CN116589791A - Ultraviolet-resistant polypropylene film and preparation method thereof - Google Patents
Ultraviolet-resistant polypropylene film and preparation method thereof Download PDFInfo
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- CN116589791A CN116589791A CN202310575012.6A CN202310575012A CN116589791A CN 116589791 A CN116589791 A CN 116589791A CN 202310575012 A CN202310575012 A CN 202310575012A CN 116589791 A CN116589791 A CN 116589791A
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- titanium dioxide
- polypropylene film
- stirring
- ultraviolet
- resistant polypropylene
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 61
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 59
- -1 polypropylene Polymers 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 8
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 8
- 239000008187 granular material Substances 0.000 claims abstract description 6
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 5
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 5
- 239000000314 lubricant Substances 0.000 claims abstract description 5
- 238000010345 tape casting Methods 0.000 claims abstract description 4
- 238000002844 melting Methods 0.000 claims abstract description 3
- 230000008018 melting Effects 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 29
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 29
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 13
- 239000004408 titanium dioxide Substances 0.000 claims description 13
- 239000012043 crude product Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000003607 modifier Substances 0.000 claims description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 10
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- UFCONGYNRWGVGH-UHFFFAOYSA-N 1-hydroxy-2,2,3,3-tetramethylpiperidine Chemical compound CC1(C)CCCN(O)C1(C)C UFCONGYNRWGVGH-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000002390 rotary evaporation Methods 0.000 claims description 8
- SIDOOGSFHDZDQO-UHFFFAOYSA-N 1-bromododec-1-ene Chemical compound CCCCCCCCCCC=CBr SIDOOGSFHDZDQO-UHFFFAOYSA-N 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 230000004224 protection Effects 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 4
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 claims description 4
- XYXJKPCGSGVSBO-UHFFFAOYSA-N 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C)=C1CN1C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C1=O XYXJKPCGSGVSBO-UHFFFAOYSA-N 0.000 claims description 3
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000003490 Thiodipropionic acid Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 3
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 235000019303 thiodipropionic acid Nutrition 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- FKIOYBLZUCCLTL-UHFFFAOYSA-N 4-butyl-2-tert-butyl-5-methylphenol Chemical compound CCCCC1=CC(C(C)(C)C)=C(O)C=C1C FKIOYBLZUCCLTL-UHFFFAOYSA-N 0.000 claims description 2
- JBTXGEJRJCNRLU-UHFFFAOYSA-N [2-(dihydroxyphosphanyloxymethyl)-3-hydroxy-2-(hydroxymethyl)propyl] dihydrogen phosphite Chemical compound OP(O)OCC(CO)(CO)COP(O)O JBTXGEJRJCNRLU-UHFFFAOYSA-N 0.000 claims description 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 230000006750 UV protection Effects 0.000 abstract description 11
- 239000011159 matrix material Substances 0.000 abstract description 10
- 230000009471 action Effects 0.000 abstract description 7
- 238000013508 migration Methods 0.000 abstract description 5
- 230000005012 migration Effects 0.000 abstract description 5
- 230000007246 mechanism Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- FDKXTQMXEQVLRF-ZHACJKMWSA-N (E)-dacarbazine Chemical compound CN(C)\N=N\c1[nH]cnc1C(N)=O FDKXTQMXEQVLRF-ZHACJKMWSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 101001047746 Homo sapiens Lamina-associated polypeptide 2, isoform alpha Proteins 0.000 description 2
- 101001047731 Homo sapiens Lamina-associated polypeptide 2, isoforms beta/gamma Proteins 0.000 description 2
- 102100023981 Lamina-associated polypeptide 2, isoform alpha Human genes 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 238000010128 melt processing Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- 229940124543 ultraviolet light absorber Drugs 0.000 description 2
- YAXWOADCWUUUNX-UHFFFAOYSA-N 1,2,2,3-tetramethylpiperidine Chemical group CC1CCCN(C)C1(C)C YAXWOADCWUUUNX-UHFFFAOYSA-N 0.000 description 1
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000005021 flexible packaging material Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an ultraviolet-resistant polypropylene film and a preparation method thereof, which belong to the technical field of polypropylene films and comprise the following raw materials in parts by weight: 100 parts of polypropylene resin, 3-4 parts of modified titanium dioxide, 0.3-0.6 part of antioxidant and 0.5-1 part of lubricant; and uniformly mixing the raw materials according to the proportion, extruding and granulating by a double-screw extruder, and carrying out tape casting after melting treatment on the granules to obtain the polypropylene film. According to the invention, the modified titanium dioxide is added into the polypropylene film raw material, so that the uniform dispersion of the nano titanium dioxide in the PP matrix can be effectively improved, the nano titanium dioxide can also generate chemical bonding action with the PP matrix, the formation of a crosslinked network structure is promoted, the migration resistance is improved, and the mechanical strength of the film is improved; and the modified titanium dioxide has various ultraviolet-resistant mechanisms, and can endow the polypropylene film with high-efficiency ultraviolet resistance.
