasonic power is 300W, the ultrasonic frequency is 30kHz, then adding 5.6 parts by weight of triethylamine, continuing ultrasonic treatment for 15min to obtain a mixed solution, adding 4.9 parts by weight of alpha-bromoisobutyryl bromide into the mixed solution, stirring at a rotating speed of 800rpm under the conditions of room temperature and nitrogen atmosphere, reacting for 24h, and centrifuging, washing and drying after the completion to obtain brominated cellulose nanocrystals.
A preparation method of high-performance degradable plastic comprises the following steps:
firstly, adding polylactic acid, polybutylene terephthalate-adipate, filler, maleic anhydride grafted polypropylene and dioctyl phthalate into a high-speed mixer according to parts by weight, and mixing for 30 minutes at a rotating speed of 600rpm to obtain a mixture; and then the mixture is put into a double-screw extruder, extruded and granulated, and the high-performance degradable plastic is obtained.
Example 3
A high-performance degradable plastic consists of the following raw materials in parts by weight:
60 parts by weight of polylactic acid, 30 parts by weight of polybutylene terephthalate-adipate, 15 parts by weight of filler, 2 parts by weight of maleic anhydride-grafted polypropylene and 3 parts by weight of dioctyl phthalate.
The filler is modified cellulose nanocrystalline.
The preparation method of the modified cellulose nanocrystalline comprises the following steps:
s1, adding 2 parts by weight of cellulose nanocrystals into 50 parts by weight of N, N-dimethylformamide, performing ultrasonic dispersion in an ice-water bath for 30min, wherein the ultrasonic power is 300W, the ultrasonic frequency is 30kHz, then adding 5.6 parts by weight of triethylamine, continuing ultrasonic treatment for 15min to obtain a mixed solution, then adding 4.9 parts by weight of alpha-bromoisobutyryl bromide into the mixed solution, stirring and reacting for 24h at a rotating speed of 800rpm under the conditions of room temperature and nitrogen atmosphere, and centrifuging, washing and drying after the completion to obtain brominated cellulose nanocrystals;
s2, adding 1 part by weight of the brominated cellulose nanocrystal obtained in the step S1 into 50 parts by weight of N, N-dimethylformamide, performing ultrasonic dispersion in an ice-water bath for 30min, wherein the ultrasonic power is 300W, the ultrasonic frequency is 30kHz, then adding 1.4 parts by weight of pentamethyldiethylenetriamine and 5.7 parts by weight of glycidyl methacrylate, adding 0.6 part by weight of cuprous bromide at room temperature under nitrogen atmosphere, then heating to 40 ℃, stirring at a rotating speed of 1000rpm under nitrogen protection, reacting for 4h, and centrifuging, washing and drying after the completion to obtain the modified cellulose nanocrystal.
A preparation method of high-performance degradable plastic comprises the following steps:
firstly, adding polylactic acid, polybutylene terephthalate-adipate, filler, maleic anhydride grafted polypropylene and dioctyl phthalate into a high-speed mixer according to parts by weight, and mixing for 30 minutes at a rotating speed of 600rpm to obtain a mixture; and then the mixture is put into a double-screw extruder, extruded and granulated, and the high-performance degradable plastic is obtained.
Example 4
A high-performance degradable plastic consists of the following raw materials in parts by weight:
60 parts by weight of polylactic acid, 30 parts by weight of polybutylene terephthalate-adipate, 15 parts by weight of filler, 2 parts by weight of maleic anhydride-grafted polypropylene and 3 parts by weight of dioctyl phthalate.
The filler is modified cellulose nanocrystalline.
