CN114573918A - High-barrier low-odor polyolefin composition and preparation method thereof - Google Patents
High-barrier low-odor polyolefin composition and preparation method thereof Download PDFInfo
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- CN114573918A CN114573918A CN202210405506.5A CN202210405506A CN114573918A CN 114573918 A CN114573918 A CN 114573918A CN 202210405506 A CN202210405506 A CN 202210405506A CN 114573918 A CN114573918 A CN 114573918A
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- deodorant
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- 239000000203 mixture Substances 0.000 title claims abstract description 58
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- -1 polypropylene Polymers 0.000 claims abstract description 83
- 239000004743 Polypropylene Substances 0.000 claims abstract description 62
- 239000000126 substance Substances 0.000 claims abstract description 61
- 239000002781 deodorant agent Substances 0.000 claims abstract description 56
- 229920001155 polypropylene Polymers 0.000 claims abstract description 56
- 239000002131 composite material Substances 0.000 claims abstract description 47
- 229920002678 cellulose Polymers 0.000 claims abstract description 43
- 239000001913 cellulose Substances 0.000 claims abstract description 43
- 239000002159 nanocrystal Substances 0.000 claims abstract description 33
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 32
- 239000007822 coupling agent Substances 0.000 claims abstract description 32
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 29
- 230000004888 barrier function Effects 0.000 claims abstract description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 5
- 150000005215 alkyl ethers Chemical class 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 56
- 238000006243 chemical reaction Methods 0.000 claims description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000003054 catalyst Substances 0.000 claims description 33
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 26
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 20
- 239000011159 matrix material Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 14
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000011787 zinc oxide Substances 0.000 claims description 13
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 12
- 229910021645 metal ion Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 11
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 9
- 239000001569 carbon dioxide Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 239000003444 phase transfer catalyst Substances 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 239000000835 fiber Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 238000001746 injection moulding Methods 0.000 claims description 5
- 238000005342 ion exchange Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- 125000004423 acyloxy group Chemical group 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 150000002148 esters Chemical group 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical group [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 4
- PPABWZVICOTUPJ-BYPYZUCNSA-N 3-[(2S)-oxiran-2-yl]propanoic acid Chemical compound OC(=O)CC[C@H]1CO1 PPABWZVICOTUPJ-BYPYZUCNSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000009472 formulation Methods 0.000 claims description 3
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 claims description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 2
- 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 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 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 2
- 229930013930 alkaloid Natural products 0.000 claims description 2
- 150000003797 alkaloid derivatives Chemical class 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 229920006228 ethylene acrylate copolymer Polymers 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- 229920006226 ethylene-acrylic acid Polymers 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical group [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 2
- 239000002585 base Substances 0.000 claims 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N n-hexene Natural products CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims 1
- 239000008188 pellet Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 21
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 abstract description 6
- 230000002045 lasting effect Effects 0.000 abstract description 2
- 235000010980 cellulose Nutrition 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 25
- 239000000047 product Substances 0.000 description 14
- 230000035943 smell Effects 0.000 description 12
- 238000004806 packaging method and process Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 238000005809 transesterification reaction Methods 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- SGOVTJSOCUCZKH-UHFFFAOYSA-H [Zn+2].P(=O)([O-])([O-])[O-].[Zr+4].P(=O)([O-])([O-])[O-] Chemical compound [Zn+2].P(=O)([O-])([O-])[O-].[Zr+4].P(=O)([O-])([O-])[O-] SGOVTJSOCUCZKH-UHFFFAOYSA-H 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000002134 carbon nanofiber Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- CTKINSOISVBQLD-VKHMYHEASA-N (S)-Glycidol Chemical compound OC[C@H]1CO1 CTKINSOISVBQLD-VKHMYHEASA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 229920001046 Nanocellulose Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 230000002452 interceptive effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241000218631 Coniferophyta Species 0.000 description 1
- 241000721662 Juniperus Species 0.000 description 1
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 description 1
- 230000007515 enzymatic degradation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a high-barrier low-odor polyolefin composition and a preparation method thereof, wherein the composition comprises the following materials in parts by weight: 80-90 parts of polyolefin, 5-15 parts of modified cellulose nanocrystals (modified CNCs), 5-10 parts of composite deodorant, 0.3-0.5 part of antioxidant and 1-2 parts of coupling agent; the modified cellulose nanocrystal has a chemical structure as shown in the following formula I:
wherein R is1Is H atom, or alkyl or alkenyl with the number of carbon atoms not more than 6; r2Is methylene or alkyl ether, when R is2The number of carbon atoms is not more than 10 when the methylene is used. The invention can realize high gas barrier effect and high odor removal effect and lasting removal effect on polypropylene.
Description
Technical Field
The invention relates to the technical field of modification of high polymer materials, in particular to a high-barrier low-odor polyolefin composition and a preparation method thereof.
Background
Polyolefin is an important downstream department in the olefin industry, has the advantages of annual high yield, wide application range, good chemical stability, corrosion resistance, no toxicity, low cost and the like, is important to economy, and plays a significant role in our daily life. Compared with other general thermoplastic plastics, the polyolefin has the advantages of small relative density, good processability, low cost, high flexibility and transparency, chemical inertness, colorlessness, translucency, no toxicity and the like, so that the polyolefin is widely applied to a plurality of fields of chemical industry, buildings, household appliances, agriculture, transportation and the like, in particular to the packaging industry. However, polyolefins and various additives can produce different degrees of odor during processing and use. Polyolefin injection molding products such as food packages, automotive upholsteries and the like, particularly PP materials have obvious peculiar smells when being heated, the safety and the wide applicability of the PP products are greatly reduced due to the smells, and the polypropylene packaging materials have poor barrier property to gases such as oxygen, carbon dioxide and the like, so that the quality in the packages is deteriorated or the smells are difficult to clean.