Description
Technical Field
The invention belongs to the technical field of polypropylene films, and particularly relates to an ultraviolet-resistant polypropylene film and a preparation method thereof.
Background
Polypropylene (PP) is a thermoplastic with excellent overall properties and has very wide application in industrial applications such as household appliances, building elements, interior trim materials, automotive parts, flexible packaging materials, etc. However, due to the characteristics of the molecular structure of polypropylene, the polypropylene has poor weather resistance under sunlight irradiation, and is particularly sensitive to ultraviolet rays, so that the polypropylene is limited to be used outdoors. The ultraviolet aging resistance of polypropylene is an important research direction of the current-stage wide technicians.
The traditional method for improving the ultraviolet resistance of polypropylene is mainly to add organic stabilizers such as organic ultraviolet absorbers, hindered amine light stabilizers and the like in the preparation process of polypropylene, but because the materials are organic compositions with lower molecular weight than polypropylene resin, the materials have certain limitation on ultraviolet light absorption and free radical capture, and migration and degradation can occur along with the extension of the service time, so that the ultraviolet resistance of the material can be gradually reduced and finally lose effectiveness.
The nano-scale inorganic material has strong ultraviolet shielding function, has the excellent characteristics of no toxicity, stability, no migration and the like, and can better overcome the defects of the organic stabilizer. Currently, inorganic ultraviolet light absorbers mainly include inorganic particles and metal oxides, such as carbon black, titanium dioxide, activated zinc oxide, aluminum oxide, and the like. The inorganic material has low compatibility with the PP matrix, and the surface of the inorganic material is treated by a coupling agent in the prior art to improve the defect, but the problems of unobvious improving effect and single ultraviolet resistance mechanism still exist, and the high requirement on the increasingly development of ultraviolet resistance is difficult to meet.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an ultraviolet-resistant polypropylene film and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
an ultraviolet-resistant polypropylene film comprises the following raw materials in parts by weight: 100 parts of polypropylene resin, 3-4 parts of modified titanium dioxide, 0.3-0.6 part of antioxidant and 0.5-1 part of lubricant;
the preparation method of the polypropylene film comprises the following steps:
and uniformly mixing the raw materials according to the proportion, extruding and granulating by a double-screw extruder, and carrying out tape casting after melting treatment on the granules to obtain the polypropylene film.
Further, the antioxidant is selected from one or a combination of tetrapentaerythritol ester, 1,3, 5-tri (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4, 6-trione, thiodipropionic acid dilaurate, 1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, triphenyl phosphite and pentaerythritol bisphosphite.
Further, the lubricant is selected from one or a combination of stearic acid amide, polyethylene wax, oleic acid amide, erucic acid amide, paraffin, glycerol tristearate and methyl silicone oil.
