CN116444959A - Plastic bottle and manufacturing method thereof - Google Patents
Plastic bottle and manufacturing method thereof Download PDFInfo
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- CN116444959A CN116444959A CN202211731467.4A CN202211731467A CN116444959A CN 116444959 A CN116444959 A CN 116444959A CN 202211731467 A CN202211731467 A CN 202211731467A CN 116444959 A CN116444959 A CN 116444959A
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- Prior art keywords
- isoprene
- plastic bottle
- maleic anhydride
- styrene copolymer
- styrene
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- 239000004033 plastic Substances 0.000 title claims abstract description 71
- 229920003023 plastic Polymers 0.000 title claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 54
- 239000011347 resin Substances 0.000 claims abstract description 54
- 239000000155 melt Substances 0.000 claims abstract description 20
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000001746 injection moulding Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000000071 blow moulding Methods 0.000 claims abstract description 6
- 238000001125 extrusion Methods 0.000 claims abstract description 5
- 229920001577 copolymer Polymers 0.000 claims description 53
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 40
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 26
- 239000003999 initiator Substances 0.000 claims description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 20
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 18
- -1 acrylic ester Chemical class 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 7
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 6
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 3
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- 238000004806 packaging method and process Methods 0.000 abstract description 4
- 208000006930 Pseudomyxoma Peritonei Diseases 0.000 description 45
- 229920000306 polymethylpentene Polymers 0.000 description 45
- 229920000139 polyethylene terephthalate Polymers 0.000 description 39
- 239000005020 polyethylene terephthalate Substances 0.000 description 39
- 230000000052 comparative effect Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 230000001976 improved effect Effects 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000014171 carbonated beverage Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- JKJJSJJGBZXUQV-UHFFFAOYSA-N methyl 2-methylidenebutanoate Chemical compound CCC(=C)C(=O)OC JKJJSJJGBZXUQV-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000013616 tea Nutrition 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application discloses a plastic bottle and a manufacturing method thereof, belonging to the field of plastic packaging containers. The plastic bottle is prepared from the following raw materials: 76-83 parts of PET resin, 4-8 parts of first PMP resin, 12-18 parts of second PMP resin and 0.5-1.5 parts of compatilizer containing isoprene-styrene blocks; the melt index of the first PMP resin is 100-110 g/10min, and the melt index of the second PMP resin is 21-26 g/10min. The manufacturing method of the plastic bottle comprises the following steps: and uniformly stirring the PET resin, the first PMP resin, the second PMP resin and the compatilizer containing the isoprene-styrene block, then carrying out melt extrusion to obtain plastic master batches, carrying out injection molding on the plastic master batches into a mold, opening the mold to obtain a bottle blank, and carrying out blow molding to obtain the plastic bottle. The PET plastic bottle has the advantages of improving the heat resistance and the mechanical property of the PET plastic bottle.
Description
Technical Field
The present application relates to the field of plastic packaging containers, and in particular to a plastic bottle and a method for manufacturing the same.
Background
The plastic bottle has wide application in life, and various mineral water bottles, beverage bottles, oil drums and the like are made of plastic, and compared with packaging containers made of other materials such as glass, metal and the like, the plastic bottle has the advantages of light weight, breakage resistance and low cost.
With the development of processing technology, PET, namely polyethylene terephthalate, becomes the main stream of raw materials of plastic bottles, has good mechanical properties, can be recycled after being used as plastic bottles, meets the requirements of green and environmental protection, and has good chemical resistance and stability, so that the PET is suitable for packaging carbonated beverages, fruit juice beverages and tea beverages. The PET plastic bottle has the defects of insufficient heat resistance and easy deformation at 70-75 ℃ so as to influence the use effect of the PET plastic bottle.
In order to improve the heat resistance of PET plastic bottles, it is common practice to blend PET with a resin having good heat resistance, such as PEN, but in practical production applications, it is found that blending of PET with these heat-resistant resins results in lower mechanical properties of PET plastic bottles, which still affects the use.
Disclosure of Invention
In order to improve the heat resistance and mechanical properties of PET plastic bottles, the application provides a plastic bottle and a manufacturing method thereof.
