CN106391130A - Catalyst composition for olefin polymerization and preparation method thereof - Google Patents
Catalyst composition for olefin polymerization and preparation method thereof Download PDFInfo
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- CN106391130A CN106391130A CN201610690971.2A CN201610690971A CN106391130A CN 106391130 A CN106391130 A CN 106391130A CN 201610690971 A CN201610690971 A CN 201610690971A CN 106391130 A CN106391130 A CN 106391130A
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- polystyrene resin
- ethylenediamine
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract description 8
- 150000001336 alkenes Chemical class 0.000 title abstract description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 18
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 18
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920005990 polystyrene resin Polymers 0.000 claims abstract description 17
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 9
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 9
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 9
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 8
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 8
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 8
- 229910000080 stannane Inorganic materials 0.000 claims description 8
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- KXCAEQNNTZANTK-UHFFFAOYSA-N stannane Chemical compound [SnH4] KXCAEQNNTZANTK-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 4
- 239000005977 Ethylene Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000006384 oligomerization reaction Methods 0.000 abstract description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 abstract 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- 239000011734 sodium Substances 0.000 abstract 1
- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-UHFFFAOYSA-N 0.000 abstract 1
- 239000008096 xylene Substances 0.000 abstract 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- -1 ethylene, propylene Chemical group 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 238000010668 complexation reaction Methods 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000006894 reductive elimination reaction Methods 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- B01J35/19—
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/122—Metal aryl or alkyl compounds
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
- B01J31/1658—Polymer immobilised coordination complexes, e.g. organometallic complexes immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/24—Catalytic processes with metals
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
- C07C2531/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24 of titanium, zirconium or hafnium
Abstract
The invention discloses a catalyst composition for olefin polymerization and a preparation method thereof. The catalyst composition is prepared from 20-30 parts by weight of chloracetylated polystyrene resin, 1-2 parts by weight of ethylenediamine, 4-6 parts by weight of sodium bicarbonate, 0.3-0.5 parts by weight of isopropyl chloroplatinate, 4-5 parts by weight of zirconium tetrachloride, 2-4 parts by weight of sodium metaaluminate, 1-2 parts by weight of tributylstannane, 2-3 parts by weight of triisobutylaluminum, 4-6 parts by weight of carboxymethyl cellulose, 80-100 parts by weight of tetrahydrofuran, 150-200 parts by weight of anhydrous ethanol, and a proper amount of acetone and xylene. The catalyst composition provided by the invention has high activity in an ethylene oligomerization reaction, has a simple system, is easy to prepare and control and has little damage to the environment.
Description
Invention field
The invention belongs to chemical material field, concretely relate to a kind of carbon monoxide-olefin polymeric for olefinic polymerization and
Its preparation method.
Background technology
The whole world widely uses polymer and the copolymer of lower alpha-olefins at present, and particularly ethylene, propylene and butylene gathers
Compound.The general manufacturing price of these polymer products is relatively low, and they show many useful Business Performances.Work as vinyl polymerization
When, method is thus relatively uncomplicated, because ethylene molecule is added to the side in the polymer chain of growth during product types are not polymerized
The impact of formula.The polymer product of ethylene is not typically presented in stereoisomer.However, when propylene polymerization,
On polymer chain, the presence of pending methyl group result in several stereomeric probabilities, depends on propylene molecules to be added on growing chain
Mode.Most of commercial polypropylene are derived from the propylene molecules stereospecific addition of isotactic configuration.Containing three-dimensional in a large number
The polymer molecule of irregular propylene units is unbodied, or amorphous, and this form is not as isotactic form
By demand.
Mechenism of diene polymerization is the theme of great majority research it is believed that including producing a undersaturated electron deficiency metal kind,
It forms intermediate alkyl olefin complex with olefin complexation, subsequently carries out quick transalkylation reaction to provide a polymerization
Thing growing chain.The reaction retransferring after olefin complexation is carried out continuously, until carrying out terminating step or reaction stopping.Adopt several at present
Kind of method is producing and to stablize the unsaturated electron deficiency metallic catalyst of these catalyst system and catalyzings.Activated transition metal coordination compound comes
The stable unsaturation transition-metal catalyst process of offer olefinic polyreaction is the key component of this mechanism.Adopt several at present
The method of kind, to produce and to stablize the unsaturated electron deficiency metallic catalyst of these catalyst system and catalyzings, including taking halogen reaction by force, protonates anti-
Should, the then Reductive elimination reaction of alkane or hydrogen or oxidation reaction.Remain to combination property in olefin(e) oligomerization field
The demand of excellent new catalyst.Therefore, how to obtain the Novel Ligands compound for olefin oligomerization catalyst, thus opening
Send there is high activity and selective olefin polymerization catalysis be the present invention research emphasis.
