CN113980380A - High and low temperature resistant plastic bottle cap and manufacturing process thereof - Google Patents
High and low temperature resistant plastic bottle cap and manufacturing process thereof Download PDFInfo
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- CN113980380A CN113980380A CN202111490444.4A CN202111490444A CN113980380A CN 113980380 A CN113980380 A CN 113980380A CN 202111490444 A CN202111490444 A CN 202111490444A CN 113980380 A CN113980380 A CN 113980380A
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- 229920003023 plastic Polymers 0.000 title claims abstract description 30
- 239000004033 plastic Substances 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 239000003607 modifier Substances 0.000 claims abstract description 38
- -1 polyethylene Polymers 0.000 claims abstract description 34
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 19
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 19
- 239000004698 Polyethylene Substances 0.000 claims abstract description 17
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 16
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 16
- 229920000573 polyethylene Polymers 0.000 claims abstract description 16
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 11
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 11
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims abstract description 9
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims abstract description 9
- 239000000945 filler Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 31
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 10
- 235000013824 polyphenols Nutrition 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- 235000006708 antioxidants Nutrition 0.000 claims description 8
- NDHZYIWVQSXGQE-UHFFFAOYSA-N trimethyl-[5-[2-(5-trimethylstannylthiophen-2-yl)ethenyl]thiophen-2-yl]stannane Chemical group S1C([Sn](C)(C)C)=CC=C1C=CC1=CC=C([Sn](C)(C)C)S1 NDHZYIWVQSXGQE-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229920001221 xylan Polymers 0.000 claims description 7
- 150000004823 xylans Chemical class 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000007983 Tris buffer Substances 0.000 claims description 6
- 229910021538 borax Inorganic materials 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- NQHJWFYVHSKTLX-UHFFFAOYSA-N phosphoric acid;toluene Chemical compound OP(O)(O)=O.CC1=CC=CC=C1 NQHJWFYVHSKTLX-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 6
- 239000004328 sodium tetraborate Substances 0.000 claims description 6
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 6
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 claims description 6
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- BWHOZHOGCMHOBV-UHFFFAOYSA-N benzylideneacetone Chemical compound CC(=O)C=CC1=CC=CC=C1 BWHOZHOGCMHOBV-UHFFFAOYSA-N 0.000 claims description 3
- 238000000071 blow moulding Methods 0.000 claims description 3
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229940079877 pyrogallol Drugs 0.000 claims description 3
- COHOGNZHAUOXPA-UHFFFAOYSA-N trimethyl(phenyl)stannane Chemical compound C[Sn](C)(C)C1=CC=CC=C1 COHOGNZHAUOXPA-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- PFTAWBLQPZVEMU-DZGCQCFKSA-N (+)-catechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-DZGCQCFKSA-N 0.000 claims description 2
- 229930014669 anthocyanidin Natural products 0.000 claims description 2
- 150000001452 anthocyanidin derivatives Chemical class 0.000 claims description 2
- 235000008758 anthocyanidins Nutrition 0.000 claims description 2
- ADRVNXBAWSRFAJ-UHFFFAOYSA-N catechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3ccc(O)c(O)c3 ADRVNXBAWSRFAJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000005487 catechin Nutrition 0.000 claims description 2
- 229950001002 cianidanol Drugs 0.000 claims description 2
- 229920002770 condensed tannin Polymers 0.000 claims description 2
- 229920001461 hydrolysable tannin Polymers 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 239000012744 reinforcing agent Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000012745 toughening agent Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 17
- 239000002131 composite material Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000001954 sterilising effect Effects 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- 235000013361 beverage Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/10—Applications used for bottles
Abstract
The invention provides a high and low temperature resistant plastic bottle cap and a manufacturing process thereof, belonging to the field of high-performance plastics and comprising the following components in parts by weight: 60-75 parts of high-density polyethylene, 8-16 parts of temperature-resistant modified master batch, 4-8 parts of low-molecular-weight branched polyethylene, 1-4 parts of maleic anhydride grafted polypropylene, 1-4 parts of pentadiene, 2-4 parts of filler and 1-10 parts of first auxiliary agent; the temperature-resistant modified master batch is composed of low-density polyethylene, a temperature-resistant modifier and a second auxiliary agent, and the mass ratio of the temperature-resistant modified master batch to the second auxiliary agent is 50: (25-45): (1-5); the invention improves the high and low temperature resistance of the HDPE material by adding the modifier on the basis of the existing HDPE material.
