CN117362946A - Nanocellulose modified polyester composite material and preparation method thereof - Google Patents
Nanocellulose modified polyester composite material and preparation method thereof Download PDFInfo
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- CN117362946A CN117362946A CN202311335386.7A CN202311335386A CN117362946A CN 117362946 A CN117362946 A CN 117362946A CN 202311335386 A CN202311335386 A CN 202311335386A CN 117362946 A CN117362946 A CN 117362946A
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- polyester composite
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- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 229920000728 polyester Polymers 0.000 title claims abstract description 54
- 229920001046 Nanocellulose Polymers 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229920002678 cellulose Polymers 0.000 claims abstract description 80
- 239000001913 cellulose Substances 0.000 claims abstract description 80
- 239000002159 nanocrystal Substances 0.000 claims abstract description 33
- 229920005989 resin Polymers 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 31
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims abstract description 26
- PLFDWSDBRBNQLQ-UHFFFAOYSA-N 1,3,9-triazaspiro[4.5]decane-2,4-dione Chemical compound N1C(=O)NC(=O)C11CNCCC1 PLFDWSDBRBNQLQ-UHFFFAOYSA-N 0.000 claims abstract description 23
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 23
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 19
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical group CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 16
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 16
- 239000007822 coupling agent Substances 0.000 claims abstract description 16
- 239000000314 lubricant Substances 0.000 claims abstract description 16
- 239000002064 nanoplatelet Substances 0.000 claims abstract description 13
- 229920000137 polyphosphoric acid Polymers 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims description 54
- 239000003960 organic solvent Substances 0.000 claims description 28
- 239000003999 initiator Substances 0.000 claims description 22
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 claims description 14
- 239000011261 inert gas Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 9
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 9
- BTWDORUWKSZROD-UHFFFAOYSA-N 3-(1,1-difluoroprop-2-enyl)-1h-quinoxalin-2-one Chemical compound C1=CC=C2N=C(C(F)(F)C=C)C(O)=NC2=C1 BTWDORUWKSZROD-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 6
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 4
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 abstract description 10
- 238000003878 thermal aging Methods 0.000 abstract description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 24
- 239000005020 polyethylene terephthalate Substances 0.000 description 24
- 230000032683 aging Effects 0.000 description 7
- 239000002135 nanosheet Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002114 nanocomposite Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- AIZQDPWDLCZOMG-UHFFFAOYSA-N 3-fluoro-1h-quinoxalin-2-one Chemical group C1=CC=C2NC(=O)C(F)=NC2=C1 AIZQDPWDLCZOMG-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229920000229 biodegradable polyester Polymers 0.000 description 1
- 239000004622 biodegradable polyester Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/329—Phosphorus containing acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
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 provides a nano-cellulose modified polyester composite material and a preparation method thereof, which relate to the technical field of composite materials and are prepared from the following raw materials in parts by weight: 100 parts of PET resin, 5-8 parts of modified cellulose nanocrystals, 10-15 parts of graphene nanoplatelets, 0.5-0.8 part of phosphorus pentoxide, 0.3-0.5 part of polyphosphoric acid, 1-3 parts of coupling agent, 0.6-1 part of antioxidant, 0.3-0.5 part of lubricant and 0.8-1.2 part of compatilizer; the modified cellulose nanocrystalline is 2-acrylamide-2-methylpropanesulfonic acid, methyl methacrylate, allyl salicylate, vinyl trimethoxy silane and 3- (1, 1-difluoro-2-propylene-1-yl) -2 (1H) -quinoxalinone co-modified cellulose nanocrystalline. The nano cellulose modified polyester composite material has the advantages of good mechanical property, good thermal aging resistance, good barrier property and long service life.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a nano cellulose modified polyester composite material and a preparation method thereof.
Background
The molecular structure of the polyester determines the excellent performance, the molecular structure of the PET polyester (polyethylene terephthalate) is highly regular, the molecular arrangement is compact, and the molecular chain segment contains a rigid benzene ring structure, so that the PET has good physical and mechanical properties and is widely applied to a plurality of fields such as medical equipment, packaging materials, textile materials and the like. However, the pure PET resin has the defects of poor high temperature resistance, poor barrier property, insufficient impact toughness, aging resistance, mechanical properties and the like, so that the PET polyester product has the problems of variability, short shelf life and the like. Polyester composites made by adding some inorganic, organic or organic hybrid particles to PET resins are a common approach to solve the above problems.