Further, the modified titanium dioxide is prepared by the steps of:
s1, adding terephthalic acid, tetramethyl piperidinol and toluene (a water carrying agent) into a three-neck round bottom flask connected with a thermometer and a stirrer, heating to 150 ℃ under stirring, adding p-toluenesulfonic acid (a catalyst), continuously heating to 180 ℃ for stirring reflux reaction, ending the reaction after 6 hours, cooling to room temperature, washing a product with deionized water, removing toluene by rotary evaporation to obtain a crude product, adding acetone into the crude product, stirring and refluxing for 30 minutes, filtering while the crude product is hot, standing the filtrate, cooling to separate out crystals, filtering, and drying to obtain an intermediate; the molar ratio of the terephthalic acid to the tetramethylpiperidinol is 1:1; the dosage of the p-toluenesulfonic acid is 0.2 percent of the mass of the terephthalic acid;
the terephthalic acid and tetramethyl piperidinol are subjected to esterification reaction, and only one-COOH at one end of terephthalic acid molecule is reacted under the action of bit resistance by controlling the mol ratio of the terephthalic acid to the tetramethyl piperidinol to be 1:1, so that an intermediate is obtained, and the process is as follows:
s2, placing the intermediate and methylene dichloride in a three-neck flask, keeping the temperature at 25-30 ℃, and stirring to uniformly mix the intermediate and the methylene dichloride; uniformly mixing bromododecene, sodium carbonate and THF (tetrahydrofuran), slowly dripping the mixture into a three-necked flask by adopting a constant-pressure dropping funnel, stirring while dripping, continuously stirring at 25-30 ℃ for reaction for 3 hours after dripping, removing most of solvents (dichloromethane and THF) by rotary evaporation after reaction, adding distilled water, uniformly mixing, extracting for multiple times by using ethyl acetate, washing an organic phase for multiple times by using saturated NaCl aqueous solution, and then using anhydrous Na 2 SO 4 Drying, suction filtering, and finally removing ethyl acetate by reduced pressure distillation to obtain a modifier; the ratio of the amounts of intermediate, bromododecene and sodium carbonate was 30.5g:24.7g:5.3g;
under the action of sodium carbonate, nucleophilic substitution reaction is carried out on-NH-on the intermediate molecule and-Cl on bromododecene molecule, so as to obtain the modifier, and the reaction process is as follows:
s3, at N 2 Under the protection, adding a modifier, triethylamine (acid binding agent) and DMF (N, N-dimethylformamide) into a three-neck flask, adding pretreated titanium dioxide and DIC (N, N-diisopropylcarbodiimide, dehydrating agent), performing ultrasonic treatment for 10-15min, stirring at room temperature for reaction for 3h, performing centrifugal separation after the reaction is finished, washing with DMF and ethanol water solution for 3-4 times in sequence, and finally drying the product in a vacuum oven at 60 ℃ for 5-6h to obtain modified titanium dioxide; the ratio of the amounts of modifier, triethylamine, pretreated titania and DIC was 51.6g:10.1g:20g:12.6g;
pretreating titanium dioxide surface grafted-NH under the action of triethylamine and DIC 2 Amidation reaction with-COOH on modifier molecule to obtain modified titania, and the process is as follows:
the surface of the obtained modified titanium dioxide is grafted with an organic molecular chain through chemical action, which is equivalent to forming a layer of organic layer on the surface of the nano titanium dioxide, so that the compatibility of the nano titanium dioxide and a PP matrix can be improved, the organic molecular chain contains a long fatty chain (C12), the fatty chain has extremely high similar compatibility with the PP molecular main chain, and the fatty chain has extremely high flexibility, so that the interfacial compatibility of the nano titanium dioxide and the PP matrix can be further improved, the uniform dispersion of the nano titanium dioxide in the matrix is promoted, the effect of an inorganic ultraviolet light absorber is fully exerted, and the mechanical property of the PP film is not negatively influenced; in addition, the tail end of the fatty chain contains unsaturated carbon-carbon double bonds, and the unsaturated carbon-carbon double bonds can participate in the polymerization process in the melt blending process with the PP resin, generate chemical action with the PP matrix, and play a micro-crosslinking effect while enhancing the interaction between the nano titanium dioxide and the matrix, so that the migration resistance can be improved, and the mechanical strength (the promotion of a crosslinked network structure) of the film can be improved; in addition, the grafted organic molecular chain contains tetramethyl piperidine functional group, which belongs to organic light stabilizer, and the group is oxidized into nitroxide free radical TMPO by photoelectron excitation, which can effectively capture free radical R in polymer degradation chain reaction to generate TMPO.R, further remove peroxidation free radical ROO to generate inert ROOR, and the group and nano titanium dioxide have different ultraviolet resistance mechanisms and have synergistic effect, thus endowing the PP film with high-efficiency ultraviolet resistance.
