CN112375170A - Ternary random copolymerization polypropylene, preparation method thereof, polypropylene pipe containing ternary random copolymerization polypropylene and preparation method of polypropylene pipe - Google Patents
Ternary random copolymerization polypropylene, preparation method thereof, polypropylene pipe containing ternary random copolymerization polypropylene and preparation method of polypropylene pipe Download PDFInfo
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- CN112375170A CN112375170A CN202011373691.1A CN202011373691A CN112375170A CN 112375170 A CN112375170 A CN 112375170A CN 202011373691 A CN202011373691 A CN 202011373691A CN 112375170 A CN112375170 A CN 112375170A
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- polypropylene
- ternary random
- propylene
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- -1 polypropylene Polymers 0.000 title claims abstract description 113
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 109
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 109
- 238000007334 copolymerization reaction Methods 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 22
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 37
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005977 Ethylene Substances 0.000 claims abstract description 10
- 230000009471 action Effects 0.000 claims abstract description 5
- 238000010574 gas phase reaction Methods 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract 2
- 239000003963 antioxidant agent Substances 0.000 claims description 38
- 230000003078 antioxidant effect Effects 0.000 claims description 38
- 229910052736 halogen Inorganic materials 0.000 claims description 19
- 150000002367 halogens Chemical class 0.000 claims description 19
- 239000002250 absorbent Substances 0.000 claims description 14
- 230000002745 absorbent Effects 0.000 claims description 14
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical group CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 14
- 229920005630 polypropylene random copolymer Polymers 0.000 claims description 14
- 229920005604 random copolymer Polymers 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- QEPVYYOIYSITJK-UHFFFAOYSA-N cyclohexyl-ethyl-dimethoxysilane Chemical compound CC[Si](OC)(OC)C1CCCCC1 QEPVYYOIYSITJK-UHFFFAOYSA-N 0.000 claims description 8
- XFAOZKNGVLIXLC-UHFFFAOYSA-N dimethoxy-(2-methylpropyl)-propan-2-ylsilane Chemical compound CO[Si](C(C)C)(OC)CC(C)C XFAOZKNGVLIXLC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000000741 silica gel Substances 0.000 claims description 7
- 229910002027 silica gel Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 6
- 238000001125 extrusion Methods 0.000 abstract description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000002657 fibrous material Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- 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 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZAAQJFLUOUQAOG-UHFFFAOYSA-N 4-benzyl-2,6-ditert-butylphenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=CC=CC=2)=C1 ZAAQJFLUOUQAOG-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229920001585 atactic polymer Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229920001580 isotactic polymer Polymers 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- 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
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- 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
- 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
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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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)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to the technical field of polymer synthesis, and discloses ternary random copolymerization polypropylene, which comprises 2.5-4.5 wt% of ethylene, 11.2-3.2 wt% of butene and the balance of propylene. The preparation method is disclosed, propylene is subjected to prepolymerization reaction in a prepolymerization reactor under the combined action of a main catalyst, a cocatalyst and an external electron donor to obtain a propylene prepolymer; and (3) reacting the propylene prepolymer with fresh propylene, ethylene and butene-1 in a gas-phase reaction kettle to obtain the ternary random copolymerization polypropylene. The ternary random copolymerization polypropylene is suitable for production of polypropylene extruded pipes, the produced pipes have good low-temperature impact resistance, low glass transition temperature and good rigidity and toughness balance, and the extrusion processability of the polypropylene pipes can be improved.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to ternary random copolymerization polypropylene and a preparation method thereof, a polypropylene pipe containing the ternary random copolymerization polypropylene and a preparation method of the polypropylene pipe.
Background
Polypropylene, a thermoplastic resin made by polymerizing propylene. The methyl-arranged position is divided into isotactic polypropylene (isotatic polypropylene), atactic polypropylene (atactic polypropylene) and syndiotactic polypropylene (syndiotactic polypropylene). Wherein, the methyl arranged on the same side of the molecular main chain is called isotactic polypropylene; the random polypropylene is called when methyl groups are arranged on two sides of a molecular main chain without order; the alternating arrangement of methyl groups on both sides of the molecular backbone is known as syndiotactic polypropylene. In general, in the polypropylene resin produced industrially, the isotactic polypropylene content is about 95%, and the remainder is atactic polypropylene or syndiotactic polypropylene. The industrial polypropylene product uses isotactic polymer as main component, and the use of atactic polymer is less.
