CN114426731A - Polypropylene material and preparation method and application thereof - Google Patents
Polypropylene material and preparation method and application thereof Download PDFInfo
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- CN114426731A CN114426731A CN202011181867.3A CN202011181867A CN114426731A CN 114426731 A CN114426731 A CN 114426731A CN 202011181867 A CN202011181867 A CN 202011181867A CN 114426731 A CN114426731 A CN 114426731A
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- polypropylene
- antioxidant
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- propylene
- polypropylene material
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- -1 Polypropylene Polymers 0.000 title claims abstract description 75
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 74
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 71
- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 49
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 47
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 39
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 37
- 239000001257 hydrogen Substances 0.000 claims abstract description 37
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 31
- 239000000047 product Substances 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 21
- 150000002367 halogens Chemical class 0.000 claims abstract description 21
- 230000002745 absorbent Effects 0.000 claims abstract description 17
- 239000002250 absorbent Substances 0.000 claims abstract description 17
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 230000035484 reaction time Effects 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 5
- 239000006096 absorbing agent Substances 0.000 claims description 4
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 229960001545 hydrotalcite Drugs 0.000 claims description 4
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 4
- 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 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 239000002530 phenolic antioxidant Substances 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- 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 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 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 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
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 13
- 239000000155 melt Substances 0.000 description 8
- 239000000498 cooling water Substances 0.000 description 7
- 239000012467 final product Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000002954 polymerization reaction product Substances 0.000 description 6
- 238000011282 treatment Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000003679 aging effect Effects 0.000 description 2
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical group C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- RJZNFXWQRHAVBP-UHFFFAOYSA-I aluminum;magnesium;pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Al+3] RJZNFXWQRHAVBP-UHFFFAOYSA-I 0.000 description 1
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a polypropylene material, which comprises the following components and/or reaction products of the following components: polypropylene, an antioxidant and a halogen absorbent. The synthesis method of the polypropylene comprises the following steps: 1) carrying out prepolymerization on raw materials containing propylene, a catalyst and an electron donor to obtain a prepolymerization product; 2) subjecting the pre-polymerized product to a first polymerization reaction with propylene and hydrogen to obtain a first polymerization product; 3) and carrying out second polymerization reaction on the first polymerization product, propylene and hydrogen to obtain the polypropylene. The polypropylene material has a low melt flow rate, and can meet the raw material requirement of PP extruded sheets.
Description
Technical Field
The invention relates to the technical field of polypropylene, in particular to a polypropylene material and a preparation method and application thereof.
Background
The polypropylene extruded sheet has the characteristics of light weight, uniform thickness, smooth and flat surface, good heat resistance, high mechanical strength, excellent chemical stability, electrical insulation property, no toxicity and the like, can be widely applied to the fields of chemical containers, machinery, electronics, electrical appliances, food packaging, medicine, decoration, water treatment and the like, can replace stainless steel, wood and other structural materials to be used for manufacturing water tanks, packaging containers, automobile parts and the like, acid and alkali resistant equipment, electroplating equipment, solar photovoltaic equipment, environmental protection equipment, waste water and waste gas discharge equipment, washing towers, dust-free rooms, equipment of semiconductor factories and related industries, and is also a preferred material for manufacturing plastic water tanks.
Disclosure of Invention
The raw material for producing the PP extruded sheet is mainly homo-polypropylene with low melt flow rate. The thickness of the plate is generally 2-50 mm, and the width of the plate is not more than 25 m. The market demand for sheet materials with a thickness of more than 20mm has increased year by year in recent years. The thick plate has low production speed, requires low melt flow rate of resin, is easy to extrude and form and has good rigidity.
The invention aims to provide a polypropylene material, a preparation method and application thereof, wherein the polypropylene material has a low melt flow rate and can meet the raw material requirement of a PP extruded sheet.
In a first aspect, the present invention provides a process for synthesizing polypropylene, comprising the steps of:
1) carrying out prepolymerization on raw materials containing propylene, a catalyst and an electron donor to obtain a prepolymerization product;
2) subjecting the pre-polymerized product to a first polymerization reaction with propylene and hydrogen to obtain a first polymerization product;
3) and carrying out second polymerization reaction on the first polymerization product, propylene and hydrogen to obtain the polypropylene.
According to some embodiments of the invention, the catalyst in step 1) comprises a main catalyst and a cocatalyst.
