CN116731251A - Bimodal polyethylene polymer, preparation method and application thereof, and stone paper - Google Patents
Bimodal polyethylene polymer, preparation method and application thereof, and stone paper Download PDFInfo
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- CN116731251A CN116731251A CN202210210919.8A CN202210210919A CN116731251A CN 116731251 A CN116731251 A CN 116731251A CN 202210210919 A CN202210210919 A CN 202210210919A CN 116731251 A CN116731251 A CN 116731251A
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- polyethylene polymer
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- -1 polyethylene Polymers 0.000 title claims abstract description 99
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 97
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 97
- 229920000642 polymer Polymers 0.000 title claims abstract description 93
- 230000002902 bimodal effect Effects 0.000 title claims abstract description 90
- 239000004575 stone Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000009826 distribution Methods 0.000 claims abstract description 26
- 239000000155 melt Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims description 52
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 42
- 239000005977 Ethylene Substances 0.000 claims description 42
- 239000003054 catalyst Substances 0.000 claims description 40
- 238000007334 copolymerization reaction Methods 0.000 claims description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims description 31
- 239000001257 hydrogen Substances 0.000 claims description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 30
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 29
- 239000004711 α-olefin Substances 0.000 claims description 27
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 26
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical group CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 11
- 230000001105 regulatory effect Effects 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012968 metallocene catalyst Substances 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- 229920001038 ethylene copolymer Polymers 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 235000011147 magnesium chloride Nutrition 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 14
- 239000000203 mixture Substances 0.000 abstract description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000010998 test method Methods 0.000 description 6
- 238000010096 film blowing Methods 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012967 coordination catalyst Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- 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
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
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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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the field of high polymer materials, and discloses a bimodal polyethylene polymer, a preparation method and application thereof, and stone paper. The bimodal polyethylene polymer comprises: the bimodal polyethylene polymer has a weight average molecular weight of 20 to 40 x 10 4 The method comprises the steps of carrying out a first treatment on the surface of the The molecular weight distribution is 10-30; the polyethylene composition has a melt flow ratio (21.6/5.0) of 25 to 40;the melt index of the bimodal polyethylene polymer at 190 ℃ under 5.0kg is 0.01-10g/10min. The bimodal polyethylene polymer provided by the invention has bimodal and wide molecular weight distribution, low fluidity and good mechanical properties; the bimodal polyethylene polymer provided by the invention is used for stone paper, has good compatibility with calcium carbonate, and the CV value of the prepared stone paper can be less than 3%, and the density is as high as 1.18g/cm 3 And the stiffness is as high as 0.4, and a better technical effect is obtained.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a bimodal polyethylene polymer, a preparation method and application thereof and stone paper.
Background
The stone paper making production realizes no pollution without adding water and chemical reagent, and is superior to the traditional paper making. The cost of the stone paper product is 20% -30% lower than that of the traditional paper product, so that the stone paper making process not only accords with the national low-carbon and green environment-friendly advocates, but also reduces the cost of the product, improves the competitiveness of enterprises, and is a trend of research and development of paper making technology in the future.
The stone paper is finally produced in a film blowing mode, in general, the polyethylene molecular weight distribution required by an extrusion molding product is wider, the polyethylene molecular weight distribution required by an injection molding product is narrower, and the molecular weight distribution of a blow molding product is in the middle, but as a large amount of inorganic calcium carbonate is added into the mixture of the blown stone paper, the ratio of the inorganic calcium carbonate to the mixture reaches 70-80%, the produced stone paper can be made to be thin and uniform only with good enough compatibility, the writing can be clear after printing, and the pattern color is bright; on the other hand, polyethylene materials are required to have good film forming properties.
Disclosure of Invention
The invention aims to solve the problems of poor compatibility of polyethylene powder and calcium carbonate and poor stiffness of prepared stone paper in the prior art, and provides a bimodal polyethylene polymer, wherein the polyethylene composition has the characteristics of bimodal distribution and wide distribution of molecular weight and low fluidity; the bimodal polyethylene polymer is applied to stone paper, so that the CV value of the stone paper is less than 3%, and the bimodal polyethylene polymer has higher density and stiffness.