At home and abroad, the volatile organic substances are usually adsorbed by adding an inorganic adsorbent through a porous structure, but the adverse effect of desorption exists, so that the high-efficiency volatile organic substances are not easy to remove. In addition, although the content of volatile organic compounds can be reduced by using multi-stage vacuum and baking, the required process conditions and equipment are difficult to obtain in practice, and thus, the method is not suitable for batch operation.
Therefore, the polyolefin material has better and longer barrier effect on gas on the basis of improving the product quality in order to remove the odor of the polyolefin product.
Disclosure of Invention
In order to solve the technical problems, a high-barrier low-odor polyolefin composition and a preparation method thereof are provided. The composition can remove the odor of polyolefin and enables the polyolefin material to have better and longer barrier effect on gas.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a high-barrier low-odor polyolefin composition comprises the following materials in parts by weight: 80-90 parts of polyolefin, 5-15 parts of modified cellulose nanocrystals (modified CNCs), 5-10 parts of composite deodorant, 0.3-0.5 part of antioxidant and 1-2 parts of coupling agent;
the modified cellulose nanocrystal has a chemical structure as shown in the following formula I:
wherein R is1Is H atom, or alkyl or alkenyl with the number of carbon atoms not more than 6; r2Is methylene or alkyl ether, when R is2The number of carbon atoms is not more than 10 when the methylene is used.
Further, the polyolefin is one or more of polyethylene, polypropylene, ethylene-1-hexene copolymer, propylene-1-hexene copolymer, ethylene-1-octene copolymer, propylene-octene copolymer, poly-1-butene, polyoctene, poly-4-methyl-1-pentene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid or acrylate copolymer and cycloolefin polymer.
Further, the composite deodorant is prepared by loading metal ions and other deodorant on a porous matrix serving as a carrier, wherein the porous matrix is one or more of zeolite, nano-silica and zirconium phosphate; the other smell removing agent is one or more of alkaloid, fendorin and dodecyl quaternary ammonium salt, the metal ions are one or more of zinc ions, silver ions and copper ions, and the metal ions are loaded on the porous matrix in the form of oxide, simple substance or other compounds; the mass ratio of the porous matrix to the plant deodorant to the metal ions is (2-5): 1-2.5.
Preferably, the composite deodorant is prepared by loading fendorin, dodecyl quaternary ammonium salt and zinc ions on zirconium phosphate serving as a carrier, wherein the mass ratio of the zirconium phosphate to the fendorin to the dodecyl quaternary ammonium salt to the zinc ions is (2-5) to 1:1.2: 1. The zirconium phosphate has a layered structure, can perform ion exchange, has selective adsorption and catalytic performance, has high thermal stability and acid and alkali resistance, and can be used as an antibacterial deodorant. The fendorin is a concentrated commercial product obtained by extracting and refining various plants such as conifers, junipers and the like, has good effects of removing formaldehyde, peculiar smell and VOC, and is a commercial product in the market such as JP-ECO fendorin and the like. The dodecyl quaternary ammonium salt is a non-oxidized cationic surfactant, has good effects of disinfection, sterilization and odor removal, and simultaneously, the long-chain alkyl of the dodecyl quaternary ammonium salt plays a role in promoting the compounding of the compound odor removal agent and the polyolefin matrix.
Still further, the preparation method of the compound deodorant comprises the following steps: calculating the raw material dosage according to the mass ratio of each substance in the composite deodorant, then dispersing the porous matrix in water, adding a water-soluble metal ion precursor, uniformly stirring, carrying out ion exchange reaction at 50-120 ℃ for 30min-24h, then carrying out solid-liquid separation, drying, crushing, and calcining at 700-800 ℃ for 1-3h to obtain metal-loaded porous matrix ions; and then dispersing the other deodorant in water, uniformly mixing the other deodorant with the metal ions loaded on the porous matrix, and drying to obtain the composite deodorant.
Further, the antioxidant is a mixture of the antioxidant 1010 and the antioxidant 168 which are mixed according to any proportion; the coupling agent is any one of isopropyl tri (dioctyl pyrophosphate acyloxy) titanate and isopropyl tri dioctyl phosphate acyloxy titanate.
Further, the preparation method of the modified cellulose nanocrystal comprises the following steps:
(1) removing impurities from carbon dioxide in a reaction kettle, reacting an epoxy compound with a chemical structure shown in a formula II with carbon dioxide at 30-40 ℃ for 10-16h under the action of a metal oxide catalyst and a phase transfer catalyst under stirring, cooling to room temperature after the reaction is finished, and relieving pressure to obtain a compound with a chemical structure shown in a formula III;
wherein R is1Is H atom, or alkyl or alkenyl with the number of carbon atoms not more than 6; r is2Is methylene or an alkyl ether, when R2The number of carbon atoms is not more than 10 when the methylene is adopted;
(2) and (3) carrying out ester exchange reaction on the compound with the chemical structure shown in the formula III, Cellulose Nanocrystals (CNCs), alkali and a catalyst at the temperature of 110-160 ℃ for 4-8h, recovering the catalyst, washing a product to be neutral, and drying to obtain the modified cellulose nanocrystals (modified CNCs) with the chemical structure shown in the formula I.
