CN113845620A - Impact-resistant co-polypropylene and preparation method thereof, polypropylene composition, modified polypropylene and preparation method thereof - Google Patents
Impact-resistant co-polypropylene and preparation method thereof, polypropylene composition, modified polypropylene and preparation method thereof Download PDFInfo
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- CN113845620A CN113845620A CN202111121433.9A CN202111121433A CN113845620A CN 113845620 A CN113845620 A CN 113845620A CN 202111121433 A CN202111121433 A CN 202111121433A CN 113845620 A CN113845620 A CN 113845620A
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 112
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 112
- -1 polypropylene Polymers 0.000 title claims abstract description 87
- 239000000203 mixture Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 31
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000000155 melt Substances 0.000 claims abstract description 13
- 239000003112 inhibitor Substances 0.000 claims abstract description 12
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920001971 elastomer Polymers 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 7
- 230000002779 inactivation Effects 0.000 claims abstract description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 20
- 239000005977 Ethylene Substances 0.000 claims description 20
- 239000002667 nucleating agent Substances 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 6
- 239000002216 antistatic agent Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002671 adjuvant Substances 0.000 claims description 3
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 claims description 3
- 150000001282 organosilanes Chemical group 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000003426 co-catalyst Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 238000001746 injection moulding Methods 0.000 abstract description 8
- 239000000047 product Substances 0.000 description 50
- 229920001577 copolymer Polymers 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group 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
- 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 group 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 2
- 230000009471 action Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical group [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
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 1
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 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
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
Landscapes
- 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 polypropylene materials, in particular to impact-resistant co-polypropylene and a preparation method thereof, a polypropylene composition, modified polypropylene and a preparation method thereof; the method for preparing the impact co-polypropylene comprises the following steps: (1) in the presence of a main catalyst, a cocatalyst, an external electron donor and hydrogen, carrying out homopolymerization on the first propylene to obtain a product 1 containing homopolymerized polypropylene; (2) mixing the product, second propylene, ethylene, hydrogen and an oxygen-nitrogen inhibitor for copolymerization reaction to obtain a product 2 containing copolymerized polypropylene; (3) and (3) carrying out inactivation treatment on the product 2 to obtain the impact-resistant co-polypropylene. The impact-resistant co-polypropylene prepared by the invention has the rubber content of 18.1-22 wt% and the melt index of 69-75g/10min, and has good application prospect in the field of thin-wall injection molding.
Description
Technical Field
The invention relates to the technical field of polypropylene materials, in particular to impact-resistant co-polypropylene and a preparation method thereof, a polypropylene composition, modified polypropylene and a preparation method thereof.
Background
Polypropylene (PP) is a high molecular material synthesized by polycondensation or copolymerization of propylene and ethylene as monomers under the action of a catalyst.
The high-melt-index impact copolymer polypropylene is a multi-component multi-phase high polymer system which takes a propylene homopolymer as a matrix and consists of ethylene, a propylene random copolymer (rubber disperse phase) and an ethylene-propylene multi-block copolymer, has excellent flow property, good machining property and low-temperature-resistant impact resistance, is widely applied to large injection molding thin-wall products such as injection molding household appliances, automobile parts, furniture, toys and the like, at present, various domestic petrochemical companies develop a series of impact copolymer polypropylene materials with melt flow rate of 0.2-40g/10min in sequence, and the large-scale stable production of the impact copolymer polypropylene with MFR (melt flow rate) more than 60 is difficult to realize.
CN112321950A discloses a high impact polypropylene material having a melt index distribution of between 5 and 15g/10min and a tensile strength distribution of between 17 and 19MPa, however the development and production of high impact co-polypropylene materials having a melt flow rate of greater than 60g/10min is still relatively rare. The polypropylene material has poor fluidity in the processing process of injection molding equipment, and the prepared large-scale thin-wall product has the problems of insufficient mechanical property, poor rigidity and toughness balance and the like, and the performance of the polypropylene material still needs to be improved.