The preparation method of the modified cellulose nanocrystalline comprises the following steps:
s1, adding 4 parts by weight of cellulose nanocrystals into 200 parts by weight of 50wt% ethanol aqueous solution, stirring for 3 hours at room temperature at a rotating speed of 600rpm, then adding 6 parts by weight of 3-aminopropyl triethoxysilane, continuously stirring for 20 minutes, then heating to 80 ℃, continuously stirring for reacting for 3.5 hours, and centrifuging, washing and drying after the completion of the reaction to obtain the aminated cellulose nanocrystals;
s2, adding 2 parts by weight of the aminated cellulose nanocrystalline obtained in the step S1 into 50 parts by weight of N, N-dimethylformamide, performing ultrasonic dispersion in an ice-water bath for 30min, wherein the ultrasonic power is 300W, the ultrasonic frequency is 30kHz, then adding 5.6 parts by weight of triethylamine, continuing ultrasonic treatment for 15min to obtain a mixed solution, then adding 4.9 parts by weight of alpha-bromoisobutyryl bromide into the mixed solution, stirring and reacting for 24h at a rotating speed of 800rpm under the conditions of room temperature and nitrogen atmosphere, and centrifuging, washing and drying after the completion to obtain the brominated cellulose nanocrystalline;
s3, adding 1 part by weight of the brominated cellulose nanocrystal obtained in the step S2 into 50 parts by weight of N, N-dimethylformamide, performing ultrasonic dispersion in an ice-water bath for 30min, wherein the ultrasonic power is 300W, the ultrasonic frequency is 30kHz, then adding 1.4 parts by weight of pentamethyldiethylenetriamine and 5.7 parts by weight of glycidyl methacrylate, adding 0.6 part by weight of cuprous bromide at room temperature under nitrogen atmosphere, then heating to 40 ℃, stirring at a rotating speed of 1000rpm under nitrogen protection, reacting for 4h, and centrifuging, washing and drying after the completion to obtain the modified cellulose nanocrystal.
A preparation method of high-performance degradable plastic comprises the following steps:
firstly, adding polylactic acid, polybutylene terephthalate-adipate, filler, maleic anhydride grafted polypropylene and dioctyl phthalate into a high-speed mixer according to parts by weight, and mixing for 30 minutes at a rotating speed of 600rpm to obtain a mixture; and then the mixture is put into a double-screw extruder, extruded and granulated, and the high-performance degradable plastic is obtained.
Example 5
A high-performance degradable plastic consists of the following raw materials in parts by weight:
60 parts by weight of polylactic acid, 30 parts by weight of polybutylene terephthalate-adipate, 15 parts by weight of filler, 2 parts by weight of maleic anhydride-grafted polypropylene and 3 parts by weight of dioctyl phthalate.
The filler is modified cellulose nanocrystalline.
The preparation method of the modified cellulose nanocrystalline comprises the following steps:
s1, adding 4 parts by weight of cellulose nanocrystals into 200 parts by weight of 50wt% ethanol aqueous solution, stirring for 3 hours at room temperature at a rotating speed of 600rpm, then adding 6 parts by weight of 3-aminopropyl triethoxysilane, continuously stirring for 20 minutes, then heating to 80 ℃, continuously stirring for reacting for 3.5 hours, and centrifuging, washing and drying after the completion of the reaction to obtain the aminated cellulose nanocrystals;
s2, adding 2 parts by weight of the aminated cellulose nanocrystalline obtained in the step S1 into 50 parts by weight of N, N-dimethylformamide, performing ultrasonic dispersion in an ice-water bath for 30min, wherein the ultrasonic power is 300W, the ultrasonic frequency is 30kHz, then adding 5.6 parts by weight of triethylamine, continuing ultrasonic treatment for 15min to obtain a mixed solution, then adding 4.9 parts by weight of alpha-bromoisobutyryl bromide into the mixed solution, stirring and reacting for 24h at a rotating speed of 800rpm under the conditions of room temperature and nitrogen atmosphere, and centrifuging, washing and drying after the completion to obtain the brominated cellulose nanocrystalline;
s3, adding 1 part by weight of the brominated cellulose nanocrystal obtained in the step S2 into 50 parts by weight of N, N-dimethylformamide, performing ultrasonic dispersion in an ice-water bath for 30min, wherein the ultrasonic power is 300W, the ultrasonic frequency is 30kHz, then adding 1.4 parts by weight of pentamethyldiethylenetriamine and 5.7 parts by weight of benzyl methacrylate, adding 0.6 part by weight of cuprous bromide in a room temperature and nitrogen atmosphere, then heating the temperature to 40 ℃, stirring the mixture at a rotating speed of 1000rpm under the protection of nitrogen, reacting for 4h, and centrifuging, washing and drying after the completion of the reaction, thus obtaining the modified cellulose nanocrystal.