Polypropylene (PP) resins have the advantages of low density, good heat resistance, and good stiffness, hardness, and weldability, among which good stress cracking resistance and chemical resistance are particularly prominent. Compared with a high-density polyethylene product, the polypropylene product has better transparency, so that the polypropylene product is widely applied to the novel building pipe industry. The polypropylene random copolymer pipe (PPR pipe) prepared from the propylene random copolymer base stock has the advantages of light weight, excellent impact resistance, good long-term creep resistance, pressure resistance, heat resistance, chemical corrosion resistance and the like, and is a new-generation energy-saving environment-friendly plastic pipe. However, at present, a considerable part of domestic polypropylene products depend on import, and the domestic quality is not good enough, wherein the polypropylene structure of the PPR pipe is poor in comprehensive performance, especially low-temperature impact resistance compared with the similar products abroad, so that the produced polypropylene (PP-R) pipe has the condition of cracking or breakage in winter construction.
Disclosure of Invention
< problems to be solved by the present invention >
The current polypropylene pipe has the technical problem of poor low-temperature impact resistance and crack or damage of the pipe.
In order to solve the above problems, a first object of the present invention is to provide a terpolymer polypropylene which can obtain high impact resistance at low temperature, has a low glass transition temperature, and has good extrusion processability.
The second objective of the present invention is to provide a preparation method of ternary random copolymerization polypropylene, such that the polymerization monomer can fully contact the reactive center, thereby improving the reactivity.
The third purpose of the invention is to provide a ternary random copolymerization polypropylene pipe which has lower glass transition temperature and better rigidity and toughness balance.
The fourth purpose of the invention is to provide a preparation method of the ternary random copolymerization polypropylene pipe.
< technical solution adopted in the present invention >
The invention provides ternary random copolymerization polypropylene, which comprises 2.5-4.5 wt% of ethylene, 11.2-3.2 wt% of butene and the balance of propylene.
The second aspect of the present invention provides a method for preparing a terpolymer polypropylene, comprising the steps of:
propylene is subjected to prepolymerization reaction in a prepolymerization reactor under the combined action of a main catalyst, a cocatalyst and an external electron donor to obtain a propylene prepolymer;
reacting the propylene prepolymer with fresh propylene, ethylene and butene-1 in a gas phase reaction kettle to obtain ternary random copolymerization polypropylene;
the main catalyst is a ZN catalyst, and comprises 12-22 wt% of magnesium, 3-10 wt% of silica gel, 1.5-5 wt% of titanium, 36-65 wt% of halogen, 5-15 wt% of internal electron donor and 0.03-0.08 wt% of boron; the internal electron donor is dibutyl phthalate, and the external electron donor is a compound of isobutyl isopropyl dimethoxysilane and cyclohexyl ethyl dimethoxysilane.
The catalyst system is used for catalyzing propylene polymerization by utilizing a ZN catalyst/X-Donor catalyst system, and comprises a main catalyst, a cocatalyst and an external electron Donor. The catalyst system can slow down the decay speed of propylene polymerization reaction and maintain a fast and stable reaction rate for a long time. The method utilizes the ZN catalyst/X-Donor catalyst system and the larger porosity and pore size distribution of polypropylene (PP), ensures that a polymerization monomer diffuses into pores in a longer time and fully contacts with a reaction active center, so that the catalyst shows stable and long-acting characteristics, and the prepared ternary random copolymerization polypropylene has high impact resistance and lower glass transition temperature at a low temperature.
Thirdly, the invention provides a ternary random copolymerization polypropylene pipe, which comprises 98.82-99.4 parts of ternary random copolymerization polypropylene, 0.4-0.8 part of main antioxidant, 0.15-0.3 part of auxiliary antioxidant and 0.05-0.08 part of halogen absorbent in parts by weight.