According to a first aspect of the present invention there is provided a bimodal polyethylene polymer having a weight average molecular weight of 20 x 10 4 -40×10 4 The method comprises the steps of carrying out a first treatment on the surface of the The molecular weight distribution is 10-30; the polyethylene composition has a melt flow ratio (21.6/5.0) of 25 to 40;
the melt index of the bimodal polyethylene polymer at 190 ℃ under 5.0kg load is 0.01-10g/10min.
According to a second aspect of the present invention, there is provided a process for preparing the aforementioned polyethylene composition, the process comprising:
(1) Adding ethylene into a reaction system containing a catalyst and a cocatalyst for a first homopolymerization reaction or adding ethylene and C3-C12 alpha olefin for a first copolymerization reaction, and regulating the molecular weight by using hydrogen to obtain a component A;
(2) Adding ethylene and/or C3-C12 alpha-olefin and hydrogen mixed component B into a reaction system containing catalyst and cocatalyst 1 Then adding the component A to carry out a second copolymerization reaction to obtain a bimodal polyethylene polymer; or (b)
Adding ethylene, C3-C12 alpha-olefin and hydrogen into a reaction system containing a catalyst and a cocatalyst to perform a third copolymerization reaction to obtain a polymer component B 2 Then carrying out a second copolymerization reaction with the component A to obtain a bimodal polyethylene polymer;
preferably, component A and component B 1 The mass ratio is 1.1-1.8:1; component A and component B 2 The mass ratio is 1.1-1.8:1.
According to a third aspect of the present invention there is provided the use of the bimodal polyethylene polymerisation in stone paper.
According to a fourth aspect of the present invention there is provided a stone paper comprising the bimodal polyethylene polymer as described above.
Compared with the prior art, the bimodal polyethylene polymer provided by the invention has bimodal distribution and wide distribution of molecular weight distribution and low fluidity; the bimodal polyethylene polymer provided by the invention is used for stone paper, has good compatibility with calcium carbonate, and the CV value of the prepared stone paper can be less than 3%, and the density is as high as 1.15g/cm 3 And the stiffness is as high as 0.4, and a better technical effect is obtained.
Detailed Description
No endpoints of the ranges and any values disclosed herein are limited to the precise range or value, and such range or value should be understood to encompass values that are close to the range or value. 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, and are contemplated as specifically disclosed herein.
In the present invention, the C3 to C12 alpha olefin means an alpha olefin having 3 to 12 carbon atoms.
According to a first aspect of the present invention there is provided a bimodal polyethylene polymer having a weight average molecular weight of 20 x 10 4 -40×10 4 The method comprises the steps of carrying out a first treatment on the surface of the The molecular weight distribution is 10-30; the bimodal polyethylene polymer melt flow ratio (21.6/5.0) is 25 to 40, preferably 30 to 40; the melt index of the bimodal polyethylene polymer at 190 ℃ under 5.0kg is 0.01-10g/10min. The bimodal polyethylene polymer melt flow ratio (21.6/5.0) represents the ratio of the melt index number at 190℃under 21.6kg load to the melt index number at 190℃under 5.0kg load. The bimodal polyethylene polymer has bimodal distribution, wide distribution and low flowability of molecular weight distribution.
According to a preferred embodiment of the invention, the bimodal polyethylene polymer has a number average molecular weight of 10000-30000, preferably 11000-15000, more preferably 11000-13000. The foregoing components are advantageous for achieving broad distribution, low flowability of the bimodal polyethylene polymer.
According to a preferred embodiment of the invention, the bimodal polyethylene polymer density is in the range of 0.95 to 0.96g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The foregoing components facilitate a broad distribution and low flowability of the bimodal polyethylene polymer.