A preparation method of high-performance degradable plastic comprises the following steps:
firstly, adding polylactic acid, polybutylene terephthalate-adipate, filler, maleic anhydride grafted polypropylene and dioctyl phthalate into a high-speed mixer according to parts by weight, and mixing for 30 minutes at a rotating speed of 600rpm to obtain a mixture; and then the mixture is put into a double-screw extruder, extruded and granulated, and the high-performance degradable plastic is obtained.
Example 6
A high-performance degradable plastic consists of the following raw materials in parts by weight:
60 parts by weight of polylactic acid, 30 parts by weight of polybutylene terephthalate-adipate, 15 parts by weight of filler, 2 parts by weight of maleic anhydride-grafted polypropylene and 3 parts by weight of dioctyl phthalate.
The filler is modified cellulose nanocrystalline.
The preparation method of the modified cellulose nanocrystalline comprises the following steps:
s1, adding 4 parts by weight of cellulose nanocrystals into 200 parts by weight of 50wt% ethanol aqueous solution, stirring for 3 hours at room temperature at a rotating speed of 600rpm, then adding 6 parts by weight of 3-aminopropyl triethoxysilane, continuously stirring for 20 minutes, then heating to 80 ℃, continuously stirring for reacting for 3.5 hours, and centrifuging, washing and drying after the completion of the reaction to obtain the aminated cellulose nanocrystals;
s2, adding 2 parts by weight of the aminated cellulose nanocrystalline obtained in the step S1 into 50 parts by weight of N, N-dimethylformamide, performing ultrasonic dispersion in an ice-water bath for 30min, wherein the ultrasonic power is 300W, the ultrasonic frequency is 30kHz, then adding 5.6 parts by weight of triethylamine, continuing ultrasonic treatment for 15min to obtain a mixed solution, then adding 4.9 parts by weight of alpha-bromoisobutyryl bromide into the mixed solution, stirring and reacting for 24h at a rotating speed of 800rpm under the conditions of room temperature and nitrogen atmosphere, and centrifuging, washing and drying after the completion to obtain the brominated cellulose nanocrystalline;
s3, adding 1 part by weight of the brominated cellulose nanocrystal obtained in the step S2 into 50 parts by weight of N, N-dimethylformamide, performing ultrasonic dispersion in an ice-water bath for 30min, wherein the ultrasonic power is 300W, the ultrasonic frequency is 30kHz, then adding 1.4 parts by weight of pentamethyldiethylenetriamine and 5.7 parts by weight of monomer, adding 0.6 part by weight of cuprous bromide in a room temperature and nitrogen atmosphere, then heating the temperature to 40 ℃, stirring and reacting for 4h at a rotating speed of 1000rpm under the protection of nitrogen, and centrifuging, washing and drying after the completion to obtain the modified cellulose nanocrystal.
The monomer is a mixture of glycidyl methacrylate and benzyl methacrylate, wherein the mass ratio of the glycidyl methacrylate to the benzyl methacrylate is 1:2.
A preparation method of high-performance degradable plastic comprises the following steps:
firstly, adding polylactic acid, polybutylene terephthalate-adipate, filler, maleic anhydride grafted polypropylene and dioctyl phthalate into a high-speed mixer according to parts by weight, and mixing for 30 minutes at a rotating speed of 600rpm to obtain a mixture; and then the mixture is put into a double-screw extruder, extruded and granulated, and the high-performance degradable plastic is obtained.
Test example 1
Mechanical property evaluation: the high-performance degradable plastic prepared in each embodiment is prepared into a standard dumbbell type injection molding by an injection molding machine, and the standard dumbbell type injection molding is according to the national standard: GB/T1040.2-2006 determination of Plastic tensile Properties part 2: test conditions for molded and extruded plastics.
The specific experimental method comprises the following steps: total length of test specimen=170 mm, width=10 mm, thickness=4 mm, gauge length=80 mm, distance between clamps=115 mm, stretching rate is 50mm/min, and average value is obtained by measuring 5 times of each group of samples in parallel.