In a first aspect, the present application provides a plastic bottle that adopts the following technical scheme:
the plastic bottle is prepared from the following raw materials in parts by weight:
76-83 parts of PET resin;
4-8 parts of first PMP resin;
12-18 parts of a second PMP resin;
0.5 to 1.5 portions of compatilizer containing isoprene-styrene block;
the melt index of the first PMP resin is 100-110 g/10min, and the melt index of the second PMP resin is 21-26 g/10min.
By adopting the technical scheme, the PMP resin is poly 4-methyl-1-pentene, and the PMP has the excellent characteristics of polyolefin, is small in density and light in weight, has good heat resistance and high temperature resistance, can improve the thermal deformation temperature of PET, and improves the heat resistance of PET plastic bottles.
The compatilizer containing the isoprene-styrene block is added, and under the cooperation of two PMPs with different melt indexes, the compatibility advantages of the loose chain segments of the PMPs and the isoprene-styrene block are brought into play, the interfacial bonding property of the PMPs and PET is improved, the structural characteristics of the PMPs are brought into play to a greater extent, the requirements on mechanical properties are met, the PET plastic bottle obtains better heat resistance, and the air impermeability and the mechanical properties are balanced.
Alternatively, the compatibilizer comprising an isoprene-styrene block is selected from maleic anhydride grafted acrylate-isoprene-styrene copolymers.
By adopting the technical scheme, the isoprene-styrene chain segment in the compatilizer is compatible with PMP, and the compatibility of acrylic ester and PET and the compatibility of maleic anhydride and PET are good, so that the maleic anhydride grafted acrylic ester-isoprene-styrene copolymer is used as a compatible bridge, the compatibilization effect on PET and PMP is achieved, the heat resistance of the PET plastic bottle is improved, and the low-temperature brittleness of the plastic bottle is improved.
Optionally, the acrylic acid ester in the maleic anhydride grafted acrylic acid ester-isoprene-styrene copolymer is selected from one or more of ethyl acrylate, ethyl methacrylate, propyl methacrylate and butyl acrylate.
By adopting the technical scheme, the ethyl acrylate, the ethyl methacrylate, the propyl methacrylate and the butyl acrylate in the acrylic ester have good compatibility with PET, thereby playing a role in compatibilization.
Alternatively, the maleic anhydride grafted acrylate-isoprene-styrene copolymer is selected from maleic anhydride grafted ethyl methacrylate-isoprene-styrene copolymer and maleic anhydride grafted butyl acrylate-isoprene-styrene copolymer, and the weight ratio of the maleic anhydride grafted ethyl methacrylate-isoprene-styrene copolymer to the maleic anhydride grafted butyl acrylate-isoprene-styrene copolymer is 1 (0.35-0.6).
By adopting the technical scheme, the compatibility agent which takes the ethyl methacrylate and the butyl acrylate as chain segments is compounded for use, and the air impermeability and the low temperature resistance of the PEI plastic bottle are improved.
In a second aspect, the present application provides a method for manufacturing a plastic bottle, which adopts the following technical scheme:
a method of manufacturing a plastic bottle comprising the steps of:
mixing PET resin, first PMP resin, second PMP resin and compatilizer containing isoprene-styrene block at 120-140 ℃, stirring uniformly, then carrying out melt extrusion to obtain plastic master batch, carrying out melt injection molding on the plastic master batch into a mold, opening the mold to obtain a bottle blank, and carrying out blow molding on the bottle blank to obtain the plastic bottle.
By adopting the technical scheme, the raw materials are premixed at 120-140 ℃, the moisture in the raw materials is removed, the raw materials are fully mixed, the uniformity of each part is improved after melting, and the PET and PMP compatibility during melting is facilitated.
Optionally, the melt extrusion process is carried out in a twin-screw extruder, wherein the temperature of the first region of the twin-screw extruder is 190 ℃ to 200 ℃, the temperature of the second region of the twin-screw extruder is 200 ℃ to 210 ℃, the temperature of the third region of the twin-screw extruder is 225 ℃ to 235 ℃, the temperature of the fourth region of the twin-screw extruder is 255 ℃ to 260 ℃, the temperature of the fifth region of the twin-screw extruder is 260 ℃ to 265 ℃, and the temperature of the sixth region of the twin-screw extruder is 265 ℃ to 270 ℃.
By adopting the technical scheme, under the progressive temperature of each section, the raw materials are effectively promoted to be melted and uniformly dispersed, the internal viscosity of the double-screw extruder is moderate, and the heat resistance and the mechanical property of the PET plastic bottle are improved.