According to a preferred embodiment of the invention, the bimodal polyethylene polymer has a degree of methyl branching of 0.2 to 0.5/100C; the foregoing bimodal polyethylene polymers are advantageous for achieving broad distribution and low flowability of the bimodal polyethylene polymers.
According to a preferred embodiment of the present invention, the bimodal polyethylene polymer has a melt index of 0.05-5g/10min under a load of 5.0kg at 190 ℃; preferably 0.05-1.8g/10min; the foregoing bimodal polyethylene polymers are advantageous for achieving broad distribution and low flowability of the bimodal polyethylene polymers.
According to a preferred embodiment of the invention, the bimodal polyethylene polymer has a melt index of 6-18g/10min at 190℃under 21.6kg load; preferably 10-14g/10min; the bimodal polyethylene polymer is beneficial to realizing wide distribution and low flowability of the bimodal polyethylene polymer.
According to a preferred embodiment of the present invention, the bimodal polyethylene polymer has a melt index of 0.01-0.2g/10min at 190℃under a load of 2.16 kg; the foregoing bimodal polyethylene polymers are advantageous for achieving broad distribution and low flowability of the bimodal polyethylene polymers.
According to a preferred embodiment of the invention, the bimodal polyethylene polymer comprises: ethylene homo-and/or copolymers; the ethylene copolymer is a copolymer of ethylene monomer and C3-C12 alpha olefin.
According to a preferred embodiment of the invention, the C3 to C12 alpha-olefins are selected from C3 to C8 alpha-olefins; preferably, the C3-C8 alpha olefin is selected from one or more of propylene, 1-butene, 1-hexane, 4-methyl-1-pentene and 1-octene; is beneficial to realizing wide distribution and low fluidity of the bimodal polyethylene polymer.
The object of the present invention can be achieved by a bimodal polyethylene polymer having the aforementioned characteristics of the present invention, and the preparation method thereof is not particularly limited, and according to a second aspect of the present invention, there is provided a preparation method of the bimodal polyethylene polymer, comprising:
(1) Adding ethylene into a reaction system containing a catalyst and a cocatalyst for a first homopolymerization reaction or adding ethylene and C3-C12 alpha olefin for a first copolymerization reaction, and regulating the molecular weight by using hydrogen to obtain a component A;
(2) Adding ethylene and/or C3-C12 alpha-olefin and hydrogen mixed component B into a reaction system containing catalyst and cocatalyst 1 Then adding the component A to carry out a second copolymerization reaction to obtain a bimodal polyethylene polymer; or (b)
In the presence of a catalyst and a co-catalystAdding ethylene, C3-C12 alpha-olefin and hydrogen into the reaction system of the catalyst to perform a third copolymerization reaction to obtain a polymer component B 2 Then carrying out a second copolymerization reaction with the component A to obtain a bimodal polyethylene polymer;
preferably, component A and component B 1 The mass ratio is 1.1-1.8:1; component A and component B 2 The mass ratio is 1.1-1.8:1.
In the present invention, the aforementioned production method may be carried out in a series reactor method, for example,
(1) Adding a catalyst and a cocatalyst into a first reaction kettle, adding ethylene to perform a first homopolymerization reaction or adding ethylene and C3-C12 alpha olefin to perform a first copolymerization reaction, and regulating the molecular weight by using hydrogen to obtain a component A;
(2) Adding catalyst and cocatalyst into the second reaction kettle, adding ethylene and/or mixed component B of alpha-olefin of C3-C12 and hydrogen 1 And adding the component A to carry out a second copolymerization reaction to obtain the bimodal polyethylene polymer.