Disclosure of Invention
The invention aims to solve the problems that in the prior art, the melt index of a copolymerization impact-resistant polypropylene material is low, the flowability is poor when the copolymerization impact-resistant polypropylene material is applied to the processing process of large-sized thin-wall products, and the obtained products have insufficient mechanical properties and poor rigidity-toughness balance, and provides an impact-resistant copolymerization polypropylene and a preparation method thereof, a polypropylene composition, a modified polypropylene and a preparation method thereof.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing an impact co-polypropylene, the method comprising:
(1) in the presence of a main catalyst, a cocatalyst, an external electron donor and hydrogen, carrying out homopolymerization on the first propylene to obtain a product 1 containing homopolymerized polypropylene;
(2) mixing the product 1, second propylene, ethylene, hydrogen and an oxygen-nitrogen inhibitor for copolymerization reaction to obtain a product 2 containing copolymerized polypropylene, wherein the molar ratio of the ethylene to the second propylene is 0.2-0.3:1, and the molar ratio of the hydrogen to the second propylene is 0.015-0.04: 1;
(3) and (3) carrying out inactivation treatment on the product 2 to obtain the impact-resistant co-polypropylene.
In a second aspect, the present invention provides an impact co-polypropylene prepared according to the process of the first aspect.
In a third aspect, the present invention provides a polypropylene composition comprising the impact co-polypropylene of the second aspect and an adjuvant.
The fourth aspect of the present invention provides a method for producing a modified polypropylene, comprising: the polypropylene composition according to the third aspect is extrusion molded.
In a fifth aspect, the present invention provides a modified polypropylene prepared by the method of the fourth aspect.
By the technical scheme, the invention prepares the impact copolymer polypropylene by polymerizing propylene, ethylene, hydrogen and a catalyst system under the action of certain temperature and pressure, wherein the rubber content of the impact copolymer polypropylene is 18.1-22 wt% (based on the total amount of the impact copolymer polypropylene), and the melt index (MFR) at 230 ℃ and under the load of 2.16kg is as high as 69-75g/10 min; the further prepared modified polypropylene has good fluidity and excellent rigidity and toughness balance, and has good application prospect in the field of thin-wall injection molding.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As previously mentioned, the first aspect of the present invention provides a method for preparing a co-polypropylene, the method comprising:
(1) in the presence of a main catalyst, a cocatalyst, an external electron donor and hydrogen, carrying out homopolymerization on the first propylene to obtain a product 1 containing homopolymerized polypropylene;
(2) mixing the product 1, second propylene, ethylene, hydrogen and an oxygen-nitrogen inhibitor for copolymerization reaction to obtain a product 2 containing copolymerized polypropylene, wherein the molar ratio of the ethylene to the second propylene is 0.2-0.3:1, and the molar ratio of the hydrogen to the second propylene is 0.015-0.04: 1;
(3) and (3) carrying out inactivation treatment on the product 2 to obtain the impact-resistant co-polypropylene.
According to the invention, under the preferable conditions, the main catalyst is magnesium chloride loaded with a titanium solid component and an internal electron donor, and is preferably a Ziegler Natta catalyst; for example, SAL catalysts are available, which are commercially available.
Preferably, the cocatalyst is selected from aluminium alkyls, preferably aluminium trialkyls; for example, it may be one of triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum and tri-n-octylaluminum, and triethylaluminum is most preferable.
Preferably, the external electron donor is an organosilane, preferably at least one of Tetraethoxysilane (TEOS), diisopropyldimethoxysilane (DIPDMS) and n-propyltriethoxysilane (NPTEOS).
In the invention, the product characteristics of the obtained product containing the homopolymerized polypropylene can be controlled by controlling the molar ratio of the cocatalyst to the main catalyst and the molar ratio of the cocatalyst to the external electron donor, wherein under the preferable condition, the molar ratio of aluminum in the cocatalyst to magnesium (Al/Mg) in the main catalyst is 2-6:1, and preferably 4-4.5: 1; the molar ratio of aluminum in the cocatalyst to silicon (Al/Si) in the external electron donor is 5-10: 1, preferably 6 to 8: 1.
in some preferred embodiments of the present invention, in step (1), the conditions of the homopolymerization reaction at least satisfy: the homopolymerization temperature is 60-70 ℃, and the homopolymerization pressure is 2-2.3 MPa.