According to a preferred embodiment of the present invention, the main catalyst is a fourth-generation Z-N catalyst, which uses a combination of an aromatic diester and a siloxane, such as DQC-401 of oka company, beijing, and has the characteristics of high polymerization activity, high stereospecificity, hydrogen equilibrium, etc., less catalyst particle breakage, and low polymer fine powder content.
According to a preferred embodiment of the invention, the cocatalyst comprises triethylaluminium.
According to a preferred embodiment of the invention, the electron donor is dicyclopentyldimethoxysilane.
According to a preferred embodiment of the present invention, the molar ratio of the main catalyst to the cocatalyst is 1: 2-1: 5.
according to a preferred embodiment of the invention, the molar ratio between the cocatalyst and the propylene is between 0.1 and 0.35.
According to a preferred embodiment of the present invention, the molar ratio of the cocatalyst to the electron donor is between 5 and 20.
According to a preferred embodiment of the present invention, the reaction temperature in step 1) is 12-30 ℃, the reaction pressure is 2.5-5.0MPa, and the reaction time is 8-30 min.
According to a preferred embodiment of the present invention, the step 1) comprises:
propylene is pre-polymerized in a pre-polymerization reactor under the combined action of a main catalyst, a cocatalyst and an external electron donor to generate a pre-polymerization product.
According to a preferred embodiment of the present invention, the hydrogen concentration in step 2) is 140-300ppm, the reaction temperature is 70 + -5 ℃, the reaction pressure is 2.5-5.0MPa, and the reaction time is 40-48 min.
According to a preferred embodiment of the present invention, the step 2) comprises:
feeding the prepolymerization product obtained in the step 1), fresh propylene and hydrogen into a first loop reactor to perform a first polymerization reaction to obtain a first polymerization product.
According to a preferred embodiment of the invention, the hydrogen concentration in step 3) is 1400-3000ppm, the temperature is 70 + -5 ℃, the reaction pressure is 3.2-3.6MPa, and the reaction time is 20-40 min.
According to a preferred embodiment of the present invention, the step 3) comprises:
feeding the first polymerization product obtained in the step 3), fresh propylene and hydrogen into a second loop reactor to perform a second polymerization reaction to obtain the polypropylene.
In a second aspect, the present invention provides a polypropylene obtainable according to the above process.
According to a preferred embodiment of the invention, the polypropylene has a melt flow rate of 1.0 to 1.5g/10min, an isotacticity of greater than 96%, a flexural modulus of 1400 to 2000MPa, and a tensile yield stress of greater than 32 MPa.
In a third aspect, the present invention provides a polypropylene material comprising and/or the reaction product of: polypropylene, antioxidant and halogen absorber; wherein the polypropylene of the second aspect of the polypropylene.
According to some embodiments of the invention, the antioxidant comprises a primary antioxidant and a secondary antioxidant.
According to some specific embodiments of the invention, the primary antioxidant is selected from one or more of phenolic antioxidants.
According to some preferred embodiments of the present invention, the phenolic antioxidant comprises one or more of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] or n-octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
According to some embodiments of the invention, the secondary antioxidant is selected from one or more of phosphite antioxidants.
According to some preferred embodiments of the present invention, the phosphite antioxidant comprises one or more of bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite or tris [2, 4-di-tert-butylphenyl ] phosphite.
In the invention, the antioxidant is used for improving the processing stability and the thermal-oxidative aging property of the material, and the antioxidant adopts a phenol antioxidant, or a phosphite antioxidant, or a mixture of the phenol antioxidant and the phosphite antioxidant, and the antioxidant system can provide the sufficient processing stability and the thermal-oxidative aging property for the material.
According to some embodiments of the invention, the halogen absorber comprises one or more of calcium stearate or hydrotalcite.
According to some embodiments of the invention, the hydrotalcite is selected from one or more of layered dihydroxy magnesium aluminum hydroxide.
According to some embodiments of the invention, the polypropylene, the antioxidant and the halogen absorbent are in parts by weight:
95-99.9 parts of polypropylene,
0.01 to 0.5 portion of antioxidant,
0.01-0.5 of halogen absorbent.
According to some embodiments of the invention, the polypropylene is present in an amount of 95.5 to 99.8 parts by weight.
According to some embodiments of the invention, the antioxidant is present in an amount of 0.02 to 0.3 parts by weight.