The fourth aspect of the invention provides a preparation method of a ternary random copolymerization polypropylene pipe, which comprises the following steps:
weighing ternary random copolymer polypropylene, a main antioxidant, an auxiliary antioxidant and a halogen absorbent in proportion and blending to obtain a blend;
and (3) putting the blend into a double-screw extruder to be extruded to obtain the ternary random copolymerization polypropylene pipe.
< advantageous effects achieved by the present invention >
(1) The ternary random copolymerization polypropylene is suitable for producing polypropylene extruded pipes, the produced pipes have good low-temperature impact resistance, low glass transition temperature and good rigidity and toughness balance, and the extrusion processability of the polypropylene pipes can be improved;
(2) the preparation method of the ternary random copolymerization polypropylene optimizes and improves the structure of the polypropylene material for preparing the pipe, improves the molecular weight distribution of the finished product of the polypropylene pipe, wherein the molecular weight distribution is more than or equal to 7, and the molecular weight distribution of the common polypropylene material added with ethylene is 5.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The invention provides ternary random copolymerization polypropylene, which comprises 2.5-4.5 wt% of ethylene, 11.2-3.2 wt% of butene and the balance of propylene.
In the invention, the melt flow rate of the polypropylene is 0.3g/10 min-1 g/10 min.
The second aspect of the present invention provides a method for preparing a terpolymer polypropylene, comprising the steps of:
propylene is subjected to prepolymerization reaction in a prepolymerization reactor under the combined action of a main catalyst, a cocatalyst and an external electron donor to obtain a propylene prepolymer;
and (3) reacting the propylene prepolymer with fresh propylene, ethylene and butene-1 in a gas-phase reaction kettle to obtain the ternary random copolymerization polypropylene.
In the invention, the main catalyst is a ZN catalyst, and the components comprise, by weight, 12-22% of magnesium, 3-10% of silica gel, 1.5-5% of titanium, 36-65% of halogen, 5-15% of an internal electron donor and 0.03-0.08% of boron; the internal electron Donor is dibutyl phthalate, and the external electron Donor is a compound (X-Donor) of isobutyl isopropyl dimethoxysilane and cyclohexyl ethyl dimethoxysilane.
In the present invention, the molar ratio of isobutylisopropyldimethoxysilane to cyclohexylethyldimethoxysilane was 5: 4.
In the present invention, the titanium is provided by titanium tetrachloride.
In this example, the halogen is chlorine.
In the invention, the temperature of the reaction kettle is 60-75 ℃, and the reaction pressure is 1.8-2.8 MPa.
In the present invention, the hydrogen concentration is 150ppm to 350 ppm.
In the invention, the ethylene/propylene is 100 kg/t-500 kg/t; the ratio of butene-1/propylene is 90kg/t to 350 kg/t.
Thirdly, the invention provides a ternary random copolymerization polypropylene pipe, which comprises 98.82-99.4 parts of ternary random copolymerization polypropylene, 0.4-0.8 part of main antioxidant, 0.15-0.3 part of auxiliary antioxidant and 0.05-0.08 part of halogen absorbent in parts by weight.
In the invention, the main antioxidant comprises an antioxidant 1010 and an antioxidant 1330, and the main antioxidant comprises the following components in percentage by weight: 0.2-0.5 parts, antioxidant 1330: 0.2 to 0.3 portion.
In the present invention, the antioxidant aid includes antioxidant 168.
In the present invention, the halogen absorbent includes calcium stearate.
The fourth aspect of the invention provides a preparation method of a ternary random copolymerization polypropylene pipe, which comprises the following steps:
weighing ternary random copolymer polypropylene, a main antioxidant, an auxiliary antioxidant and a halogen absorbent in proportion and blending to obtain a blend;
and (3) putting the blend into a double-screw extruder to be extruded to obtain the ternary random copolymerization polypropylene pipe.
In the invention, the temperature of each section of the barrel of the double-screw extruder is 180-250 ℃, and the temperature of the granulating water is 70-80 ℃.
< example >
Example 1
(1) Preparation of ternary random copolymerized polypropylene
Propylene is subjected to prepolymerization reaction in a prepolymerization reactor under the combined action of a main catalyst, a cocatalyst and an external electron donor to obtain a prepolymerization reaction product.