TABLE 1 tensile Strength of high Performance degradable plastics
| Tensile strength, MPa | |
| Example 1 | 42.3 |
| Example 2 | 45.8 |
| Example 3 | 52.0 |
| Example 4 | 55.9 |
| Example 5 | 56.1 |
| Example 6 | 58.7 |
The above results show that the mechanical properties of example 2 are superior to those of example 1, probably because the hydrophilicity of the cellulose nanocrystals resulted in poor interfacial adhesion with the polymer matrix, difficulty in dispersion in the polymer matrix, and slightly improved dispersibility after bromination. Compared with the embodiment 2, the mechanical properties of the embodiment 3 are obviously improved, and the cellulose nanocrystal which is subjected to further modification is mainly probably grafted with macromolecular polymers on the surface, so that the cellulose nanocrystal has stronger attraction with polylactic acid chains, and contains a large number of hydrophobic groups, so that the surface hydrophobicity is greatly improved, the interfacial adhesion between the modified cellulose nanocrystal and a polymer matrix is obviously improved, and the improvement of the mechanical properties of plastics is facilitated. Compared with the embodiment 3, the mechanical properties of the embodiment 4 are further improved, and the cellulose nanocrystal surface mainly contains more hydroxyl groups and can be subjected to acylation reaction, but the density of acylated graft bromine groups can be greatly reduced due to the large density of the hydroxyl groups on the surface of the cellulose nanocrystal, so that a silane layer with primary amine groups is formed on the outer surface of the original cellulose nanocrystal through silylation reaction, the acylation reaction is facilitated, and an initiator is fixed on the cellulose nanocrystal surface; in the atom transfer radical polymerization reaction carried out in the step S3, the cellulose nanocrystal modified by the amination and the acylation can be used as an initiator of the polymerization reaction, can also play a role of a cross-linking agent, and promotes further improvement of mechanical properties of plastics. In the embodiment 6, glycidyl methacrylate and benzyl methacrylate are used as monomers together, and the mechanical properties of the polymer are superior to those of the embodiment 4 and the embodiment 5, and the single monomer is mainly probably because the glycidyl methacrylate and the benzyl methacrylate can form a macromolecular polymer through free radical polymerization reaction, and meanwhile, the glycidyl methacrylate contains an epoxy group, and the benzyl methacrylate contains a hydrophobic benzene ring, and the glycidyl methacrylate and the benzyl methacrylate act together, so that the oxygen content in the modified cellulose nanocrystal is increased, the hydrophobicity of the modified cellulose nanocrystal is also improved, the interfacial compatibility between the modified cellulose nanocrystal and a polymer matrix is greatly improved, and the improvement of the comprehensive properties of plastics is facilitated.
Test example 2
Degradation performance evaluation: according to GB/T19811-2005 standard of determination of disintegration degree of Plastic Material under defined composting conditions, a simulated soil degradation experiment is tested, and the specific test method is as follows:
the high-performance degradable plastics prepared in the above examples were molded into specimens (25 mm. Times.25 mm. Times.1 mm in size) by an injection molding machine, and then the specimens were dried in a vacuum oven at 60℃for 12 hours, and each specimen was precisely weighed and recorded by a balance, and recorded as m 0 Then each group of samples are respectively buried in self-made cartons filled with commercial flower-growing nutrient soil, the depth is 5cm, the distance is 3cm, the cartons are placed in a blast drying oven after the burying, the temperature is set at 58 ℃, the relative humidity of the soil is regulated to 60%, and then the degradation experiment is started (the humidity of the soil is ensured to be 60% in the whole experiment process). Sampling respectively at 30 days and 60 days of composting degradation experiment, taking three parallel samples from each group, washing with water, placing in a vacuum oven, drying at 60deg.C for 12 hr, accurately weighing with balance, and recording as m n (n is 30, 60). The weight loss ratio calculation formula is as follows:
weight loss (%) = (m) 0 -m n )/m 0 ×100％
TABLE 2 degradation Performance test results
| Weight loss rate of 30 days,% | 60 days weight loss rate, percent | |
| Example 1 | 15.2 | 47.2 |
| Example 2 | 16.5 | 49.7 |
| Example 3 | 22.1 | 57.8 |
| Example 6 | 25.4 | 62.6 |
The invention adopts the bio-based thermoplastic polymer materials, namely polylactic acid and polybutylene terephthalate-adipic acid, as main raw materials, and is assisted with a series of nano-filler-cellulose nanocrystalline, brominated cellulose nanocrystalline and modified cellulose nanocrystalline with degradation performance, so that the good degradation performance of the raw materials is fully utilized, and the prepared plastic has excellent mechanical performance and good degradation performance.
