CN116410382A - Polypropylene and application thereof, and method and device for continuously preparing polypropylene - Google Patents
Polypropylene and application thereof, and method and device for continuously preparing polypropylene Download PDFInfo
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- CN116410382A CN116410382A CN202111656996.8A CN202111656996A CN116410382A CN 116410382 A CN116410382 A CN 116410382A CN 202111656996 A CN202111656996 A CN 202111656996A CN 116410382 A CN116410382 A CN 116410382A
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- -1 Polypropylene Polymers 0.000 title claims abstract description 94
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 69
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 43
- 239000000178 monomer Substances 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 26
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 22
- 239000004711 α-olefin Substances 0.000 claims description 36
- 230000008569 process Effects 0.000 claims description 22
- 239000000725 suspension Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 13
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 claims description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- 239000005977 Ethylene Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229940099259 vaseline Drugs 0.000 claims description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 4
- NDAOWAVNIYQCLK-UHFFFAOYSA-N 3,3-bis(methoxymethyl)heptane Chemical compound CCCCC(CC)(COC)COC NDAOWAVNIYQCLK-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 claims description 3
- NHYFIJRXGOQNFS-UHFFFAOYSA-N dimethoxy-bis(2-methylpropyl)silane Chemical compound CC(C)C[Si](OC)(CC(C)C)OC NHYFIJRXGOQNFS-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
- 239000004264 Petrolatum Substances 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 229940066842 petrolatum Drugs 0.000 claims description 2
- 235000019271 petrolatum Nutrition 0.000 claims description 2
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004078 waterproofing Methods 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 230000032683 aging Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical group CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- MBBWTVUFIXOUBE-UHFFFAOYSA-L zinc;dicarbamodithioate Chemical compound [Zn+2].NC([S-])=S.NC([S-])=S MBBWTVUFIXOUBE-UHFFFAOYSA-L 0.000 description 1
Images
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/04—Pressure vessels, e.g. autoclaves
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to the technical field of polymer production, and discloses polypropylene, application thereof, and a method and a device for continuously preparing polypropylene. The method is carried out in a device comprising at least two reaction kettles connected in series in sequence, the method comprising: (1) Introducing propylene or a first monomer composition containing propylene into a reaction kettle I in the presence of a catalyst I to carry out polymerization reaction to obtain a first material flow; (2) The first stream and the second monomer composition are introduced into a reaction vessel II for contact reaction in the presence of a catalyst II. The polypropylene prepared by the method can effectively solve the problems of poor rigidity and toughness balance performance and low notch impact strength of the polypropylene material, and the prepared polypropylene material has the advantages of uniform phase, excellent rigidity and toughness balance performance and high notch impact strength, and also has good cohesive property and surface tension.
Description
Technical Field
The invention relates to the technical field of polymer production, in particular to polypropylene, application thereof, and a method and a device for continuously preparing polypropylene.
Background
The polypropylene is used for preparing waterproof coiled material in the prior art, and is mainly prepared by mixing polypropylene with asphalt, and blending and modifying with additives such as an anti-aging agent, a flame retardant, a filler and the like.
However, polypropylene has poor balance of rigidity and toughness, low notched impact strength, and is particularly severe at low temperatures, and because of these significant disadvantages, polypropylene has limited its wider range of applications. Therefore, improvement of impact properties of polypropylene has become an important issue in polypropylene modification studies.
At present, blending modification and catalytic polymerization are often adopted to improve the impact performance of polypropylene, wherein the blending modification of polypropylene is limited by the dispersion degree of a system, the comprehensive performance is influenced, and a post-processing step is added, so that the cost is higher; the traditional catalytic polymerization method mostly adopts double-reactor multistage polymerization, ethylene copolymerization is introduced, the alloy content of the copolymer reaches a certain time, the balance of rigidity and toughness of polypropylene can be realized, but when the ethylene content in the polypropylene is too high, the problems of low use temperature and the like are caused.
Therefore, a method capable of continuously preparing polypropylene is developed, so that the polypropylene material with excellent rigidity-toughness balance and high notch impact strength is obtained, and is very important for industrial production of the polypropylene material.
Disclosure of Invention
The invention aims to solve the problems of poor rigidity and toughness balance performance and low notch impact strength of polypropylene in the prior art.