The existing polyester composite material often causes the problems of insufficient processing fluidity, poor performance stability, short service life and the like of products due to improper selection of added functional auxiliary agents and fillers. In addition, the polyester composite materials on the market have the defects that the functional auxiliary agent and the filler are easy to migrate to the surface of the material in the long-term use process due to the insufficient compatibility between the functional auxiliary agent and the filler and the PET resin base material, so that the material performance is rapidly reduced, and the material performance cannot meet the use requirement in a short time. Therefore, the preparation of the modified polyester composite material with excellent comprehensive performance and performance stability is important in searching for a more suitable modifier and a modification method.
Cellulose Nanocrystalline (CNC) is a nano material prepared by taking plants as raw materials, has a plurality of excellent properties, such as excellent mechanical properties, large rigidity, large specific surface area, wide sources, reproducibility and the like, and can not only improve the strength and modulus of the material, but also improve the brittleness of the material after being added into a polyester resin matrix; and the acting force between polyesters can be enhanced, and the high temperature resistance, the barrier property and the mechanical property of the polyester material can be effectively improved. However, the incompatibility between the cellulose which is a hydrophilic material and the hydrophobic unsaturated polyester causes the problems of uneven dispersion, agglomeration and the like of CNC in a polyester resin matrix. Therefore, the key to modifying the polyester composite with cellulose nanocrystals is to improve the compatibility between the two.
The Chinese patent application No. 201410140289.7 discloses a biodegradable polyester/cellulose nanocomposite and a preparation method thereof, in particular a compatibilizer modified polycaprolactone/cellulose nanocomposite and a preparation method thereof. The compatibilizer can obviously improve the dispersion of cellulose in polycaprolactone and improve the mechanical properties of the nanocomposite. The compatibilizer has biocompatibility and biodegradability, and is beneficial to the application of the nanocomposite in biological medicines. The nanocomposite prepared by melt blending is simple and convenient to operate, has simple production process and is easy to realize large-scale production. However, the thermal aging resistance and mechanical properties of the composite material still need to be further improved.
Therefore, the nano cellulose modified polyester composite material with good mechanical property, good heat aging resistance, good barrier property and long service life and the preparation method thereof are developed, meet the market demand, have wide market value and application prospect, and have great significance for promoting the development of the field of polyester composite materials.
Disclosure of Invention
In view of the above problems, the invention aims to provide a nanocellulose modified polyester composite material with good mechanical properties, good thermal aging resistance, barrier property and long service life and a preparation method thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the nano cellulose modified polyester composite material is prepared from the following raw materials in parts by weight: 100 parts of PET resin, 5-8 parts of modified cellulose nanocrystals, 10-15 parts of graphene nanoplatelets, 0.5-0.8 part of phosphorus pentoxide, 0.3-0.5 part of polyphosphoric acid, 1-3 parts of coupling agent, 0.6-1 part of antioxidant, 0.3-0.5 part of lubricant and 0.8-1.2 part of compatilizer; the modified cellulose nanocrystalline is 2-acrylamide-2-methylpropanesulfonic acid, methyl methacrylate, allyl salicylate, vinyl trimethoxy silane and 3- (1, 1-difluoro-2-propylene-1-yl) -2 (1H) -quinoxalinone co-modified cellulose nanocrystalline.
Preferably, the compatilizer is compatilizer KO-311.
Preferably, the lubricant is at least one of pentaerythritol stearate and ethylene bis-stearamide.
Preferably, the antioxidant is at least one of antioxidant 1010 and antioxidant 168.
Preferably, the coupling agent is at least one of a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH 570.
Preferably, the source of the graphene nanoplatelets is not particularly required, and in one embodiment of the present invention, the graphene nanoplatelets are manufactured according to the method of the embodiment 1 of the chinese patent application No. 202010483769.9.
Preferably, the preparation method of the modified cellulose nanocrystalline comprises the following steps: dispersing cellulose nanocrystals in an organic solvent, then sequentially adding vinyl trimethoxy silane, 2-acrylamide-2-methylpropanesulfonic acid, methyl methacrylate, allyl salicylate, 3- (1, 1-difluoro-2-propylene-1-yl) -2 (1H) -quinoxalinone and an initiator into the organic solvent, stirring the mixture in an inert gas atmosphere at 60-70 ℃ for reaction for 3-5 hours, and removing the solvent by rotary evaporation to obtain the modified cellulose nanocrystals.