Description
Technical Field
The invention relates to the field of high-performance plastics, in particular to a high-low temperature resistant plastic bottle cap and a manufacturing process thereof.
Background
The bottle cap is an important part of food and beverage packaging and is the place where consumers first contact with products. The bottle cap has the functions of keeping the sealing performance of the content products, preventing the opening of the bottle cap from being stolen and ensuring the safety, so the bottle cap is widely applied to bottled products, and is a key product for packaging bottle containers in upstream industries of food, drinking, wine, chemical industry and pharmaceutical industry.
The main raw material of the plastic bottle cap is polypropylene or polyethylene, in order to ensure that food or beverage does not deteriorate, a high-temperature sterilization process is usually included in the production and processing process, but the high-temperature sterilization temperature reaches 121 ℃, and the sterilization time is usually 15-30min, however, the plastic bottle cap in the prior art is usually not high-temperature resistant or has poor high-temperature resistant effect, and particularly, the bottle cap produced by PE plastic is easy to deform in the high-temperature sterilization process, so that the sealing performance of the bottle cap is affected, and the leakage or the rapid deterioration of food is caused.
On the other hand, in the use process of food or beverage, refrigeration or freezing is often required, while the plastic bottle caps in the prior art can resist low temperature, but have poor toughness and impact resistance at low temperature and high brittleness, so that the plastic bottle caps are easy to crack in the refrigeration or freezing process, and the bottle caps in the prior art cannot simultaneously meet the mechanical strength, toughness and impact resistance in a wide temperature use range.
Disclosure of Invention
Aiming at the problems, the invention provides a high and low temperature resistant plastic bottle cap and a manufacturing process thereof.
The purpose of the invention is realized by adopting the following technical scheme:
the high and low temperature resistant plastic bottle cap comprises the following components in parts by weight: 60-75 parts of high-density polyethylene, 8-16 parts of temperature-resistant modified master batch, 4-8 parts of low-molecular-weight branched polyethylene, 1-4 parts of maleic anhydride grafted polypropylene, 1-4 parts of pentadiene, 2-4 parts of filler and 1-10 parts of first auxiliary agent;
the temperature-resistant modified master batch is composed of low-density polyethylene, a temperature-resistant modifier and a second auxiliary agent, and the mass ratio of the temperature-resistant modified master batch to the second auxiliary agent is 50: (25-45): (1-5).
Preferably, the high density polyethylene has a density of 0.93 to 0.95g/cm3The melt flow rate is 10-35g/10 min.
Preferably, the low molecular weight branched polyethylene is a copolymer of ethylene and hexene having a weight average molecular weight of 5910, a dispersion coefficient of 1.1, and a branching content of 3.4 branches per 1000 main chain carbon atoms on average.
Preferably, the filler is nanoparticles of calcium carbonate or silica.
Preferably, the first auxiliary agent comprises one or more of an antioxidant, a compatilizer, a toughening agent and a reinforcing agent.
Preferably, the low density polyethylene has a density of 0.915-0.925g/cm3The melt flow rate is 0.1-10g/10 min.