In order to achieve the above object, the present invention provides in a first aspect a process for continuously preparing polypropylene, which process is carried out in an apparatus comprising at least two reaction vessels connected in series in sequence, said process comprising:
(1) Introducing propylene or a first monomer composition containing propylene into a reaction kettle I in the presence of a catalyst I to carry out polymerization reaction to obtain a first material flow;
(2) Introducing the first stream and a second monomer composition into a reaction kettle II in the presence of a catalyst II to carry out contact reaction;
the catalyst I and the catalyst II are the same and are Ziegler-Natta catalysts, and the catalyst I contains an organic aluminum compound, an external electron donor compound, an internal electron donor compound and a titanium-containing solid active center component;
the first monomer composition also contains ethylene and/or alpha olefin;
the second monomer composition contains propylene, ethylene and alpha olefin;
the alpha olefin is selected from C 6 -C 20 At least one of the alpha olefins of (a).
In a second aspect the present invention provides polypropylene obtainable by the process according to the first aspect.
The third aspect of the invention provides the application of the polypropylene in the second aspect in the waterproof coiled material of the building.
The fourth aspect of the invention provides a device for continuously preparing polypropylene, which comprises a reaction kettle I and a reaction kettle II which are connected in series, wherein the reaction kettle I is provided with a catalyst I inlet, a propylene inlet or a first monomer composition inlet and a first material flow outlet, and the reaction kettle II is provided with a catalyst II inlet, a second monomer composition inlet and a first material flow inlet communicated with the first material flow outlet.
The polypropylene prepared by the method can effectively solve the problems of poor rigidity and toughness balance performance and low notch impact strength of the polypropylene material, and the prepared polypropylene material has the advantages of uniform phase, excellent rigidity and toughness balance performance and high notch impact strength, and also has good cohesive property and surface tension.
In particular, the inventor also finds that the invention prepares the polypropylene material in a device comprising at least two reaction kettles which are connected in series in turn, is not limited by the output of a screw extruder, effectively solves the problem of limited processing productivity of the traditional method, has simple preparation process, does not generate byproducts in the whole process, has high cleanliness, can effectively reduce the production cost, and is beneficial to large-scale industrial production.
Drawings
FIG. 1 is a polarizing microscope image of polypropylene produced in example 1 of the present invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present invention, unless otherwise stated, the material level refers to the height of the solids in the reaction vessel.
In the present invention, unless otherwise stated, the pressures are gauge pressures.
As previously stated, a first aspect of the present invention provides a process for the continuous preparation of polypropylene, the process being carried out in an apparatus comprising at least two reaction vessels connected in series in sequence, the process comprising:
(1) Introducing propylene or a first monomer composition containing propylene into a reaction kettle I in the presence of a catalyst I to carry out polymerization reaction to obtain a first material flow;
(2) Introducing the first stream and a second monomer composition into a reaction kettle II in the presence of a catalyst II to carry out contact reaction;
the catalyst I and the catalyst II are the same and are Ziegler-Natta catalysts, and the catalyst I contains an organic aluminum compound, an external electron donor compound, an internal electron donor compound and a titanium-containing solid active center component;
the first monomer composition also contains ethylene and/or alpha olefin;
the second monomer composition contains propylene, ethylene and alpha olefin;
the alpha olefin is selected from C 6 -C 20 At least one of the alpha olefins of (a).
Preferably, the alpha olefin is selected from C 8 -C 12 At least one of the alpha olefins of (a).
According to a particularly preferred embodiment, the alpha olefin is selected from at least one of n-decene, 1-undecene, 1-octene, 1-nonene. The inventors found that in this preferred case, a polypropylene material having a higher notched impact strength and a better balance of stiffness and toughness can be obtained.
Preferably, in step (1), the method further comprises: firstly, contacting and mixing the catalyst I with a solvent to obtain a first suspension, and then introducing the first suspension into a reaction kettle I to participate in the polymerization reaction. The inventors found that with this preferred embodiment, a polypropylene material with better flexural modulus mechanical properties can be obtained.
The contact mixing is not particularly limited in the present invention, as long as the catalyst I can be uniformly dispersed in the solvent, and stirring, ultrasonic and shaking can be adopted. Preferably, in step (1), the conditions of contact mixing include at least: the stirring speed is 5-50rpm, the temperature is 10-90 ℃, and the average residence time is 2-200min. More preferably, in step (1), the conditions of contact mixing include at least: the stirring speed is 20-50rpm, the temperature is 20-60 ℃, and the average residence time is 100-150min.