Further, the pretreated titanium dioxide is prepared by the steps of:
dissolving a silane coupling agent KH550 in an ethanol water solution (volume fraction of 50%), stirring for 10-15min at room temperature on a magnetic stirrer, adding nano titanium dioxide into the mixed solution, raising the temperature to 75-80 ℃, stirring for 50-60min at a high speed, centrifugally separating, washing with the ethanol water solution for 3-4 times, vacuum drying, and grinding to obtain pretreated titanium dioxide; the dosage ratio of the silane coupling agent KH550, the ethanol water solution and the nano-titanium dioxide is 33.2g:350mL:10g.
The invention has the beneficial effects that:
according to the invention, the modified titanium dioxide is added into the polypropylene film raw material, so that the uniform dispersion of the nano titanium dioxide in the PP matrix can be effectively improved, the nano titanium dioxide can also generate chemical bonding action with the PP matrix, the formation of a crosslinked network structure is promoted, the migration resistance is improved, and the mechanical strength of the film is improved; and the modified titanium dioxide has various ultraviolet-resistant mechanisms, and can endow the polypropylene film with high-efficiency ultraviolet resistance.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparing pretreated titanium dioxide:
33.2g of silane coupling agent KH550 is firstly dissolved in 350mL of ethanol water solution (volume fraction 50%), stirred on a magnetic stirrer for 15min at room temperature, then 10g of nano titanium dioxide is added into the mixed solution, the temperature is raised to 80 ℃, the mixture is stirred for 60min at high speed, centrifugal separation is carried out, the mixture is washed by the ethanol water solution for 4 times, and the pretreated titanium dioxide is obtained by vacuum drying and grinding.
Example 2
Preparing modified titanium dioxide:
s1, adding 0.1mol of terephthalic acid, 0.1mol of tetramethyl piperidinol and 50mL of toluene into a three-neck round bottom flask connected with a thermometer and a stirrer, heating to 150 ℃ under stirring, adding 0.3g of p-toluenesulfonic acid, continuously heating to 180 ℃ for stirring reflux reaction, ending the reaction after 6 hours, cooling to room temperature, washing a product with deionized water, removing toluene by rotary evaporation to obtain a crude product, adding 150mL of acetone into the crude product, stirring and refluxing for 30min, filtering while the crude product is hot, standing the filtrate, cooling to separate out crystals, filtering, and drying to obtain an intermediate;
s2, placing 30.5g of the intermediate and 150mL of dichloromethane in a three-neck flask, keeping the temperature at 25 ℃, and stirring to uniformly mix the intermediate and the 150mL of dichloromethane; uniformly mixing 24.7g of bromododecene, 5.3g of sodium carbonate and 50mL of THF, slowly dripping the mixture into a three-neck flask by adopting a constant pressure dropping funnel, stirring while dripping, continuously stirring at 25 ℃ for 3 hours after dripping, removing most of solvent (dichloromethane and THF) by rotary evaporation after reaction, adding distilled water, uniformly mixing, extracting for multiple times by using ethyl acetate, washing an organic phase for multiple times by using anhydrous Na after washing an organic phase by using a saturated NaCl aqueous solution 2 SO 4 Drying, suction filtering, and finally removing ethyl acetate by reduced pressure distillation to obtain a modifier;
s3, at N 2 Under the protection, 51.6g of modifier, 10.1g of triethylamine and 300mL of DMF are added into a three-necked flask, 20g of pretreated titanium dioxide prepared in example 1 and 12.6g of DIC are added, ultrasonic treatment is carried out for 10min, stirring reaction is carried out at room temperature for 3h, centrifugal separation is carried out after the reaction is finished, DMF and ethanol aqueous solution are sequentially used for washing for 3 times, and finally the product is put into a vacuum oven at 60 ℃ for drying for 5h, thus obtaining the modified titanium dioxide.
Example 3
Preparing modified titanium dioxide:
s1, adding 0.2mol of terephthalic acid, 0.2mol of tetramethyl piperidinol and 100mL of toluene into a three-neck round bottom flask connected with a thermometer and a stirrer, heating to 150 ℃ under stirring, adding 0.6g of p-toluenesulfonic acid, continuously heating to 180 ℃ for stirring reflux reaction, ending the reaction after 6 hours, cooling to room temperature, washing a product with deionized water, removing toluene by rotary evaporation to obtain a crude product, adding 300mL of acetone into the crude product, stirring and refluxing for 30min, filtering while the crude product is hot, standing the filtrate, cooling to separate out crystals, filtering, and drying to obtain an intermediate;
s2, placing 61g of intermediate and 300mL of dichloromethane in a three-neck flask, keeping the temperature at 30 ℃, and stirring to uniformly mix the intermediate and the dichloromethane; 49.4g of bromododecene, 10.6g of sodium carbonate and 100mL of THF are evenly mixed and then slowly dripped into a three-neck flask by adopting a constant pressure dripping funnel, the mixture is stirred while dripping, and the mixture is continuously stirred at 30 ℃ after dripping is finishedStirring for 3h, removing most of solvent (dichloromethane and THF) by rotary evaporation, adding distilled water, mixing, extracting with ethyl acetate for multiple times, washing organic phase with saturated NaCl aqueous solution for multiple times, and using anhydrous Na 2 SO 4 Drying, suction filtering, and finally removing ethyl acetate by reduced pressure distillation to obtain a modifier;
s3, at N 2 Under the protection, 103.2g of modifier, 20.2g of triethylamine and 600mL of DMF are added into a three-necked flask, 40g of pretreated titanium dioxide prepared in example 1 and 25.2g of DIC are added, ultrasonic treatment is carried out for 15min, stirring reaction is carried out at room temperature for 3h, centrifugal separation is carried out after the reaction is finished, DMF and ethanol aqueous solution are sequentially used for washing for 4 times, and finally the product is put into a vacuum oven at 60 ℃ for drying for 6h, so as to obtain the modified titanium dioxide.
Example 4
Preparing a polypropylene film:
1000g of polypropylene resin, 30g of modified titanium dioxide prepared in example 2, 3g of tetrapentaerythritol ester and 5g of stearic acid amide are uniformly mixed, extruded and granulated by a double screw extruder, and the granules are subjected to melt processing and then subjected to a tape casting step to obtain the polypropylene film.
Example 5
Preparing a polypropylene film:
1000g of polypropylene resin, 35g of the modified titanium dioxide prepared in example 3, 4.5g of 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4, 6-trione and 7.5g of polyethylene wax are uniformly mixed, extruded and granulated by a twin screw extruder, and the granules are melted and treated, and then subjected to a casting step to obtain the polypropylene film.
Example 6
Preparing a polypropylene film:
1000g of polypropylene resin, 40g of modified titanium dioxide prepared in example 2, 6g of thiodipropionic acid dilaurate and 10g of oleamide are uniformly mixed, extruded and granulated by a double screw extruder, and the granules are subjected to melt processing and then subjected to a casting step to obtain the polypropylene film.
Comparative example
The modified titanium dioxide in example 4 is changed into common nano titanium dioxide, and the rest raw materials and the preparation process are unchanged to obtain the polypropylene film.
The polypropylene films obtained in examples 4 to 6 and comparative example were cut into test samples, and the following performance tests were performed:
tensile properties: the transverse and machine direction tensile strengths of the films were tested with reference to GB/T1040.3-2006;
ultraviolet resistance: placing the sample on an ageing-resistant experiment frame of a xenon lamp, carrying out ultraviolet light source irradiation experiments, respectively testing the mechanical strength of the film sample after ageing for 9d and 27d, and calculating the strength retention rate;
the results are shown in the following table:
as can be seen from the data in the table, the polypropylene film prepared by the invention has higher mechanical strength and ultraviolet resistance; according to the data of the comparative example, the nano titanium dioxide can be uniformly distributed in the film after being modified, so that the film is endowed with high-efficiency ultraviolet resistance, and the mechanical property of the film is not negatively influenced.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (9)
1. An ultraviolet-resistant polypropylene film comprises the following raw materials in parts by weight: 100 parts of polypropylene resin, 3-4 parts of modified titanium dioxide, 0.3-0.6 part of antioxidant and 0.5-1 part of lubricant, and is characterized in that the modified titanium dioxide is prepared by the following steps:
s1, adding terephthalic acid, tetramethyl piperidinol and toluene into a three-neck round bottom flask connected with a thermometer and a stirrer, heating to 150 ℃ under stirring, adding p-toluenesulfonic acid, continuously heating to 180 ℃ for stirring reflux reaction, ending the reaction after 6 hours, cooling to room temperature, and purifying to obtain an intermediate;
s2, placing the intermediate and methylene dichloride in a three-neck flask, keeping the temperature at 25-30 ℃, and stirring to uniformly mix the intermediate and the methylene dichloride; uniformly mixing bromododecene, sodium carbonate and THF, slowly dripping the mixture into a three-neck flask by adopting a constant-pressure dropping funnel, stirring while dripping, continuously stirring at 25-30 ℃ for reaction for 3 hours after dripping, removing most of solvent by rotary evaporation after the reaction is finished, adding distilled water, uniformly mixing, extracting for multiple times by using ethyl acetate, washing an organic phase for multiple times by using saturated NaCl aqueous solution, and then using anhydrous Na 2 SO 4 Drying, suction filtering, and finally removing ethyl acetate by reduced pressure distillation to obtain a modifier;
s3, at N 2 Under the protection, adding a modifier, triethylamine and DMF into a three-neck flask, adding pretreated titanium dioxide and DIC, performing ultrasonic treatment for 10-15min, stirring at room temperature for reaction for 3h, performing centrifugal separation after the reaction is finished, washing with DMF and ethanol water solution for 3-4 times in sequence, and finally drying the product in a vacuum oven at 60 ℃ for 5-6h to obtain the modified titanium dioxide.
2. The ultraviolet resistant polypropylene film according to claim 1, wherein the purification process in step S1 is: washing the product with deionized water, removing toluene by rotary evaporation to obtain a crude product, adding acetone into the crude product, stirring and refluxing for 30min, filtering while the crude product is hot, standing the filtrate, cooling to separate out crystals, filtering and drying to obtain the intermediate.
3. The ultraviolet resistant polypropylene film according to claim 1, wherein the molar ratio of terephthalic acid to tetramethylpiperidinol used in step S1 is 1:1; the amount of p-toluenesulfonic acid used was 0.2% by mass of terephthalic acid.
4. The ultraviolet resistant polypropylene film according to claim 1, wherein the ratio of the amounts of the intermediate, bromododecene and sodium carbonate used in step S2 is 30.5g:24.7g:5.3g.
5. The ultraviolet resistant polypropylene film according to claim 1, wherein the ratio of modifier, triethylamine, pretreated titanium dioxide and DIC used in step S3 is 51.6g:10.1g:20g:12.6g.
6. The ultraviolet resistant polypropylene film according to claim 1, wherein the pretreated titanium dioxide in step S3 is prepared by the steps of:
dissolving a silane coupling agent KH550 in an ethanol water solution, stirring on a magnetic stirrer at room temperature for 10-15min, adding nano titanium dioxide into the mixed solution, raising the temperature to 75-80 ℃, stirring at a high speed for 50-60min, centrifugally separating, washing with the ethanol water solution for 3-4 times, vacuum drying, and grinding to obtain pretreated titanium dioxide.
7. The ultraviolet resistant polypropylene film according to claim 1, wherein the antioxidant is selected from one of tetrapentaerythritol ester, 1,3, 5-tris (4-t-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4, 6-trione, thiodipropionic acid dilaurate, 1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, triphenyl phosphite, pentaerythritol bisphosphite, or a combination thereof.
8. The ultraviolet resistant polypropylene film according to claim 1, wherein the lubricant is selected from one or a combination of stearic acid amide, polyethylene wax, oleic acid amide, erucic acid amide, paraffin wax, glycerol tristearate, methyl silicone oil.
9. The method for preparing the ultraviolet-resistant polypropylene film according to claim 1, which is characterized by comprising the following steps:
and uniformly mixing the raw materials according to the proportion, extruding and granulating by a double-screw extruder, and carrying out tape casting after melting treatment on the granules to obtain the polypropylene film.
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