In the present invention, the aforementioned production process may be carried out in two or more parallel reactors, for example,
(1) Adding a catalyst and a cocatalyst into a first reaction kettle, adding ethylene to perform a first homopolymerization reaction or adding ethylene and C3-C12 alpha olefin to perform a first copolymerization reaction, and regulating the molecular weight by using hydrogen to obtain a component A;
(2) Adding a catalyst and a cocatalyst into a second reaction kettle, adding ethylene and/or alpha-olefin of C3-C12 and hydrogen to perform a third polymerization reaction to obtain a polymer component B 2 The method comprises the steps of carrying out a first treatment on the surface of the And then carrying out a second copolymerization reaction with the component A to obtain the bimodal polyethylene polymer.
According to the invention, an inert liquid, such as a C5-C10 alkane, may be added to the reactor for preparing the bimodal polyethylene polymer for cooling the reactor, e.g. hexane may be added to the reactor for cooling the reactor prior to the polymerization. The inert liquid can be selected by the person skilled in the art according to the temperature regulation requirement of the reaction kettle, and the inert liquid or the inert liquid is used or not, so long as the temperature of each polymerization reaction in the invention can be ensured.
According to a preferred embodiment of the invention, component A and component B 1 The mass ratio is 1.1-1.8:1; component A and component B 2 The mass ratio is 1.1-1.8:1.
According to a preferred embodiment of the present invention, the first homo-or copolymerization reaction conditions comprise: the reaction temperature is 60-100 ℃; the reaction time is 0.5-6 hours.
According to a preferred embodiment of the present invention, the second copolymerization conditions include: the reaction temperature is 60-100 ℃; the reaction time is 0.5-6 hours.
According to a preferred embodiment of the present invention, the third copolymerization reaction conditions include: the reaction temperature is 60-100 ℃; the reaction time is 0.5 to 6 hours
According to a preferred embodiment of the present invention, in the first homo-or copolymerization, the hydrogen gas: the alpha olefin of C3-C12: the mass ratio of the ethylene is (0.002-7.0): 0-3): 1.
According to a preferred embodiment of the present invention, in the second copolymerization reaction, hydrogen: the alpha olefin of C3-C12: the mass ratio of the ethylene is (0.002-0.3): (0.002-1): 1.
according to a preferred embodiment of the present invention, the catalyst comprises a metal coordination catalyst; preferably, the catalyst is selected from at least one of Ziegler-Natta catalysts (Z-N catalysts), metallocene catalysts, non-metallocene catalysts and chromium catalysts; preferably a ziegler-natta catalyst. The use of the foregoing catalysts for preparing polyethylene compositions is advantageous for achieving broad distribution, low flowability of bimodal polyethylene polymers.
According to the invention, the cocatalyst is selected from one or more of trialkylaluminum, alkylaluminum halides, preferably, the cocatalyst is selected from triethylaluminum; the use of the foregoing cocatalysts to prepare polyethylene compositions is advantageous for achieving broad distribution and low flowability of bimodal polyethylene polymers.
According to the present invention, each of the catalysts of the present invention may be independently supported or unsupported on a carrier, and according to a preferred embodiment of the present invention, the catalyst is supported on a carrier selected from one or more of an aluminum-containing carrier, a silica-containing carrier, and a magnesium dichloride-based carrier; the catalyst is supported on the carrier, so that the wide distribution and low fluidity of the bimodal polyethylene polymer are realized.
According to a preferred embodiment of the invention, the catalyst is supported on MgCl 2 TiCl of (2) 4 A catalyst; preferably, the cocatalyst is triethylaluminium.
According to a third aspect of the present invention there is provided the use of the bimodal polyethylene polymerisation in stone paper.
According to a fourth aspect of the present invention there is provided a stone paper comprising the bimodal polyethylene polymer of the first aspect of the present invention and the bimodal polyethylene polymer prepared by the preparation method of the present invention; the bimodal polyethylene polymer provided by the invention is used for stone paper, has good compatibility with calcium carbonate, ensures that the produced stone paper is thin and uniform in thickness, and can be printed to obtain clear writing and bright pattern color.
According to a preferred embodiment of the invention, the stone paper has a CV value of 1% to 4.5, preferably 1% to 3%; at CV values in this range, the stone paper thickness was uniform.