Preferably, the temperature-resistant modifier comprises a first modifier, and the preparation method of the first modifier comprises the following steps:
weighing polyvinyl alcohol, dissolving the polyvinyl alcohol in dimethyl sulfoxide, adding xylan and borax after fully stirring and dissolving, adding butyraldehyde after continuously stirring and mixing, stirring and heating to 70-80 ℃, keeping the temperature for 1-30min, adding a dimethyl sulfoxide solution of polyphenol while hot, continuously keeping the temperature, stirring and reacting for 0.5-1h, slowly adding p-toluenesulfonamide while stirring, continuously keeping the temperature, stirring and reacting for 4-6h, dropwise adding a dimethyl sulfoxide solution of ferric chloride after the reaction is finished, continuously keeping the temperature and stirring for 10-30min after the dropwise adding is finished, slowly adding a mixed system into cyclohexane after cooling, fully stirring until no precipitate is separated out, separating the precipitate, washing with absolute ethyl alcohol and deionized water in sequence, crushing and grinding after vacuum drying to prepare the first modifier;
the weight average molecular weight of the polyvinyl alcohol is 14.6-18.6 ten thousand, the hydrolysis degree is not less than 98%, the polyphenol is one or more of pyrogallol, anthocyanidin, catechin, hydrolysable tannin and condensed tannin, and the mass ratio of the polyvinyl alcohol to the xylan, the borax, the butyraldehyde, the polyphenol, the p-toluenesulfonamide and the ferric chloride is 10: (3.2-3.3): (1.3-1.5): (1.6-1.7): (0.45-0.5): (0.8-0.9): (0.09-0.11).
Preferably, the temperature-resistant modifier comprises a second modifier, and the preparation method of the second modifier comprises the following steps:
respectively weighing 1, 2-bis (5- (trimethylstannyl) thiophene-2-yl) ethylene and 3, 6-bis (5-bromothiophene-2-yl) -2, 5-bis (2-decyltetradecyl) -2, 5-dihydropyrrole-1, 4-diketone, dissolving in a dry toluene solution, fully mixing, adding palladium tris (dibenzylidene acetone) and toluene phosphoric acid, fully mixing again, sealing a reaction system, carrying out heating and stirring reaction under the microwave condition, wherein the microwave power is 300-, fully stirring until no precipitate is separated out, separating the precipitate, washing with methanol and deionized water in sequence, drying in vacuum, crushing and grinding to prepare the second modifier;
wherein the mass ratio of the 1, 2-bis (5- (trimethylstannyl) thiophen-2-yl) ethylene to the 3, 6-bis (5-bromothiophen-2-yl) -2, 5-bis (2-decyltetradecyl) -2, 5-dihydropyrrole-1, 4-dione, the dipalladium tris (benzylidene) acetone, the toluene phosphoric acid, and the trimethyl (phenyl) tin is (45-50): 100: (1.6-1.8): (2.4-2.6): (21-24).
The structure of 1, 2-bis (5- (trimethylstannyl) thiophen-2-yl) ethylene is as follows:
the structure of 3, 6-bis (5-bromothien-2-yl) -2, 5-bis (2-decyltetradecyl) -2, 5-dihydropyrrole-1, 4-dione is as follows:
preferably, the second auxiliary agent is one or more of an antioxidant, a compatilizer and a filler.
Another object of the present invention is to provide a manufacturing process of the plastic bottle cap with high and low temperature resistance, which specifically comprises the following steps:
weighing the components according to the ratio, banburying the low molecular weight branched polyethylene, the pentadiene, the maleic anhydride grafted polypropylene and the first auxiliary agent, then blending the mixture with the high density polyethylene and the temperature-resistant modified master batch, and then extruding, granulating and blow molding.
The invention has the beneficial effects that:
(1) the invention improves the high and low temperature resistance of the high density polyethylene material by adding the modifier on the basis of the existing high density polyethylene material and the auxiliary agent thereof, in particular, the invention adds the first modifier, utilizes the physical and chemical multi-crosslinking network structure formed among polyethylene, xylan and boron atoms under the crosslinking action of polyphenol and iron ions, can further consolidate the function on the basis of the original high density polyethylene molecular structure, avoids the occurrence of the slippage phenomenon among high density polyethylene macromolecular chains, improves the anti-shearing function of the composite bottle cap material, and can obviously improve the high temperature resistance of the composite bottle cap material, namely the composite bottle cap material can destroy the weak interaction only when absorbing higher heat, and then has the influence on the macromolecular chains, so the composite bottle cap material can bear higher temperature, furthermore, the invention also improves the water resistance and the affinity compatibility with the main body of the polyethylene material by grafting high-density hydrophobic groups on the main chain of the polyvinyl alcohol through an acetal reaction under the catalysis of acid.