Preferably, in step (1), the weight ratio of the catalyst I to the solvent is in the range of 0.0003 to 0.0008:1.
Preferably, in the step (1), the solvent is in a weight ratio of 0.5-2:1 and petrolatum.
More preferably, in step (1), the weight ratio of the white oil to the vaseline in the solvent is 0.8 to 2:1. in this preferred case, a polypropylene material having more excellent mechanical properties can be obtained.
According to a particularly preferred embodiment, in step (1), the first monomer composition is present in a molar ratio of 1:0.001-0.2 propylene and ethylene.
More preferably, in step (1), the molar ratio of the propylene content to the ethylene content in the first monomer composition is 1:0.05-0.1.
According to another particularly preferred embodiment, in step (1), the first monomer composition is present in a molar ratio of 1:0.001 to 0.1 propylene and alpha olefin.
More preferably, in step (1), the molar ratio of the propylene content to the alpha olefin content in the first monomer composition is 1:0.005-0.08.
According to yet another particularly preferred embodiment, in step (1), the first monomer composition is present in a molar ratio of 1:0.001 to 0.2:0.001 to 0.1 of a combination of propylene, ethylene and alpha olefins.
More preferably, in step (1), the first monomer composition is present in a molar ratio of 1:0.001 to 0.1:0.001 to 0.05 of a combination of propylene, ethylene and alpha olefins.
Preferably, in step (1), the method further comprises: before introducing the first suspension into the reaction kettle I, dispersing the alpha olefin in the first suspension to obtain a second suspension, and then introducing the second suspension into the reaction kettle I.
Preferably, in step (1), the polymerization conditions include: the pressure is 2.0-2.4MPa, the temperature is 55-75 ℃, the average residence time is 0.2-1.2h, and the material level is 55-87%.
More preferably, in step (1), the polymerization conditions include: the pressure is 2.2-2.4MPa, the temperature is 60-75 ℃, the average residence time is 0.8-1.2h, and the material level is 60-87%. In this preferred case, a polypropylene material having a better balance of rigidity and toughness can be obtained.
Preferably, in step (2), the second monomer composition has a content molar ratio of 1:0.1-0.3:0.01 to 0.1 of a combination of propylene, ethylene and alpha olefins.
More preferably, in step (2), the second monomer composition has a content molar ratio of 1:0.15-0.2:0.02-0.06 of a combination of propylene, ethylene and alpha olefins.
Preferably, in step (2), the conditions of the contact reaction include: the pressure is 2.0-2.4MPa, the temperature is 55-85 ℃, the average residence time is 0.4-1.4h, and the material level is 55-87%.
More preferably, in step (2), the conditions of the contact reaction include: the pressure is 2.1-2.4MPa, the temperature is 70-85 ℃, the average residence time is 1-1.4h, and the material level is 80-87%. In this preferred case, polypropylene having better mechanical properties such as notched impact strength and flexural modulus can be obtained.
Preferably, in the catalyst I, the content molar ratio of the solid active center component containing titanium, calculated as titanium element, and the organoaluminum compound, calculated as aluminum element, is 2 to 4:1.
preferably, the internal electron donor compound is a phthalate ester and/or ether compound.
Preferably, the organoaluminum compound is selected from at least one of triethylaluminum, triisobutylaluminum, tri-n-butylaluminum and trihexylaluminum.
Preferably, the external electron donor compound is selected from at least one of 1, 3-dialkoxypropane, 2-ethyl-2-butyl-1, 3-dimethoxypropane, cyclohexylmethyldimethoxysilane, diisobutyldimethoxysilane, 9-bis (methoxymethyl) fluorene.
As previously stated, the second aspect of the present invention provides polypropylene produced by the process of the first aspect.
As previously mentioned, a third aspect of the present invention provides the use of the polypropylene according to the second aspect in a construction waterproofing membrane.
As previously mentioned, a fourth aspect of the present invention provides an apparatus for continuously producing polypropylene, the apparatus comprising a reactor I and a reactor II connected in series, wherein the reactor I is provided with a catalyst I inlet, a propylene inlet or a first monomer composition inlet, a first stream outlet, and the reactor II is provided with a catalyst II inlet, a second monomer composition inlet, a first stream inlet in communication with the first stream outlet.
The invention will be described in detail below by way of examples. In the following examples, all of the raw materials used were commercial products unless otherwise specified.