Preferably, the mass ratio of the cellulose nanocrystalline to the organic solvent to the vinyl trimethoxy silane to the 2-acrylamido-2-methylpropanesulfonic acid to the methyl methacrylate to the allyl salicylate to the 3- (1, 1-difluoro-2-propen-1-yl) -2 (1H) -quinoxalinone to the initiator is 3 (10-15): (0.8-1.2): 1:1 (0.3-0.5): (0.1-0.3): (0.06-0.1).
Preferably, the organic solvent is at least one of dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone.
Preferably, the initiator is azobisisobutyronitrile; the inert gas is any one of nitrogen, helium, neon and argon.
Preferably, the source of the cellulose nanocrystalline is not particularly required, and in one embodiment of the present invention, the cellulose nanocrystalline is manufactured according to the method of example 1 of the chinese patent application No. 201910560135.6.
Preferably, the PET resin is at least one of a PET resin of Xiamen Tenglong DSR TL-103 in China, a PET008L resin produced by Aclo computers company in Canada, and a PET resin of YS-W01 petrochemical industry in Hainan of China.
The invention also aims at providing a preparation method of the nanocellulose modified polyester composite material, which comprises the following steps: uniformly mixing the raw materials in parts by weight, grinding the raw materials and sieving the raw materials with a 200-400-mesh sieve to obtain a mixed material, then adding the mixed material into o-chlorophenol, uniformly stirring the mixed material at 90-110 ℃, pouring the mixed material into a mould, and drying the mixed material at 180-210 ℃ to constant weight to obtain the nano-cellulose modified polyester composite material.
Preferably, the mass ratio of the mixed material to the o-chlorophenol is 1 (3-5).
Compared with the prior art, the invention has the beneficial effects that:
(1) The preparation method of the nano cellulose modified polyester composite material disclosed by the invention is characterized in that the raw materials are uniformly mixed according to parts by weight, and then dispersed and cast for molding, special equipment is not needed, the energy consumption is low, the investment is low, the preparation efficiency and the finished product qualification rate are high, and the preparation method is suitable for continuous large-scale production; the preparation method of the dispersed casting molding can effectively avoid the decomposition of cellulose nanocrystalline during the extrusion molding of an extruder, and simultaneously can save energy consumption.
(2) The invention discloses a nano cellulose modified polyester composite material which is prepared from the following raw materials in parts by weight: 100 parts of PET resin, 5-8 parts of modified cellulose nanocrystals, 10-15 parts of graphene nanoplatelets, 0.5-0.8 part of phosphorus pentoxide, 0.3-0.5 part of polyphosphoric acid, 1-3 parts of coupling agent, 0.6-1 part of antioxidant, 0.3-0.5 part of lubricant and 0.8-1.2 part of compatilizer; through the mutual matching and combined action of the raw materials, the prepared composite material has the advantages of good mechanical property, good heat aging resistance, good barrier property and long service life.
(3) According to the nano cellulose modified polyester composite material disclosed by the invention, the addition of the graphene nano sheets can not only improve the mechanical properties of the composite material, but also be beneficial to improving the barrier property; the modified cellulose nanocrystalline is 2-acrylamide-2-methylpropanesulfonic acid, methyl methacrylate, allyl salicylate, vinyl trimethoxy silane and 3- (1, 1-difluoro-2-propylene-1-yl) -2 (1H) -quinoxalinone co-modified cellulose nanocrystalline. The surface of the cellulose nanocrystals is modified with a hydrophobic structure, particularly an ester structure is introduced, so that the compatibility between the cellulose nanocrystals and PET resin base materials is improved, the internal compactness of the material is further improved, and the performance stability of the material is better; simultaneously, the introduced amido, salicylate, trimethoxy silane and fluoroquinoxalinone structures can endow the material with excellent heat aging resistance, mechanical property and barrier property under the multiple actions of electronic effect, steric effect and conjugation effect, so that the service life of the material is prolonged; the sulfonic group on the 2-acrylamide-2-methylpropanesulfonic acid can also react chemically with benzene rings on the molecular structure of PET resin under the catalysis of phosphorus pentoxide and polyphosphoric acid, and monomers containing unsaturated olefinic bonds can react in a polymerization way under the action of an initiator; the trimethoxy structure on the vinyl trimethoxy silane can react with the hydroxyl on the cellulose nanocrystals, and the interaction enables the inside of the composite material to form an interpenetrating network structure, so that the physical property and the performance stability of the composite material are effectively improved, and the service life of the composite material is further prolonged.