In the invention, in the step (1), hydrogen is used as a chain transfer agent for homopolymerization, has the functions of adjusting molecular weight and controlling the melt index of the product, and can enable the prepared product 1 containing the homopolymerized polypropylene to have a higher melt index by controlling the ratio of the first propylene to the hydrogen, and preferably, the molar ratio of the hydrogen to the first propylene is 0.03-0.04: 1, more preferably 0.03 to 0.036: 1.
in some preferred embodiments of the present invention, the homopolypropylene in the homopolypropylene-containing product 1 obtained in step (1) has a melt index (MFR) of 140-146g/10min at 230 ℃ and a load of 2.16 kg.
In some preferred embodiments of the present invention, in step (2), the copolymerization reaction conditions at least satisfy: the copolymerization temperature is 60-70 ℃, and the copolymerization pressure is 2-2.3 MPa.
In the invention, in the step (2), the content of ethylene in the rubber phase (ethylene-propylene rubber) can be adjusted by adjusting the content of ethylene and propylene; the higher the content of ethylene-propylene rubber, the higher the impact resistance of product 2, while too low an ethylene content also leads to an increase in the viscosity of product 2, clogging of equipment and lines, and therefore the molar ratio of ethylene to propylene must be controlled within a specific range, preferably the molar ratio of ethylene to said second propylene is from 0.21 to 0.29: 1.
in the present invention, in the step (2), hydrogen is used as a chain transfer agent for copolymerization, which has the functions of adjusting molecular weight and controlling melt index of the product, and the ratio of the second propylene to hydrogen is controlled to enable the prepared product 2 containing the copolymerized polypropylene to have a higher melt index, and preferably, the molar ratio of hydrogen to the second propylene is 0.02-0.025: 1.
in the invention, the production load of the product 1 is 35000kg/h, the polymerization load of the product 2 is 48000kg/h, and the dosage of the main catalyst is 6-7 kg/h.
In the invention, the total ethylene content in the product 2 is adjusted by adjusting the yield ratio of the second reactor, wherein the yield ratio of the second reactor is adjusted by the adding amount of the oxygen nitrogen inhibitor, so that the total content of the ethylene structural units in the product 2 is 8.5-9.5 wt%; preferably, the amount of the oxygen nitrogen inhibitor is 6.8-7.5 kg/h.
According to the present invention, it is preferable that the copolymerized polypropylene-containing product 2 is subjected to a deactivation treatment capable of deactivating the main catalyst contained in the copolymerized polypropylene-containing product 2 and removing volatile components contained therein, under the conditions that the deactivation treatment comprises: nitrogen and steam are mixed to form wet steam and then are introduced into the product 2, and the product 2 is subjected to stripping gas to promote the removal of residual hydrocarbons in the product 2 and simultaneously deactivate residual catalyst in the product 2.
According to a particularly preferred embodiment of the present invention, a process for preparing impact co-polypropylene comprises:
(1) in a first horizontal reactor, in the presence of a main catalyst (SAL catalyst), a cocatalyst (trialkylaluminum), an external electron donor (organosilane) and hydrogen, homopolymerizing first propylene at the homopolymerization temperature of 60-70 ℃ and the homopolymerization pressure of 2-2.3MPa to obtain a product 1 containing homopolymerized polypropylene, wherein the molar ratio of the hydrogen to the first propylene is 0.03-0.036: 1; the molar ratio of aluminum in the cocatalyst to magnesium (Al/Mg) in the main catalyst is 4-4.5: 1; the molar ratio of aluminum in the cocatalyst to silicon (Al/Si) in the external electron donor is 6-8: 1, the dosage of the main catalyst is 6-7 kg/h;
the MFR of the homopolypropylene in the homopolypropylene-containing product 1 was 140-146g/10min at 230 ℃ and a load of 2.16 kg;
(2) mixing the product 1, second propylene, ethylene, hydrogen and an oxygen-nitrogen inhibitor in a second horizontal reactor, and carrying out copolymerization reaction under the conditions that the copolymerization temperature is 60-70 ℃ and the copolymerization pressure is 2-2.3MPa to obtain a product 2 containing copolymerized polypropylene, wherein the molar ratio of the ethylene to the second propylene is 0.21-0.29:1, the molar ratio of hydrogen to the second propylene is from 0.02 to 0.025: 1; the dosage of the oxygen and nitrogen inhibitor is 6.8-7.5 kg/h;
(3) and (3) carrying out inactivation treatment on the product 2 containing the copolymerization polypropylene to obtain the impact-resistant copolymerization polypropylene.