In the above reaction process, the CNCs is a one-dimensional fiber structure material, the chemical structure has a plurality of hydroxyl groups, a hydroxyl group is integrally shown and marked in the chemical equation for the convenience of expression, the spherical shape outside the CNCs in the reaction equation has no limitation on the microstructure of the CNCs, the marked hydroxyl group is only used for explaining that the hydroxyl group on the chemical structure of the CNCs can perform an ester exchange reaction with the compound having the chemical structure of formula iii, and is not used for limiting the reaction in which only one hydroxyl group participates, but also can be used for reacting a plurality of hydroxyl groups on the chemical structure with the compound having the chemical structure of formula iii, and the degree of ester exchange is related to the amount of raw materials. In the above reaction, step 1 is a ring-opening addition reaction of carbon dioxide to an epoxy compound to generate a cyclic carbonate compound (iii), and step 2 is a transesterification reaction of the ring-opening of the cyclic carbonate compound and hydroxyl groups on the cellulose nanocrystals under the action of alkali and a catalyst to obtain a compound with a corresponding chemical structure i accompanied by the production of an alkoxide by-product. The carbonate bond on the compound with the chemical structure I is a rigid group, so that the mechanical enhancement effect on polyolefin can be achieved, alkyl ester or alkenyl ester which is connected subsequently has better compatibility on polyolefin, the dispersion effect of inorganic cellulose nanocrystals in polyolefin can be improved, and the modified CNCs and the polyolefin have better interface binding property and are uniformly dispersed in a matrix.
Further, in step 1, the metal oxide catalyst is zinc oxide, the phase transfer catalyst is tetrabutylammonium iodide or tetrabutylammonium bromide, and the epoxy compound having the chemical structure of formula II is preferably (S) -glycidylacetate or 2-methyl-2-epoxyethylmethyl acrylate; the molar ratio of the epoxy compound with the chemical structure shown in the formula II to the carbon dioxide is (1-1.2): (0.01-0.04), the total amount of the metal oxide catalyst and the phase transfer catalyst is 0.2-0.5% of the molar amount of the epoxy compound with the chemical structure shown in the formula II, and the mass ratio of the metal oxide catalyst to the phase transfer catalyst is 1: 0.8.
Further, in the step 2, the alkali is sodium hydroxide or potassium hydroxide, the catalyst is stannous octoate and/or dibutyltin dilaurate, the fiber length of the cellulose nanocrystal is 50-500nm, and the fiber diameter is 5-20 nm; the mass ratio of the cellulose nanocrystal to the compound with the chemical structure shown in the formula III to the alkali is (2-2.5) to (12-18) to (1-3), and the addition amount of the catalyst is 0.6-1% of the mass of the cellulose nanocrystal.
According to another aspect of the invention, the preparation method of the high-barrier low-odor polyolefin composition comprises the steps of premixing polyolefin, modified cellulose nanocrystals, a composite deodorant, an antioxidant and a coupling agent uniformly according to a formula, carrying out melt blending extrusion at the temperature of 210 ℃ below zero to obtain granules, and carrying out injection molding.
The beneficial technical effects are as follows:
according to the invention, the polypropylene composition material with high barrier property and low odor can be obtained by adding the modified CNCs and the composite deodorant into the polypropylene material. According to the invention, on one hand, CNCs are modified, alkyl ester groups which simultaneously have carbonate rigid groups and can have good compatibility with a polypropylene matrix are grafted through hydroxyl groups in the molecular structure of CNCs, and the cellulose and carbonate rigid groups simultaneously improve the mechanical property of polypropylene and enable a cellulose inorganic material to have good compatibility with polypropylene; in addition, CNCs are independently used to have no effect on the odor removal of polypropylene, and a composite odor removal agent is independently used to have a common odor removal effect on polypropylene, but the modified CNCs and the composite odor removal agent with zirconium phosphate loaded with fendorin, dodecyl quaternary ammonium salt and zinc ions can achieve a high gas barrier effect on polypropylene, a high odor removal effect and a lasting odor removal effect.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless specifically stated otherwise, the numerical values set forth in these examples do not limit the scope of the invention. Techniques, methods known to those of ordinary skill in the relevant art may not be discussed in detail, but are intended to be part of the specification where appropriate. In all examples shown and discussed herein, any particular value should be construed as merely illustrative, and not limiting. Thus, other examples of the exemplary embodiments may have different values.
The experimental methods, for which specific conditions are not noted in the following examples, are generally determined according to national standards; if no corresponding national standard exists, the method is carried out according to the universal international standard or the standard requirement proposed by related enterprises. Unless otherwise indicated, all parts are parts by weight and all percentages are percentages by weight.