According to the invention, the density of the stone paper is related to the addition amount of polyethylene, and the higher the addition amount is, the higher the film blowing density is, preferably, the density of the stone paper is 1.15g/cm 3 。
According to a preferred embodiment of the invention, the stone paper has a stiffness of 0.1-0.6, preferably 0.3-0.5.
The present invention will be described in detail by way of examples, but it should be understood that the scope of the present invention is not limited by the examples.
In the following examples, the method for testing bimodal polyethylene polymers comprises:
1) Melt flow rate test method; GB/T3682-2000.
2) The density test method is GB/T1033-1996D method.
3) Molecular weight related test using gel permeation chromatography: ASTM6474-12;
4) Methyl branching degree test method: GB/T6040-2002.
Example 1
(1) Adding hexane into a first closed polymerization reaction kettle, adding a cocatalyst triethylaluminum and a catalyst loaded on MgCl under the condition of stirring 2 TiCl on the upper part 4 Adding ethylene into the catalyst to carry out homopolymerization reaction, and regulating the molecular weight by using hydrogen, wherein the mass ratio of the hydrogen to the ethylene is 6:1, a step of; the reaction pressure is 0.6MPa, the reaction temperature is 85 ℃, and the polymer component A is obtained after 1h of reaction;
(2) Adding hexane into a second closed polymerization reactor, adding triethylaluminum and MgCl under stirring 2 TiCl on the upper part 4 Adding ethylene, 1-butene and hydrogen (hydrogen: 1-butene: ethylene mass ratio is 0.02:0.006:1), and adding component A to carry out copolymerization reaction; wherein the mass ratio of the polymer component A to the materials in the second closed polymerization reaction kettle before mixing is 1.8:1; the reaction pressure is 0.2MPa, the reaction temperature is 78 ℃, and the bimodal polyethylene polymer is obtained after 1.2h of reaction. The bimodal polyethylene polymer test results are shown in table 1.
Example 2
(1) Adding hexane into a first closed polymerization reaction kettle, adding a cocatalyst triethylaluminum and a catalyst loaded on MgCl under the condition of stirring 2 TiCl on the upper part 4 The catalyst is added with ethylene and 1-butene for copolymerization reaction, hydrogen is used for regulating molecular weight, and the hydrogen is used for: 1-butene: the mass ratio of ethylene is 0.11:0.004:1; the reaction pressure is 0.6MPa, the reaction temperature is 84 ℃, and the component A is obtained after 0.7h of reaction;
(2) Adding hexane into a second closed polymerization reaction kettle, adding a catalyst-assisting agent triethylaluminum and MgCl under the condition of stirring 2 TiCl on the upper part 4 Adding ethylene, 1-butene and hydrogen (hydrogen: 1-butene: ethylene mass ratio is 0.0014:0.006:1) into a catalyst, and adding a component A to carry out copolymerization; wherein the mass ratio of the polymer component A to the materials in the second closed polymerization reaction kettle before mixing is 1.1:1; reaction pressure of 0.2The reaction temperature is 76 ℃ under the pressure of MPa, and the bimodal polyethylene polymer is obtained after 1.4h of reaction. The bimodal polyethylene polymer test results are shown in table 1.
Example 3
(1) Adding hexane into a first closed polymerization reaction kettle, adding a cocatalyst triethylaluminum and a catalyst loaded on MgCl under the condition of stirring 2 TiCl on the upper part 4 Catalyst, adding ethylene to carry out homopolymerization reaction, and regulating molecular weight by hydrogen, wherein the hydrogen is as follows: 1-butene: the mass ratio of ethylene is 0.11:0.003:1; the reaction pressure is 0.6MPa, the reaction temperature is 85 ℃, and the component A is obtained after 1h of reaction;
(2) Adding hexane into a second closed polymerization reactor, adding triethylaluminum and MgCl under stirring 2 TiCl on the upper part 4 Adding ethylene, 1-hexene and hydrogen (hydrogen: 1-hexene: ethylene mass ratio is 0.02:0.004:1), and adding component A to carry out copolymerization reaction; wherein the mass ratio of the polymer component A to the materials in the second closed polymerization reaction kettle before mixing is 1.5:1; the reaction pressure is 0.2MPa, the reaction temperature is 78 ℃, and the bimodal polyethylene polymer is obtained after 1.2h of reaction. The bimodal polyethylene polymer test results are shown in table 1.