(2) According to the invention, by adding the second modifier, 1, 2-bis (5- (trimethylstannyl) thiophene-2-yl) ethylene and 3, 6-bis (5-bromothiophene-2-yl) -2, 5-bis (2-decyltetradecyl) -2, 5-dihydropyrrole-1, 4-diketone are taken as composite monomers to prepare the conjugated modified polymer with good mechanical flexibility, and the low-temperature brittleness of the composite bottle cap material is obviously reduced by matching with the plasticizing effect of low-molecular-weight branched polyethylene, so that the toughness and the impact resistance of the composite bottle cap material at low temperature are enhanced.
Detailed Description
The invention is further described with reference to the following examples.
Example 1
The embodiment relates to a high and low temperature resistant plastic bottle cap material which comprises the following components in parts by mass: 65 parts of high-density polyethylene, 12 parts of temperature-resistant modified master batch, 6 parts of low-molecular-weight branched polyethylene, 3 parts of maleic anhydride grafted polypropylene, 2 parts of pentadiene, 3 parts of nano calcium carbonate, 1 part of antioxidant and 0.5 part of HDPE-GMAH compatilizer;
the temperature-resistant modified master batch is composed of low-density polyethylene, a temperature-resistant modifier and nano silicon dioxide, and the mass ratio of the low-density polyethylene to the temperature-resistant modifier is 50: 35: 2;
the density of the high-density polyethylene is 0.935g/cm3The melt flow rate is 15g/10 min;
the low molecular weight branched polyethylene is a copolymer of ethylene and hexene, the weight average molecular weight is 5910, the dispersion coefficient is 1.1, and the branching content is that the average branched chain contains 3.4 branched chains per 1000 main chain carbon atoms;
the density of the low-density polyethylene is 0.915g/cm3The melt flow rate is 1.8g/10 min;
the temperature-resistant modifier is a first modifier, and the preparation method of the first modifier comprises the following steps:
weighing polyvinyl alcohol, dissolving the polyvinyl alcohol in dimethyl sulfoxide, adding xylan and borax after fully stirring and dissolving, adding butyraldehyde after continuously stirring and mixing, stirring and heating to 70-80 ℃, keeping the temperature for 1-30min, adding a dimethyl sulfoxide solution of polyphenol while hot, continuously keeping the temperature, stirring and reacting for 0.5-1h, slowly adding p-toluenesulfonamide while stirring, continuously keeping the temperature, stirring and reacting for 4-6h, dropwise adding a dimethyl sulfoxide solution of ferric chloride after the reaction is finished, continuously keeping the temperature and stirring for 10-30min after the dropwise adding is finished, slowly adding a mixed system into cyclohexane after cooling, fully stirring until no precipitate is separated out, separating the precipitate, washing with absolute ethyl alcohol and deionized water in sequence, crushing and grinding after vacuum drying to prepare the first modifier;
the weight average molecular weight of the polyvinyl alcohol is 14.6-18.6 ten thousand, the hydrolysis degree is not less than 98%, the polyphenol is pyrogallol, and the mass ratio of the polyvinyl alcohol to the xylan, the borax, the butyraldehyde, the polyphenol, the p-toluenesulfonamide and the ferric chloride is 10: 3.2: 1.4: 1.65: 0.45: 0.82: 0.09;
the manufacturing process of the high and low temperature resistant plastic bottle cap specifically comprises the following steps:
weighing the components according to the ratio, banburying the low molecular weight branched polyethylene, the pentadiene, the maleic anhydride grafted polypropylene, the filler, the antioxidant and the compatilizer, then mixing the mixture with the high-density polyethylene and the temperature-resistant modified master batch, then extruding, granulating and blow molding.