Optionally, the screw speed of the double-screw extruder is 210-240 r/min.
Optionally, the compatilizer containing the isoprene-styrene block is a maleic anhydride grafted acrylate-isoprene-styrene copolymer, and the preparation method of the maleic anhydride grafted acrylate-isoprene-styrene copolymer comprises the following steps:
mixing styrene, an emulsifying agent and water under stirring, adding isoprene, heating to 60-70 ℃, adding a first initiator, reacting for 7-10 h, then adding acrylic ester, styrene, dodecyl mercaptan and the first initiator, continuing to react for 4-6 h, then adding sulfuric acid, dehydrating, and drying the product to obtain an acrylic ester-isoprene-styrene copolymer;
mixing the acrylic ester-isoprene-styrene copolymer, maleic anhydride and a second initiator, melting, extruding, and granulating to obtain the maleic anhydride grafted acrylic ester-isoprene-styrene copolymer.
By adopting the technical scheme, the copolymerization grafting section of isoprene and styrene is firstly carried out for subsequent grafting of acrylic ester to obtain the acrylic ester-isoprene-styrene copolymer, and then maleic anhydride is grafted in a melt grafting mode, so that the maleic anhydride grafted acrylic ester-isoprene-styrene copolymer is obtained, and the compatibility of the maleic anhydride grafted acrylic ester-isoprene-styrene copolymer to PET and PMP is better improved.
Optionally, the weight ratio of the styrene to the isoprene to the acrylic ester is 1 (0.96-1.14): 0.56-0.77); the weight ratio of the acrylic ester-isoprene-styrene copolymer to the maleic anhydride is 1 (0.026-0.044).
In summary, the present application has the following beneficial effects:
1. according to the preparation method, the PMP resin and the compatilizer containing the isoprene-styrene block are added, under the cooperation of the PMP with two different melt indexes, the compatibility advantages of the loose chain segments of the PMP and the isoprene-styrene block are brought into play, the interfacial bonding property of the PMP and PET is improved, the structural characteristics of the PMP are brought into play to a greater extent, the requirements on mechanical properties are met, and the PET plastic bottle is enabled to obtain better heat resistance and is balanced in terms of air impermeability and mechanical properties.
2. The application further uses the maleic anhydride grafted acrylic ester-isoprene-styrene copolymer as a compatilizer, and when the acrylic ester in the compatilizer is compounded by the methyl ethyl acrylate and the butyl acrylate, the air impermeability and the low-temperature brittleness resistance of the PET plastic bottle are better improved.
Detailed Description
The present application is described in further detail in connection with the following.
Preparation example
Preparation example 1
Preparation of a compatilizer:
styrene, isoprene, acrylic ester, an emulsifying agent, dodecyl mercaptan and a first initiator are weighed. Wherein the acrylic ester is ethyl methacrylate; the emulsifier is OP-10; the first initiator is potassium persulfate.
Mixing 0.5kg of styrene, 0.08kg of emulsifying agent and 10kg of water under stirring, adding 0.96kg of isoprene, heating to 60 ℃, adding 0.02kg of first initiator, reacting for 10 hours, then adding 0.56kg of acrylic ester, 0.5kg of styrene, 0.02kg of dodecyl mercaptan and 0.02kg of first initiator, continuing reacting for 6 hours, then adding 0.06kg of 20wt% sulfuric acid solution, centrifuging, dehydrating, and drying the product to obtain the acrylic ester-isoprene-styrene copolymer.
Weighing an acrylic ester-isoprene-styrene copolymer, maleic anhydride and a second initiator; wherein the second initiator is benzoyl peroxide.
1kg of an acrylate-isoprene-styrene copolymer, 0.026kg of maleic anhydride and 0.01kg of a second initiator were mixed, melted at 200℃and then extruded, and pelletized to obtain a maleic anhydride grafted acrylate-isoprene-styrene copolymer.
Preparation example 2
Preparation of a compatilizer:
styrene, isoprene, acrylic ester, an emulsifying agent, dodecyl mercaptan and a first initiator are weighed. Wherein the acrylic ester is butyl acrylate; the emulsifier is OP-10; the first initiator is potassium persulfate.