Detailed Description
In order to better understand the technical solution of the present invention, the following describes the product of the present invention in further detail with reference to examples.
Example 1
The nano cellulose modified polyester composite material is prepared from the following raw materials in parts by weight: 100 parts of PET resin, 5 parts of modified cellulose nanocrystals, 10 parts of graphene nanoplatelets, 0.5 part of phosphorus pentoxide, 0.3 part of polyphosphoric acid, 1 part of coupling agent, 0.6 part of antioxidant, 0.3 part of lubricant and 0.8 part of compatilizer; the modified cellulose nanocrystalline is 2-acrylamide-2-methylpropanesulfonic acid, methyl methacrylate, allyl salicylate, vinyl trimethoxy silane and 3- (1, 1-difluoro-2-propylene-1-yl) -2 (1H) -quinoxalinone co-modified cellulose nanocrystalline.
The compatilizer is compatilizer KO-311; the lubricant is pentaerythritol stearate; the antioxidant is antioxidant 1010; the coupling agent is a silane coupling agent KH550; the graphene nano-sheets are prepared according to the method of the Chinese patent application example 1 with the application number of 202010483769.9.
The preparation method of the modified cellulose nanocrystalline comprises the following steps: dispersing cellulose nanocrystals in an organic solvent, then sequentially adding vinyl trimethoxy silane, 2-acrylamide-2-methylpropanesulfonic acid, methyl methacrylate, allyl salicylate, 3- (1, 1-difluoro-2-propylene-1-yl) -2 (1H) -quinoxalinone and an initiator into the organic solvent, stirring the mixture in an inert gas atmosphere at 60 ℃ for reacting for 3 hours, and removing the solvent by rotary evaporation to obtain modified cellulose nanocrystals; the mass ratio of the cellulose nanocrystals to the organic solvent to the vinyl trimethoxysilane to the 2-acrylamido-2-methylpropanesulfonic acid to the methyl methacrylate to the allyl salicylate to the 3- (1, 1-difluoro-2-propen-1-yl) -2 (1H) -quinoxalinone to the initiator is 3:10:0.8:1:1:0.3:0.1:0.06; the organic solvent is dimethyl sulfoxide; the initiator is azodiisobutyronitrile; the inert gas is nitrogen; the cellulose nanocrystalline is prepared according to the method of the Chinese patent application example 1 with the application number of 201910560135.6.
The PET resin was PET008L resin produced by Aclo computers, canada.
The preparation method of the nanocellulose modified polyester composite material comprises the following steps: uniformly mixing the raw materials in parts by weight, grinding the raw materials and sieving the raw materials with a 200-mesh sieve to obtain a mixed material, adding the mixed material into o-chlorophenol, uniformly stirring the mixed material at 90 ℃, pouring the mixed material into a mould, and drying the mixed material at 180 ℃ to constant weight to obtain the nano-cellulose modified polyester composite material; the mass ratio of the mixed material to the o-chlorophenol is 1:3.
Example 2
The nano cellulose modified polyester composite material is prepared from the following raw materials in parts by weight: 100 parts of PET resin, 6 parts of modified cellulose nanocrystals, 11 parts of graphene nanoplatelets, 0.6 part of phosphorus pentoxide, 0.35 part of polyphosphoric acid, 1.5 parts of coupling agent, 0.7 part of antioxidant, 0.35 part of lubricant and 0.9 part of compatilizer; the modified cellulose nanocrystalline is 2-acrylamide-2-methylpropanesulfonic acid, methyl methacrylate, allyl salicylate, vinyl trimethoxy silane and 3- (1, 1-difluoro-2-propylene-1-yl) -2 (1H) -quinoxalinone co-modified cellulose nanocrystalline.
The compatilizer is compatilizer KO-311; the lubricant is ethylene bis stearamide; the antioxidant is antioxidant 168; the coupling agent is silane coupling agent KH560; the graphene nano-sheets are prepared according to the method of the Chinese patent application example 1 with the application number of 202010483769.9.