According to some embodiments of the invention, the primary antioxidant is present in an amount of 0.01 to 0.15 parts by weight.
According to some embodiments of the present invention, the secondary antioxidant is present in an amount of 0.01 to 0.15 parts by weight.
According to some specific embodiments of the present invention, the halogen absorbent is 0.02 to 0.1 parts by weight.
In a fourth aspect, the present invention provides a preparation method of the polypropylene material, including: and mixing the polypropylene, the antioxidant and the halogen absorbent, and extruding and granulating to obtain the polypropylene material.
According to some embodiments of the invention, the method of preparing the polypropylene material comprises:
step 1: mixing polypropylene, a main antioxidant, an auxiliary antioxidant and a halogen absorbent in proportion to obtain a mixed material;
step 2: and adding the mixed material into an extruder, and extruding and granulating to obtain the polypropylene material.
According to some embodiments of the invention, the extruder has a load of 28 to 33 tons/hour, a screw speed of 170 to 250 revolutions per minute, an extrusion barrel temperature of 170 to 240 ℃ and a cooling water temperature of 55 to 65 ℃.
In a third aspect, the present invention provides an application of the polypropylene material in the preparation of a sheet material, and preferably includes performing extrusion molding treatment on the polypropylene material to obtain the sheet material.
Compared with the prior art, the invention has the beneficial effects that:
(1) the antioxidant and the halogen absorbent are added into the polypropylene for co-extrusion granulation, so that the melt flow rate of a final product is 1.0-1.5 g/10min, the tensile yield stress is greater than 32MPa, and the flexural modulus is greater than 1400 MPa.
(2) The polypropylene material can be directly used for extruding plates without modification, thereby reducing intermediate links and lowering production cost.
Detailed Description
In order that the present invention may be more readily understood, the following detailed description of the invention is given by way of example only, and is not intended to limit the scope of the invention.
The operations and treatments involved in the present invention are conventional in the art unless otherwise specified.
The apparatus used in the present invention is an apparatus conventional in the art unless otherwise specified.
In the following examples, the primary antioxidant was 3- (3, 5-bis-butyl-4-hydroxycyclohexyl) propionate (1010). The auxiliary antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite (168). The halogen absorbent is calcium stearate.
The external electron donor is dicyclopentyldimethoxysilane. The catalyst was DQC-401. The cocatalyst is triethyl aluminum.
Example 1
(1) Propylene is polymerized to generate polypropylene through a prepolymerization reactor under the combined action of a main catalyst, a cocatalyst and an external electron donor, the mass ratio of the cocatalyst to the propylene is 0.16, the mass ratio of the cocatalyst to the external electron donor is 10, the reaction temperature is 20 ℃, the reaction pressure is 3.4MPa, and the reaction time is 9 minutes.
(2) And (2) enabling the prepolymerization reaction product obtained in the step (1), fresh propylene and hydrogen to enter a first loop reactor for continuous polymerization reaction, controlling the concentration of the hydrogen entering the first loop reactor to be 220ppm, the reaction temperature to be 70 ℃, the reaction pressure to be 3.4MPa, and the reaction time to be 42 minutes.
(3) And (3) allowing the polymerization reaction product obtained in the step (2), fresh propylene and hydrogen to enter a second loop reactor for continuous polymerization, controlling the concentration of the hydrogen entering the second loop reactor to be 2200ppm, the reaction temperature to be 70 ℃, the reaction pressure to be 3.4MPa, the reaction time to be 25 minutes, and preparing the polypropylene powder with the melt flow rate of 1.35g/10 min.
(4) Uniformly mixing the polypropylene powder obtained in the step (3), 0.075 part of antioxidant, 0.15 part of auxiliary antioxidant and 0.05 part of halogen absorbent, extruding by using an extruder, wherein the load of the extruder is 29 tons/h, the rotating speed of a screw is 240 revolutions per minute, the temperature of each section of a barrel of the extruder is 210 ℃, the temperature of cooling water is 60 ℃, and controlling the MFR of a final product to be 1.35g/10 min.
The mechanical properties of the obtained product are shown in the invention effect attached table 1.
Example 2
(1) Propylene is polymerized to generate polypropylene through a prepolymerization reactor under the combined action of a main catalyst, a cocatalyst and an external electron donor, the mass ratio of the cocatalyst to the propylene is 0.18, the mass ratio of the cocatalyst to the external electron donor is 9, the reaction temperature is 21 ℃, the reaction pressure is 3.4MPa, and the reaction time is 10 minutes.
