CN112375303A - Transparent polypropylene material for high-gloss extrusion blow-molded bottle and preparation method thereof - Google Patents
Transparent polypropylene material for high-gloss extrusion blow-molded bottle and preparation method thereof Download PDFInfo
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- -1 polypropylene Polymers 0.000 title claims abstract description 141
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 132
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 131
- 239000000463 material Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000001125 extrusion Methods 0.000 title claims abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 47
- 239000011347 resin Substances 0.000 claims abstract description 47
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 33
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000002250 absorbent Substances 0.000 claims abstract description 10
- 230000002745 absorbent Effects 0.000 claims abstract description 10
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 10
- 150000002367 halogens Chemical class 0.000 claims abstract description 10
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 39
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 26
- 239000005977 Ethylene Substances 0.000 claims description 26
- 238000007334 copolymerization reaction Methods 0.000 claims description 26
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 23
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 23
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 23
- 239000002216 antistatic agent Substances 0.000 claims description 22
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical group [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 18
- 235000013539 calcium stearate Nutrition 0.000 claims description 18
- 239000008116 calcium stearate Substances 0.000 claims description 18
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000008187 granular material Substances 0.000 claims description 7
- BGHBLQKNCVRIKV-UHFFFAOYSA-N OP(O)OP(O)O.OCC(CO)(CO)CO.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O BGHBLQKNCVRIKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002530 phenolic antioxidant Substances 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 235000013305 food Nutrition 0.000 abstract description 7
- 238000012545 processing Methods 0.000 abstract description 7
- 229940079593 drug Drugs 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 4
- 238000004806 packaging method and process Methods 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- 238000010101 extrusion blow moulding Methods 0.000 description 7
- 239000012780 transparent material Substances 0.000 description 5
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 241000251730 Chondrichthyes Species 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 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
- 238000000465 moulding Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a transparent polypropylene material for a high-gloss extrusion-blow bottle and a preparation method thereof, belonging to the field of high polymer materials. The invention provides a transparent polypropylene material for a high-gloss extrusion blow-molded bottle, which comprises the following components in percentage by weight: 99.27 to 99.71 percent of polypropylene resin, 0.18 to 0.40 percent of transparent agent, 0.03 to 0.10 percent of main antioxidant, 0.05 to 0.15 percent of auxiliary antioxidant and 0.03 to 0.08 percent of halogen absorbent. The high-gloss transparent polypropylene material for the extrusion blow-molded bottle has the characteristics of good processing performance, high glossiness, high transparency, good rigidity and toughness balance, high strength and high food safety, and can be suitable for transparent packaging containers of foods, medicines and daily necessities which are required to be extruded and blown.
Description
Technical Field
The invention relates to a transparent polypropylene material for a high-gloss extrusion-blow bottle and a preparation method thereof, belonging to the field of high polymer materials.
Background
Many products processed by the Extrusion Blow Molding (EBM) process are used in daily life, and the demand in china is also increasing year by year. Consumers prefer to have direct access to the contents when purchasing, and squeeze-blow bottle products of transparent materials are popular. The materials for extruding and blowing into bottles in the market mainly comprise PVC, PE, PP, PET, PETG, PC and the like. However, PE materials cannot produce transparent type products; the PVC material has high density, heavy bottle weight, poor environmental protection and chemical stability, has the problems of migration and dissolution of the auxiliary agent, and cannot be directly used for contacting food and medicines; PET, PETG and PC materials suffer from the disadvantages of high density, bottle weight and high cost. The extrusion-blown polypropylene bottle has the characteristics of light bottle weight, good transparency, good glossiness, good environmental protection, good heat resistance, good moisture barrier property, extrudability, capability of producing special-shaped bottles and the like, and the density of the polypropylene is lower than that of other transparent materials, so that the extrusion-blown polypropylene bottle has the advantage in cost. With the development of the industry, it is more and more common to use extrusion blow transparent polypropylene containers for the packaging industry. In China, some well-known daily product manufacturers such as drip, Weilushi, adidas and the like have related extrusion-blown transparent polypropylene products to be put on the market, and some packages for edible oil gradually try to use transparent polypropylene.