Mixing 0.5kg of styrene, 0.08kg of emulsifying agent and 10kg of water under stirring, adding 1.14kg of isoprene, heating to 70 ℃, adding 0.02kg of first initiator, reacting for 7 hours, then adding 0.77kg of acrylic ester, 0.5kg of styrene, 0.02kg of dodecyl mercaptan and 0.02kg of first initiator, continuing reacting for 4 hours, then adding 0.06kg of 20wt% sulfuric acid solution, centrifuging, dehydrating, and drying the product to obtain the acrylic ester-isoprene-styrene copolymer.
Weighing an acrylic ester-isoprene-styrene copolymer, maleic anhydride and a second initiator; wherein the second initiator is benzoyl peroxide.
1kg of an acrylate-isoprene-styrene copolymer, 0.044kg of maleic anhydride and 0.01kg of a second initiator were mixed, melted, extruded and pelletized to obtain a maleic anhydride grafted acrylate-isoprene-styrene copolymer.
Preparation example 3
The present preparation differs from preparation 1 in that the acrylate is ethyl acrylate.
Preparation example 4
Preparation of a compatilizer:
weighing methyl methacrylate-butadiene-styrene copolymer, maleic anhydride and a second initiator; wherein the second initiator is benzoyl peroxide.
Mixing methyl methacrylate-butadiene-styrene copolymer, maleic anhydride and a second initiator, melting, extruding and granulating to obtain the maleic anhydride grafted methyl methacrylate-butadiene-styrene copolymer.
Examples
The melt index was measured under conditions of 260℃melting and a load of 5kg.
Example 1
The manufacturing method of the plastic bottle comprises the following steps:
weighing PET resin, first PMP resin, second PMP resin and compatilizer. Wherein the melt index of the first PMP resin is 110g/10min, the melt index of the second PMP resin is 26g/10min, and the compatibilizer is the maleic anhydride-grafted acrylate-isoprene-styrene copolymer prepared in preparation example 1.
7.6kg of PET resin, 0.4kg of first PMP resin, 1.2kg of second PMP resin and 0.05kg of compatilizer are put into a stirrer, mixed at 120 ℃, stirred uniformly, then put into a double-screw extruder for melting, the temperature of a first area of 190 ℃, the temperature of a second area of 200 ℃, the temperature of a third area of 225 ℃, the temperature of a fourth area of 255 ℃, the temperature of a fifth area of 260 ℃ and the temperature of a sixth area of 265 ℃ of the double-screw extruder are respectively equal to 210r/min, extruded, plastic master batches are prepared, then the plastic master batches are subjected to melting injection molding into a mold, then put into an injection molding machine, the mold is subjected to injection molding at 265 ℃ to obtain bottle blanks, and then the bottle blanks are subjected to blow molding, so that the plastic bottle is manufactured.
Example 2
The manufacturing method of the plastic bottle comprises the following steps:
weighing PET resin, first PMP resin, second PMP resin and compatilizer. Wherein the melt index of the first PMP resin is 100g/10min, the melt index of the second PMP resin is 21g/10min, and the compatibilizer is the maleic anhydride-grafted acrylate-isoprene-styrene copolymer prepared in preparation example 1.
Putting 8.3kg of PET resin, 0.8kg of first PMP resin, 1.8kg of second PMP resin and 0.15kg of compatilizer into a stirrer, mixing at 140 ℃, stirring uniformly, putting into a double-screw extruder for melting, putting into a first region temperature 200 ℃, a second region temperature 210 ℃, a third region temperature 235 ℃, a fourth region temperature 260 ℃, a fifth region temperature 265 ℃ and a sixth region temperature 270 ℃ of the double-screw extruder, extruding at the screw rotating speed of 240r/min of the double-screw extruder to obtain plastic master batches, melting and injecting the plastic master batches into a mold, putting into an injection molding machine, injecting at 265 ℃ into the mold, opening to obtain bottle blanks, and blow molding the bottle blanks to obtain the plastic bottles.
Example 3
This example differs from example 2 in that the compatibilizer is an acrylate-isoprene-styrene copolymer prepared in preparation example 1.
Example 4
This example differs from example 2 in that the compatibilizer is a maleic anhydride-grafted acrylate-isoprene-styrene copolymer prepared in preparation example 2.