Description of cellulose: crystalline and amorphous states exist in the cellulose structure due to the presence of hydrogen bonds in the cellulose molecules. The amorphous cellulose may be removed by mechanical, enzymatic degradation or chemical processes to yield nanocellulose. Nanocellulose can be generally divided into three categories, depending on size, preparation method and source: cellulose, process for producing the same, and process for producing the sameNanofibers (CNF), Cellulose Nanocrystals (CNC), and Bacterial Nanocellulose (BNC). The nano-cellulose is prepared by extracting from the microcrystalline cellulose structure from top to bottom. The aspect ratio of CNF is generally larger, the diameter is generally between 5 and 20nm, and the length can reach micron level. CNFs are usually obtained by mechanical treatment of pulp, and therefore CNFs still contain more amorphous regions and are not very crystalline. And CNC is usually a nano-rod-shaped or fibrous structure prepared by removing amorphous cellulose from pulp through sulfuric acid hydrolysis, and has relatively high crystallinity. The diameter of the CNC is about 5-20nm, and the length of the CNC is 50-500 nm. CNC surfaces prepared by sulfuric acid hydrolysis will contain a sulfuric acid matrix and thus the CNC surface is negatively charged. Due to electrostatic repulsion, CNC can be well dispersed in water. The following examples select the degree of crystallinity (f)c) Cellulose Nanocrystals (CNC) of 70-85%, average fiber length 100 + -15 nm, average fiber diameter 5-20nm were modified.
Examples the polyolefins in the following examples take polypropylene as an example, and polyolefin articles for corresponding uses are generally obtained by changing the kind of polyolefin according to the property characteristics of the polyolefin.
Example 1
The high-barrier low-odor polypropylene composition comprises the following materials in parts by weight: 80 parts of polypropylene, 15 parts of modified cellulose nanocrystals (modified CNCs), 10 parts of composite deodorant, 0.5 part of antioxidant and 2 parts of coupling agent;
the preparation method of the modified CNCs comprises the following steps:
(1) 142g of ethylene oxide methyl 2-methyl-2-acrylate (II, 1mol), 0.28g of zinc oxide catalyst and tetrabutylammonium iodide phase transfer (CHIN) catalyst (the mass ratio of zinc oxide to CHIN is 1:0.8) are added into a 50mL autoclave; then 1MPa of high-purity CO is introduced into the reaction kettle2(purity is at least 99.9%) slowly releasing pressure to normal pressure, repeating the operation for three times, and then keeping the temperature of the reaction kettleHeating to 40 deg.C, stirring, and introducing CO2(1MPa, 0.019mol) is reacted for 14h, then the reaction is stopped, and after the reaction kettle is cooled to room temperature, the pressure is slowly released, so that the compound with the chemical structure shown in the formula III is obtained;
(2) adding 2g of CNCs, 16g of a chemical structure compound shown in the formula III, 0.012g of dibutyltin dilaurate catalyst and 1g of sodium hydroxide into a reaction bottle, stirring, carrying out transesterification reaction at 140 ℃ for 8h, then finishing the reaction, recovering the catalyst, washing the product with deionized water for multiple times until the product is neutral to obtain modified CNCs (I), and placing the modified CNCs (I) into a vacuum oven for drying and then sealing for storage.
The composite deodorant is prepared by loading fendorin, dodecyl dimethyl benzyl ammonium chloride and zinc ions on zirconium phosphate serving as a carrier, wherein the mass ratio of the zirconium phosphate to the fendorin to the dodecyl dimethyl benzyl ammonium chloride to the zinc ions is 2.5:1:1.2: 1; the preparation method of the compound deodorant comprises the following steps: calculating the use amount of raw materials according to the mass ratio of substances in the composite deodorant, dispersing a zirconium phosphate porous matrix in water (the dispersion is carried out according to the amount of 0.2g/mL, ultrasonic dispersion can be adopted in the dispersion process), adding zinc nitrate (a zinc ion source), uniformly stirring, carrying out ion exchange reaction at 60 ℃ for 30min, then carrying out solid-liquid separation, drying, crushing, and calcining at 750 ℃ for 2h to obtain zirconium phosphate zinc-loaded ions; and dispersing the fendorin and the dodecyl dimethyl benzyl ammonium chloride in water, uniformly mixing with the zirconium phosphate zinc-loaded ions, and drying to obtain the composite deodorant.
Wherein, the antioxidant is a compound mixture of 1010 and 168 in equal proportion; the coupling agent is isopropyl tri (dioctyl pyrophosphato acyloxy) titanate.
The preparation method of the high-barrier low-odor polypropylene composition of the embodiment comprises the following steps: uniformly premixing the polypropylene, the modified CNCs, the composite deodorant, the antioxidant and the coupling agent according to the proportion, then carrying out melt blending extrusion at the temperature of 180-210 ℃ to obtain granules, and then carrying out injection molding to obtain the packaging product.
Example 2
The high-barrier low-odor polypropylene composition comprises the following materials in parts by weight: 80 parts of polypropylene, 15 parts of modified cellulose nanocrystals (modified CNCs), 8 parts of composite deodorant, 0.4 part of antioxidant and 1.5 parts of coupling agent;
among them, the preparation method of modified CNCs was the same as in example 1 except that:
(1) a50 mL autoclave was charged with 116g of (S) -glycidylacetate (II, 1mol), 0.46g of zinc oxide catalyst and tetrabutylammonium iodide phase transfer (CHIN) catalyst (zinc oxide to CHIN mass ratio of 1: 0.8); then 1MPa of high-purity CO is introduced into the reaction kettle2(purity is at least 99.9 percent), slowly releasing pressure to normal pressure, repeating the operation for three times, heating the reaction kettle to 30 ℃, starting stirring, and introducing CO2(1MPa, 0.019mol) is reacted for 10 hours, then the reaction is stopped, and the pressure is slowly released after the reaction kettle is cooled to room temperature, so that the compound with the chemical structure shown in the formula III is obtained;
(2) adding 2.2g of CNCs, 17.6g of a chemical structure compound shown in the formula III, 0.022g of dibutyltin dilaurate catalyst and 2g of sodium hydroxide into a reaction bottle, carrying out transesterification reaction at 120 ℃ under stirring for 6h, then finishing the reaction, recovering the catalyst, washing the product with deionized water for multiple times until the product is neutral to obtain modified CNCs (I), and placing the modified CNCs (I) into a vacuum oven for drying and then sealing for storage.