(2) And (2) enabling the prepolymerization reaction product obtained in the step (1), fresh propylene and hydrogen to enter a first loop reactor for continuous polymerization reaction, controlling the concentration of the hydrogen entering the first loop reactor to be 160ppm, the reaction temperature to be 70 ℃, the reaction pressure to be 3.4MPa, and the reaction time to be 48 minutes.
(3) And (3) allowing the polymerization reaction product obtained in the step (2), fresh propylene and hydrogen to enter a second loop reactor for continuous polymerization, controlling the concentration of the hydrogen entering the second loop reactor to be 1600ppm, the reaction temperature to be 70 ℃, the reaction pressure to be 3.4MPa, the reaction time to be 27 minutes, and preparing the polypropylene powder with the melt flow rate of 1.10g/10 min.
(4) Uniformly mixing the polypropylene powder obtained in the step (3), 0.08 part of antioxidant, 0.16 part of auxiliary antioxidant and 0.06 part of halogen absorbent, extruding by using an extruder, wherein the load of the extruder is 30 tons/hour, the rotating speed of a screw is 244 revolutions per minute, the temperature of each section of a barrel of the extruder is 210 ℃, the temperature of cooling water is 60 ℃, the MFR of a final product is controlled to be 1.08g/10min, and the performances are shown in Table 1.
The mechanical properties of the obtained product are shown in the invention effect attached table 1.
Example 3
(1) Propylene is polymerized to generate polypropylene through a prepolymerization reactor under the combined action of a main catalyst, a cocatalyst and an external electron donor, the mass ratio of the cocatalyst to the propylene is 0.17, the mass ratio of the cocatalyst to the external electron donor is 11, the reaction temperature is 19 ℃, the reaction pressure is 3.4MPa, and the reaction time is 9 minutes.
(2) And (2) enabling the prepolymerization reaction product obtained in the step (1), fresh propylene and hydrogen to enter a first loop reactor for continuous polymerization reaction, controlling the concentration of the hydrogen entering the first loop reactor to be 290ppm, the reaction temperature to be 70 ℃, the reaction pressure to be 3.4MPa, and the reaction time to be 49 minutes.
(3) And (3) allowing the polymerization reaction product obtained in the step (2), fresh propylene and hydrogen to enter a second loop reactor for continuous polymerization, controlling the concentration of the hydrogen entering the second loop reactor to be 2900ppm, the reaction temperature to be 70 ℃, the reaction pressure to be 3.4MPa, the reaction time to be 26 minutes, and preparing the polypropylene powder with the melt flow rate of 1.50g/10 min.
(4) And (3) uniformly mixing the polypropylene powder obtained in the step (3), 0.07 part of antioxidant, 0.14 part of auxiliary antioxidant and 0.05 part of halogen absorbent, and extruding by using an extruder, wherein the load of the extruder is 31 tons/h, the rotating speed of a screw is 244 rpm, the temperature of each section of a barrel of the extruder is 210 ℃, the temperature of cooling water is 60 ℃, and the MFR of a final product is controlled to be 1.48g/10 min.
The mechanical properties of the obtained product are shown in the invention effect attached table 1.
Example 4
(1) Propylene is polymerized to generate polypropylene through a prepolymerization reactor under the combined action of a main catalyst, a cocatalyst and an external electron donor, the mass ratio of the cocatalyst to the propylene is 0.16, the mass ratio of the cocatalyst to the external electron donor is 10, the reaction temperature is 20 ℃, the reaction pressure is 3.4MPa, and the reaction time is 9 minutes.
(2) And (2) enabling the prepolymerization reaction product obtained in the step (1), fresh propylene and hydrogen to enter a first loop reactor for continuous polymerization reaction, controlling the concentration of the hydrogen entering the first loop reactor to be 160ppm, the reaction temperature to be 70 ℃, the reaction pressure to be 3.4MPa, and the reaction time to be 42 minutes.
(3) And (3) allowing the polymerization reaction product obtained in the step (2), fresh propylene and hydrogen to enter a second loop reactor for continuous polymerization, controlling the concentration of the hydrogen entering the second loop reactor to be 2200ppm, the reaction temperature to be 70 ℃, the reaction pressure to be 3.4MPa, the reaction time to be 25 minutes, and preparing the polypropylene powder with the melt flow rate of 1.20g/10 min.