Example 4
(1) Adding hexane into a first closed polymerization reaction kettle, adding a cocatalyst triethylaluminum and a catalyst loaded on MgCl under the condition of stirring 2 TiCl on the upper part 4 The catalyst is added with ethylene and 1-butene for copolymerization reaction, hydrogen is used for regulating molecular weight, and the hydrogen is used for: 1-butene: the mass ratio of ethylene is 0.09:0.01:1; the reaction pressure is 0.6MPa, the reaction temperature is 84 ℃, and the component A is obtained after 0.7h of reaction;
(2) Adding hexane into a second closed polymerization reaction kettle, adding a catalyst-assisting agent triethylaluminum and MgCl under the condition of stirring 2 TiCl on the upper part 4 Adding ethylene, 1-butene and hydrogen (hydrogen: 1-butene: ethylene mass ratio is 0.01:0.006:1) into a catalyst, and adding a component A to carry out copolymerization; wherein the mass ratio of the polymer component A to the materials in the second closed polymerization reaction kettle before mixing is 1.1:1; the reaction pressure is 0.2MPa, the reaction temperature is 76 ℃, and the reaction is 1.4h to obtain the bimodal polyethylene polymer. The bimodal polyethylene polymer test results are shown in table 1.
Table 1 bimodal polyethylene polymer test results prepared in each example.
Examples 5-8 are stone paper production processes involving the bimodal polyethylene polymers of examples 1-4, operated as follows:
the first stage: banburying and extrusion granulation. The bimodal polyethylene polymer, the processing aid and the stone powder are respectively measured and fed in three feeding tanks, raw materials are banburying by a different-direction double-screw banbury mixer, the banburying block materials enter a single-screw extruder, and are dried and packaged after being granulated by the single-screw extruder, and the materials are ready to enter the next process for standby.
And a second stage: and (5) film blowing. Blowing the banburying and extruding product into film with thickness of 100um. The diameter of the screw rod of the film blowing machine adopted in the invention is 200mm, and the maximum width of blowing can reach 1140mm. The film blowing temperatures were 135, 145, 142, 148, 150×3, 140×4, 155, 150 ℃.
(2) Parameter test mode of stone paper:
1) CV value test method: the ratio of standard deviation to average is called coefficient of variation;
2) Opacity test method: GB/T1543;
3) Volatile matters: calcining in a muffle furnace, and testing the volatilized content;
4) Stiffness testing method: GB/T12914;
5) The whiteness test method comprises the following steps: GB/T7974.
Table 2 parameters of stone paper products prepared in various examples
The bimodal polyethylene polymer provided by the invention is used for stone paper, has good compatibility with calcium carbonate, and the CV value of the prepared stone paper can be less than 3%, and the density is as high as 1.18g/cm 3 And the stiffness is as high as 0.4, and a better technical effect is obtained.
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 that the individual technical features are combined 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 (11)
1. A bimodal polyethylene polymer characterized in that the bimodal polyethylene polymer has a weight average molecular weight of 20X 10 4 -40×10 4 The method comprises the steps of carrying out a first treatment on the surface of the The molecular weight distribution is 10-30; the melt flow ratio (21.6/5.0) is 25-40;
the melt index under the load of 5.0kg at 190 ℃ is 0.01-10g/10min.
2. The bimodal polyethylene polymer according to claim 1, wherein,
the bimodal polyethylene polymer density is 0.95-0.96g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or
The degree of methyl branching is 0.2 to 0.5/100C.