Example 5
This example differs from example 2 in that the compatibilizing agent is 0.039kg of the maleic anhydride-grafted acrylate-isoprene-styrene copolymer produced in production example 2 and 0.11kg of the maleic anhydride-grafted acrylate-isoprene-styrene copolymer produced in production example 3.
Example 6
This example differs from example 2 in that the compatibilizing agent is 0.11kg of the maleic anhydride-grafted acrylate-isoprene-styrene copolymer produced in production example 1 and 0.039kg of the maleic anhydride-grafted acrylate-isoprene-styrene copolymer produced in production example 2.
Example 7
This example differs from example 2 in that the compatibilizing agent is 0.056kg of the maleic anhydride-grafted acrylate-isoprene-styrene copolymer produced in production example 1 and 0.094kg of the maleic anhydride-grafted acrylate-isoprene-styrene copolymer produced in production example 2.
Comparative example
Comparative example 1
The comparative example differs from example 2 in that the first PMP resin was replaced with an equal amount of the second PMP resin, i.e., the PMP resin having a melt index of 100g/10min was added in an amount of 0 and the PMP resin having a melt index of 21g/10min was added in an amount of 2.6kg.
Comparative example 2
The difference between this comparative example and example 2 is that the second PMP resin was replaced with the same amount of the first PMP resin, i.e., the PMP resin having a melt index of 100g/10min was added in an amount of 2.6kg, and the PMP resin having a melt index of 21g/10min was added in an amount of 0.
Comparative example 3
This comparative example differs from example 2 in that no compatibilizing agent was added.
Comparative example 4
This comparative example differs from example 2 in that the compatibilizer was selected from the maleic anhydride-grafted methyl methacrylate-butadiene-styrene copolymer prepared in preparation example 4.
Blank examples
The blank example uses pure PET as a raw material, and is subjected to injection molding to form a bottle blank, and then the bottle blank is subjected to blow molding to manufacture the plastic bottle.
Performance test sanitation test: the plastic bottles prepared in each example were tested for vaporization residue with reference to GB 13113-1991 Standard for hygienic polyethylene terephthalate molded articles for food containers and packaging materials. Through tests, the evaporation residues in all the tests are less than 30mg/L, and the requirements are met.
Heat resistance test: with reference to the heat resistance requirements in QBT 2665-2004 polyethylene terephthalate (PET) bottle for hot-fill, the plastic bottles were tested for volume shrinkage at each temperature, each test at 5℃C, with a shrinkage of <3% and no change in appearance, and the temperature resistance of the plastic bottles before a shrinkage of > 3% was recorded, the temperature results being shown in Table 1.
Air impermeability test: the plastic bottles prepared in each of the examples and comparative examples were subjected to an oxygen transmission rate test using an oxygen transmission rate tester, and the results are shown in table 1.
Mechanical property test: referring to the bottle wall load test in QBT 2665-2004 polyethylene terephthalate (PET) bottle for hot filling, the test site was the bottle wall plate, and the results are shown in Table 1.
Low temperature brittleness resistance: the plastic bottles prepared in each example and comparative example were placed in an environment of-40.+ -. 2 ℃ for 8 hours, and then subjected to a bottle wall load test, the test site being a bottle wall plate, and the results are shown in Table 1.
TABLE 1
Taking the embodiment 1-2 as an example, the PET plastic bottle prepared by the application has good comprehensive effect, and under the action of the first PMP resin and the second PMP resin matched with the compatilizer, the heat-resistant temperature of the plastic bottle is improved, good mechanical properties can be maintained, the bottle wall load in normal temperature test is more than 50N, and the use requirement is met.
When PMP resins were compounded with each other at a melt index of 100 to 110g/10min and a melt index of 21 to 26g/10min, the heat resistance improvement effect of the plastic bottle was best and the mechanical properties could be maintained at a good level, as compared with comparative examples 1 to 2 and blank examples.
In comparison with examples 2, comparative examples 3 to 4 and blank examples, the compatibility of PET and PMP was improved better by using the compatibilizer containing an isoprene-styrene block, and therefore, the improvement of mechanical properties of plastic bottles was more excellent.
By comparing example 2 with example 3, it can be seen that maleic anhydride has an improved effect on the grafting of the compatibilizing agent; by comparing example 2 with examples 5-7, it can be seen that the plastic bottle has better properties in terms of air impermeability and low temperature brittleness resistance when the acrylic acid ester in the compatibilizer is compounded with ethyl methacrylate and butyl acrylate.