Because the melt strength of polypropylene is low, the processing temperature must be reduced as much as possible in the processing process to ensure normal forming, but the processing temperature of the prior transparent material can reach 230 ℃ to achieve better transparency, the contradiction between the two results in poor transparency of the polypropylene material, and meanwhile, the prior transparent extrusion-blown polypropylene product has poor fluidity, is easy to generate the phenomenon of shark skin, causes rough surface and poor glossiness, and has the problems of poor rigidity-toughness balance and insufficient strength, so that the use requirement of the transparent polypropylene extrusion-blown bottle can not be met.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the transparent polypropylene material for the high-gloss extrusion-blow bottle, which has high glossiness, transparency, strength and rigidity and toughness balance.
The invention also aims to provide a preparation method of the transparent polypropylene material for the high-gloss extrusion blow-molded bottle.
In order to achieve the purpose, the invention adopts the technical scheme that: a transparent polypropylene material for a high-gloss extrusion blow-molded bottle comprises the following components in percentage by weight: 99.27 to 99.71 percent of polypropylene resin, 0.18 to 0.40 percent of transparent agent, 0.08 to 0.25 percent of composite antioxidant and 0.03 to 0.08 percent of halogen absorbent.
Preferably, the polypropylene material comprises the following components in percentage by weight: 99.6 percent of polypropylene resin, 0.2 percent of transparent agent, 0.15 percent of composite antioxidant and 0.05 percent of halogen absorbent.
Preferably, the polypropylene material is ethylene propylene random copolymer polypropylene resin.
Preferably, the clearing agent is the clearing agent NX 8000E.
Preferably, the complex antioxidant comprises a primary antioxidant and a secondary antioxidant.
Preferably, the halogen absorbent is calcium stearate.
Preferably, in the composite antioxidant, the weight ratio of the primary antioxidant to the secondary antioxidant is 1: 1-1: 2.
The invention uses the primary antioxidant and the auxiliary antioxidant to form an antioxidant system, and provides sufficient processing stability and thermal oxygen aging property for preparing the transparent polypropylene material for the high-gloss extrusion blow-molded bottle.
Preferably, the primary antioxidant is a phenolic antioxidant, and the secondary antioxidant is a phosphite antioxidant.
Preferably, the phenolic antioxidant is at least one selected from pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and n-octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
Preferably, the phosphite antioxidant is at least one selected from bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite and tris [2, 4-di-tert-butylphenyl ] phosphite.
The invention provides a preparation method of the polypropylene material, which comprises the following steps: mixing the polypropylene resin, the transparent agent, the antioxidant and the halogen absorbent at normal temperature and normal pressure according to the weight percentage, mixing for 2-4min, adding into an extruder, extruding and granulating at the temperature of 160-230 ℃, and then placing the obtained granules in cold water for cooling to obtain the polypropylene material.
As a preferred embodiment of the preparation method of the polypropylene material of the present invention, the polypropylene resin is an ethylene-propylene random copolymer polypropylene resin, and the preparation method of the ethylene-propylene random copolymer polypropylene resin is as follows: adding propylene and ethylene into a loop reactor, adding a catalyst, a cocatalyst of triethyl aluminum, an electron donor and an antistatic agent, uniformly stirring, and controlling the reaction temperature and the reaction pressure in the loop reactor to obtain the ethylene-propylene random copolymerization polypropylene base resin.
As a preferred embodiment of the preparation method of the polypropylene material, the hydrogen concentration is 330-430 ppm, and the bonding amount of ethylene is 3.0% -3.5%; the catalyst is added according to the yield of 40 kg/ton; the weight ratio of the cocatalyst to the propylene was 0.16; the weight ratio of the cocatalyst to the electron donor is 5; the antistatic agent is 2-3 kg/h; the reaction temperature is 70 +/-1 ℃, and the reaction pressure is 3.4-3.8 MPa.
Hydrogen is used as a molecular weight regulator in polymerization reaction and is an important means for controlling the molecular weight of the produced polypropylene. Bonded ethylene content refers to the ethylene content that is completely reacted with propylene.
As a preferred embodiment of the preparation method of the polypropylene material, the catalyst is DQC-401, the cocatalyst is Triethylaluminum (TEAL), the electron DONOR DONOR-C, and the antistatic agent is Atmer 163.