And reacting the prepolymerization reaction product with fresh propylene, ethylene and butene-1 in a gas phase reaction kettle at the temperature of 65 ℃, the reaction pressure of 1.9MPa, the hydrogen concentration of 260ppm, the ethylene/propylene concentration of 400kg/t and the butene-1/propylene concentration of 200kg/t to obtain the ternary random copolymer polypropylene with the melt flow rate of 0.5 g/min. The ethylene content of the ternary random copolymerization polypropylene is 3.4 wt.%, and the ratio of butene-1 is 1.3 wt.%.
The main catalyst is ZN catalyst, and each component comprises 15% of magnesium, 5% of silica gel, 3% of titanium, 50% of chlorine, 8% of internal electron donor and 0.05% of element boron by weight percentage; the internal electron donor is dibutyl phthalate; the external electron donor is a compound of isobutyl isopropyl dimethoxysilane and cyclohexyl ethyl dimethoxysilane, and the molar ratio is 5: 4. The cocatalyst is triisobutylaluminum.
(2) Preparation of ternary random copolymerization polypropylene pipe
Uniformly mixing the ternary random copolymer polypropylene, the main antioxidant, the auxiliary antioxidant and the halogen absorbent, and extruding by an extruder to obtain the ternary random copolymer polypropylene pipe with the melt flow rate of 0.5g/10min, wherein the barrel temperature of the extruder is 180 ℃, 190 ℃, 240 ℃, 250 ℃, 260 ℃ of a die head temperature, and the pellet water temperature is 80 ℃.
The primary antioxidant 1 is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester;
the primary antioxidant 2 is 1, 3, 5-trimethyl-2, 4, 6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene;
the secondary antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite;
the halogen absorbent is calcium stearate.
The polypropylene random copolymer fiber material comprises, by weight, 99.2 parts of a polypropylene random copolymer base material, 10100.3 parts of an antioxidant, 13300.2 parts of an antioxidant, 1680.2 parts of an antioxidant and 0.06 part of a halogen absorbent.
Example 2
The present embodiment is different from embodiment 1 in that,
(1) preparation of ternary random copolymerized polypropylene
The temperature of the reaction kettle is 65 ℃, the reaction pressure is 2.1MPa, the hydrogen concentration is 200ppm, the ethylene/propylene is 350kg/t, the butene-1/propylene is 180kg/t, and the ternary random copolymerization polypropylene with the melt flow rate of 0.6g/min is obtained by reaction. The ethylene content of the ternary random copolymerization polypropylene is 2.6 wt%, and the ratio of butene-1 is 1.5 wt%.
(2) Preparation of ternary random copolymerization polypropylene pipe
The polypropylene random copolymer fiber material comprises, by weight, 99.1 parts of a polypropylene random copolymer base material, 10100.2 parts of an antioxidant, 13300.2 parts of an antioxidant, 1680.2 parts of an antioxidant and 0.06 part of a halogen absorbent.
Example 3
The present embodiment is different from embodiment 1 in that,
(1) preparation of ternary random copolymerized polypropylene
The temperature of the reaction kettle is 65 ℃, the reaction pressure is 2.2MPa, the hydrogen concentration is 250ppm, the ethylene/propylene is 480kg/t, the butene-1/propylene is 270kg/t, and the ternary random copolymerization polypropylene with the melt flow rate of 0.8g/min is obtained by reaction. The ethylene content of the ternary random copolymerization polypropylene is 4.0 wt.%, and the ratio of the butene-1 is 3.0 wt.%.
(2) Preparation of ternary random copolymerization polypropylene pipe
The polypropylene random copolymer fiber material comprises 99.4 parts by weight of polypropylene random copolymer base stock, 10100.3 parts by weight of antioxidant, 13300.3 parts by weight of antioxidant, 1680.2 parts by weight of antioxidant and 0.08 part by weight of halogen absorbent.