In the present invention, the homo-polypropylene-containing product 1 obtained has a high melt index by combining a specific molar ratio of Al/Mg and Al/Si in step (1) with a specific molar ratio of hydrogen to propylene; then copolymerizing the product 1 containing the homopolymerized polypropylene with propylene, ethylene, hydrogen and an oxygen-nitrogen inhibitor again according to a specific proportion, and producing the impact-resistant copolymerized polypropylene with high melt index and excellent mechanical property; in addition, the method provided by the invention can be used for stably producing the impact-resistant co-polypropylene in a large-scale batch manner.
In a second aspect, the present invention provides an impact co-polypropylene obtainable by the process according to the first aspect; preferably, the impact co-polypropylene has a melt index (MFR) of 69 to 75g/10min at 230 ℃ and a load of 2.16 kg.
According to the invention, the total content of ethylene structural units in the impact copolymer polypropylene is preferably from 6 to 12% by weight, preferably from 8.5 to 9.5% by weight, based on the total amount of the impact copolymer polypropylene.
According to the invention, the content of rubber phase in the impact co-polypropylene is 18.1 to 22 wt.%, based on the total amount of the impact co-polypropylene, under preferred conditions;
in a third aspect, the present invention provides a polypropylene composition comprising the impact co-polypropylene of the second aspect and an adjuvant.
In a preferred embodiment of the present invention, the auxiliary agent is selected from at least one of a primary antioxidant, a secondary antioxidant, a deacidification agent, an antistatic agent and a nucleating agent; in the granulation and forming stage of the product, the crystal nucleus of the product is reduced, the crystal nucleus density is increased, the crystallization rate is improved, the crystallinity is increased, and the rigidity and the chemical property of the product are improved by adding the auxiliary agent; under the preferable condition, the main antioxidant is an antioxidant 1010; the auxiliary antioxidant is antioxidant 168; the deacidification agent is calcium stearate; the antistatic agent is glycerol monostearate GMS 90; the nucleating agent is an organic phosphate nucleating agent, and the type of the organic phosphate nucleating agent can be known by persons skilled in the art, such as a commercial product with the brand number of NA-21 or NA-11; further preferably, the dosage ratio of the main antioxidant to the auxiliary antioxidant is 1: 1.5-3.
Under the preferred conditions according to the present invention, the weight content of the primary antioxidant in the polypropylene composition is 400-1000 ppm; preferably, the weight content of the secondary antioxidant is 1000-1500 ppm; preferably, the deacidification agent is contained in an amount of 300-800ppm by weight; preferably, the weight of the antistatic agent is 300-500 ppm; preferably, the nucleating agent is present in an amount of 1000-2000ppm by weight.
The fourth aspect of the present invention provides a method for producing a modified polypropylene, comprising: the polypropylene composition according to the third aspect is extrusion molded.
According to a particularly preferred embodiment of the present invention, the process for preparing a modified polypropylene comprises:
and (2) feeding the copolymerized polypropylene into an extrusion granulation system, adding an auxiliary agent for mixing, and heating, shearing, melting and extruding the mixture by a granulator to obtain the modified polypropylene.
In a fifth aspect, the present invention provides a modified polypropylene prepared by the method of the fourth aspect.
In some preferred embodiments of the present invention, the modified polypropylene has a melt index (MFR) of 69 to 75g/10min, a tensile yield stress of 22 to 24.3MPa, and a simple beam notched impact strength of 6.65 to 7.12kJ/m at 230 ℃ and a load of 2.16kg2(ii) a The flexural modulus is 1250-1285 MPa; the deformation temperature under load is 82-88 ℃.
The modified polypropylene obtained by the invention can be stably produced in large scale, has the advantages of high melt index and good mechanical property, can be used as a special raw material for injection-molded large-sized thin-walled products such as household electrical appliances, automobile parts and the like, can obviously shorten the injection molding cycle, reduces the production cost of processing enterprises and reduces carbon emission.
The present invention will be described in detail below by way of examples. In the following examples, the content of ethylene structural units, the content of rubber and the content of ethylene structural units in rubber in the impact-resistant copolymerized polypropylene were measured by fourier infrared spectroscopy; MFR (melt index) test method GB/T3682; the test method of the flexural modulus is GB/T9341; the testing method of the tensile yield stress is GB/T1040.2; the test method of the impact strength of the notch of the simply supported beam is GB/T1043.1; the deformation temperature under load is measured according to GB/T1634.2.