As a preferable embodiment of the preparation method of the polypropylene material, the purity of the hydrogen is more than or equal to 95%, and the water content is less than or equal to 5 x 10-6CO content of not more than 5X 10-6Total sulfur content of 1X 10 or less-6(ii) a The purity of the ethylene is more than or equal to 99.9 percent, and the water content is less than or equal to 3 multiplied by 10-6CO content of 0.03X 10 or less-6The total sulfur content is less than or equal to 3 multiplied by 10-6(ii) a The propylene polymer has a purity of 99.35% or more and a water content of 5X 10 or less-6CO content of not more than 5X 10-6，CO2The content is less than or equal to 41 multiplied by 10-6。
As a preferred embodiment of the preparation method of the polypropylene material, the melt flow rate of the polypropylene material is 1.2-2.2 g/10min according to the GB/T3682-2000 standard; the haze of the polypropylene material at a thickness of 1mm is less than or equal to 12%; according to GB/T9341-2008 standard, the flexural modulus of the polypropylene material is greater than or equal to 900 MPa; according to the GB/T1043.1-2008 standard, the impact strength of a simple beam notch of the polypropylene material is greater than or equal to 18kJ/m 2; according to GB/T1634.2-2004, the heat distortion temperature of the polypropylene material is greater than or equal to 60 ℃; the polypropylene material has a surface gloss of greater than or equal to 90.
Compared with the prior art, the invention has the beneficial effects that:
(1) the transparent polypropylene material for the high-gloss extrusion-blown bottle has the characteristics of good processing performance, high gloss, high transparency, good rigidity and toughness balance, high strength and high food safety, can be suitable for transparent packaging containers of foods, medicines and daily necessities which require extrusion-blown molding, and is particularly suitable for extrusion-blown bottle blowing with high gloss;
(2) the preparation method of the transparent polypropylene material for the high-gloss extrusion-blow bottle can reduce the cost, overcome the defects that polypropylene is difficult to process and has insufficient strength, transparency and gloss, and enable the polypropylene material to replace transparent materials which are expensive, have limited functions and are difficult to process;
(3) the preparation method of the transparent polypropylene material for the high-gloss extrusion-blow bottle provided by the invention has the advantages that the Z-NQC-401 and the cocatalyst triethylaluminum are adopted, the ethylene monomer is added in the propylene polymerization stage, the production of the propylene/ethylene copolymer product can be directly carried out on the basis that the process is not required to be greatly adjusted, and the operation is simple.
Drawings
FIG. 1 is a process development flow chart of the transparent polypropylene for high gloss extrusion blow molding provided by the invention.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
The embodiment of the invention relates to a transparent polypropylene material for a high-gloss extrusion blow-molded bottle, which comprises the following components in percentage by weight: 99.71 percent of ethylene-propylene random copolymerization polypropylene resin, 0.18 percent of NX8000E 0.18, 0.04 percent of tetra [ beta- (3, 5-di-tert-butyl-4 hydroxyphenyl) propionic acid ] pentaerythritol ester, 0.04 percent of bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite and 0.03 percent of calcium stearate.
The preparation method of the transparent polypropylene material for the high-gloss extrusion blow-molded bottle comprises the following steps: mixing ethylene-propylene random copolymer polypropylene resin, NX8000E, tetra [ beta- (3, 5-di-tert-butyl-4 hydroxyphenyl) propionic acid ] pentaerythritol ester, bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite and calcium stearate at normal temperature and normal pressure according to the weight percentage, adding the mixture into a double-screw extruder after mixing for 2min, extruding and granulating at the temperature of 160 ℃, and then placing the obtained granules in cold water for cooling to obtain the high-gloss transparent polypropylene material for extrusion blow molding.
The preparation method of the ethylene-propylene random copolymerization polypropylene resin comprises the following steps:
propylene and ethylene were fed into a loop reactor, and the catalyst DQC-401, the cocatalyst Triethylaluminum (TEAL), the electron DONOR DONOR-C, the antistatic agent Atmer163 were added. Wherein: the catalyst DQC-401 is added in accordance with a yield of 40 kg/ton; TEAL/C3 (propylene) 0.16; TEAL/doror ═ 5; the antistatic agent Atmer163 is 2kg/h, the stirring is uniform, the reaction temperature in the loop reactor is controlled to be 70 ℃, the reaction pressure is controlled to be 3.5MPa, the hydrogen concentration is 350ppm, and the bonded ethylene content is 3.5 percent, so that the ethylene-propylene random copolymerization polypropylene base resin is obtained.