Content of the invention
It is an object of the invention to provide a kind of carbon monoxide-olefin polymeric for olefinic polymerization and preparation method thereof.
For reaching above-mentioned purpose, the technical solution used in the present invention is：
A kind of carbon monoxide-olefin polymeric for olefinic polymerization, is formed by the preparation of raw material of following weight portion：Chloroacetylation polyphenyl second
Olefine resin 20-30, ethylenediamine 1-2, sodium bicarbonate 4-6, chloroplatinic acid 0.3-0.5, isopropanol 5-8, Zirconium tetrachloride. 4-5, tetrahydroxy
Close sodium aluminate 2-4, trialkyl stannane 1-2, triisobutyl aluminium 2-3, carboxymethyl cellulose 4-6, oxolane 80-100, anhydrous
Ethanol 150-200, acetone in proper, appropriate dimethylbenzene.
A kind of preparation method of the carbon monoxide-olefin polymeric for olefinic polymerization, comprises the following steps：
（1）Chloracetylated polystyrene resin, oxolane are placed in soaking at room temperature 20-24 h in reactor, are subsequently adding second
Diamidogen, sodium bicarbonate stir, and are then heated to 60-65 DEG C of insulation 15-20h, using washing with acetone and dry after washing, obtain
To ethylenediamine modification chloracetylated polystyrene resin；
（2）Ethylenediamine modification chloroethene acidifying polystyrene resins, dehydrated alcohol, chloroplatinic acid, isopropanol are added under nitrogen protection
Heat, to 70-75 DEG C, is first cooled to room temperature and stops logical nitrogen again after insulation 30-35h, through filtering, being dried, obtain ethylenediamine modification chlorine
Acetylized Polystyrene resin solid-borne platinum catalyst；
（3）Ethylenediamine modification chloracetylated polystyrene resin solid-borne platinum catalyst is added in dimethylbenzene, then adds four
Zirconium chloride, tetrahydroxy close sodium aluminate, trialkyl stannane, triisobutyl aluminium, carboxymethyl cellulose, in 160-180 DEG C of temperature
Under carry out hybrid reaction 8-10h, be dried after removing solvent, obtain final product described carbon monoxide-olefin polymeric.
Beneficial effects of the present invention：
When the carbon monoxide-olefin polymeric that the present invention provides carries out ethylene oligomerization reaction, catalyst activity is high, and catalyst system and catalyzing is relatively simple,
Easily prepared and be controlled, little to environmental hazard.
Specific embodiment
With reference to specific embodiment, technical scheme of the present invention is further described.
Embodiment 1：
A kind of carbon monoxide-olefin polymeric for olefinic polymerization, by following weight portion（kg）Preparation of raw material form：Chloroacetylation gathers
Styrene resin 20, ethylenediamine 1, sodium bicarbonate 4, chloroplatinic acid 0.3, isopropanol 5, Zirconium tetrachloride. 4, tetrahydroxy close sodium aluminate 2, three
Alkyl stannane 1, triisobutyl aluminium 2, carboxymethyl cellulose 4, oxolane 80, dehydrated alcohol 150, acetone in proper, dimethylbenzene
In right amount.
A kind of preparation method of the carbon monoxide-olefin polymeric for olefinic polymerization, comprises the following steps：
（1）Chloracetylated polystyrene resin, oxolane are placed in soaking at room temperature 20-24 h in reactor, are subsequently adding second
Diamidogen, sodium bicarbonate stir, and are then heated to 60-65 DEG C of insulation 15-20h, using washing with acetone and dry after washing, obtain
To ethylenediamine modification chloracetylated polystyrene resin；
（2）Ethylenediamine modification chloroethene acidifying polystyrene resins, dehydrated alcohol, chloroplatinic acid, isopropanol are added under nitrogen protection
Heat, to 70-75 DEG C, is first cooled to room temperature and stops logical nitrogen again after insulation 30-35h, through filtering, being dried, obtain ethylenediamine modification chlorine
Acetylized Polystyrene resin solid-borne platinum catalyst；
（3）Ethylenediamine modification chloracetylated polystyrene resin solid-borne platinum catalyst is added in dimethylbenzene, then adds four
Zirconium chloride, tetrahydroxy close sodium aluminate, trialkyl stannane, triisobutyl aluminium, carboxymethyl cellulose, in 160-180 DEG C of temperature
Under carry out hybrid reaction 8-10h, be dried after removing solvent, obtain final product described carbon monoxide-olefin polymeric.