Propylene: the purity is 99.95 percent, and the Chinese petrochemical industry Co., ltd, beijing Yanshan division;
ethylene: the purity is 99.95 percent, and the Chinese petrochemical industry Co., ltd, beijing Yanshan division;
alpha olefins: 1-undecene, 97% pure, purchased from sigma aldrich trade company;
alpha olefins: 1-octene, analytically pure, purchased from sigma aldrich trade company;
alpha olefins: 1-nonene, 96% pure, purchased from sigma aldrich trade company;
alpha olefins: 1-butene, analytically pure, purchased from sigma aldrich trade company;
catalyst-1: the internal electron donor is di-n-butyl phthalate, the external electron donor compound is 2-ethyl-2-butyl-1, 3-dimethoxy propane, the organic aluminum compound is triethyl aluminum, and the content mole ratio of the titanium-containing solid active center component calculated by titanium element to the organic aluminum compound calculated by aluminum element is 3:1, a step of;
catalyst-2: similar to catalyst-1, except that: the external electron donor compound is cyclohexyl methyl dimethoxy silane;
catalyst-3: similar to catalyst-1, except that: the external electron donor compound is diisobutyldimethoxy silane.
The data on the polymers in examples and comparative examples were obtained as follows:
the crystallization temperature and the melting temperature are tested by using a GB/T19466.3-2004 method;
the glass transition temperature is tested by using a GB/T19466.3-2004 method;
flexural modulus was tested according to the method specified in GB/T9341-2008;
the notched impact strength of the simply supported beam is measured according to the impact strength through the section 1 of the impact property of GB/T1043.1-2008 plastic simply supported beam: measured by a method of non-instrumented impact test;
contact angle of the sheet with water was tested using the method specified in ASTM D7334-2008;
the Shore hardness was measured for 15s readings using the method specified in GB/T2411-2008;
the load deformation temperature is tested by using a GB/T1634.2-2019 method, and the load is 0.45MPa.
In the following examples, talc was purchased from zheng, xi-Gui chemical company;
light stabilizers: 770, available from Qingdao Huaen corporation;
ethylene propylene rubber: 4045 available from Jilin petrochemical company.
Example 1
The catalyst-1 was used in the method of this example.
The present embodiment provides a method for continuously preparing polypropylene, the method comprising:
(1) At a stirring speed of 20rpm, the weight ratio of catalyst to solvent was 0.0003:1 (the temperature is 40 ℃ and the average residence time is 120 min) so that the catalyst is uniformly dispersed in a solvent (the dosage weight ratio of white oil to vaseline is 2:1) to obtain a first suspension, and then the first suspension is pumped into a reaction kettle I by a pressure pump, wherein the molar ratio is 1 under the conditions that the temperature is 75 ℃ and the pressure is 2.4 MPa: introducing 0.08 of propylene and ethylene into a reaction kettle I for polymerization reaction, wherein the material level is 87%, and the average residence time of polymerization is 1.2h to obtain a first material flow;
(2) At a temperature of 85 ℃ and a pressure of 2.4MPa, the first stream and a molar ratio of 1:0.17: propylene, ethylene and 1-undecene of 0.05 were introduced into a reaction vessel II for contact reaction at a level of 87% and a polymerization average residence time of 1.4 hours to give polypropylene S1.
Example 2
Catalyst-2 was used for the catalyst in the method of this example.
The present embodiment provides a method for continuously preparing polypropylene, the method comprising:
(1) At a stirring speed of 30rpm, the weight ratio of catalyst to solvent was 0.0005:1 (the temperature is 50 ℃ and the average residence time is 150 min) so that the catalyst is uniformly dispersed in a solvent (the dosage weight ratio of white oil to vaseline is 1:1) to obtain a first suspension, then 1-undecene is dispersed in the first suspension to obtain a second suspension, the second suspension is pumped into a reaction kettle I by a pressure pump, and the molar ratio is 1 under the conditions that the temperature is 70 ℃ and the pressure is 2.2 MPa: introducing 0.005 of propylene and 1-undecene into a reaction kettle I for polymerization reaction, wherein the material level is 60%, and the average residence time of polymerization is 0.8h, so as to obtain a first material flow;
(2) At a temperature of 80 ℃ and a pressure of 2.2MPa, the first stream is subjected to a molar ratio of 1:0.2:0.04 of propylene, ethylene and 1-octene are introduced into a reaction kettle II for contact reaction, the material level is 80%, and the average residence time of polymerization is 1h, so that polypropylene S2 is obtained.