The preparation method of the modified cellulose nanocrystalline comprises the following steps: dispersing cellulose nanocrystals in an organic solvent, then sequentially adding vinyl trimethoxy silane, 2-acrylamide-2-methylpropanesulfonic acid, methyl methacrylate, allyl salicylate, 3- (1, 1-difluoro-2-propylene-1-yl) -2 (1H) -quinoxalinone and an initiator into the organic solvent, stirring the mixture in an inert gas atmosphere at 62 ℃ for reaction for 3.5 hours, and then removing the solvent by rotary evaporation to obtain modified cellulose nanocrystals; the mass ratio of the cellulose nanocrystals to the organic solvent to the vinyl trimethoxysilane to the 2-acrylamido-2-methylpropanesulfonic acid to the methyl methacrylate to the allyl salicylate to the 3- (1, 1-difluoro-2-propen-1-yl) -2 (1H) -quinoxalinone to the initiator is 3:12:0.9:1:1:0.35:0.15:0.07; the organic solvent is N, N-dimethylformamide; the initiator is azodiisobutyronitrile; the inert gas is helium; the cellulose nanocrystalline is prepared according to the method of the Chinese patent application example 1 with the application number of 201910560135.6.
The PET resin was PET008L resin produced by Aclo computers, canada.
The preparation method of the nanocellulose modified polyester composite material comprises the following steps: uniformly mixing the raw materials in parts by weight, grinding, sieving with a 250-mesh sieve to obtain a mixed material, adding the mixed material into o-chlorophenol, uniformly stirring at 95 ℃, pouring into a mould, and drying at 190 ℃ to constant weight to obtain the nano-cellulose modified polyester composite material; the mass ratio of the mixed material to the o-chlorophenol is 1:3.5.
Example 3
The nano cellulose modified polyester composite material is prepared from the following raw materials in parts by weight: 100 parts of PET resin, 6.5 parts of modified cellulose nanocrystals, 13 parts of graphene nanoplatelets, 0.65 part of phosphorus pentoxide, 0.4 part of polyphosphoric acid, 2 parts of coupling agent, 0.8 part of antioxidant, 0.4 part of lubricant and 1 part of compatilizer; the modified cellulose nanocrystalline is 2-acrylamide-2-methylpropanesulfonic acid, methyl methacrylate, allyl salicylate, vinyl trimethoxy silane and 3- (1, 1-difluoro-2-propylene-1-yl) -2 (1H) -quinoxalinone co-modified cellulose nanocrystalline.
The compatilizer is compatilizer KO-311; the lubricant is pentaerythritol stearate; the antioxidant is antioxidant 1010; the coupling agent is a silane coupling agent KH570; the graphene nano-sheets are prepared according to the method of the Chinese patent application example 1 with the application number of 202010483769.9.
The preparation method of the modified cellulose nanocrystalline comprises the following steps: dispersing cellulose nanocrystals in an organic solvent, then sequentially adding vinyl trimethoxy silane, 2-acrylamide-2-methylpropanesulfonic acid, methyl methacrylate, allyl salicylate, 3- (1, 1-difluoro-2-propylene-1-yl) -2 (1H) -quinoxalinone and an initiator into the organic solvent, stirring the mixture in an inert gas atmosphere at 65 ℃ for reacting for 4 hours, and removing the solvent by rotary evaporation to obtain modified cellulose nanocrystals; the mass ratio of the cellulose nanocrystals to the organic solvent to the vinyl trimethoxysilane to the 2-acrylamido-2-methylpropanesulfonic acid to the methyl methacrylate to the allyl salicylate to the 3- (1, 1-difluoro-2-propen-1-yl) -2 (1H) -quinoxalinone to the initiator is 3:13:1:1:1:0.4:0.2:0.08; the organic solvent is N-methyl pyrrolidone; the initiator is azodiisobutyronitrile; the inert gas is neon; the cellulose nanocrystalline is prepared according to the method of the Chinese patent application example 1 with the application number of 201910560135.6.
The PET resin was PET008L resin produced by Aclo computers, canada.
The preparation method of the nanocellulose modified polyester composite material comprises the following steps: uniformly mixing the raw materials in parts by weight, grinding the raw materials and sieving the raw materials with a 300-mesh sieve to obtain a mixed material, then adding the mixed material into o-chlorophenol, uniformly stirring the mixed material at 100 ℃, pouring the mixed material into a mould, and drying the mixed material to constant weight at 195 ℃ to obtain the nano-cellulose modified polyester composite material; the mass ratio of the mixed material to the o-chlorophenol is 1:4.