The composite deodorant is prepared by loading fendorin, dodecyl dimethyl benzyl ammonium chloride and zinc ions on zirconium phosphate serving as a carrier, wherein the mass ratio of the zirconium phosphate to the fendorin to the dodecyl dimethyl benzyl ammonium chloride to the zinc ions is 2.5:1:1.2: 1; the preparation method of the compound deodorant comprises the following steps: calculating the use amount of raw materials according to the mass ratio of each substance in the composite deodorant, dispersing a zirconium phosphate porous matrix in water (dispersing according to the amount of 0.2g/mL, wherein ultrasonic dispersion can be adopted in the dispersing process), adding zinc nitrate, uniformly stirring, performing ion exchange reaction at 80 ℃ for 40min, then performing solid-liquid separation, drying, crushing, and calcining at 750 ℃ for 2h to obtain zirconium phosphate zinc-loaded ions; and dispersing the fendorin and the dodecyl dimethyl benzyl ammonium chloride in water, uniformly mixing with the zirconium phosphate zinc-loaded ions, and drying to obtain the composite deodorant.
Wherein, the antioxidant is a compound mixture of 1010 and 168 in equal proportion; the coupling agent is isopropyl tri (dioctyl pyrophosphato acyloxy) titanate.
The preparation method of the high-barrier low-odor polypropylene composition of the embodiment comprises the following steps: uniformly premixing the polypropylene, the modified CNCs, the composite deodorant, the antioxidant and the coupling agent according to the proportion, then carrying out melt blending extrusion at the temperature of 180-210 ℃ to obtain granules, and then carrying out injection molding to obtain the packaging product.
Example 3
The high-barrier low-odor polypropylene composition comprises the following materials in parts by weight: 80 parts of polypropylene, 15 parts of modified cellulose nanocrystals (modified CNCs), 10 parts of composite deodorant, 0.5 part of antioxidant and 2 parts of coupling agent;
the preparation of modified CNCs was the same as in example 2, except that: in the step (1), the dosage of (S) -glycidol acetate (II) is 1.2mol, the total dosage of zinc oxide and CHIN is 0.47g, and the reaction condition is that the compound with the compound structure shown in the formula III is obtained after 12 hours of reaction at 35 ℃; in the step (2), the amounts of CNCs, the compound having the chemical structure of formula III, the catalyst and sodium hydroxide were 2.2g, 15.8g, 0.022g and 2g, respectively, and the modified CNCs (I) having the chemical structure of example 2 were obtained by reacting at 130 ℃ for 6 hours under transesterification conditions.
The selection of the composite deodorant, the antioxidant and the coupling agent and the preparation of the polypropylene composition are the same as those in example 2.
Example 4
The high-barrier low-odor polypropylene composition comprises the following materials in parts by weight: 85 parts of polypropylene, 10 parts of modified cellulose nanocrystals (modified CNCs), 5 parts of composite deodorant, 0.4 part of antioxidant and 2 parts of coupling agent;
among them, the preparation method of modified CNCs was the same as in example 1 except that: in the step (1), the dosage of 2-methyl-2-epoxyethyl methyl acrylate (II) is 1.2mol, the total dosage of zinc oxide and CHIN is 0.34g, and the reaction condition is that the compound with the compound structure shown in the formula III is obtained after reaction for 12 hours at 40 ℃; in the step (2), the amounts of the CNCs, the compound having the chemical structure of formula III, the catalyst and sodium hydroxide were 2.1g, 16.8g, 0.021g and 2g, respectively, and the modified CNCs (I) having the chemical structure of example 1 were obtained by reacting at 150 ℃ for 5 hours.
The selection of the composite deodorant, the antioxidant and the coupling agent and the preparation of the polypropylene composition are the same as those in example 1.
Example 5
The high-barrier low-odor polypropylene composition comprises the following materials in parts by weight: 85 parts of polypropylene, 10 parts of modified cellulose nanocrystals (modified CNCs), 8 parts of composite deodorant, 0.3 part of antioxidant and 1 part of coupling agent;
among them, the preparation method of modified CNCs was the same as in example 1 except that: in the step (1), the dosage of 2-methyl-2-epoxyethyl methyl acrylate (II) is 1.1mol, the total dosage of zinc oxide and CHIN is 0.78g, and the reaction condition is that the compound with the compound structure shown in the formula III is obtained after the reaction is carried out for 10 hours at 40 ℃; in the step (2), the amounts of CNCs, the compound having the chemical structure of formula III, the catalyst and sodium hydroxide were 2.2g, 17.6g, 0.013g and 3g, respectively, and the modified CNCs (I) having the chemical structure of example 1 were obtained by reacting at 160 ℃ for 6 hours under transesterification conditions.
The selection of the composite deodorant, the antioxidant and the coupling agent and the preparation of the polypropylene composition are the same as those in example 1.