Example 3
The catalyst in the method of this example was catalyst-3.
The present embodiment provides a method for continuously preparing polypropylene, the method comprising:
(1) At a stirring speed of 40rpm, the weight ratio of catalyst to solvent was 0.0003:1 (the temperature is 60 ℃ and the average residence time is 100 min) so that the catalyst is uniformly dispersed in a solvent (the dosage weight ratio of white oil to vaseline is 0.8:1) to obtain a first suspension, then the first suspension is pumped into a reaction kettle I by a pressure pump, and the molar ratio is 1 under the conditions that the temperature is 73 ℃ and the pressure is 2.3 MPa: 0.005: introducing 0.05 of propylene, ethylene and 1-nonene into a reaction kettle I for polymerization reaction, wherein the material level is 75%, and the average residence time of polymerization is 1h to obtain a first material flow;
(2) At a temperature of 70 ℃ and a pressure of 2.1MPa, the first stream is subjected to a molar ratio of 1:0.2:0.06 of propylene, ethylene and 1-nonene are introduced into a reaction kettle II for contact reaction, the material level is 85 percent, and the average residence time of polymerization is 1.2h, thus obtaining polypropylene S3.
Example 4
This example refers to the process of example 3, except that in step (1), the molar ratio of propylene, ethylene and 1-nonene used in the first monomer composition is 1:0.005:0.08.
the remaining steps were the same as in example 3.
Polypropylene S4 is obtained.
Example 5
This example refers to the process of example 3, except that in step (1), the polymerization temperature was 55 ℃.
The remaining steps were the same as in example 3.
Polypropylene S5 is obtained.
Example 6
This example refers to the process of example 3 except that in step (2) the contact reaction temperature is 65 ℃.
The remaining steps were the same as in example 3.
Polypropylene S6 is obtained.
Example 7
This example refers to the process of example 3, except that in step (1) the components of catalyst I are introduced directly into reaction vessel I;
specifically:
(1) In the presence of catalyst I, the molar ratio is 1: introducing 0.08 of propylene and ethylene into a reaction kettle I for polymerization reaction (the temperature is 75 ℃, the pressure is 2.4 MPa), the material level is 87%, and the average residence time of polymerization is 1.2h, so as to obtain a first material flow;
(2) At a temperature of 85 ℃ and a pressure of 2.4MPa, the first stream and a molar ratio of 1:0.17: propylene, ethylene and 1-undecene of 0.05 were introduced into a reaction vessel II for contact reaction at a level of 87% and a polymerization average residence time of 1.4h to give polypropylene S7.
Example 8
This example refers to the process of example 3, except that in step (2) 1-nonene is replaced with an equimolar amount of 1-butene.
The remaining steps were the same as in example 3.
Polypropylene S8 is obtained.
Comparative example 1 (screw extrusion method)
The polypropylene is prepared by a screw extrusion method in the comparative example, and the specific steps include:
(1) 0.1g of initiator dicumyl peroxide, 1g of grafting monomer pentaerythritol triacrylate and 0.1g of free radical activity regulator zinc dithiocarbamate are dissolved in a proper amount of acetone to obtain a mixed solution:
(2) Then uniformly spraying the obtained mixed solution on the surface of 100g polypropylene particles, adding an antioxidant B215, uniformly mixing, placing in a vacuum oven at 80 ℃ for 2 hours, adding into a double-screw extruder with the length-diameter ratio of a screw of 35, wherein the temperatures of all sections of the extruder are 160 ℃, 170 ℃, 175 ℃, 170 ℃ and 165 ℃ respectively, and the screw rotating speed is 70r/min, so as to obtain the polypropylene DS1. The properties of the resulting product are shown in table 1.
TABLE 1
| Example 1 | Example 2 | Example 3 | Examples4 | Example 5 | |
| Crystallization temperature/. Degree.C | 115 | 117 | 110 | 108 | 119 |
| Melting temperature/. Degree.C | 154 | 158 | 145 | 148 | 152 |
| Glass transition temperature/DEGC | -39.6 | -35.2 | -32.0 | -34.1 | -28.9 |
| Flexural modulus/MPa | 533 | 480 | 576 | 512 | 650 |
| Notched impact strength/kJ/m of simply supported beam 2 ,-20℃ | C7.2 | C8.5 | C8.7 | C6.3 | C7.2 |
| Contact angle of sheet with water/° | 53 | 51 | 59 | 55 | 60 |
| Shore hardness of | 56 | 55 | 53 | 50 | 60 |
| Load deformation temperature/DEGC | 533 | 480 | 576 | 512 | 650 |
Table 1 (Xue 1)
| Example 6 | Example 7 | Example 8 | Comparative example 1 | |
| Crystallization temperature/. Degree.C | 114 | 118 | 121 | 128 |
| Melting temperature/. Degree.C | 153 | 158 | 161 | 167 |
| Glass transition temperature/DEGC | -23.1 | -20.3 | -25.6 | -30.2 |
| Flexural modulus/MPa | 542 | 484 | 513 | 1290 |
| Notched impact strength/kJ/m of simply supported beam 2 ,-20℃ | C6.3 | C6.2 | C5.2 | C6.2 |
| Contact angle of sheet with water/° | 76 | 86 | 92 | 104 |
| Shore hardness of | 62 | 64 | 65 | 87 |
| Load deformation temperature/DEGC | 63 | 67 | 66 | 85 |
As can be seen from the results of Table 1, the polypropylene prepared by the method of the present invention has high notched impact strength and flexural modulus, and the polypropylene prepared by the method of the present invention has good hardness and load deformation temperature.
The present invention provides an exemplary polarized light microscope image of the polypropylene product prepared in example 1, see FIG. 1.
As can be seen from FIG. 1, the polypropylene prepared by the present invention has finely divided internal crystals, and this structure contributes to achieving a balance of rigidity and toughness.
Test case
The polypropylene products prepared in examples and comparative examples were used to prepare waterproof rolls, and the prepared waterproof rolls were subjected to performance tests including tensile strength, elongation at break and the like, and tensile strength retention and elongation at break retention after aging treatment (heat aging test chamber, temperature 115.+ -. 2 ℃ C., aging time 224 days) were calculated, and specific test results are shown in Table 2.
The preparation method of the waterproof coiled material-1 comprises the following steps: 75g of the polypropylene prepared in the example, 25g of talc and 7g of light stabilizer were introduced into a screw (extrusion temperature: 180 ℃ C., rotation speed: 65 rpm) at 180 ℃ C., and stably extruded, and fed into a calender roll (temperature: 60 ℃ C., pressure: 5MPa, curling speed: 2 m/min), cooled to room temperature, and cut to obtain a barrier sheet having a thickness of 2 mm.
The preparation method of the waterproof coiled material-2 is similar to that of the waterproof coiled material-1, except that ethylene propylene rubber is added into the formula, and specifically:
30g of the polypropylene prepared in comparative example 1, 45g of ethylene propylene rubber, 25g of talc and 7g of light stabilizer were introduced into a screw (extrusion temperature: 180 ℃ C., rotational speed: 65 rpm) for stable extrusion, and fed into a calender roll (temperature: 60 ℃ C., pressure: 5MPa, curling speed: 2 m/min), cooled to room temperature and cut to obtain a barrier sheet having a thickness of 2 mm.
Tensile strength and elongation at break were measured according to the methods specified in GB/T328.9-2007;
the tensile strength retention was calculated as: (tensile strength after aging/tensile strength before aging) ×100%;
the calculation formula of the elongation at break retention is: (elongation at break after aging/elongation at break before aging). Times.100%.
TABLE 2
As can be seen from the results in Table 2, the polypropylene prepared by the method of the invention has fewer charging times, does not need to blend two base materials, and has more excellent ageing resistance under the condition of keeping equivalent mechanical properties.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (13)
1. A process for continuously producing polypropylene, comprising:
(1) Introducing propylene or a first monomer composition containing propylene into a reaction kettle I in the presence of a catalyst I to carry out polymerization reaction to obtain a first material flow;
(2) Introducing the first stream and a second monomer composition into a reaction kettle II in the presence of a catalyst II to carry out contact reaction;
the catalyst I and the catalyst II are the same and are Ziegler-Natta catalysts, and the catalyst I contains an organic aluminum compound, an external electron donor compound, an internal electron donor compound and a titanium-containing solid active center component;
the first monomer composition also contains ethylene and/or alpha olefin;
the second monomer composition contains propylene, ethylene and alpha olefin;
the alpha olefin is selected from C 6 -C 20 At least one of the alpha olefins of (a).
2. The process of claim 1, wherein the alpha olefin is selected from C 8 -C 12 At least one of the alpha olefins;
preferably, the alpha olefin is selected from at least one of n-decene, 1-undecene, 1-octene, 1-nonene.