Example 4
The nano cellulose modified polyester composite material is prepared from the following raw materials in parts by weight: 100 parts of PET resin, 7 parts of modified cellulose nanocrystals, 14 parts of graphene nanoplatelets, 0.75 part of phosphorus pentoxide, 0.45 part of polyphosphoric acid, 2.5 parts of coupling agent, 0.9 part of antioxidant, 0.45 part of lubricant and 1.1 part of compatilizer; the modified cellulose nanocrystalline is 2-acrylamide-2-methylpropanesulfonic acid, methyl methacrylate, allyl salicylate, vinyl trimethoxy silane and 3- (1, 1-difluoro-2-propylene-1-yl) -2 (1H) -quinoxalinone co-modified cellulose nanocrystalline.
The compatilizer is compatilizer KO-311; the lubricant is a mixture formed by mixing pentaerythritol stearate and ethylene bis-stearamide according to a mass ratio of 3:5; the antioxidant is a mixture formed by mixing an antioxidant 1010 and an antioxidant 168 according to a mass ratio of 1:3; the coupling agent is a mixture formed by mixing a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH570 according to a mass ratio of 1:3:4; the graphene nano-sheets are prepared according to the method of the Chinese patent application example 1 with the application number of 202010483769.9.
The preparation method of the modified cellulose nanocrystalline comprises the following steps: dispersing cellulose nanocrystals in an organic solvent, then sequentially adding vinyl trimethoxy silane, 2-acrylamide-2-methylpropanesulfonic acid, methyl methacrylate, allyl salicylate, 3- (1, 1-difluoro-2-propylene-1-yl) -2 (1H) -quinoxalinone and an initiator into the organic solvent, stirring the mixture in an inert gas atmosphere at 68 ℃ for reacting for 4.5 hours, and then removing the solvent by rotary evaporation to obtain modified cellulose nanocrystals; the mass ratio of the cellulose nanocrystals to the organic solvent to the vinyl trimethoxysilane to the 2-acrylamido-2-methylpropanesulfonic acid to the methyl methacrylate to the allyl salicylate to the 3- (1, 1-difluoro-2-propen-1-yl) -2 (1H) -quinoxalinone to the initiator is 3:14:1.1:1:1:0.45:0.25:0.09; the organic solvent is a mixture formed by mixing dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone according to a mass ratio of 1:2:1; the initiator is azodiisobutyronitrile; the inert gas is argon; the cellulose nanocrystalline is prepared according to the method of the Chinese patent application example 1 with the application number of 201910560135.6.
The PET resin was PET008L resin produced by Aclo computers, canada.
The preparation method of the nanocellulose modified polyester composite material comprises the following steps: uniformly mixing the raw materials in parts by weight, grinding the raw materials and sieving the raw materials with a 350-mesh sieve to obtain a mixed material, adding the mixed material into o-chlorophenol, uniformly stirring the mixed material at 105 ℃, pouring the mixed material into a mould, and drying the mixed material at 200 ℃ to constant weight to obtain the nano-cellulose modified polyester composite material; the mass ratio of the mixed material to the o-chlorophenol is 1:4.5.
Example 5
The nano cellulose modified polyester composite material is prepared from the following raw materials in parts by weight: 100 parts of PET resin, 8 parts of modified cellulose nanocrystals, 15 parts of graphene nanoplatelets, 0.8 part of phosphorus pentoxide, 0.5 part of polyphosphoric acid, 3 parts of coupling agent, 1 part of antioxidant, 0.5 part of lubricant and 1.2 parts of compatilizer; the modified cellulose nanocrystalline is 2-acrylamide-2-methylpropanesulfonic acid, methyl methacrylate, allyl salicylate, vinyl trimethoxy silane and 3- (1, 1-difluoro-2-propylene-1-yl) -2 (1H) -quinoxalinone co-modified cellulose nanocrystalline.
The compatilizer is compatilizer KO-311; the lubricant is pentaerythritol stearate; the antioxidant is antioxidant 1010; the coupling agent is silane coupling agent KH560; the graphene nano-sheets are prepared according to the method of the Chinese patent application example 1 with the application number of 202010483769.9.
The preparation method of the modified cellulose nanocrystalline comprises the following steps: dispersing cellulose nanocrystals in an organic solvent, then sequentially adding vinyl trimethoxy silane, 2-acrylamide-2-methylpropanesulfonic acid, methyl methacrylate, allyl salicylate, 3- (1, 1-difluoro-2-propylene-1-yl) -2 (1H) -quinoxalinone and an initiator into the organic solvent, stirring the mixture in an inert gas atmosphere at 70 ℃ for reacting for 5 hours, and removing the solvent by rotary evaporation to obtain modified cellulose nanocrystals; the mass ratio of the cellulose nanocrystals to the organic solvent to the vinyl trimethoxysilane to the 2-acrylamido-2-methylpropanesulfonic acid to the methyl methacrylate to the allyl salicylate to the 3- (1, 1-difluoro-2-propen-1-yl) -2 (1H) -quinoxalinone to the initiator is 3:15:1.2:1:1:0.5:0.3:0.1; the organic solvent is N, N-dimethylformamide; the initiator is azodiisobutyronitrile; the inert gas is nitrogen; the cellulose nanocrystalline is prepared according to the method of the Chinese patent application example 1 with the application number of 201910560135.6.