Example 1
(1) In a first horizontal reactor, in the presence of a main catalyst (SAL catalyst), a cocatalyst (triethylaluminum), an external electron donor (NPTEOS) and hydrogen, carrying out homopolymerization on first propylene under the conditions that the homopolymerization temperature is 66 ℃ and the homopolymerization pressure is 2.1MPa to obtain a product 1 containing homopolymerized polypropylene, wherein the molar ratio of the hydrogen to the first propylene is 0.035: 1; the molar ratio of aluminum in the cocatalyst to magnesium (Al/Mg) in the main catalyst is 4: 1; the molar ratio of aluminum in the cocatalyst to silicon in the external electron donor (Al/Si) is 7.5: 1, the dosage of the main catalyst is 6.96 kg/h; the polymerization load of product 1 was 35000 kg/h;
in the product 1 containing homopolypropylene at 230 ℃ and a load of 2.16kg, the homopolypropylene has an MFR of 146g/10 min;
(2) and mixing the product 1, second propylene, ethylene, hydrogen and an oxygen-nitrogen inhibitor in a second horizontal reactor, and carrying out copolymerization reaction under the conditions that the copolymerization temperature is 66 ℃ and the copolymerization pressure is 2.1MPa to obtain a product 2 containing copolymerized polypropylene, wherein the molar ratio of the ethylene to the second propylene is 0.29:1, the molar ratio of hydrogen to the second propylene is 0.022: 1; the dosage of the oxygen and nitrogen inhibitor is 7.36 kg/h; the polymerization load of product 2 was 48000 kg/h;
(3) introducing mixed gas of nitrogen and steam into a second horizontal reactor, and carrying out inactivation treatment on the product 2 to obtain impact-resistant co-polypropylene;
(4) feeding the copolymerized polypropylene into a granulator, adding 500ppm by weight of primary antioxidant 1010, 1000ppm by weight of antioxidant 168, 500ppm by weight of calcium stearate deacidification agent, 300ppm by weight of antistatic agent GMS90 and 1500ppm by weight of organic aluminum phosphate salt nucleating agent NA-21 (commercially available) at 230 ℃, uniformly mixing to obtain a mixture, and then shearing, melting and extruding the mixture to obtain modified polypropylene granules;
the properties of the modified polypropylene pellets obtained in this example are shown in Table 1.
TABLE 1
Examples 2 to 9 and comparative examples 1 to 5
The process of example 1 was followed except that the material ratios of the respective materials are shown in Table 2, the results of the property test of the obtained impact-resistant copolymerized polypropylene are shown in Table 3, and the properties of the obtained modified polypropylene are shown in tables 4 and 5.
TABLE 2
TABLE 3
As can be seen from Table 3, the copolymer polypropylene obtained by the method of the present invention has a total ethylene content of 8.5 to 9.5% by weight, a rubber phase content of 18.1 to 25% by weight, and a melt index of 69 to 75g/10min, and has good processing flowability.
Example 10
Following the procedure of example 1, except that an organophosphate nucleating agent NA-11 (commercially available) was used in place of the nucleating agent NA-21, the properties of the resulting modified polypropylene were as shown in tables 4 and 5.
Example 11
Following the procedure of example 1, except for using a nucleating agent TD-431 (commercially available) in place of the nucleating agent NA-21, the properties of the resulting modified polypropylene were as shown in tables 4 and 5.
TABLE 4
TABLE 5
As can be seen from tables 4 and 5, the modified polypropylene obtained by the invention has good appearance, high melt index and good processing fluidity for downstream processing enterprises, can obviously shorten the injection molding processing and forming period and reduce the production cost of the processing enterprises; the simple beam notch has high impact strength and good product toughness, and has good application prospect in thin-wall injection molding.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. A process for preparing an impact co-polypropylene, characterized in that the process comprises:
(1) in the presence of a main catalyst, a cocatalyst, an external electron donor and hydrogen, carrying out homopolymerization on the first propylene to obtain a product 1 containing homopolymerized polypropylene;
(2) mixing the product 1, second propylene, ethylene, hydrogen and an oxygen-nitrogen inhibitor for copolymerization reaction to obtain a product 2 containing copolymerized polypropylene, wherein the molar ratio of the ethylene to the second propylene is 0.2-0.3:1, and the molar ratio of the hydrogen to the second propylene is 0.015-0.04: 1;
(3) and (3) carrying out inactivation treatment on the product 2 to obtain the impact-resistant co-polypropylene.