Example 6
The high-barrier low-odor polypropylene composition comprises the following materials in parts by weight: 85 parts of polypropylene, 10 parts of modified cellulose nanocrystals (modified CNCs), 10 parts of composite deodorant, 0.5 part of antioxidant and 1.5 parts of coupling agent;
the preparation method of the modified CNCs is the same as that in example 2, except that: in the step (1), the dosage of (S) -glycidol acetate (II) is 1.1mol, the total dosage of zinc oxide and CHIN is 0.64g, and the reaction conditions are 40 ℃ for 12h to obtain a compound with a compound structure shown in a formula III; in the step (2), the amounts of CNCs, the compound having the chemical structure of formula III, the catalyst and sodium hydroxide were 2g, 15g, 0.02g and 3g, respectively, and the modified CNCs (I) having the chemical structure of example 2 were obtained by reacting at 140 ℃ for 6 hours under transesterification conditions.
The selection of the composite deodorant, the antioxidant and the coupling agent and the preparation of the polypropylene composition are the same as those in example 2.
Example 7
The high-barrier low-odor polypropylene composition comprises the following materials in parts by weight: 90 parts of polypropylene, 5 parts of modified cellulose nanocrystals (modified CNCs), 5 parts of composite deodorant, 0.5 part of antioxidant and 2 parts of coupling agent;
the modified CNCs were prepared by the same method as in example 1, except that: in the step (1), the dosage of 2-methyl-2-epoxyethyl methyl acrylate (II) is 1.1mol, the total dosage of zinc oxide and CHIN is 0.55g, and the reaction condition is that the compound with the compound structure shown in the formula III is obtained after reaction for 12 hours at 40 ℃; in the step (2), the amounts of CNCs, the compound having the chemical structure of formula III, the catalyst and sodium hydroxide were 2.1g, 17.6g, 0.0126g and 3g, respectively, and the modified CNCs (I) having the chemical structure of example 1 were obtained by conducting the transesterification reaction at 160 ℃ for 7 hours.
The selection of the composite deodorant, the antioxidant and the coupling agent and the preparation of the polypropylene composition are the same as those in example 1.
Example 8
The high-barrier low-odor polypropylene composition comprises the following materials in parts by weight: 90 parts of polypropylene, 5 parts of modified cellulose nanocrystals (modified CNCs), 8 parts of composite deodorant, 0.3 part of antioxidant and 1.5 parts of coupling agent;
the preparation method of the modified CNCs is the same as that in example 2, except that: in the step (1), the dosage of (S) -glycidol acetate (II) is 1.1mol, the total dosage of zinc oxide and CHIN is 0.70g, and the reaction condition is that the compound with the compound structure shown in the formula III is obtained after reaction for 10h at 40 ℃; in the step (2), the amounts of CNCs, the compound having the chemical structure of formula III, the catalyst and sodium hydroxide were 2g, 15.8g, 0.016g and 3g, respectively, and the modified CNCs (I) having the chemical structure of example 2 were obtained by reacting at 150 ℃ for 6 hours.
The selection of the composite deodorant, the antioxidant and the coupling agent and the preparation of the polypropylene composition are the same as those in example 2.
Example 9
The high-barrier low-odor polypropylene composition comprises the following materials in parts by weight: 90 parts of polypropylene, 5 parts of modified cellulose nanocrystals (modified CNCs), 10 parts of composite deodorant, 0.4 part of antioxidant and 1 part of coupling agent;
among them, the preparation method of modified CNCs was the same as in example 1 except that: in the step (1), the dosage of 2-methyl-2-epoxyethyl methyl acrylate (II) is 1.2mol, the total dosage of zinc oxide and CHIN is 0.60g, and the reaction condition is that the compound with the compound structure shown in the formula III is obtained after 10 hours of reaction at 35 ℃; in the step (2), the amounts of CNCs, the compound having the chemical structure of formula III, the catalyst and sodium hydroxide were 2.2g, 17.6g, 0.016g and 2g, respectively, and the modified CNCs (I) having the chemical structure of example 1 were obtained by reacting at 120 ℃ for 8 hours under transesterification conditions.
The selection of the composite deodorant, the antioxidant and the coupling agent and the preparation of the polypropylene composition are the same as those in example 1.
Comparative example 1
The polypropylene composition of the comparative example comprises the following materials in parts by weight: 100 parts of polypropylene, 0.5 part of antioxidant and 2 parts of coupling agent, and the selection of the substances and the preparation of the composition are the same as those in the example 1.
Comparative example 2
The polypropylene composition of this comparative example comprises the following materials in parts by weight: 100 parts of polypropylene, 10 parts of composite deodorant, 0.5 part of antioxidant and 2 parts of coupling agent, and the selection of the substances and the preparation of the composition are the same as those in example 3.
Comparative example 3
The polypropylene composition of this comparative example comprises the following materials in parts by weight: 100 parts of polypropylene, 15 parts of modified CNCs (modified CNCs in example 3), 0.5 part of antioxidant, 2 parts of coupling agent, and the selection of other substances and the preparation of the composition are the same as those in example 3.
Comparative example 4
The polypropylene composition of this comparative example comprises the following materials in parts by weight: 100 parts of polypropylene, 15 parts of modified CNCs, 0.5 part of antioxidant, 2 parts of coupling agent and selection and combination of other substancesThe preparation of the compound was the same as in example 3. The preparation method of the modified CNCs of this comparative example is as follows: will 10g CNCS20g of fumaric acid and 100g of toluene are added into a reaction bottle with a stirring device, a condensing device and a nitrogen protection device, and N is introduced2Stirring until the mixture is completely dissolved, then heating the reaction system to 80 ℃, opening condensed water, and continuously introducing N2Dropwise adding 0.08g of dibutyltin dilaurate serving as a catalyst into the reactor, and finishing the reaction after reacting for 5 hours; after cooling, adding the mixture into ethanol to modify CNCSPrecipitating and centrifuging, washing with ethanol for multiple times, centrifuging, testing pH value to be neutral, and modifying CNCSDrying in a vacuum oven to obtain the modified CNC of the comparative exampleS(having no-O-CO-O-carbonate rigid groups compared to the chemical structure of the modified CNCs in example 4).