Example 2
The embodiment relates to a plastic bottle cap material with high and low temperature resistance, which is different from the plastic bottle cap material in embodiment 1 in that the temperature-resistant modifier is a second modifier, and the preparation method of the second modifier comprises the following steps:
respectively weighing 1, 2-bis (5- (trimethylstannyl) thiophen-2-yl) ethylene (CAS number: 477789-30-3) and 3, 6-bis (5-bromothiophen-2-yl) -2, 5-bis (2-decyltetradecyl) -2, 5-dihydropyrrole-1, 4-diketone (provided by Jiangsu Giara biological science and technology Co., Ltd.) and dissolving in dry toluene solution, fully mixing, adding palladium tris (dibenzylidene acetone) and toluene phosphoric acid, fully mixing again, sealing the reaction system, carrying out heating and stirring reaction under microwave condition with microwave power of 300-, fully stirring, cooling, adding trichloroethylene for dilution after cooling, transferring into a methanol solution after dilution, fully stirring until no precipitate is separated out, separating the precipitate, washing with methanol and deionized water in sequence, drying in vacuum, crushing and grinding to obtain the second modifier;
wherein the mass ratio of the 1, 2-bis (5- (trimethylstannyl) thiophen-2-yl) ethylene and the 3, 6-bis (5-bromothiophen-2-yl) -2, 5-bis (2-decyltetradecyl) -2, 5-dihydropyrrole-1, 4-dione, the dipalladium tris (benzylidene) acetone, the toluene phosphoric acid, and the trimethyl (phenyl) tin is 46: 100: 1.7: 2.5: 22.
example 3
The embodiment relates to a high and low temperature resistant plastic bottle cap material which comprises the following components in parts by mass: 65 parts of high-density polyethylene, 12 parts of temperature-resistant modified master batch, 6 parts of low-molecular-weight branched polyethylene, 3 parts of maleic anhydride grafted polypropylene, 2 parts of pentadiene, 3 parts of nano calcium carbonate, 1 part of antioxidant and 0.5 part of HDPE-GMAH compatilizer;
the temperature-resistant modified master batch is composed of low-density polyethylene, a temperature-resistant modifier and nano silicon dioxide, and the mass ratio of the low-density polyethylene to the temperature-resistant modifier is 50: 35: 2;
the density of the high-density polyethylene is 0.935g/cm3The melt flow rate is 15g/10 min;
the low molecular weight branched polyethylene is a copolymer of ethylene and hexene, the weight average molecular weight is 5910, the dispersion coefficient is 1.1, and the branching content is that the average branched chain contains 3.4 branched chains per 1000 main chain carbon atoms;
the density of the low-density polyethylene is 0.915g/cm3The melt flow rate is 1.8g/10 min;
the heat-resistant modifier is prepared from the following components in a mass ratio of 1: 1, the method for preparing the first modifier is the same as that of example 1, and the method for preparing the second modifier is the same as that of example 2.
Comparative example
The plastic bottle cap material comprises the following components in parts by weight: 65 parts of high-density polyethylene, 3 parts of maleic anhydride grafted polypropylene, 2 parts of pentadiene, 3 parts of nano calcium carbonate, 1 part of antioxidant and 0.5 part of HDPE-GMAH compatilizer.
The temperature-resistant mechanical properties of the bottle cap materials prepared in examples 1-3 and comparative example were measured, and the measurement results were as follows:
finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The high and low temperature resistant plastic bottle cap is characterized by comprising the following components in parts by weight: 60-75 parts of high-density polyethylene, 8-16 parts of temperature-resistant modified master batch, 4-8 parts of low-molecular-weight branched polyethylene, 1-4 parts of maleic anhydride grafted polypropylene, 1-4 parts of pentadiene, 2-4 parts of filler and 1-10 parts of first auxiliary agent;
the temperature-resistant modified master batch is composed of low-density polyethylene, a temperature-resistant modifier and a second auxiliary agent, and the mass ratio of the temperature-resistant modified master batch to the second auxiliary agent is 50: (25-45): (1-5).
2. The high and low temperature resistant plastic bottle cap as claimed in claim 1, wherein the density of the high density polyethylene is 0.93-0.95g/cm3The melt flow rate is 10-35g/10 min.
3. The high and low temperature resistant plastic bottle cap as claimed in claim 1, wherein the branched polyethylene with low molecular weight is a copolymer of ethylene and hexene, and has a weight average molecular weight of 5910, a dispersion coefficient of 1.1, and a branching content of 3.4 branches per 1000 main chain carbon atoms on average.