Example 2
The embodiment of the invention relates to a transparent polypropylene material for a high-gloss extrusion blow-molded bottle, which comprises the following components in percentage by weight: 99.6 percent of ethylene propylene random copolymerization polypropylene resin, 0.2 percent of NX8000E 0.2, 0.075 percent of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester, 0.075 percent of tris [2, 4-di-tert-butylphenyl ] phosphite and 0.05 percent of calcium stearate.
The preparation method of the transparent polypropylene material for the high-gloss extrusion blow-molded bottle comprises the following steps: mixing ethylene-propylene random copolymer polypropylene resin, NX8000E, 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, tris [2, 4-di-tert-butylphenyl ] phosphite and calcium stearate at normal temperature and normal pressure according to the weight percentage, adding the mixture into a double-screw extruder after mixing for 3min, extruding and granulating at 230 ℃, and then placing the obtained granules in cold water for cooling to obtain the high-gloss transparent polypropylene material for extrusion blow-molded bottles.
The preparation method of the ethylene-propylene random copolymerization polypropylene resin comprises the following steps:
propylene and ethylene were fed into a loop reactor, and the catalyst DQC-401, the cocatalyst Triethylaluminum (TEAL), the electron DONOR DONOR-C, the antistatic agent Atmer163 were added. Wherein: the catalyst DQC-401 is added in accordance with a yield of 40 kg/ton; TEAL/C3 (propylene) 0.16; TEAL/doror ═ 5; the antistatic agent Atmer163 is 3kg/h, the stirring is uniform, the reaction temperature in the loop reactor is controlled to be 71 ℃, the reaction pressure is controlled to be 3.7MPa, the hydrogen concentration is 370ppm, and the bonded ethylene content is 3.3 percent, so that the ethylene-propylene random copolymerization polypropylene base resin is obtained.
Example 3
The embodiment of the invention relates to a transparent polypropylene material for a high-gloss extrusion blow-molded bottle, which comprises the following components in percentage by weight: 99.27% of ethylene-propylene random copolymer polypropylene resin, 0.4% of NX8000E 0.4%, 0.125% of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 0.125% of bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite and 0.08% of calcium stearate.
The preparation method of the transparent polypropylene material for the high-gloss extrusion blow-molded bottle comprises the following steps: mixing ethylene-propylene random copolymer polypropylene resin, NX8000E, tetra [ beta- (3, 5-di-tert-butyl-4 hydroxyphenyl) propionic acid ] pentaerythritol ester, bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite and calcium stearate at normal temperature and normal pressure according to the weight percentage, adding the mixture into a double-screw extruder after mixing for 4min, extruding and granulating at the temperature of 180 ℃, and then putting the obtained granules into cold water for cooling to obtain the high-gloss transparent polypropylene material for extrusion blow molding.
The preparation method of the ethylene-propylene random copolymerization polypropylene resin comprises the following steps:
propylene and ethylene were fed into a loop reactor, and the catalyst DQC-401, the cocatalyst Triethylaluminum (TEAL), the electron DONOR DONOR-C, the antistatic agent Atmer163 were added. Wherein: the catalyst DQC-401 is added in accordance with a yield of 40 kg/ton; TEAL/C3 (propylene) 0.16; TEAL/doror ═ 5; the antistatic agent Atmer163 is 2kg/h, the stirring is uniform, the reaction temperature in the loop reactor is controlled to be 71 ℃, the reaction pressure is controlled to be 3.7MPa, the hydrogen concentration is 370ppm, and the bonded ethylene content is 3.4 percent, so that the ethylene-propylene random copolymerization polypropylene base resin is obtained.
Example 4
The embodiment of the invention relates to a transparent polypropylene material for a high-gloss extrusion blow-molded bottle, which comprises the following components in percentage by weight: 99.56 percent of ethylene-propylene random copolymerization polypropylene resin, 0.2 percent of NX8000E 0.2, 0.07 percent of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester, 0.14 percent of tris [2, 4-di-tert-butylphenyl ] phosphite and 0.03 percent of calcium stearate.
The preparation method of the transparent polypropylene material for the high-gloss extrusion blow-molded bottle comprises the following steps: mixing ethylene-propylene random copolymer polypropylene resin, NX8000E, 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, tris [2, 4-di-tert-butylphenyl ] phosphite and calcium stearate at normal temperature and normal pressure according to the weight percentage, adding the mixture into a double-screw extruder after mixing for 4min, extruding and granulating at the temperature of 230 ℃, and then placing the obtained granules in cold water for cooling to obtain the high-gloss transparent polypropylene material for extrusion blow-molding bottles.
The preparation method of the ethylene-propylene random copolymerization polypropylene resin comprises the following steps: propylene and ethylene were fed into a loop reactor, and the catalyst DQC-401, the cocatalyst Triethylaluminum (TEAL), the electron DONOR DONOR-C, the antistatic agent Atmer163 were added. Wherein: the catalyst DQC-401 is added in accordance with a yield of 40 kg/ton; TEAL/C3 (propylene) 0.16; TEAL/doror ═ 5; the antistatic agent Atmer163 is 2kg/h, the stirring is uniform, the reaction temperature in the loop reactor is controlled to be 70 ℃, the reaction pressure is controlled to be 3.5MPa, the hydrogen concentration is 410ppm, and the bonded ethylene content is 3.2 percent, so that the ethylene-propylene random copolymerization polypropylene base resin is obtained.
Example 5
The embodiment of the invention relates to a transparent polypropylene material for a high-gloss extrusion blow-molded bottle, which comprises the following components in percentage by weight: 99.6 percent of ethylene propylene random copolymerization polypropylene resin, 0.2 percent of NX8000E 0.2, 0.075 percent of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester, 0.075 percent of tris [2, 4-di-tert-butylphenyl ] phosphite and 0.05 percent of calcium stearate.
The preparation method of the transparent polypropylene material for the high-gloss extrusion blow-molded bottle comprises the following steps: mixing ethylene-propylene random copolymer polypropylene resin, NX8000E, 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, tris [2, 4-di-tert-butylphenyl ] phosphite and calcium stearate at normal temperature and normal pressure according to the weight percentage, adding the mixture into a double-screw extruder after mixing for 2min, extruding and granulating at 230 ℃, and then placing the obtained granules in cold water for cooling to obtain the high-gloss transparent polypropylene material for extrusion blow-molded bottles.
The preparation method of the ethylene-propylene random copolymerization polypropylene resin comprises the following steps: propylene and ethylene were fed into a loop reactor, and the catalyst DQC-401, the cocatalyst Triethylaluminum (TEAL), the electron DONOR DONOR-C, the antistatic agent Atmer163 were added. Wherein: the catalyst DQC-401 is added in accordance with a yield of 40 kg/ton; TEAL/C3 (propylene) 0.16; TEAL/doror ═ 5; the antistatic agent Atmer163 is 3kg/h, the stirring is uniform, the reaction temperature in the loop reactor is controlled to be 71 ℃, the reaction pressure is controlled to be 3.7MPa, the hydrogen concentration is 390ppm, and the bonded ethylene content is 3.4 percent, so that the ethylene-propylene random copolymerization polypropylene base resin is obtained.
Comparative example 1
The comparative example is a polypropylene material comprising, in weight percent: 99.6 percent of ethylene propylene random copolymerization polypropylene resin, 0.2 percent of NX8000E 0.2, 0.075 percent of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester, 0.075 percent of tris [2, 4-di-tert-butylphenyl ] phosphite and 0.05 percent of calcium stearate.
Propylene and ethylene were fed into a loop reactor, and the catalyst DQC-401, the cocatalyst Triethylaluminum (TEAL), the electron DONOR DONOR-C, the antistatic agent Atmer163 were added. Wherein: the catalyst DQC-401 is added in accordance with a yield of 40 kg/ton; TEAL/C3(propylene) 0.16; TEAL/doror ═ 5; the antistatic agent Atmer163 was 3 kg/h. Stirring uniformly, controlling the reaction temperature in the loop reactor to be 71 ℃, the reaction pressure to be 3.6MPa, the hydrogen concentration to be 360ppm and the bonded ethylene content to be 2.1 percent, thereby obtaining the ethylene-propylene random copolymerization polypropylene base resin.
According to the proportion, transparent agent NX8000E, 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester, tris [2, 4-di-tert-butylphenyl ] phosphite and calcium stearate are added into the ethylene-propylene random copolymerization polypropylene base resin according to the weight percentage, mixed for 4 minutes at normal temperature and normal pressure, and then granulated by a double-screw extruder, the temperature is controlled at 230 ℃, and the transparent polypropylene material for extrusion blow bottles with poor rigidity and toughness balance is obtained.
Comparative example 2:
the comparative example is a polypropylene material comprising, in weight percent: 99.71 percent of ethylene-propylene random copolymerization polypropylene resin, 0.07 percent of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, 0.14 percent of tris [2, 4-di-tert-butylphenyl ] phosphite and 0.08 percent of calcium stearate.
Propylene and ethylene were fed into a loop reactor, and the catalyst DQC-401, the cocatalyst Triethylaluminum (TEAL), the electron DONOR DONOR-C, the antistatic agent Atmer163 were added. Wherein: the catalyst DQC-401 is added in accordance with a yield of 40 kg/ton; TEAL/C3(propylene) 0.16; TEAL/doror ═ 5; the antistatic agent Atmer163 was 3 kg/h. Stirring uniformly, controlling the reaction temperature in the loop reactor to be 71 ℃, the reaction pressure to be 3.8MPa, the hydrogen concentration to be 400ppm and the bonded ethylene content to be 3.2 percent, thereby obtaining the ethylene-propylene random copolymerization polypropylene base resin.
Adding 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester, tris [2, 4-di-tert-butylphenyl ] phosphite and calcium stearate into the ethylene-propylene random copolymerization polypropylene base resin according to the proportion, mixing for 2 minutes at normal temperature and normal pressure, and then granulating by adopting a double-screw extruder at the temperature of 160 ℃ to obtain the polypropylene material with poor transparency and glossiness.
Comparative example 3:
the comparative example is a polypropylene material comprising, in weight percent: 99.6 percent of ethylene propylene random copolymerization polypropylene resin, 39880.2 percent of clearing agent, 0.075 percent of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester, 0.075 percent of tris [2, 4-di-tert-butylphenyl ] phosphite and 0.05 percent of calcium stearate.
Propylene and ethylene were fed into a loop reactor, and the catalyst DQC-401, the cocatalyst Triethylaluminum (TEAL), the electron DONOR DONOR-C, the antistatic agent Atmer163 were added. Wherein: the catalyst DQC-401 is added in accordance with a yield of 40 kg/ton; TEAL/C3(propylene) 0.16; TEAL/doror ═ 5; the antistatic agent Atmer163 was 3 kg/h. Stirring evenly, controlling the reaction temperature in the loop reactor to be 70 ℃, the reaction pressure to be 3.7MPa, the hydrogen concentration to be 380ppm and the bonded ethylene content to be 3.4 percent, therebyTo obtain the ethylene-propylene random copolymerization polypropylene base resin.
According to the proportion, a transparent agent 3988, 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, tris [2, 4-di-tert-butylphenyl ] phosphite and 0.05% of calcium stearate are added into ethylene-propylene random copolymerization polypropylene base resin, mixed for 4 minutes at normal temperature and normal pressure, and then granulated by adopting a double-screw extruder, wherein the temperature is controlled at 230 ℃, so that the polypropylene material with poor glossiness is obtained.
Experimental example 1
The experimental example is the detection of the physical and chemical properties of the transparent polypropylene material for the high-gloss extrusion-blow bottle
The experimental method comprises the following steps: the polypropylene materials prepared in inventive example 1, example 2, example 3, example 4 and example 5, and comparative example 1, comparative example 2 and comparative example 3 were tested for the following physical properties in a conventional test return: melt flow rate, tensile yield stress, simple beam notched impact strength, flexural modulus, load deflection temperature, haze, thickness, bottle clarity, outer surface gloss, inner surface gloss.
The results of the experiment are shown in table 1.
TABLE 1 physical and chemical properties of transparent polypropylene material for high gloss squeeze-blow bottles
As can be seen from the data in Table 1, in comparative examples 1 to 3 described above, the amount of bonded ethylene is small, resulting in poor impact strength, as compared with examples 1 to 5; comparative example 2 is the material with higher haze and poor gloss without adding a clearing agent; comparative example 3 is a bottle with higher haze and lower gloss with the addition of a conventional clearing agent. Examples 1-5 use DQC-401 as a catalyst and triethylaluminum as a cocatalyst, by controlling the hydrogen concentration to 330-430 ppm and the ethylene concentration to 3.0% -3.5%The ethylene-propylene random copolymerization polypropylene base resin is obtained, and then the transparent polypropylene for the extrusion blow-molding bottle with high gloss and meeting the performance requirement is obtained by being assisted with a transparent agent, an antioxidant and a halogen absorbent for extrusion granulation. The material has the following performance requirements: the melt flow rate is 1.2-2.2 g/10 min; the haze (1mm) is less than or equal to 12 percent; the flexural modulus is more than or equal to 900 MPa; the impact strength of the simply supported beam gap is more than or equal to 18kJ/m2(ii) a The thermal deformation temperature is more than or equal to 60 ℃; the surface glossiness of the bottle is more than or equal to 90. The material has good processability, glossiness, transparency, rigidity and toughness balance and food safety, and is suitable for transparent packaging containers of foods, medicines and daily necessities which require extrusion blow molding. The new material can reduce the cost, overcome the defects of difficult processing of polypropylene and insufficient strength, transparency and glossiness, and realize the replacement of other transparent materials which are expensive, have limited functions and are difficult to process.
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, and 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 transparent polypropylene material for the high-gloss extrusion blow-molded bottle is characterized by comprising the following components in percentage by weight: 99.27 to 99.71 percent of polypropylene resin, 0.18 to 0.40 percent of transparent agent, 0.08 to 0.25 percent of composite antioxidant and 0.03 to 0.08 percent of halogen absorbent.
2. The polypropylene material of claim 1, wherein the polypropylene material comprises the following components in weight percent: 99.6 percent of polypropylene resin, 0.2 percent of transparent agent, 0.15 percent of composite antioxidant and 0.05 percent of halogen absorbent.
3. The polypropylene material according to claim 1 or 2, wherein the polypropylene material is an ethylene propylene random copolymer polypropylene resin; the transparent agent is NX 8000E; the compound antioxidant comprises a primary antioxidant and a secondary antioxidant; the halogen absorbent is calcium stearate.
4. The polypropylene material according to claim 3, wherein in the composite antioxidant, the weight ratio of the primary antioxidant to the secondary antioxidant is 1: 1-1: 2; the primary antioxidant is a phenol antioxidant, and the secondary antioxidant is a phosphite antioxidant.
5. The polypropylene material of claim 4, wherein the phenolic antioxidant is selected from at least one of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and n-octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; the phosphite antioxidant is at least one selected from bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite and tris [2, 4-di-tert-butylphenyl ] phosphite.
6. A process for the preparation of a polypropylene material according to any one of claims 1 to 5, wherein the process comprises: mixing polypropylene resin, a transparent agent, an antioxidant and a halogen absorbent at normal temperature and normal pressure for 2-4min according to the weight percentage, adding the mixture into an extruder, extruding and granulating at the temperature of 160-230 ℃, and then placing the obtained granules in cold water for cooling to obtain the polypropylene material.
7. The method according to claim 6, wherein the polypropylene resin is an ethylene-propylene random copolymer polypropylene resin, and the method for preparing the ethylene-propylene random copolymer polypropylene resin comprises: adding propylene and ethylene into a loop reactor, adding a catalyst, a cocatalyst of triethyl aluminum, an electron donor and an antistatic agent, uniformly stirring, and controlling the reaction temperature and the reaction pressure in the loop reactor to obtain the ethylene-propylene random copolymerization polypropylene base resin.
8. The preparation method of claim 7, wherein the hydrogen concentration is 330-430 ppm, and the bonding amount of ethylene is 3.0% -3.5%; the catalyst is added according to the yield of 40 kg/ton; the weight ratio of the cocatalyst to the propylene was 0.16; the weight ratio of the cocatalyst to the electron donor is 5; the antistatic agent is 2-3 kg/h; the reaction temperature is 70 +/-1 ℃, and the reaction pressure is 3.4-3.8 MPa.
9. The method of claim 7 or 8, wherein the catalyst is DQC-401, the cocatalyst is triethylaluminum, the electron DONOR is DONOR-C, and the antistatic agent is Atmer 163.
10. The method according to claim 6, wherein the melt flow rate of the polypropylene material is 1.2-2.2 g/10min according to GB/T3682-2000 standard; the haze of the polypropylene material at a thickness of 1mm is less than or equal to 12%; according to GB/T9341-2008 standard, the flexural modulus of the polypropylene material is greater than or equal to 900 MPa; according to the GB/T1043.1-2008 standard, the impact strength of the polypropylene material in the gaps of the simply supported beams is greater than or equal to 18kJ/m2(ii) a According to GB/T1634.2-2004, the heat distortion temperature of the polypropylene material is greater than or equal to 60 ℃; the polypropylene material has a surface gloss of greater than or equal to 90.
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