The formulations of the above examples and comparative examples are shown in Table 1.
TABLE 1 example and comparative example formulations
| Examples | PP | Modified CNCs | Compound deodorant | Antioxidant agent | Coupling agent |
| Example 1 | 80 | 15 | 5 | 0.3 | 1 |
| Example 2 | 80 | 15 | 8 | 0.4 | 1.5 |
| Example 3 | 80 | 15 | 10 | 0.5 | 2 |
| Example 4 | 85 | 10 | 5 | 0.4 | 2 |
| Example 5 | 85 | 10 | 8 | 0.3 | 1 |
| Example 6 | 85 | 10 | 10 | 0.5 | 1.5 |
| Example 7 | 90 | 5 | 5 | 0.5 | 2 |
| Example 8 | 90 | 5 | 8 | 0.3 | 1.5 |
| Example 9 | 90 | 5 | 10 | 0.4 | 1 |
| Comparative example 1 | 100 | 0 | 0 | 0.5 | 2 |
| Comparative example 2 | 100 | 0 | 10 | 0.5 | 2 |
| Comparative example 3 | 100 | 15 | 0 | 0.5 | 2 |
| Comparative example 4 | 100 | 15 | 0 | 0.5 | 2 |
The products of the above examples and comparative examples were tested for mechanical properties, odor, carbon dioxide transmission coefficient, oxygen transmission coefficient and water vapor permeability, and the specific data are detailed in tables 2 and 3. Wherein the Water Vapor Transmission Rate (WVTR) is obtained by putting calcium chloride into a packaging container and sealing the container (the material of the packaging container is the packaging article of the polypropylene composition of the above examples and comparative examples), weighing, and then weighing after putting the container under conditions of 90 RH% humidity and 35 ℃ for 24 hours.
Odor test standard specification, grade 1: no smell; and 2, stage: smells, but no interfering smells; and 3, level: has obvious smell but no interference smell; 4, level: an interfering odor; and 5, stage: strong interfering odor; and 6, level: there is an intolerable smell. The specific steps are that a sealed packaging container (the material of the packaging container is the packaging product of the polypropylene composition of the above examples and comparative examples) is put into an oven with the temperature of 80 ℃, the odor is graded after 2h, 24h, 7d, 15d and 30d, and a plurality of testers smell the odor when grading the odor, and then the average value is obtained. The results are shown in Table 3.
TABLE 2 mechanical Properties and gas permeability of the materials
TABLE 3 odor rating of materials
As can be seen from tables 2 and 3, compared with the pure PP of comparative example 1, the tensile strength and the bending strength of the polypropylene composition of the present invention are improved to some extent with the increase of the content of the modified CNCs, which shows that the modified CNCs have a reinforcing effect on polypropylene, on one hand, the mechanical properties of the material can be improved due to the higher crystallinity of the cellulose, on the other hand, the mechanical properties of the material can be improved by introducing the-O-CO-O-carbonate rigid group into the structure of the CNCs, and simultaneously, the carbon dioxide transmission coefficient, the oxygen transmission coefficient and the water vapor transmission rate of the packaging material of the polypropylene composition are obviously improved. Example 3 compared to comparative example 1, the oxygen transmission coefficient decreased by about 97.66%, the tensile strength increased by 78%, and the flexural modulus increased by 42%.
Example 3 compared with comparative example 3, comparative example 3 was added with only modified CNCs without the compound deodorant, and compared with pure PP, both the mechanical properties and the gas barrier properties were significantly improved, but the modified CNCs alone did not substantially exert an effect on odor removal, and only when the modified CNCs and the compound deodorant were used in combination, the effect of 1+1 > 2 was exerted, which indicates that there is a certain synergistic interaction principle between the two.
Compared with the comparative example 2, the comparative example 2 is not added with the modified CNCs, but only added with the composite deodorant, so that the addition of the composite deodorant has no influence on the basic mechanical property of the pure PP basically, but can reduce the odor of the material, and the odor of the material can be further reduced under the condition that the modified CNCs and the composite deodorant are both used in the example 3, so that the modified CNCs not only have a good gas blocking effect, but also play a good positive role in catalyzing/adsorbing and removing the odor, and have good durability on the gas removing effect.
In conclusion, under the combined action of the modified CNC and the composite deodorant, the odor removal effect is obviously improved, and meanwhile, the odor performance is improved but not reduced along with the passage of time, so that the odor removal effect can be improved through chemical and physical adsorption or catalysis under the condition that the high barrier property of the polypropylene composition package is ensured, and finally, the high-barrier and low-odor packaging product is prepared.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (10)
1. The high-barrier low-odor polyolefin composition is characterized by comprising the following materials in parts by weight: 80-90 parts of polyolefin, 5-15 parts of modified cellulose nanocrystals (modified CNCs), 5-10 parts of composite deodorant, 0.3-0.5 part of antioxidant and 1-2 parts of coupling agent;
the modified cellulose nanocrystal has a chemical structure as shown in the following formula I:
wherein R is1Is H atom, or alkyl or alkenyl with the number of carbon atoms not more than 6; r is2Is methylene or an alkyl ether, when R2The number of carbon atoms is not more than 10 when the methylene is adopted.