3. The method according to claim 1 or 2, wherein in step (1), the method further comprises: firstly, contacting and mixing the catalyst I with a solvent to obtain a first suspension, and then introducing the first suspension into a reaction kettle I to participate in the polymerization reaction;
preferably, in step (1), the weight ratio of the catalyst I to the solvent is in the range of 0.0003 to 0.0008:1;
preferably, in the step (1), the solvent is in a weight ratio of 0.5-2:1 and petrolatum;
preferably, in step (1), the weight ratio of the white oil to the vaseline in the solvent is 0.8-2:1.
4. a process according to any one of claims 1 to 3, wherein in step (1), the first monomer composition is present in a molar ratio of 1:0.001 to 0.2 of a combination of propylene and ethylene;
preferably, in step (1), the molar ratio of the propylene content to the ethylene content in the first monomer composition is 1:0.05-0.1.
5. A process according to any one of claims 1 to 3, wherein in step (1), the first monomer composition is present in a molar ratio of 1:0.001 to 0.1 of a combination of propylene and an alpha olefin;
preferably, in step (1), the molar ratio of the propylene content to the alpha-olefin content in the first monomer composition is 1:0.005-0.08.
6. A process according to claim 3, wherein in step (1), the first monomer composition is present in a molar ratio of 1:0.001 to 0.2:0.001 to 0.1 of a combination of propylene, ethylene and alpha olefins;
preferably, in step (1), the first monomer composition is present in a molar ratio of 1:0.001 to 0.1:0.001 to 0.05 of a combination of propylene, ethylene and alpha olefins;
preferably, in step (1), the method further comprises: before introducing the first suspension into the reaction kettle I, dispersing the alpha olefin in the first suspension to obtain a second suspension, and then introducing the second suspension into the reaction kettle I.
7. The method according to any one of claims 1 to 6, wherein in step (1), the polymerization conditions include: the pressure is 2.0-2.4MPa, the temperature is 55-75 ℃, the average residence time is 0.2-1.2h, and the material level is 55-87%;
preferably, in step (1), the polymerization conditions include: the pressure is 2.2-2.4MPa, the temperature is 60-75 ℃, the average residence time is 0.8-1.2h, and the material level is 60-87%.
8. The process according to any one of claims 1 to 7, wherein in step (2), the second monomer composition is present in a molar ratio of 1:0.1-0.3:0.01 to 0.1 of a combination of propylene, ethylene and alpha olefins;
preferably, in step (2), the second monomer composition has a content molar ratio of 1:0.15-0.2:0.02-0.06 of a combination of propylene, ethylene and alpha olefins.
9. The method according to any one of claims 1 to 8, wherein in step (2), the conditions of the contact reaction include: the pressure is 2.0-2.4MPa, the temperature is 55-85 ℃, the average residence time is 0.4-1.4h, and the material level is 55-87%;
preferably, in step (2), the conditions of the contact reaction include: the pressure is 2.1-2.4MPa, the temperature is 70-85 ℃, the average residence time is 1-1.4h, and the material level is 80-87%.
10. The process according to any one of claims 1 to 9, wherein in the catalyst I the molar ratio of the titanium-containing solid active center component in terms of titanium element to the organoaluminum compound in terms of aluminum element is from 2 to 4:1, a step of;
preferably, the internal electron donor compound is phthalate and/or ether compound;
preferably, the organoaluminum compound is selected from at least one of triethylaluminum, triisobutylaluminum, tri-n-butylaluminum and trihexylaluminum;
preferably, the external electron donor compound is selected from at least one of 1, 3-dialkoxypropane, 2-ethyl-2-butyl-1, 3-dimethoxypropane, cyclohexylmethyldimethoxysilane, diisobutyldimethoxysilane, 9-bis (methoxymethyl) fluorene.
11. Polypropylene obtainable by the process according to any one of claims 1 to 10.
12. Use of the polypropylene according to claim 11 in construction waterproofing membrane.
13. The device for continuously preparing polypropylene is characterized by comprising a reaction kettle I and a reaction kettle II which are connected in series, wherein a catalyst I inlet, a propylene inlet or a first monomer composition inlet and a first material flow outlet are arranged on the reaction kettle I, and a catalyst II inlet, a second monomer composition inlet and a first material flow inlet communicated with the first material flow outlet are arranged on the reaction kettle II.
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