4. The high and low temperature resistant plastic bottle cap as claimed in claim 1, wherein the filler is nanoparticles of calcium carbonate or silica.
5. The high and low temperature resistant plastic bottle cap according to claim 1, wherein the first auxiliary agent comprises one or more of an antioxidant, a compatilizer, a toughening agent and a reinforcing agent.
6. The high and low temperature resistant plastic bottle cap as claimed in claim 1, wherein the density of the low density polyethylene is 0.915-0.925g/cm3The melt flow rate is 0.1-10g/10 min.
7. The plastic bottle cap according to claim 1, wherein the temperature modifier comprises a first modifier, and the first modifier is prepared by a method comprising the following steps:
weighing polyvinyl alcohol, dissolving the polyvinyl alcohol in dimethyl sulfoxide, adding xylan and borax after fully stirring and dissolving, adding butyraldehyde after continuously stirring and mixing, stirring and heating to 70-80 ℃, keeping the temperature for 1-30min, adding a dimethyl sulfoxide solution of polyphenol while hot, continuously keeping the temperature, stirring and reacting for 0.5-1h, slowly adding p-toluenesulfonamide while stirring, continuously keeping the temperature, stirring and reacting for 4-6h, dropwise adding a dimethyl sulfoxide solution of ferric chloride after the reaction is finished, continuously keeping the temperature and stirring for 10-30min after the dropwise adding is finished, slowly adding a mixed system into cyclohexane after cooling, fully stirring until no precipitate is separated out, separating the precipitate, washing with absolute ethyl alcohol and deionized water in sequence, crushing and grinding after vacuum drying to prepare the first modifier;
the weight average molecular weight of the polyvinyl alcohol is 14.6-18.6 ten thousand, the hydrolysis degree is not less than 98%, the polyphenol is one or more of pyrogallol, anthocyanidin, catechin, hydrolysable tannin and condensed tannin, and the mass ratio of the polyvinyl alcohol to the xylan, the borax, the butyraldehyde, the polyphenol, the p-toluenesulfonamide and the ferric chloride is 10: (3.2-3.3): (1.3-1.5): (1.6-1.7): (0.45-0.5): (0.8-0.9): (0.09-0.11).
8. The plastic bottle cap with high and low temperature resistance as claimed in claim 1, wherein the temperature modifier comprises a second modifier, and the second modifier is prepared by a method comprising the following steps:
respectively weighing 1, 2-bis (5- (trimethylstannyl) thiophene-2-yl) ethylene and 3, 6-bis (5-bromothiophene-2-yl) -2, 5-bis (2-decyltetradecyl) -2, 5-dihydropyrrole-1, 4-diketone, dissolving in a dry toluene solution, fully mixing, adding palladium tris (dibenzylidene acetone) and toluene phosphoric acid, fully mixing again, sealing a reaction system, carrying out heating and stirring reaction under the microwave condition, wherein the microwave power is 300-, fully stirring until no precipitate is separated out, separating the precipitate, washing with methanol and deionized water in sequence, drying in vacuum, crushing and grinding to prepare the second modifier;
wherein the mass ratio of the 1, 2-bis (5- (trimethylstannyl) thiophen-2-yl) ethylene to the 3, 6-bis (5-bromothiophen-2-yl) -2, 5-bis (2-decyltetradecyl) -2, 5-dihydropyrrole-1, 4-dione, the dipalladium tris (benzylidene) acetone, the toluene phosphoric acid, and the trimethyl (phenyl) tin is (45-50): 100: (1.6-1.8): (2.4-2.6): (21-24).
9. The high and low temperature resistant plastic bottle cap according to claim 1, wherein the second auxiliary agent is one or more of an antioxidant, a compatilizer and a filler.
10. The process for manufacturing a plastic bottle cap resistant to high and low temperatures according to any one of claims 1 to 9, comprising the steps of:
weighing the components according to the ratio, banburying the low molecular weight branched polyethylene, the pentadiene, the maleic anhydride grafted polypropylene and the first auxiliary agent, then blending the mixture with the high density polyethylene and the temperature-resistant modified master batch, and then extruding, granulating and blow molding.
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