Claims (10)
1. The high-performance degradable plastic is characterized by comprising the following raw materials:
polylactic acid, polybutylene terephthalate-adipate, filler, compatilizer and plasticizer.
2. The high performance degradable plastic of claim 1, wherein the filler is any one of cellulose nanocrystals, brominated cellulose nanocrystals, modified cellulose nanocrystals.
3. The high performance degradable plastic of claim 2, wherein the preparation method of the brominated cellulose nanocrystalline comprises the following steps:
adding 1-3 parts by weight of cellulose nanocrystalline into 40-60 parts by weight of N, N-dimethylformamide, performing ultrasonic dispersion in an ice-water bath for 20-40min, adding 5-6 parts by weight of triethylamine, continuing ultrasonic treatment for 10-30min to obtain a mixed solution, adding 4-6 parts by weight of alpha-bromoisobutyryl bromide into the mixed solution, reacting for 18-30h at room temperature under the condition of nitrogen atmosphere, centrifuging, washing and drying after the completion of the reaction to obtain the brominated cellulose nanocrystalline.
4. The high performance degradable plastic according to claim 2, wherein the preparation method of the modified cellulose nanocrystals comprises the following steps:
s1, adding 1-3 parts by weight of cellulose nanocrystals into 40-60 parts by weight of N, N-dimethylformamide, performing ultrasonic dispersion in an ice-water bath for 20-40min, then adding 5-6 parts by weight of triethylamine, continuing ultrasonic treatment for 10-30min to obtain a mixed solution, adding 4-6 parts by weight of alpha-bromoisobutyryl bromide into the mixed solution, reacting for 18-30h at room temperature under the condition of nitrogen atmosphere, and centrifuging, washing and drying after the completion to obtain brominated cellulose nanocrystals;
s2, adding 0.5-1.5 parts by weight of the brominated cellulose nanocrystalline obtained in the step S1 into 40-60 parts by weight of N, N-dimethylformamide, performing ultrasonic dispersion in an ice-water bath for 20-40min, adding 1-2 parts by weight of an auxiliary agent and 5-6 parts by weight of a monomer, adding 0.4-0.8 part by weight of a catalyst at room temperature under nitrogen atmosphere, heating to 35-45 ℃, reacting for 3-5h under nitrogen protection, and centrifuging, washing and drying after the completion to obtain the modified cellulose nanocrystalline.
5. The high performance degradable plastic according to claim 2, wherein the preparation method of the modified cellulose nanocrystals comprises the following steps:
s1, adding 2-5 parts by weight of cellulose nanocrystals into 180-220 parts by weight of 40-60wt% ethanol water solution, stirring for 2-5 hours at room temperature, then adding 5-7 parts by weight of silane coupling agent, continuously stirring for 15-30 minutes, then heating to 70-90 ℃, continuously stirring for reacting for 3-4 hours, and centrifuging, washing and drying after finishing to obtain the aminated cellulose nanocrystals;
s2, adding 1-3 parts by weight of the aminated cellulose nanocrystalline obtained in the step S1 into 40-60 parts by weight of N, N-dimethylformamide, performing ultrasonic dispersion in an ice-water bath for 20-40min, then adding 5-6 parts by weight of triethylamine, continuing ultrasonic treatment for 10-30min to obtain a mixed solution, adding 4-6 parts by weight of alpha-bromoisobutyryl bromide into the mixed solution, reacting for 18-30h at room temperature under the condition of nitrogen atmosphere, and centrifuging, washing and drying after finishing to obtain brominated cellulose nanocrystalline;
s3, adding 0.5-1.5 parts by weight of the brominated cellulose nanocrystalline obtained in the step S2 into 40-60 parts by weight of N, N-dimethylformamide, performing ultrasonic dispersion in an ice-water bath for 20-40min, adding 1-2 parts by weight of an auxiliary agent and 5-6 parts by weight of a monomer, adding 0.4-0.8 part by weight of a catalyst at room temperature under nitrogen atmosphere, heating to 35-45 ℃, reacting for 3-5h under nitrogen protection, and centrifuging, washing and drying after the completion to obtain the modified cellulose nanocrystalline.