The PET resin was PET008L resin produced by Aclo computers, canada.
The preparation method of the nanocellulose modified polyester composite material comprises the following steps: uniformly mixing the raw materials in parts by weight, grinding the raw materials and sieving the raw materials with a 400-mesh sieve to obtain a mixed material, adding the mixed material into o-chlorophenol, uniformly stirring the mixed material at 110 ℃, pouring the mixed material into a mould, and drying the mixed material at 210 ℃ to constant weight to obtain the nano-cellulose modified polyester composite material; the mass ratio of the mixed material to the o-chlorophenol is 1:5.
Comparative example 1
A nanocellulose-modified polyester composite is substantially the same as example 1, except that graphene nanoplatelets and vinyltrimethoxysilane are not added.
Comparative example 2
A nanocellulose-modified polyester composite substantially the same as in example 1, except that 3- (1, 1-difluoro-2-propen-1-yl) -2 (1H) -quinoxalinone and 2-acrylamido-2-methylpropanesulfonic acid were not added.
In order to further illustrate the unexpected positive technical effects obtained by the products of the embodiments of the present invention, the nanocellulose modified polyester composite materials prepared by the embodiments are subjected to relevant performance detection, the test results are shown in table 1, and the test method is as follows:
(1) Tensile properties: tensile strength was tested according to GB/T1040.1-2018.
(2) Thermal aging resistance: after each example of polyester material product is respectively put into hot air at 85 ℃ for artificial accelerated aging for 96 hours, the heat aging resistance is measured by the retention rate of tensile strength, and the larger the numerical value is, the better the heat aging resistance is.
(3) Oxygen barrier properties: an Ox-TranMOdel2/21 type oxygen permeation instrument (gas: high purity oxygen, temperature: 23.+ -. 1 ℃ C., sample size: 50 cm) was used 2 ) The oxygen permeability of each product was tested according to astm d3985-2005 standard.
TABLE 1
| Project | Tensile Strength | Permeability of oxygen | Thermal aging resistance |
| Unit (B) | MPa | cc/m 2 -day | ％ |
| Example 1 | 81.2 | 3.3024 | 98.5 |
| Example 2 | 82.0 | 3.1569 | 99.0 |
| Example 3 | 83.1 | 3.0176 | 99.3 |
| Example 4 | 84.6 | 2.8931 | 99.5 |
| Example 5 | 85.0 | 2.7617 | 99.9 |
| Comparative example 1 | 70.5 | 4.1205 | 95.6 |
| Comparative example 2 | 75.3 | 3.6130 | 94.1 |
As can be seen from Table 1, compared with the comparative product, the nanocellulose modified polyester composite disclosed by the embodiment of the invention has more excellent mechanical properties, thermal aging resistance and barrier property, and the addition of graphene nanoplatelets, vinyl trimethoxysilane, 3- (1, 1-difluoro-2-propen-1-yl) -2 (1H) -quinoxalinone and 2-acrylamido-2-methylpropanesulfonic acid is beneficial to improving the above properties.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention in any way; those of ordinary skill in the art will readily implement the invention as described above; however, those skilled in the art will appreciate that many modifications, adaptations, and variations of the present invention are possible in light of the above teachings without departing from the scope of the invention; meanwhile, any equivalent changes, modifications and evolution of the above embodiments according to the essential technology of the present invention still fall within the scope of the present invention.
Claims (9)
1. The nano cellulose modified polyester composite material is characterized by being prepared from the following raw materials in parts by weight: 100 parts of PET resin, 5-8 parts of modified cellulose nanocrystals, 10-15 parts of graphene nanoplatelets, 0.5-0.8 part of phosphorus pentoxide, 0.3-0.5 part of polyphosphoric acid, 1-3 parts of coupling agent, 0.6-1 part of antioxidant, 0.3-0.5 part of lubricant and 0.8-1.2 part of compatilizer; the modified cellulose nanocrystalline is 2-acrylamide-2-methylpropanesulfonic acid, methyl methacrylate, allyl salicylate, vinyl trimethoxy silane and 3- (1, 1-difluoro-2-propylene-1-yl) -2 (1H) -quinoxalinone co-modified cellulose nanocrystalline.