2. The high barrier low odor polyolefin composition according to claim 1 wherein said polyolefin is one or more of polyethylene, polypropylene, ethylene-1-hexene copolymer, propylene and 1-hexene copolymer, ethylene-1-octene copolymer, propylene and octene copolymer, poly-1-butene, polyoctene, poly-4-methyl-1-pentene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid or acrylate copolymer, cyclic olefin polymer.
3. The high-barrier low-odor polyolefin composition according to claim 1, wherein the composite odor eliminating agent is prepared by loading metal ions and other odor eliminating agents on a porous matrix;
wherein the porous matrix is one or more of zeolite, nano-silica and zirconium phosphate;
the other smell removing agents are one or more of alkaloid, fendorin and dodecyl quaternary ammonium salt;
the metal ions are one or more of zinc ions, silver ions and copper ions, and the metal ions are loaded on the porous matrix in the form of oxides, simple substances or other compounds;
the mass ratio of the porous matrix to the plant deodorant to the metal ions is (2-5): 1-2.5.
4. The high-barrier low-odor polyolefin composition according to claim 3, wherein the composite odor removing agent is prepared by loading fendorin, dodecyl quaternary ammonium salt and zinc ions on zirconium phosphate as a carrier, wherein the mass ratio of the zirconium phosphate to the fendorin to the dodecyl quaternary ammonium salt to the zinc ions is (2-5) to 1:1.2: 1.
5. The high-barrier low-odor polyolefin composition according to claim 4, wherein the preparation method of the composite deodorant comprises the following processes: calculating the use amount of raw materials according to the mass ratio of all substances in the composite deodorant, then dispersing the porous matrix in water, adding a water-soluble metal ion precursor, uniformly stirring, carrying out ion exchange reaction at 50-120 ℃ for 30min-24h, then carrying out solid-liquid separation, drying, crushing, and calcining at 700-800 ℃ for 1-3h to obtain metal-loaded porous matrix ions; and then dispersing the other deodorant in water, uniformly mixing the other deodorant with the metal ions loaded on the porous matrix, and drying to obtain the composite deodorant.
6. The high barrier low odor polyolefin composition according to any of claims 1-5 wherein said antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in any proportion; the coupling agent is any one of isopropyl tri (dioctyl pyrophosphato acyloxy) titanate and isopropyl tri-dioctyl phosphato acyloxy titanate.
7. The high barrier low odor polyolefin composition according to any of claims 1-5, wherein the preparation method of the modified cellulose nanocrystals comprises the following processes:
(1) removing impurities from carbon dioxide in a reaction kettle, reacting an epoxy compound with a chemical structure shown in a formula II with carbon dioxide at 30-40 ℃ for 10-16h under the action of a metal oxide catalyst and a phase transfer catalyst under stirring, cooling to room temperature after the reaction is finished, and relieving pressure to obtain a compound with a chemical structure shown in a formula III;
wherein R is1Is H atom, or alkyl or alkenyl with the number of carbon atoms not more than 6; r2Is methylene or an alkyl ether, when R2The number of carbon atoms is not more than 10 when the methylene is adopted;
(2) and (3) carrying out ester exchange reaction on the compound with the chemical structure shown in the formula III, Cellulose Nanocrystals (CNCs), alkali and a catalyst at the temperature of 110-160 ℃ for 4-8h, recovering the catalyst, washing a product to be neutral, and drying to obtain the modified cellulose nanocrystals (modified CNCs) with the chemical structure shown in the formula I.
8. The high barrier low odor polyolefin composition of claim 7 wherein in step 1 said metal oxide catalyst is zinc oxide, said phase transfer catalyst is tetrabutylammonium iodide or tetrabutylammonium bromide, said epoxy compound having the chemical structure of formula ii is preferably (S) -glycidylacetate or oxiranylmethyl 2-methyl-2-acrylate;
the molar ratio of the epoxy compound with the chemical structure shown in the formula II to the carbon dioxide is (1-1.2) - (0.01-0.04), the total amount of the metal oxide catalyst and the phase transfer catalyst is 0.2-0.5% of the molar amount of the epoxy compound with the chemical structure shown in the formula II, and the mass ratio of the metal oxide catalyst to the phase transfer catalyst is 1: 0.8.
9. The high barrier low odor polyolefin composition of claim 7 wherein in step 2 said base is sodium hydroxide or potassium hydroxide, said catalyst is stannous octoate and/or dibutyltin dilaurate, said cellulose nanocrystals have a fiber length of 50-500nm and a fiber diameter of 5-20 nm; the mass ratio of the cellulose nanocrystal to the compound with the chemical structure shown in the formula III to the alkali is (2-2.5) to (12-18) to (1-3), and the addition amount of the catalyst is 0.6-1% of the mass of the cellulose nanocrystal.
10. The method for preparing a high-barrier low-odor polyolefin composition as claimed in any one of claims 1 to 9, wherein the polyolefin, the modified cellulose nanocrystals, the composite deodorant, the antioxidant and the coupling agent are pre-mixed uniformly according to the formulation, and then melt-blended and extruded at 210 ℃ at 180 ℃ to obtain pellets, and then injection molding is performed.
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