6. The high performance degradable plastic of claim 5, wherein the silane coupling agent is any one of 3-aminopropyl triethoxysilane, 3-aminopropyl methyldimethoxysilane, N-2-aminoethyl-3-aminopropyl methyldiethoxysilane.
7. The high performance degradable plastic of claim 4 or 5, wherein the monomer is glycidyl methacrylate and/or benzyl methacrylate.
8. The high performance degradable plastic of claim 1, wherein the compatibilizer is any of maleic anhydride, maleic anhydride grafted polypropylene, ethylene-propylene multiblock copolymer.
9. The high performance degradable plastic according to claim 1, wherein the plasticizer is any one of ethylene glycol, citric acid ester, dioctyl phthalate, and glycerin.
10. A method for preparing a high performance degradable plastic according to any one of claims 1-9, comprising the steps of:
firstly, adding polylactic acid, polybutylene terephthalate, filler, compatilizer and plasticizer into a high-speed mixer according to parts by weight for mixing to obtain a mixture; and then the mixture is put into a double-screw extruder, extruded and granulated, and the high-performance degradable plastic is obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311584470.2A CN117362963A (en) | 2023-11-25 | 2023-11-25 | High-performance degradable plastic and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311584470.2A CN117362963A (en) | 2023-11-25 | 2023-11-25 | High-performance degradable plastic and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117362963A true CN117362963A (en) | 2024-01-09 |
Family
ID=89402532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311584470.2A Pending CN117362963A (en) | 2023-11-25 | 2023-11-25 | High-performance degradable plastic and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117362963A (en) |
-
2023
- 2023-11-25 CN CN202311584470.2A patent/CN117362963A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111718591B (en) | Lignin-containing bio-based composite material and preparation method thereof | |
| CN108948690B (en) | Polylactic acid-lignin-starch composite material and preparation method thereof | |
| CN112961474B (en) | Preparation method of polylactic acid/epoxy vegetable oil all-bio-based composite material | |
| JPH07126449A (en) | Biodegradable chemically-combined-starch-containing polyethylene composition and its production | |
| CN108948689B (en) | Polylactic acid-lignin composite material modified by reactive extrusion method and preparation method thereof | |
| CN114292364B (en) | Silane grafted polypropylene, crosslinked polypropylene material and preparation method thereof | |
| CN109401045B (en) | Special material for high-performance functionalized alloy modified polypropylene corrugated pipe and preparation method thereof | |
| CN110791952B (en) | Modified cellulose fiber and preparation method and application thereof | |
| CN113652067A (en) | Method for preparing carbon fiber polylactic acid composite material | |
| CN104292391A (en) | Melting production method for unsaturated anhydride grafted chlorinated polyethylene | |
| CN116574329B (en) | Preparation process of stretch-resistant polypropylene packaging film | |
| CN116640269B (en) | Composite material based on recycled plastic and preparation method thereof | |
| CN115785582B (en) | Environment-friendly and efficient silane crosslinked polypropylene material and preparation method thereof | |
| CN117362963A (en) | High-performance degradable plastic and preparation method thereof | |
| CN111607209B (en) | High-performance polypropylene carbonate composition and preparation method thereof | |
| CN115216093A (en) | Environment-friendly degradable plastic bag and preparation method thereof | |
| CN116285284A (en) | CO (carbon monoxide) 2 Composition of base biodegradable copolymer, preparation method and application thereof | |
| CN117700965A (en) | Biodegradable PLA composite material | |
| CN107759990A (en) | A kind of full biological poly lactic acid composite and preparation method thereof | |
| CN107698714A (en) | A kind of itaconic anhydride grafted polylactic acid copolymer and its preparation method and application | |
| CN110936584B (en) | Processing method of polyvinyl alcohol hollow container | |
| CN114426764A (en) | Flame-retardant environment-friendly packaging film and preparation method thereof | |
| CN118772614A (en) | PC/PET alloy material, preparation method and application thereof | |
| CN117327339A (en) | Impact-resistant weather-resistant high-modulus composite material for high-density polyethylene corrugated pipe | |
| CN117362948A (en) | Carbon dioxide-based high-temperature-resistant alloy and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |