CN114854138B - Degradable environment-friendly polyethylene packaging material for cosmetics - Google Patents
Degradable environment-friendly polyethylene packaging material for cosmetics Download PDFInfo
- Publication number
- CN114854138B CN114854138B CN202210670832.9A CN202210670832A CN114854138B CN 114854138 B CN114854138 B CN 114854138B CN 202210670832 A CN202210670832 A CN 202210670832A CN 114854138 B CN114854138 B CN 114854138B
- Authority
- CN
- China
- Prior art keywords
- packaging material
- polyethylene
- stirring
- degradable environment
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- -1 polyethylene Polymers 0.000 title claims abstract description 83
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 77
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 77
- 239000002537 cosmetic Substances 0.000 title claims abstract description 24
- 239000005022 packaging material Substances 0.000 title claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 239000011141 cosmetic packaging material Substances 0.000 claims abstract description 20
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 20
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 16
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 16
- 150000004700 cobalt complex Chemical class 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005977 Ethylene Substances 0.000 claims abstract description 8
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 46
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 30
- APZPSKFMSWZPKL-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(CO)CO APZPSKFMSWZPKL-UHFFFAOYSA-N 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000002390 rotary evaporation Methods 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 15
- 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 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 13
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000003963 antioxidant agent Substances 0.000 claims description 9
- 230000003078 antioxidant effect Effects 0.000 claims description 9
- 239000000314 lubricant Substances 0.000 claims description 9
- 238000007792 addition Methods 0.000 claims description 8
- 238000013375 chromatographic separation Methods 0.000 claims description 8
- 238000011097 chromatography purification Methods 0.000 claims description 8
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- HSAYSFNFCZEPCN-UHFFFAOYSA-N 3-(dimethylamino)propane-1-thiol Chemical compound CN(C)CCCS HSAYSFNFCZEPCN-UHFFFAOYSA-N 0.000 claims description 7
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 7
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- GQPVFBDWIUVLHG-UHFFFAOYSA-N [2,2-bis(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical class CC(=C)C(=O)OCC(CO)(CO)COC(=O)C(C)=C GQPVFBDWIUVLHG-UHFFFAOYSA-N 0.000 claims description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims 1
- 238000005956 quaternization reaction Methods 0.000 claims 1
- 230000004888 barrier function Effects 0.000 abstract description 8
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 125000004185 ester group Chemical group 0.000 abstract description 3
- 239000000945 filler Substances 0.000 abstract description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OTZCUZNBNWORAD-UHFFFAOYSA-N CC[Co] Chemical compound CC[Co] OTZCUZNBNWORAD-UHFFFAOYSA-N 0.000 description 3
- 241001391944 Commicarpus scandens Species 0.000 description 3
- 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 group 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 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- CZFMLDUNXATLOW-XKZIYDEJSA-N (5z)-5-[[3-(2-hydroxyethoxymethyl)thiophen-2-yl]methylidene]-10-methoxy-2,2,4-trimethyl-1h-chromeno[3,4-f]quinolin-9-ol Chemical group C1=CC=2NC(C)(C)C=C(C)C=2C2=C1C=1C(OC)=C(O)C=CC=1O\C2=C/C=1SC=CC=1COCCO CZFMLDUNXATLOW-XKZIYDEJSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 239000010409 thin film Substances 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
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
- B65D65/466—Bio- or photodegradable packaging materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a degradable environment-friendly polyethylene cosmetic packaging material, which belongs to the technical field of packaging materials and comprises the following raw materials: modified polyethylene copolymer, polyvinyl alcohol, cross-linking agent and compatilizer; the modified polyethylene copolymer is prepared by the following steps: adding dimethyl carbonate, 2-dimethylene-1,3-dioxepane, functional monomer, organic cobalt complex and AI BN into a high-pressure reaction kettle, stirring and heating, then pressurizing by using ethylene, and preserving heat and pressure to obtain the modified polyethylene copolymer. The invention takes 2-dimethylene-1,3-dioxepane as comonomer to introduce ester group into the main chain of polyethylene, thus improving the degradation performance of polyethylene, and adopts functional monomer as comonomer second monomer and takes polyvinyl alcohol as filler, thus not only improving the degradability of the packaging material for polyethylene cosmetics, but also improving the elasticity, temperature resistance and barrier property of the packaging material for polyethylene cosmetics.
Description
Technical Field
The invention belongs to the technical field of packaging materials, and particularly relates to a degradable environment-friendly polyethylene cosmetic packaging material.
Background
The cosmetic packaging material comprises a packaging hose, a hard packaging box and a packaging film. And the packaging hose is a material directly used for containing cosmetics, plays the roles of blocking and quality guaranteeing, and directly influences the storage and quality of the cosmetics. At present, the tube body and the tube head of a packaging hose for cosmetics are made of polyethylene, and the good chemical resistance of the polyethylene is utilized, so that the polyethylene can contain the cosmetics without being corroded by the cosmetics. However, polyethylene does not have degradability, and the packaging tube for cosmetics is difficult to recycle, and has a problem of large usage amount, which is not favorable for the green development of cosmetic packaging materials.
Therefore, a degradable environment-friendly polyethylene cosmetic packaging material is needed, which is a technical problem to be solved urgently for the current cosmetic hose material.
Disclosure of Invention
The invention aims to provide a degradable environment-friendly polyethylene cosmetic packaging material to solve the problems in the background art.
The purpose of the invention can be realized by the following technical scheme:
a degradable environment-friendly polyethylene cosmetic packaging material comprises the following raw materials: modified polyethylene copolymer, polyvinyl alcohol, cross-linking agent and compatilizer.
As a further scheme of the degradable environment-friendly polyethylene cosmetic packaging material, the cosmetic packaging material also comprises an antioxidant and/or a lubricant.
As a further scheme of the degradable environment-friendly polyethylene cosmetic packaging material, the cosmetic packaging material comprises the following raw materials in parts by weight: 70-120 parts of modified polyethylene copolymer, 20-45 parts of polyvinyl alcohol, 6-15 parts of cross-linking agent, 3-10 parts of compatilizer, 2-4 parts of antioxidant and 1-4 parts of lubricant.
Further, the modified polyethylene copolymer is prepared by the following steps:
adding dimethyl carbonate, 2-dimethylene-1,3-dioxepane, a functional monomer, an organic cobalt complex and AIBN into a high-pressure reaction kettle, stirring and heating to 70-75 ℃, then pressurizing to 20-25bar by using ethylene, preserving heat and maintaining pressure for reaction for 20-24h, decompressing, centrifugally precipitating by using normal hexane, dissolving by using chloroform, repeatedly centrifugally precipitating by using normal hexane and dissolving by using chloroform, finally obtaining a precipitate, filtering and drying to obtain the modified polyethylene copolymer, wherein the dosage ratio of the dimethyl carbonate, the 2-dimethylene-1,3-dioxepane, the functional monomer, the organic cobalt complex and the AIBN is 20mL.
In the reaction, an organic cobalt complex is used for regulating and controlling copolymerization reaction of ethylene, 2-dimethylene-1,3-dioxepan and a functional monomer, firstly, 2-dimethylene-1,3-dioxepan is subjected to ring-opening polymerization reaction under the action of the organic cobalt complex, and then, the copolymerization reaction is performed with ethylene and the functional monomer in a reaction system under the action of an initiator to obtain a modified polyethylene copolymer, so that an ester group (introduced by 2-dimethylene-1,3-dioxepan ring opening) is introduced into a molecular chain of the copolymer, the degradability of the copolymer is improved, and meanwhile, the introduced functional monomer is introduced to introduce a functional bond of a nitrogen-oxygen bond into a branched chain, and the nitrogen-oxygen bond is easy to break at high temperature to generate a nitrogen-oxygen free radical, so that high-temperature crosslinking is performed, the formation of a network structure in the modified polyethylene copolymer is promoted, and the temperature resistance and elasticity of the modified polyethylene copolymer are improved.
Further, the functional monomer is prepared by the following steps:
adding methacrylic acid, p-toluenesulfonic acid and diethylene glycol dimethyl ether into a four-neck flask with a nitrogen introducing device, a stirring rod, a condensing device and a thermometer, stirring for 10min to uniformly mix, introducing nitrogen to form a nitrogen atmosphere, heating to 60-70 ℃, slowly dropwise adding a diethylene glycol dimethyl ether solution containing 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxygen free radical, stirring for reacting for 4-6h after the addition is finished, and performing chromatographic purification and separation to obtain an intermediate; adding the intermediate and tetrahydrofuran into a four-neck flask with a nitrogen introducing device, a stirring rod, a condensing device and a thermometer, stirring for 10min to uniformly mix, slowly dropwise adding the tetrahydrofuran containing dibenzoyl peroxide, stirring at room temperature for reacting for 8-12h, and carrying out chromatographic purification and separation to obtain a functional monomer, wherein the molar ratio of methacrylic acid, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxygen radical and dibenzoyl peroxide is 1.
In the reaction, firstly, the condensation reaction of carboxyl in methacrylic acid and hydroxyl in 4-hydroxyl-2,2,6,6-tetramethylpiperidine-1-oxygen free radical is utilized, then the free radical coupling reaction of free radical in 4-hydroxyl-2,2,6,6-tetramethylpiperidine-1-oxygen free radical and dibenzoyl peroxide is utilized to obtain the functional monomer, so that the functional bond of nitrogen-oxygen bond is connected into the functional monomer, the functional bond is easy to break at high temperature to generate nitrogen-oxygen free radical, and then high-temperature crosslinking is carried out, the formation of a network structure in the modified polyethylene copolymer is promoted, and the temperature resistance and the elasticity of the modified polyethylene copolymer are improved.
Further, the cross-linking agent is prepared by the following steps:
a1, adding pentaerythritol, p-toluenesulfonic acid and tetrahydrofuran into a four-neck flask with a nitrogen introducing device, a stirring rod, a condensing device and a thermometer, stirring for 10min, introducing nitrogen for protection, heating to 65-70 ℃, dropwise adding methacrylic acid while stirring, heating to reflux after adding, stirring for reaction for 1-2h, reducing the temperature to 30 ℃, and carrying out reduced pressure rotary evaporation to obtain pentaerythritol monomethacrylate; adding pentaerythritol monomethacrylate and tetrahydrofuran into a four-neck flask with a nitrogen introducing device, a stirring rod, a condensing device and a thermometer, stirring for 10min, introducing nitrogen for protection, adding 3- (dimethylamino) -1-propanethiol at the temperature of-2-0 ℃, heating to 20-40 ℃, stirring for reaction for 8-12h, and carrying out reduced pressure rotary evaporation at the temperature of 40 ℃ to obtain the pentaerythritol monomethacrylate derivative, wherein the molar ratio of pentaerythritol to methacrylic acid to 3- (dimethylamino) -1-propanethiol is 1;
in the reaction summary, firstly, pentaerythritol monomethacrylate is obtained by the reaction of pentaerythritol and methacrylic acid, and then the addition reaction of the double bond in pentaerythritol monomethacrylate and the thiol bond in 3- (dimethylamino) -1-propanethiol is utilized to obtain the pentaerythritol monomethacrylate derivative, so that 1 mole of the compound contains 3 moles of hydroxyl groups;
a2, adding pentaerythritol monomethacrylate derivatives and toluene into a three-necked bottle with a stirrer, a thermometer and a reflux device, stirring for 10min, heating to 90 ℃, adding toluene containing a quaternizing agent, stirring for reaction for 10-12h, and carrying out reduced pressure rotary evaporation to obtain the quaternizing pentaerythritol dimethacrylate derivatives, wherein the dosage ratio of the pentaerythritol monomethacrylate derivatives to the quaternizing agent is 32g, the quaternizing agent is 1-bromoalkane, and the number of alkyl groups is 3-6;
in the above reaction, it is known that a quaternized pentaerythritol dimethacrylate derivative obtained by a reaction of a tertiary amine structure in a pentaerythritol monomethacrylate derivative with a quaternizing agent contains 3 moles of hydroxyl groups and 1 mole of a quaternary ammonium salt structure in 1 mole of the compound;
a3, adding quaternary ammonium salinized pentaerythritol monomethacrylate derivative, anhydrous potassium carbonate, epichlorohydrin and toluene into a three-necked bottle with a stirrer, a thermometer and a reflux device, stirring for 10min, heating to 75 ℃, stirring for 8-10h, then cooling to 65 ℃, adding sodium hydroxide solid, stirring for reaction for 4-6h, carrying out suction filtration, and carrying out reduced pressure rotary evaporation on the filtrate to obtain the cross-linking agent, wherein the dosage ratio of the quaternary ammonium salinized pentaerythritol monomethacrylate derivative, the anhydrous potassium carbonate, the epichlorohydrin and the sodium hydroxide solid is 63.12-0.15mol.
In the above reaction, the hydroxyl group is epoxidized by a two-step epoxidation reaction of the hydroxyl group in the quaternized pentaerythritol dimethacrylate derivative and epichlorohydrin, and the epoxidized hydroxyl group is used as a crosslinking agent.
The invention has the beneficial effects that:
in order to solve the problems mentioned in the technical background, the invention takes 2-dimethylene-1,3-dioxepan as a comonomer to introduce ester groups into the main chain of polyethylene, improves the degradation performance of polyethylene, simultaneously adopts a self-made functional monomer as a copolymerization second monomer, and takes polyvinyl alcohol as a filler, thereby not only improving the degradability of the packaging material for polyethylene cosmetics, but also improving the elasticity, temperature resistance and barrier property of the packaging material for polyethylene cosmetics;
firstly, the self-made functional monomer contains a functional bond of a nitrogen-oxygen bond and a phenyl group, so that the functional bond of the nitrogen-oxygen bond is introduced into a branched chain of the polyethylene material, and the nitrogen-oxygen bond is easy to break at high temperature to generate a nitroxide free radical, so that high-temperature crosslinking is performed, the formation of a network structure in the modified polyethylene copolymer is promoted, and the temperature resistance and elasticity of the modified polyethylene copolymer are improved;
secondly, the high barrier property of the polyvinyl alcohol is utilized, the barrier property of the polyethylene material is improved, the difficult processing property of the polyvinyl alcohol material is considered, the compatilizer is used for promoting the mixing uniformity of the polyvinyl alcohol and the modified polyethylene copolymer, meanwhile, the epoxy group in the cross-linking agent in the mixing system and the hydroxyl group in the polyvinyl alcohol are subjected to cross-linking reaction, the polyvinyl alcohol is solidified, the barrier property of the polyethylene material is improved, the self-made cross-linking agent contains a quaternary ammonium salt structure, the antibacterial property of the packaging material for the polyethylene cosmetics is endowed, and the damage of bacteria to nutrient substances in the cosmetics is prevented,
in conclusion, the packaging material for the polyethylene cosmetics provided by the invention has good degradability, barrier property, thermal stability and antibacterial property.
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. 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.
Example 1
Preparation of the crosslinking agent:
a1, adding 0.1mol of pentaerythritol, 0.23g of p-toluenesulfonic acid and 80mL of tetrahydrofuran into a four-neck flask with a nitrogen introducing device, a stirring rod, a condensing device and a thermometer, stirring for 10min, introducing nitrogen for protection, heating to 65 ℃, dropwise adding 0.1mol of methacrylic acid under stirring, heating to reflux after the addition is finished, stirring for reaction for 2h, cooling to 30 ℃, and carrying out reduced pressure rotary evaporation to obtain pentaerythritol monomethacrylate; adding the obtained pentaerythritol monomethacrylate and 100mL of tetrahydrofuran into a four-neck flask with a nitrogen introducing device, a stirring rod, a condensing device and a thermometer, stirring for 10min, introducing nitrogen for protection, adding 0.1mol of 3- (dimethylamino) -1-propanethiol at the temperature of-2 ℃, heating to 20 ℃, stirring for reaction for 12h, and then carrying out reduced pressure rotary evaporation at the temperature of 40 ℃ to obtain a pentaerythritol monomethacrylate derivative;
a2, adding 32g of pentaerythritol monomethacrylate derivative and 70mL of toluene into a three-necked bottle with a stirrer, a thermometer and a reflux device, stirring for 10min, heating to 90 ℃, adding 60mL of toluene containing 0.1mol of quaternizing agent, stirring for reaction for 10h, and carrying out reduced pressure rotary evaporation to obtain the quaternizing pentaerythritol dimethacrylate derivative, wherein the quaternizing agent is 1-bromoalkane, and the number of alkyl is 3;
a3, adding 63.1g of quaternary ammonium salinized pentaerythritol monomethacrylate derivative, 0.12mol of anhydrous potassium carbonate, 0.45mol of epichlorohydrin and toluene into a three-necked bottle with a stirrer, a thermometer and a reflux device, stirring for 10min, heating to 75 ℃, stirring for 8h, cooling to 65 ℃, adding 0.2mol of sodium hydroxide solid, stirring for reaction for 4-6h, carrying out suction filtration, and carrying out reduced pressure rotary evaporation on the filtrate to obtain the cross-linking agent.
Example 2
Preparation of the crosslinking agent:
a1, adding 0.1mol of pentaerythritol, 0.6g of p-toluenesulfonic acid and 80mL of tetrahydrofuran into a four-neck flask with a nitrogen introducing device, a stirring rod, a condensing device and a thermometer, stirring for 10min, introducing nitrogen for protection, heating to 70 ℃, dropwise adding 0.1mol of methacrylic acid under stirring, heating to reflux after the addition is finished, stirring for reaction for 1h, reducing to 30 ℃, and carrying out reduced pressure rotary evaporation to obtain pentaerythritol monomethacrylate; adding the obtained pentaerythritol monomethacrylate and 100mL of tetrahydrofuran into a four-neck flask with a nitrogen introducing device, a stirring rod, a condensing device and a thermometer, stirring for 10min, introducing nitrogen for protection, adding 0.1mol of 3- (dimethylamino) -1-propanethiol at 0 ℃, heating to 40 ℃ after the addition, stirring for reaction for 8h, and then carrying out reduced pressure rotary evaporation at 40 ℃ to obtain a pentaerythritol monomethacrylate derivative;
a2, adding 32g of pentaerythritol monomethacrylate derivative and 70mL of toluene into a three-necked bottle with a stirrer, a thermometer and a reflux device, stirring for 10min, heating to 90 ℃, adding 60mL of toluene containing 0.1mol of quaternizing agent, stirring for reaction for 12h, and carrying out reduced pressure rotary evaporation to obtain the quaternizing pentaerythritol dimethacrylate derivative, wherein the quaternizing agent is 1-bromoalkane, and the number of alkyl is 6;
a3, adding 63.1g of quaternary ammonium salinized pentaerythritol monomethacrylate derivative, 0.15mol of anhydrous potassium carbonate, 0.5mol of epichlorohydrin and toluene into a three-necked bottle with a stirrer, a thermometer and a reflux device, stirring for 10min, heating to 75 ℃, stirring for 10h, cooling to 65 ℃, adding 0.25mol of sodium hydroxide solid, stirring for 6h, carrying out suction filtration, and carrying out reduced pressure rotary evaporation on the filtrate to obtain the cross-linking agent.
Example 3
Preparation of functional monomer:
adding 0.1mol of methacrylic acid, 0.26g of p-toluenesulfonic acid and 80mL of diethylene glycol dimethyl ether into a four-neck flask with a nitrogen introducing device, a stirring rod, a condensing device and a thermometer, stirring for 10min to uniformly mix, introducing nitrogen to form a nitrogen atmosphere, heating to 60-DEG C, slowly dropwise adding 70mL of diethylene glycol dimethyl ether solution containing 0.1mol of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxygen free radical, stirring for 6h after the addition is finished, and performing chromatographic purification and separation to obtain an intermediate; adding the obtained intermediate and 60mL of tetrahydrofuran into a four-neck flask with a nitrogen introducing device, a stirring rod, a condensing device and a thermometer, stirring for 10min to uniformly mix, slowly dropwise adding 40mL of tetrahydrofuran containing 0.1mol of dibenzoyl peroxide, stirring at room temperature for reaction for 8h, and carrying out chromatographic purification and separation to obtain the functional monomer.
Example 4
Preparation of functional monomer:
adding 0.1mol of methacrylic acid, 0.7g of p-toluenesulfonic acid and 80mL of diethylene glycol dimethyl ether into a four-neck flask with a nitrogen introducing device, a stirring rod, a condensing device and a thermometer, stirring for 10min to uniformly mix, introducing nitrogen to form a nitrogen atmosphere, heating to 70 ℃, slowly dropwise adding 70mL of diethylene glycol dimethyl ether solution containing 0.1mol of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxygen free radical, stirring for 4h after addition, and carrying out chromatographic purification and separation to obtain an intermediate; adding the obtained intermediate and 60mL of tetrahydrofuran into a four-neck flask with a nitrogen introducing device, a stirring rod, a condensing device and a thermometer, stirring for 10min to uniformly mix, slowly dropwise adding 40mL of tetrahydrofuran containing 0.1mol of dibenzoyl peroxide, stirring at room temperature for reaction for 12h, and carrying out chromatographic purification and separation to obtain the functional monomer.
Example 5
Preparation of modified polyethylene copolymer:
adding 20mL of dimethyl carbonate, 6g of 2-dimethylene-1,3-dioxepane, 2g of the functional monomer prepared in the example 3, 0.1mmol of organic cobalt complex and 0.6mmol of AIBN into a high-pressure reaction kettle, stirring and heating to 70 ℃, then pressurizing to 20bar by using ethylene, carrying out heat preservation and pressure maintaining reaction for 20 hours, relieving pressure, carrying out centrifugal precipitation by using n-hexane, dissolving by using chloroform, repeating the centrifugal precipitation by using n-hexane and the dissolving operation by using chloroform, finally obtaining precipitate, filtering and drying to obtain the modified polyethylene copolymer, wherein the organic cobalt complex is disalicylamido ethyl cobalt.
Example 6
Preparation of modified polyethylene copolymer:
adding 20mL of dimethyl carbonate, 7g of 2-dimethylene-1,3-dioxepane, 4g of the functional monomer prepared in the example 3, 0.13mmol of organic cobalt complex and 0.7mmol of AIBN into a high-pressure reaction kettle, stirring and heating to 75 ℃, then pressurizing to 25bar by using ethylene, carrying out heat preservation and pressure maintaining reaction for 24 hours, carrying out pressure relief, carrying out centrifugal precipitation by using n-hexane, dissolving by using chloroform, repeating the centrifugal precipitation by using n-hexane and the dissolving operation by using chloroform, finally obtaining a precipitate, filtering and drying to obtain the modified polyethylene copolymer, wherein the organic cobalt complex is disalicylamido ethyl cobalt.
Example 7
A degradable environment-friendly polyethylene cosmetic packaging material comprises the following raw materials in parts by weight: 70 parts of the modified polyethylene copolymer prepared in example 5, 20 parts of polyvinyl alcohol, 6 parts of the crosslinking agent prepared in example 1,3 parts of a compatibilizer, 2 parts of an antioxidant and 1 part of a lubricant; the compatilizer is a polyethylene maleic anhydride graft, the antioxidant is antioxidant 1010, and the lubricant is polyethylene wax.
Example 8
A degradable environment-friendly polyethylene cosmetic packaging material comprises the following raw materials in parts by weight: 100 parts of the modified polyethylene copolymer prepared in example 5, 35 parts of polyvinyl alcohol, 11 parts of the crosslinking agent prepared in example 1, 6 parts of a compatibilizer, 3 parts of an antioxidant, 2 parts of a lubricant; the compatilizer is a polyethylene maleic anhydride graft, the antioxidant is antioxidant 1010, and the lubricant is polyethylene wax.
Example 9
A degradable environment-friendly polyethylene cosmetic packaging material comprises the following raw materials in parts by weight: 120 parts of the modified polyethylene copolymer prepared in example 5, 45 parts of polyvinyl alcohol, 15 parts of the crosslinking agent prepared in example 1, 10 parts of a compatibilizer, 4 parts of an antioxidant and 4 parts of a lubricant; the compatilizer is a polyethylene maleic anhydride graft, the antioxidant is antioxidant 1010, and the lubricant is polyethylene wax.
Comparative example 1
Compared with the example 7, the degradable environment-friendly polyethylene cosmetic packaging material is prepared by replacing modified polyethylene copolymer in the raw materials with polyethylene copolymer prepared by the following steps in equal quantity, and the rest are the same:
adding 20mL of dimethyl carbonate, 6g of 2-dimethylene-1,3-dioxepane, 0.1mmol of organic cobalt complex and 0.6mmol of AIBN into a high-pressure reaction kettle, stirring and heating to 70 ℃, then pressurizing to 20bar by using ethylene, preserving heat and maintaining pressure for reaction for 20 hours, relieving pressure, centrifugally precipitating by using n-hexane, dissolving by using chloroform, repeatedly carrying out operations of centrifugally precipitating by using n-hexane and dissolving by using chloroform, finally obtaining precipitate, filtering and drying to obtain the modified polyethylene copolymer, wherein the organic cobalt complex is disalicylamido ethylcobalt.
Comparative example 2
Compared with the example 8, the degradable environment-friendly polyethylene cosmetic packaging material has the advantages that the modified polyethylene copolymer in the raw materials is replaced by polyethylene in the same amount, and the rest is the same.
Comparative example 3
Compared with the example 9, the degradable environment-friendly polyethylene cosmetic packaging material has the advantages that the crosslinking agent in the raw materials is replaced by trimethylolpropane triglycidyl ether in an equivalent amount, and the rest are the same.
Comparative example 4
Compared with the packaging material of the example 7, the degradable environment-friendly polyethylene cosmetic packaging material has the same components except that the polyvinyl alcohol in the raw materials is deleted.
Example 10
The packaging materials described in examples 7 to 9 and comparative examples 1 to 3 were compounded, melted, extruded, shaped into polyethylene cosmetic materials, as known to those skilled in the art, and then subjected to the following performance tests:
tensile strength and elongation at break: testing according to the standard GB/T1040; 5 test samples are adopted, and the final result is averaged;
degradation performance: and (3) soil burying degradation: cutting a film with a certain size, fully drying to constant weight (W0), marking and burying the film at a position about 10cm below the ground surface, taking out after 3 months, cleaning with water and ethanol, weighing (W1) after drying, and calculating the weight loss rate, wherein the weight loss rate (%) = (W1-W0)/W0 multiplied by 100%; 5 test samples are adopted, and the final result is averaged;
water absorption: testing according to GB/T1034, drying a sample (10 cm multiplied by 10 cm) at 85 ℃ at room temperature, weighing m0, then immersing the sample in distilled water for 24 hours, taking out a thin film sample, absorbing surface moisture by using filter paper, weighing m1, calculating water absorption rate = (m 1-m 0)/m 0 multiplied by 100%, taking 5 test samples, and averaging the final results;
thermal stability: performing characterization analysis on the flame retardant sample dried by the vacuum oven for 8 hours by using a thermogravimetric analyzer; under the N2 environment as the test environment, the flow rate of N2 is 60mL/min, the heating rate is 10 ℃/min, the temperature range is 25-800 ℃, and the Tg is 5%;
barrier properties: testing according to GB/T1038;
antibacterial property: testing according to ASTM E2149-2010, wherein the test flora is Escherichia coli and common staphylococcus aureus;
the above test data are shown in table 1.
TABLE 1
As can be seen from the data in table 1, the polyethylene packaging materials obtained in examples 7 to 9 have excellent barrier properties, degradability, and thermal stability, and also have certain antibacterial properties.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to 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 invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. 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 illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (8)
1. The degradable environment-friendly polyethylene cosmetic packaging material is characterized in that: the method comprises the following raw materials: modified polyethylene copolymer, polyvinyl alcohol, cross-linking agent and compatilizer;
the modified polyethylene copolymer is prepared by the following steps:
adding dimethyl carbonate, 2-dimethylene-1,3-dioxepane, functional monomer, organic cobalt complex and AIBN into a high-pressure reaction kettle, stirring and heating to 70-75 ℃, then pressurizing to 20-25bar by using ethylene, carrying out heat preservation and pressure maintaining reaction for 20-24h, and carrying out post-treatment to obtain a modified polyethylene copolymer;
the functional monomer is prepared by the following steps:
uniformly mixing methacrylic acid, p-toluenesulfonic acid and diethylene glycol dimethyl ether, introducing nitrogen to form a nitrogen atmosphere, heating to 60-70 ℃, slowly dropwise adding a diethylene glycol dimethyl ether solution containing 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxygen free radical, stirring for reacting for 4-6 hours after the addition is finished, and performing chromatographic purification and separation to obtain an intermediate; uniformly mixing the intermediate and tetrahydrofuran, slowly dropwise adding the tetrahydrofuran containing dibenzoyl peroxide, stirring at room temperature for reacting for 8-12h, and performing chromatographic purification and separation to obtain a functional monomer;
the cross-linking agent is prepared by the following steps:
a1, adding and uniformly mixing pentaerythritol monomethacrylate and tetrahydrofuran, introducing nitrogen for protection, adding 3- (dimethylamino) -1-propanethiol at the temperature of-2-0 ℃, heating to 20-40 ℃, stirring for reaction for 8-12h, and carrying out reduced pressure rotary evaporation to obtain a pentaerythritol monomethacrylate derivative;
a2, uniformly mixing a pentaerythritol monomethacrylate derivative and toluene, heating to 90 ℃, adding toluene containing a quaternizing agent, stirring for reaction for 10-12h, and carrying out reduced pressure rotary evaporation to obtain a quaternization pentaerythritol dimethacrylate derivative;
a3, uniformly mixing quaternary ammonium salinized pentaerythritol monomethacrylate derivative, anhydrous potassium carbonate, epichlorohydrin and toluene, heating to 75 ℃, stirring for 8-10h, cooling to 65 ℃, adding sodium hydroxide solid, stirring for reaction for 4-6h, performing suction filtration, and performing reduced pressure rotary evaporation on the filtrate to obtain the cross-linking agent.
2. The packaging material for degradable environment-friendly polyethylene cosmetics according to claim 1, wherein: the dosage ratio of dimethyl carbonate, 2-dimethylene-1,3-dioxepan, functional monomer, organic cobalt complex and AIBN is 20mL, and is as follows, wherein the dosage ratio is (6-7g).
3. The packaging material for degradable environment-friendly polyethylene cosmetics according to claim 1, wherein: the cosmetic packaging material comprises the following raw materials in parts by weight: 70-120 parts of modified polyethylene copolymer, 20-45 parts of polyvinyl alcohol, 6-15 parts of cross-linking agent, 3-10 parts of compatilizer, 2-4 parts of antioxidant and 1-4 parts of lubricant.
4. The packaging material for degradable environment-friendly polyethylene cosmetics according to claim 1, wherein: the molar ratio of the methacrylic acid to the 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxygen radical to the dibenzoyl peroxide is 1.
5. The packaging material for degradable environment-friendly polyethylene cosmetics according to claim 1, wherein: in step A1, the molar ratio of pentaerythritol, methacrylic acid, and 3- (dimethylamino) -1-propanethiol is 1.
6. The packaging material for degradable environment-friendly polyethylene cosmetics according to claim 1, wherein: the dosage ratio of the pentaerythritol monomethacrylate derivative to the quaternizing agent in the step A2 is 32g.
7. The packaging material for degradable environment-friendly polyethylene cosmetics according to claim 1, wherein: in the step A2, the quaternizing agent is 1-bromoalkane, wherein the number of alkyl groups is 3-6.
8. The packaging material for degradable environment-friendly polyethylene cosmetics according to claim 1, wherein: in the step A3, the using ratio of the quaternary ammonium salinized pentaerythritol monomethacrylate derivative to the anhydrous potassium carbonate to the epichlorohydrin to the solid sodium hydroxide is 63.1g, and the using ratio is as follows.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210670832.9A CN114854138B (en) | 2022-06-15 | 2022-06-15 | Degradable environment-friendly polyethylene packaging material for cosmetics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210670832.9A CN114854138B (en) | 2022-06-15 | 2022-06-15 | Degradable environment-friendly polyethylene packaging material for cosmetics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114854138A CN114854138A (en) | 2022-08-05 |
| CN114854138B true CN114854138B (en) | 2023-03-17 |
Family
ID=82624204
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210670832.9A Active CN114854138B (en) | 2022-06-15 | 2022-06-15 | Degradable environment-friendly polyethylene packaging material for cosmetics |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114854138B (en) |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4307759C1 (en) * | 1993-03-11 | 1994-04-28 | Wacker Chemie Gmbh | Biodegradable vinyl] ester copolymers for packaging film etc. - comprises vinyl] acetate etc. cyclic ketene acetal, esp. 2-methylene-1,3-dioxepane |
| JP4190093B2 (en) * | 1999-06-24 | 2008-12-03 | 株式会社Ａｄｅｋａ | Piperidine derivative polymer and polymer composition containing the same |
| CN1093120C (en) * | 1999-10-21 | 2002-10-23 | 复旦大学 | Trigger containing TEMPO polymer and its preparing process |
| FR2814749B1 (en) * | 2000-10-03 | 2003-06-13 | Atofina | COMPOSITION DELAYING TOASTING |
| CN103242612A (en) * | 2013-05-28 | 2013-08-14 | 上海博疆新材料科技有限公司 | Polyvinyl alcohol composition and application thereof |
| CN103865076B (en) * | 2014-03-07 | 2016-04-27 | 济南大学 | Hyperbranched type static inhibitor of a kind of quaternary ammonium salt and preparation method thereof |
| CN109880028B (en) * | 2019-02-28 | 2021-11-02 | 中国科学院上海有机化学研究所 | Graphene surface grafted free radical polymer composite material, preparation method and application |
| CN111303326B (en) * | 2020-04-09 | 2021-07-06 | 中国科学技术大学 | Polyolefin material with controllable degradation units and high monomer utilization rate and preparation method thereof |
-
2022
- 2022-06-15 CN CN202210670832.9A patent/CN114854138B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114854138A (en) | 2022-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102492162B (en) | A kind of epsilon-polylysine polyvinyl alcohol compound bio antibacterial film and preparation method thereof | |
| CN105566663B (en) | A method of improving polyvinyl alcohol film water resistance and compliance with polydioxanone and P (CPP-SA)-polyethylene glycol | |
| US6426121B1 (en) | Dual crosslinkable emulsion polymers at ambient conditions | |
| JP5639588B2 (en) | Polyoxymethylene compositions and articles made therefrom | |
| CN114854138B (en) | Degradable environment-friendly polyethylene packaging material for cosmetics | |
| CN115418085A (en) | Biodegradable PBAT/PLA blending film | |
| CN113601929A (en) | High-performance agricultural greenhouse film | |
| EP0546570B1 (en) | Vinyl alcohol copolymer having terminal amino group | |
| CN113683764B (en) | Branched PPC-based membrane and preparation method thereof | |
| US5015707A (en) | Preparation of poly-β-alanine from acrylamide | |
| CN112195682B (en) | Waterproof and oilproof environment-friendly fluorine-free coating and preparation method thereof | |
| CN113563637A (en) | Diphenylamine-type rubber antioxidant as well as preparation method and application thereof | |
| CN105542480B (en) | The method that one kind polycaprolactone improves polyvinyl alcohol film water resistance and compliance with P (CPP SA) polyethylene glycol | |
| CN112538242A (en) | Environment-friendly full-degradable novel garbage bag and preparation thereof | |
| CN114891291B (en) | Antistatic packaging plastic film | |
| CN103380237A (en) | Degradable fibers | |
| JP7356404B2 (en) | Agricultural films and geomembranes | |
| EP0578291A2 (en) | In situ compatibilization of PPE/polyethylene copolymer blends | |
| JP2021102663A (en) | Resin composition | |
| CN107955350B (en) | Full-biodegradable drug-resistant mulching film composition and preparation method thereof | |
| CN117230656B (en) | Waterproof agent for paper pulp molding material and preparation method | |
| JP4347987B2 (en) | Polyolefin resin film for agriculture | |
| CN114315887A (en) | Silane coupling agent with low VOC (volatile organic compounds) emission and preparation method and application thereof | |
| CN116694047A (en) | Water-blocking biodegradable mulching film and preparation method thereof | |
| JP2022033010A (en) | Polyvinyl alcohol-based resin composition and molding using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 523000 area B2, D and E2, building 2, Guanghui Industrial Zone, Tongsha Science Park, Dongcheng Street, Dongguan City, Guangdong Province Patentee after: Guangdong Antop Polymer Technology Co.,Ltd. Address before: 523000 area B2, D and E2, building 2, Guanghui Industrial Zone, Tongsha Science Park, Dongcheng Street, Dongguan City, Guangdong Province Patentee before: Guangdong Antopu Polymer Technology Co.,Ltd. |