The present embodiment is merely illustrative of the present application and is not limiting of the present application, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as necessary, but are protected by patent laws within the scope of the claims of the present application.
Claims (9)
1. A plastic bottle, characterized in that: the composite material is prepared from the following raw materials in parts by weight:
76-83 parts of PET resin;
4-8 parts of a first PMP resin;
12-18 parts of a second PMP resin;
0.5-1.5 parts of a compatilizer containing an isoprene-styrene block;
the melt index of the first PMP resin is 100-110 g/10min, and the melt index of the second PMP resin is 21-26 g/10min.
2. A plastic bottle according to claim 1, wherein: the compatibilizer containing an isoprene-styrene block is selected from maleic anhydride grafted acrylate-isoprene-styrene copolymers.
3. A plastic bottle according to claim 2, wherein: the acrylic acid ester in the maleic anhydride grafted acrylic acid ester-isoprene-styrene copolymer is selected from one or more of ethyl acrylate, ethyl methacrylate, propyl methacrylate and butyl acrylate.
4. A plastic bottle according to claim 2, wherein: the maleic anhydride grafted acrylic ester-isoprene-styrene copolymer is selected from maleic anhydride grafted ethyl methacrylate-isoprene-styrene copolymer and maleic anhydride grafted butyl acrylate-isoprene-styrene copolymer, and the weight ratio of the maleic anhydride grafted ethyl methacrylate-isoprene-styrene copolymer to the maleic anhydride grafted butyl acrylate-isoprene-styrene copolymer is 1 (0.35-0.6).
5. A method for manufacturing a plastic bottle, characterized in that: a method for manufacturing a plastic bottle according to any one of claims 1-4, comprising the steps of:
mixing PET resin, first PMP resin, second PMP resin and compatilizer containing isoprene-styrene block at 120-140 ℃, stirring uniformly, then carrying out melt extrusion to obtain plastic master batch, carrying out melt injection molding on the plastic master batch into a mold, opening the mold to obtain a bottle blank, and carrying out blow molding on the bottle blank to obtain the plastic bottle.
6. The method for manufacturing a plastic bottle according to claim 5, wherein: the melt extrusion process is performed in a twin-screw extruder, wherein the temperature of the first region of the twin-screw extruder is 190-200 ℃, the temperature of the second region of the twin-screw extruder is 200-210 ℃, the temperature of the third region of the twin-screw extruder is 225-235 ℃, the temperature of the fourth region of the twin-screw extruder is 255-260 ℃, the temperature of the fifth region of the twin-screw extruder is 260-265 ℃, and the temperature of the sixth region of the twin-screw extruder is 265-270 ℃.
7. The method for manufacturing a plastic bottle according to claim 6, wherein: the screw rotating speed of the double-screw extruder is 210-240 r/min.
8. The method for manufacturing a plastic bottle according to claim 5, wherein: the compatilizer containing the isoprene-styrene block is a maleic anhydride grafted acrylate-isoprene-styrene copolymer, and the preparation method of the maleic anhydride grafted acrylate-isoprene-styrene copolymer comprises the following steps:
stirring and mixing styrene, an emulsifying agent and water, adding isoprene, heating to 60-70 ℃, adding a first initiator, reacting for 7-10 hours, then adding acrylic ester, styrene, dodecyl mercaptan and the first initiator, continuously reacting for 4-6 hours, then adding sulfuric acid, dehydrating, and drying the product to obtain an acrylic ester-isoprene-styrene copolymer;
mixing the acrylic ester-isoprene-styrene copolymer, maleic anhydride and a second initiator, melting, extruding, and granulating to obtain the maleic anhydride grafted acrylic ester-isoprene-styrene copolymer.
9. The method for manufacturing a plastic bottle according to claim 8, wherein: the weight ratio of the styrene to the isoprene to the acrylic ester is 1 (0.96-1.14): 0.56-0.77; the weight ratio of the acrylic ester-isoprene-styrene copolymer to the maleic anhydride is 1 (0.026-0.044).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117659644A (en) * | 2023-11-29 | 2024-03-08 | 佛山华新恒丰聚酯包装有限公司 | PET explosion-proof plastic bottle and preparation method thereof |
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