(4) Uniformly mixing the polypropylene powder obtained in the step (3), 0.075 part of antioxidant, 0.15 part of auxiliary antioxidant and 0.05 part of halogen absorbent, extruding by using an extruder, wherein the load of the extruder is 29 tons/h, the rotating speed of a screw is 240 revolutions per minute, the temperature of each section of a barrel of the extruder is 210 ℃, the temperature of cooling water is 60 ℃, and controlling the MFR of a final product to be 1.18g/10 min.
The mechanical properties of the obtained product are shown in the invention effect attached table 1.
Example 5
(1) Propylene is polymerized to generate polypropylene through a prepolymerization reactor under the combined action of a main catalyst, a cocatalyst and an external electron donor, the mass ratio of the cocatalyst to the propylene is 0.16, the mass ratio of the cocatalyst to the external electron donor is 10, the reaction temperature is 20 ℃, the reaction pressure is 3.4MPa, and the reaction time is 9 minutes.
(2) And (2) enabling the prepolymerization reaction product obtained in the step (1), fresh propylene and hydrogen to enter a first loop reactor for continuous polymerization reaction, controlling the concentration of the hydrogen entering the first loop reactor to be 220ppm, the reaction temperature to be 70 ℃, the reaction pressure to be 3.4MPa, and the reaction time to be 42 minutes.
(3) And (3) allowing the polymerization reaction product obtained in the step (2), fresh propylene and hydrogen to enter a second loop reactor for continuous polymerization, controlling the concentration of the hydrogen entering the second loop reactor to be 2800ppm, the reaction temperature to be 70 ℃, the reaction pressure to be 3.4MPa, the reaction time to be 25 minutes, and preparing the polypropylene powder with the melt flow rate of 1.42g/10 min.
(4) Uniformly mixing the polypropylene powder obtained in the step (3), 0.075 part of antioxidant, 0.15 part of auxiliary antioxidant and 0.05 part of halogen absorbent, extruding by using an extruder, wherein the load of the extruder is 29 tons/h, the rotating speed of a screw is 240 revolutions per minute, the temperature of each section of a barrel of the extruder is 210 ℃, the temperature of cooling water is 60 ℃, and controlling the MFR of a final product to be 1.40g/10 min.
The mechanical properties of the obtained product are shown in the invention effect attached table 1.
Example 6
(1) Propylene is polymerized to generate polypropylene through a prepolymerization reactor under the combined action of a main catalyst, a cocatalyst and an external electron donor, the mass ratio of the cocatalyst to the propylene is 0.16, the mass ratio of the cocatalyst to the external electron donor is 10, the reaction temperature is 20 ℃, the reaction pressure is 3.4MPa, and the reaction time is 9 minutes.
(2) And (2) enabling the prepolymerization reaction product obtained in the step (1), fresh propylene and hydrogen to enter a first loop reactor for continuous polymerization reaction, controlling the concentration of the hydrogen entering the first loop reactor to be 220ppm, the reaction temperature to be 70 ℃, the reaction pressure to be 3.4MPa, and the reaction time to be 42 minutes.
(3) And (3) allowing the polymerization reaction product obtained in the step (2), fresh propylene and hydrogen to enter a second loop reactor for continuous polymerization, controlling the concentration of the hydrogen entering the second loop reactor to be 2200ppm, the reaction temperature to be 70 ℃, the reaction pressure to be 3.4MPa, the reaction time to be 25 minutes, and preparing the polypropylene powder with the melt flow rate of 1.35g/10 min.
(4) Uniformly mixing the polypropylene powder obtained in the step (3), 0.1 part of antioxidant, 0.2 part of auxiliary antioxidant and 0.05 part of halogen absorbent, extruding by using an extruder, wherein the load of the extruder is 29 tons/h, the rotating speed of a screw is 240 revolutions per minute, the temperature of each section of a barrel of the extruder is 210 ℃, the temperature of cooling water is 60 ℃, and controlling the MFR of a final product to be 1.34g/10 min.
The mechanical properties of the obtained product are shown in the invention effect attached table 1.