Embodiment 2：
A kind of carbon monoxide-olefin polymeric for olefinic polymerization, by following weight portion（kg）Preparation of raw material form：Chloroacetylation gathers
Styrene resin 25, ethylenediamine 1.5, sodium bicarbonate 5, chloroplatinic acid 0.4, isopropanol 6, Zirconium tetrachloride. 4.5, tetrahydroxy close sodium aluminate
3rd, trialkyl stannane 1.5, triisobutyl aluminium 2.5, carboxymethyl cellulose 5, oxolane 90, dehydrated alcohol 175, acetone are fitted
Amount, appropriate dimethylbenzene.
Preparation method is with embodiment 1.
Embodiment 3：
A kind of carbon monoxide-olefin polymeric for olefinic polymerization, by following weight portion（kg）Preparation of raw material form：Chloroacetylation gathers
Styrene resin 30, ethylenediamine 2, sodium bicarbonate 6, chloroplatinic acid 0.5, isopropanol 8, Zirconium tetrachloride. 5, tetrahydroxy close sodium aluminate 4, three
Alkyl stannane 2, triisobutyl aluminium 3, carboxymethyl cellulose 6, oxolane 100, dehydrated alcohol 200, acetone in proper, dimethylbenzene
In right amount.
Preparation method is with embodiment 1.
The performance test results such as following table institute of the carbon monoxide-olefin polymeric for olefinic polymerization that above-described embodiment 1-3 is obtained
Show：
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Activity, 106g.mol/L.h | 3.7 | 4.6 | 2.8 |
| Isotactic index, % | 98.5 | 97.8 | 98.5 |
| C4Content, % | 17.5 | 18.7 | 18.4 |
| C6-C18Content, % | 78.6 | 79.2 | 76.5 |
Claims (2)
1. a kind of carbon monoxide-olefin polymeric for olefinic polymerization is it is characterised in that formed by the preparation of raw material of following weight portion：Chlorine
Acetylized Polystyrene resin 20-30, ethylenediamine 1-2, sodium bicarbonate 4-6, chloroplatinic acid 0.3-0.5, isopropanol 5-8, four chlorinations
Zirconium 4-5, tetrahydroxy close sodium aluminate 2-4, trialkyl stannane 1-2, triisobutyl aluminium 2-3, carboxymethyl cellulose 4-6, tetrahydrochysene furan
Mutter 80-100, dehydrated alcohol 150-200, acetone in proper, appropriate dimethylbenzene.
2. a kind of carbon monoxide-olefin polymeric for olefinic polymerization according to claim 1 preparation method it is characterised in that
Comprise the following steps：
（1）Chloracetylated polystyrene resin, oxolane are placed in soaking at room temperature 20-24 h in reactor, are subsequently adding second
Diamidogen, sodium bicarbonate stir, and are then heated to 60-65 DEG C of insulation 15-20h, using washing with acetone and dry after washing, obtain
To ethylenediamine modification chloracetylated polystyrene resin；
（2）Ethylenediamine modification chloroethene acidifying polystyrene resins, dehydrated alcohol, chloroplatinic acid, isopropanol are added under nitrogen protection
Heat, to 70-75 DEG C, is first cooled to room temperature and stops logical nitrogen again after insulation 30-35h, through filtering, being dried, obtain ethylenediamine modification chlorine
Acetylized Polystyrene resin solid-borne platinum catalyst；
（3）Ethylenediamine modification chloracetylated polystyrene resin solid-borne platinum catalyst is added in dimethylbenzene, then adds four
Zirconium chloride, tetrahydroxy close sodium aluminate, trialkyl stannane, triisobutyl aluminium, carboxymethyl cellulose, in 160-180 DEG C of temperature
Under carry out hybrid reaction 8-10h, be dried after removing solvent, obtain final product described carbon monoxide-olefin polymeric.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610690971.2A CN106391130A (en) | 2016-08-20 | 2016-08-20 | Catalyst composition for olefin polymerization and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610690971.2A CN106391130A (en) | 2016-08-20 | 2016-08-20 | Catalyst composition for olefin polymerization and preparation method thereof |
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| Publication Number | Publication Date |
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| CN106391130A true CN106391130A (en) | 2017-02-15 |
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| CN201610690971.2A Pending CN106391130A (en) | 2016-08-20 | 2016-08-20 | Catalyst composition for olefin polymerization and preparation method thereof |
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| Country | Link |
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| CN (1) | CN106391130A (en) |
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