Example 4
The present embodiment is different from embodiment 1 in that,
(1) preparation of ternary random copolymerized polypropylene
The temperature of the reaction kettle is 70 ℃, the reaction pressure is 2.1MPa, the hydrogen concentration is 300ppm, the ethylene/propylene is 500kg/t, the butene-1/propylene is 110kg/t, and the ternary random copolymerization polypropylene with the melt flow rate of 0.7g/min is obtained by reaction. The ethylene content of the ternary random copolymerization polypropylene is 4.5 wt%, and the ratio of butene-1 is 1.2 wt%.
(2) Preparation of ternary random copolymerization polypropylene pipe
The polypropylene random copolymer fiber material comprises, by weight, 99.05 parts of a polypropylene random copolymer base material, 10100.2 parts of an antioxidant, 13300.2 parts of an antioxidant, 1680.3 parts of an antioxidant and 0.08 part of a halogen absorbent.
Example 5
The present embodiment is different from embodiment 1 in that,
(1) preparation of ternary random copolymerized polypropylene
The temperature of the reaction kettle is 60 ℃, the reaction pressure is 2.3MPa, the hydrogen concentration is 200ppm, the ethylene/propylene is 420kg/t, the butene-1/propylene is 320kg/t, and the ternary random copolymerization polypropylene with the melt flow rate of 1g/min is obtained by reaction. The ethylene content of the ternary random copolymerization polypropylene is 3 wt%, and the ratio of butene-1 is 2.6 wt%.
(2) Preparation of ternary random copolymerization polypropylene pipe
The polypropylene random copolymer fiber material comprises, by weight, 98.8 parts of a polypropylene random copolymer base material, 10100.5 parts of an antioxidant, 13300.3 parts of an antioxidant, 1680.15 parts of an antioxidant and 0.05 part of a halogen absorbent.
Example 6
The difference between this embodiment and embodiment 1 is that the cocatalyst can also be trimethyl aluminum, triethyl aluminum or tributyl aluminum, or the cocatalyst can also be a combination of any combination of trimethyl aluminum, triethyl aluminum, tributyl aluminum or triisobutyl aluminum, and the ratio of the components can be adaptively adjusted according to the process requirements, and this embodiment is not specifically limited herein.
Example 7
This example differs from example 1 in that the processing aid is a primary antioxidant, a secondary antioxidant, or a halogen absorber.
Example 8
This example differs from example 1 in the pressurization parameters of the extruder. The barrel temperature of the extruder is 180 ℃, 190 ℃, 240 ℃, 250 ℃, the die head temperature is 260 ℃, and the granulating water temperature is 70 ℃.
Example 9
The difference of the embodiment 1 is that the components of the ZN catalyst are different, and the components of the ZN catalyst comprise, by weight, 20% of magnesium, 3% of silica gel, 5% of titanium, 45% of chlorine, 10% of an internal electron donor, and 0.03% of boron; the internal electron donor is dibutyl phthalate; the external electron donor is a compound of isobutyl isopropyl dimethoxysilane and cyclohexyl ethyl dimethoxysilane, and the molar ratio is 5: 4.
Example 10
The difference between the embodiment and the embodiment 1 is that the components of the ZN catalyst are different, and the components of the ZN catalyst comprise, by weight, 22% of magnesium, 10% of silica gel, 1.5% of titanium, 65% of chlorine, 5% of an internal electron donor and 0.08% of elemental boron; the internal electron donor is dibutyl phthalate; the external electron donor is a compound of isobutyl isopropyl dimethoxysilane and cyclohexyl ethyl dimethoxysilane, and the molar ratio is 5: 4.
Example 11
The difference between the embodiment and the embodiment 1 is that the components of the ZN catalyst are different, and the components of the ZN catalyst comprise, by weight, 12% of magnesium, 8% of silica gel, 3% of titanium, 36% of chlorine, 5% of an internal electron donor and 0.03% of elemental boron; the internal electron donor is dibutyl phthalate; the external electron donor is a compound of isobutyl isopropyl dimethoxysilane and cyclohexyl ethyl dimethoxysilane, and the molar ratio is 5: 4.
< test example >
The overall performance of the polypropylene pipe was measured using examples 1-5 and comparative example 1 as samples, and comparative example 1 was R200P (a commercially available polypropylene pipe), and the results are shown in Table 1.