Table 1:
the results in the table show that the product prepared by the method of asymmetric hydrogenation in the propylene polymerization process has lower melt flow rate and good rigidity compared with the existing product, and meets the processing requirements of extruded sheets.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (11)
1. A method of synthesizing polypropylene comprising the steps of:
1) carrying out prepolymerization on raw materials containing propylene, a catalyst and an electron donor to obtain a prepolymerization product;
2) subjecting the pre-polymerized product to a first polymerization reaction with propylene and hydrogen to obtain a first polymerization product;
3) and carrying out second polymerization reaction on the first polymerization product, propylene and hydrogen to obtain the polypropylene.
2. The method of claim 1, wherein the catalyst in step 1) comprises a main catalyst and a cocatalyst; preferably, the primary catalyst comprises DQC-401, and the secondary catalyst comprises triethylaluminum; the molar ratio of the cocatalyst to the propylene is 0.14-0.22; the molar ratio of the cocatalyst to the electron donor is 6-16; the reaction temperature in the step 1) is 18-28 ℃, the reaction pressure is 3.2-3.6MPa, and the reaction time is 8-15 min.
3. The method as claimed in claim 1 or 2, wherein the hydrogen concentration in step 2) is 180-260ppm, the reaction temperature is 70 ± 5 ℃, the reaction pressure is 3.2-3.6MPa, and the reaction time is 40-48 min.
4. The method as claimed in any one of claims 1 to 3, wherein the hydrogen concentration in step 3) is 1800 to 2600ppm, the reaction temperature is 70 ± 5 ℃, the reaction pressure is 3.2 to 3.6MPa, and the reaction time is 20 to 28 min.
5. Polypropylene obtained by the process according to any one of claims 1-4.
6. A polypropylene material comprising the following components and/or the reaction product of the following components: polypropylene, antioxidant and halogen absorber; wherein the polypropylene is a polypropylene obtained according to the process of any one of claims 1-4 or a polypropylene according to claim 5.
7. The polypropylene material of claim 6, wherein the antioxidant comprises a primary antioxidant and a secondary antioxidant; preferably, the primary antioxidant is selected from phenolic antioxidants, preferably comprising one or more of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] or n-octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; and/or the auxiliary antioxidant is selected from phosphite antioxidants, preferably comprising one or more of bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite or tris [2, 4-di-tert-butylphenyl ] phosphite.
8. The polypropylene material according to claim 6 or 7, wherein the halogen absorber comprises one or more of calcium stearate or hydrotalcite, preferably wherein the hydrotalcite is selected from one or more of layered dihydroxy magnesium aluminium hydroxide.
9. The polypropylene material according to any one of claims 6 to 8, wherein the polypropylene, the antioxidant and the halogen absorbent are in parts by weight:
95 to 99.9 parts of polypropylene, preferably 95.5 to 99.8 parts,
0.01-0.5 part of antioxidant, preferably 0.02-0.3 part
0.01-0.5 part of halogen absorbent, preferably 0.02-0.1 part.
10. A process for the preparation of a polypropylene material according to any one of claims 6 to 9, comprising: and mixing the polypropylene, the antioxidant and the halogen absorbent, and extruding and granulating to obtain the polypropylene material.
11. Use of the polypropylene material according to any one of claims 6 to 9 or the polypropylene material obtained by the method according to claim 8 for the production of a sheet, preferably comprising subjecting the polypropylene material to an extrusion process to obtain a sheet.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103554660A (en) * | 2013-10-21 | 2014-02-05 | 中国石油化工股份有限公司 | High-rigidity high-heat-resistance homo-polypropylene material and preparation method thereof |
| CN109054166A (en) * | 2018-06-15 | 2018-12-21 | 中国石油化工股份有限公司 | A kind of preparation method of heat-proof impact-resistant polypropylene material |
| CN109553863A (en) * | 2018-10-09 | 2019-04-02 | 中国石油化工股份有限公司 | It is a kind of to squeeze out with polypropylene material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103554660A (en) * | 2013-10-21 | 2014-02-05 | 中国石油化工股份有限公司 | High-rigidity high-heat-resistance homo-polypropylene material and preparation method thereof |
| CN109054166A (en) * | 2018-06-15 | 2018-12-21 | 中国石油化工股份有限公司 | A kind of preparation method of heat-proof impact-resistant polypropylene material |
| CN109553863A (en) * | 2018-10-09 | 2019-04-02 | 中国石油化工股份有限公司 | It is a kind of to squeeze out with polypropylene material and preparation method thereof |
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