3. The bimodal polyethylene polymer according to claim 1 or 2, wherein,
the melt index of the bimodal polyethylene polymer under the load of 5.0kg at 190 ℃ is 0.05-5g/10min; preferably 0.05-1.8g/10min; and/or
The melt index of the bimodal polyethylene polymer under the load of 2.16kg at 190 ℃ is 0.01-0.2g/10min; and/or
The bimodal polyethylene polymer has a melt index of 6-16g/10min, preferably 10-14g/10min, at 190℃under a load of 21.6 kg.
4. A bimodal polyethylene polymer according to any one of claims 1-3, wherein the bimodal polyethylene polymer comprises: ethylene homopolymers and/or ethylene copolymers; the ethylene copolymer is a copolymer of ethylene monomer and C3-C12 alpha olefin.
5. The bimodal polyethylene polymer according to claim 4, wherein,
the alpha olefin of C3-C12 is selected from alpha olefin of C3-C8;
preferably, the C3-C8 alpha olefin is selected from one or more of propylene, 1-butene, 1-hexane, 4-methyl-1-pentene and 1-octene.
6. A process for the preparation of a bimodal polyethylene polymer as claimed in any one of claims 1 to 5, wherein the process comprises:
(1) Adding ethylene into a reaction system containing a catalyst and a cocatalyst for a first homopolymerization reaction or adding ethylene and C3-C12 alpha olefin for a first copolymerization reaction, and regulating the molecular weight by using hydrogen to obtain a component A;
(2) Adding ethylene and/or C3-C12 alpha-olefin and hydrogen mixed component B into a reaction system containing catalyst and cocatalyst 1 Then adding the component A to carry out a second copolymerization reaction to obtain a bimodal polyethylene polymer; or (b)
Adding ethylene, C3-C12 alpha-olefin and hydrogen into a reaction system containing a catalyst and a cocatalyst to perform a third copolymerization reaction to obtain a polymer component B 2 Then carrying out a second copolymerization reaction with the component A to obtain a bimodal polyethylene polymer;
preferably, component A and component B 1 The mass ratio is 1.1-1.8:1; component A and component B 2 The mass ratio is 1.1-1.8:1.
7. The preparation method according to claim 6, wherein,
the first homopolymerization reaction and the first copolymerization reaction conditions each include: the reaction temperature is 60-100 ℃; the reaction time is 0.5-6 hours; and/or
The second copolymerization reaction conditions include: the reaction temperature is 60-100 ℃; the reaction time is 0.5-6 hours; and/or
The third copolymerization reaction conditions include: the reaction temperature is 60-100 ℃; the reaction time is 0.5-6 hours.
8. The production method according to claim 6 or 7, wherein in the first homo-polymerization reaction or the first copolymerization reaction, hydrogen: the alpha olefin of C3-C12: the mass ratio of the ethylene is (0.002-7.0): 0-3): 1; and/or
In the second copolymerization reaction, hydrogen: the alpha olefin of C3-C12: the mass ratio of the ethylene is (0.002-0.3): (0.002-1): 1.
9. the production process according to any one of claims 6 to 8, wherein,
in the step (1) and the step (2),
the catalyst is at least one selected from the group consisting of Ziegler-Natta catalysts, metallocene catalysts, non-metallocene catalysts and chromium catalysts, preferably Ziegler-Natta catalysts;
preferably, the cocatalyst is selected from one or more of trialkylaluminum, alkylaluminum halides, more preferably, the cocatalyst is selected from triethylaluminum; and/or
The catalyst is supported on a carrier selected from one or more of an aluminum-containing carrier, a silica-containing carrier, and a magnesium dichloride-based carrier.
10. Use of a bimodal polyethylene polymer as claimed in any one of claims 1 to 5 in stone paper.
11. A stone paper, characterised in that it comprises a bimodal polyethylene polymer as claimed in any one of claims 1 to 5.
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