TABLE 1 measurement results of different polypropylene pipe samples
As can be seen from Table 1, the polypropylene pipes of the present application have better low temperature impact resistance, lower glass transition temperature and better stiffness and toughness balance, and the pipe extrusion processability is improved compared with the comparative example 1.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The ternary random copolymerization polypropylene is characterized by comprising 2.5-4.5 wt% of ethylene, 11.2-3.2 wt% of butylene and the balance of propylene.
2. The ternary random copolymer polypropylene according to claim 1, wherein the melt flow rate of the polypropylene is from 0.3g/10min to 1g/10 min.
3. A method for preparing the ternary random copolymer polypropylene according to claim 1 or 2, comprising the steps of:
propylene is subjected to prepolymerization reaction in a prepolymerization reactor under the combined action of a main catalyst, a cocatalyst and an external electron donor to obtain a propylene prepolymer;
reacting the propylene prepolymer with fresh propylene, ethylene and butene-1 in a gas phase reaction kettle to obtain ternary random copolymerization polypropylene;
the main catalyst is a ZN catalyst, and the components comprise, by weight, 12-22% of magnesium, 3-10% of silica gel, 1.5-5% of titanium, 36-65% of halogen, 5-15% of an internal electron donor and 0.03-0.08% of boron; the internal electron donor is dibutyl phthalate, and the external electron donor is a compound of isobutyl isopropyl dimethoxysilane and cyclohexyl ethyl dimethoxysilane.
4. The method of claim 3, wherein the cocatalyst comprises at least one of trimethylaluminum, triethylaluminum, tributylaluminum, or triisobutylaluminum.
5. The method for preparing ternary random copolymer polypropylene according to claim 4, wherein the temperature of the reaction vessel is 60 ℃ to 75 ℃ and the reaction pressure is 4.2MPa to 4.8 MPa.
6. The method of claim 4, wherein the hydrogen concentration is 150ppm to 550 ppm.
7. The method for producing a ternary random copolymer polypropylene according to any one of claims 4 to 6, wherein the ethylene/propylene is 100kg/t to 500 kg/t; the ratio of butene-1/propylene is 90kg/t to 350 kg/t.
8. A ternary random copolymerization polypropylene pipe is characterized by comprising 98.82-99.4 parts of ternary random copolymerization polypropylene according to any one of claims 1-7, 0.4-0.8 part of main antioxidant, 0.15-0.3 part of auxiliary antioxidant and 0.05-0.08 part of halogen absorbent in parts by weight.
9. A method for preparing the ternary random copolymer polypropylene pipe material as claimed in claim 8, comprising the following steps:
weighing ternary random copolymer polypropylene, a main antioxidant, an auxiliary antioxidant and a halogen absorbent in proportion and blending to obtain a blend;
and (3) putting the blend into a double-screw extruder to be extruded to obtain the ternary random copolymerization polypropylene pipe.
10. The method for preparing ternary polypropylene random copolymer pipe as claimed in claim 9, wherein the barrel temperature of each section of the double screw extruder is 180-250 ℃, and the temperature of the granulating water is 70-80 ℃.
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| CN202011373691.1A CN112375170A (en) | 2020-11-30 | 2020-11-30 | Ternary random copolymerization polypropylene, preparation method thereof, polypropylene pipe containing ternary random copolymerization polypropylene and preparation method of polypropylene pipe |
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| CN1582317A (en) * | 2001-10-30 | 2005-02-16 | 巴塞尔聚烯烃意大利有限公司 | Pipe systems of polypropylene compositions |
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| CN1582317A (en) * | 2001-10-30 | 2005-02-16 | 巴塞尔聚烯烃意大利有限公司 | Pipe systems of polypropylene compositions |
| EP1845112A1 (en) * | 2006-04-12 | 2007-10-17 | Total Petrochemicals Research Feluy | Controlled distribution of active sites in Ziegler-Natta catalysts systems |
| CN106248612A (en) * | 2015-06-10 | 2016-12-21 | 中国石油天然气股份有限公司 | Method for measuring comonomer content in ethylene propylene butadiene terpolymer polypropylene |
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Application publication date: 20210219 |