2. The nanocellulose-modified polyester composite of claim 1, wherein said compatibilizer is compatibilizer KO-311; the lubricant is at least one of pentaerythritol stearate and ethylene bis-stearamide.
3. The nanocellulose-modified polyester composite of claim 1, wherein said antioxidant is at least one of antioxidant 1010, antioxidant 168; the coupling agent is at least one of silane coupling agent KH550, silane coupling agent KH560 and silane coupling agent KH 570.
4. The nanocellulose modified polyester composite material of claim 1, wherein said modified cellulose nanocrystalline preparation method comprises the steps of: dispersing cellulose nanocrystals in an organic solvent, then sequentially adding vinyl trimethoxy silane, 2-acrylamide-2-methylpropanesulfonic acid, methyl methacrylate, allyl salicylate, 3- (1, 1-difluoro-2-propylene-1-yl) -2 (1H) -quinoxalinone and an initiator into the organic solvent, stirring the mixture in an inert gas atmosphere at 60-70 ℃ for reaction for 3-5 hours, and removing the solvent by rotary evaporation to obtain the modified cellulose nanocrystals.
5. The nanocellulose-modified polyester composite material according to claim 4, wherein the mass ratio of cellulose nanocrystals, organic solvent, vinyltrimethoxysilane, 2-acrylamido-2-methylpropanesulfonic acid, methyl methacrylate, allyl salicylate, 3- (1, 1-difluoro-2-propen-1-yl) -2 (1H) -quinoxalinone, initiator is 3 (10-15): (0.8-1.2): 1:1 (0.3-0.5): (0.1-0.3): (0.06-0.1).
6. The nanocellulose-modified polyester composite of claim 4, wherein said organic solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone; the initiator is azodiisobutyronitrile; the inert gas is any one of nitrogen, helium, neon and argon.
7. The nanocellulose-modified polyester composite of claim 1, wherein said PET resin is at least one of DSR TL-103PET resin, PET008L resin, YS-W01 PET resin.
8. A method of preparing a nanocellulose modified polyester composite material as claimed in any one of claims 1 to 7 comprising the steps of: uniformly mixing the raw materials in parts by weight, grinding the raw materials and sieving the raw materials with a 200-400-mesh sieve to obtain a mixed material, then adding the mixed material into o-chlorophenol, uniformly stirring the mixed material at 90-110 ℃, pouring the mixed material into a mould, and drying the mixed material at 180-210 ℃ to constant weight to obtain the nano-cellulose modified polyester composite material.
9. The preparation method of the nanocellulose modified polyester composite material of claim 8, wherein the mass ratio of the mixed material to the o-chlorophenol is 1 (3-5).
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105754308A (en) * | 2016-03-21 | 2016-07-13 | 武汉理工大学 | Acetylated cellulose nanocrystalline composite modified biomass-based polyester material and preparation method thereof |
| WO2020069850A1 (en) * | 2018-10-03 | 2020-04-09 | Unilever N.V. | Flexible packaging film comprising nanocellulose |
| CN112899800A (en) * | 2019-11-19 | 2021-06-04 | 中国科学院理化技术研究所 | Graphene and nanocellulose modified composite fiber and preparation method thereof |
| CN114231013A (en) * | 2021-12-02 | 2022-03-25 | 田祝英 | Environment-friendly plastic building template material and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105754308A (en) * | 2016-03-21 | 2016-07-13 | 武汉理工大学 | Acetylated cellulose nanocrystalline composite modified biomass-based polyester material and preparation method thereof |
| WO2020069850A1 (en) * | 2018-10-03 | 2020-04-09 | Unilever N.V. | Flexible packaging film comprising nanocellulose |
| CN112899800A (en) * | 2019-11-19 | 2021-06-04 | 中国科学院理化技术研究所 | Graphene and nanocellulose modified composite fiber and preparation method thereof |
| CN114231013A (en) * | 2021-12-02 | 2022-03-25 | 田祝英 | Environment-friendly plastic building template material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 周娇;马晓军;: "纳米纤维素/生物塑料界面改性方法及其研究进展", 化工新型材料, no. 08, 15 August 2017 (2017-08-15), pages 115 - 17 * |
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