2. The process according to claim 1, wherein in step (1), the main catalyst is magnesium chloride loaded with a titanium solid component and an internal electron donor, preferably a Ziegler Natta catalyst;
preferably, the cocatalyst is selected from aluminium alkyls, preferably aluminium trialkyls;
preferably, the external electron donor is an organosilane, preferably at least one of tetraethoxysilane, diisopropyldimethoxysilane and n-propyltriethoxysilane.
3. A process according to claim 2, wherein the molar ratio of aluminium in the co-catalyst to magnesium in the main catalyst is from 2 to 6:1, preferably from 4 to 4.5: 1;
preferably, the molar ratio of aluminium in the cocatalyst to silicon in the external electron donor is 5-10: 1, preferably 6 to 8: 1.
4. the method according to claim 1, wherein in step (1), the homopolymerization conditions at least satisfy: the homopolymerization temperature is 60-70 ℃, and the homopolymerization pressure is 2-2.3 MPa;
preferably, in step (1), the molar ratio of hydrogen to the first propylene is from 0.03 to 0.04: 1, preferably 0.03 to 0.036: 1.
5. the process as claimed in claim 1, wherein in step (1), the melt index of the homopolypropylene in the homopolypropylene-containing product 1 is 140-146g/10min at 230 ℃ and a load of 2.16 kg.
6. The process according to any one of claims 1 to 5, wherein in step (2), the copolymerization reaction conditions at least satisfy: the copolymerization temperature is 60-70 ℃, and the copolymerization pressure is 2-2.3 MPa;
preferably, the molar ratio of ethylene to the second propylene is from 0.21 to 0.29: 1;
preferably, the molar ratio of hydrogen to said second propylene is from 0.02 to 0.025: 1;
preferably, the amount of the oxygen nitrogen inhibitor is 6.8-7.5 kg/h.
7. An impact co-polypropylene produced by the process of any one of claims 1-6.
8. The impact co-polypropylene of claim 7, wherein the impact co-polypropylene has a melt index of 69-75g/10min at 230 ℃ and a load of 2.16 kg;
preferably, the content of ethylene structural units in the impact co-polypropylene is from 8.5 to 9.5 wt%, based on the total amount of the impact co-polypropylene;
preferably, the rubber phase content of the impact co-polypropylene is from 18.1 to 22 wt.%, based on the total amount of the impact co-polypropylene.
9. A polypropylene composition comprising the impact co-polypropylene of claim 7 or 8 and an adjuvant;
preferably, the auxiliary agent is selected from at least one of a primary antioxidant, a secondary antioxidant, a deacidification agent, an antistatic agent and a nucleating agent;
preferably, the weight content of the primary antioxidant in the polypropylene composition is 400-1000 ppm;
preferably, the weight content of the secondary antioxidant is 1000-1500 ppm;
preferably, the deacidification agent is contained in an amount of 300-800ppm by weight;
preferably, the weight content of the antistatic agent is 300-500 ppm;
preferably, the weight content of the nucleating agent is 1000-2000 ppm;
preferably, the nucleating agent is selected from organic phosphate nucleating agents.
10. A process for preparing a modified polypropylene, comprising: extrusion molding the polypropylene composition of claim 9.
11. A modified polypropylene prepared according to claim 10;
preferably, the melt index of the modified polypropylene is 69-75g/10min, the tensile yield stress is 22-24.3MPa, and the impact strength of a simple beam notch is 6.65-7.12kJ/m at 230 ℃ and under the load of 2.16kg2The flexural modulus is 1250-1285MPa, and the load deformation temperature is 82-88 ℃.
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| CN110997738A (en) * | 2017-06-27 | 2020-04-10 | 埃克森美孚化学专利公司 | High impact polypropylene impact copolymers |
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| CN110997738A (en) * | 2017-06-27 | 2020-04-10 | 埃克森美孚化学专利公司 | High impact polypropylene impact copolymers |
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