CN1939935B - Removal of catalyst impurities from olefine polymer - Google Patents
Removal of catalyst impurities from olefine polymer Download PDFInfo
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- CN1939935B CN1939935B CN2005101054315A CN200510105431A CN1939935B CN 1939935 B CN1939935 B CN 1939935B CN 2005101054315 A CN2005101054315 A CN 2005101054315A CN 200510105431 A CN200510105431 A CN 200510105431A CN 1939935 B CN1939935 B CN 1939935B
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Abstract
Method for removing catalyst impurity from olefin polymer is carried out by diluting 1-10wt% silicate gelling agent into silicate solution A, diluting olefin polymer into solution B by 0-3 time organic solvent, adding solution B into solution A while strongly agitating at 700-1200 circle/min to form solution C, adding 0.5-4wt% coagulating agent into solution C while agitating, laminating, filtering and removing to obtain the final product. It's simple and convenient, has less ashes and lower content of metal Ti and Al.
Description
Technical field
The present invention relates to a kind of method that from olefin polymer, removes catalyst impurities, more particularly, the present invention relates to handle olefin polymer, remove catalyst impurities, thereby obtain the method for pure olefin polymer with silicate gelling agent.
Background technology
In the process of olefinic polymerization, need to use catalyzer, as Ziegler-Natta catalyst.Because therefore separation difficulty in olefin polymer, often contains catalyzer and impurity that a certain amount of needs are removed.This type of catalyzer or impurity are many to be existed with colloidal state, is difficult to remove totally with conventional sedimentation or filtering method.JP79-126291, JP79-114592, JP99-106425, JP99-240915, patents such as DE2729236 have been introduced the Ziegler-Natta catalyst that removes in the polymer slurries and the method for impurity, are the method for washing with pure esterification/washing or pure esterification/alcohol.These class methods have reduced metal content and ash in the product, but in the operating process or need nitrogen protection or need under pressure, operate, the easy emulsification of material, not easily separated, bring difficulty to operation.
USP4204946 has introduced among USP4420389 and the USP4705622 and has a kind ofly handled various mink cell focuses with the aqueous solution of ammonium salt or phosphonium salt under certain pressure, to remove the impurity extracting method; Introduced among the USP4539099 and a kind ofly handled oil product as jelling agent with alkoxyl group phenolic resin ethylene glycol fat, and then filtering method.The former needs pressurized operation, and is higher to equipment requirements; As jelling agent, cost is higher with alkoxyl group resol ethylene glycol for the latter.
Introduced among the CN1030282C and a kind ofly from olefin polymer and mink cell focus, removed the method for impurity, it is characterized in that in the material that contains impurity, adding silicate gelling agent, removed impurity by silicate gelling agent and interaction and impurities with silicate gelling agent.But also there is certain defective in this method: after adding condensing agent, the silicate gelling agent that comprises impurity condenses into bigger gel piece, gel piece is deposited on reactor wall and the pipeline, cause the obstruction of reactor valves and pipeline easily, be difficult to separate complete with methods such as general centrifugal, filtration, sedimentation and washings, implementation result is poor; Impure material and the two proportion of silicate gelling agent differ bigger, and the contact effect is bad, make in olefin polymer after the processing or the mink cell focus foreign matter content still higher.
Summary of the invention
The present invention overcomes the shortcoming of prior art, and a kind of method of removing catalyst impurities in the deolefination polymkeric substance is provided.
Characteristics of the present invention are olefin polymer is added in the silicate solutions, and the interaction by silicate gelling agent and colloid or solid impurity makes catalyst impurities and liquid separation.Concrete operations are as follows, and the add-on of each material is a benchmark with the weight of olefin polymer:
(1) the silicate gelling agent with 1-10 weight % is diluted with water to silicate solutions A, and the water yield is 10-20 a times of silicate gelling agent weight,
(2) olefin polymer is formed solution B with 0-3 organic solvent diluting doubly,
(3) under 700-1200 rev/min brute force stirring, solution B is added in the solution A, stirs and form solution C,
(4) in solution C, add 0.5-4 weight % condensing agent and fully stirring,
(5) layering is filtered, and removes impurity, obtains purified olefin polymer.
During standing demix, can wash upper oil phase 1-3 time with water.
Silicate gelling agent of the present invention is commonly called as water glass or silicon sol, and its modulus is 1-4, preferred 2-3; The preferred 3-7 weight of consumption %.
Condensing agent of the present invention is selected from low mass molecule alcohol or low molecular acid, as methyl alcohol, ethanol, or acetic acid, oxalic acid, sulfuric acid.The preferred 1-2 weight of the consumption of low mass molecule alcohol or low molecular acid condensing agent %.
Organic solvent of the present invention is alkanes, olefines, aromatic hydrocarbons, or their mixture, or the solvent of other energy dissolved olefin polymkeric substance, and its consumption is 0-3 a times of olefin polymer weight.
It is C that described olefin polymer typically refers to the carbon number
6-C
30Soap wax destructive distillation mixed olefins and/or pure alpha-olefin (containing two keys or a plurality of pairs of keys) be raw material, at Ziegler-Natta catalyst, i.e. TiCl
3/ Al (i-C
4H
9)
3Effect under polymerization, thereby the mixture of olefin polymer that obtains and Ziegler-Natta catalyst.Wherein, the molecular weight of product olefin polymer is between 10-300 ten thousand, and Ti, Al residual content are 2300-2600 μ g/g.
The powerful stirring of the present invention is different from common stirring, and is meant that rotating speed surpasses 700 rev/mins stirring, selects 700-1200 rev/min.Stir by brute force and can make these two proportion of olefin polymer and silicate solutions differ very big material thorough mixing; Catalyst impurities and silicate gelling agent in the olefin polymer are fully acted on; After adding condensing agent, the silicate gelling agent that comprises catalyst impurities is distributed in the water rapidly.
Compared with prior art, beneficial effect of the present invention is mainly reflected in following aspect:
(1) silicate gelling agent can be well with the olefin polymer thorough mixing, separate;
(2) the Canon of ash drops to below the 50 μ g/g in the olefin polymer after handling through this method, and the Canon of the content of Ti, Al metal drops to below the 10 μ g/g;
(3) easy and simple to handle, equipment requirements is simple, and raw material is easy to get and is cheap.
The present invention is applicable to the process that removes catalyst impurities from olefin polymer, is specially adapted to remove from the olefin polymer as pour depressant for lubricating oil and lubricating oil dewaxing auxiliary agent the process of catalyst impurities.
Embodiment
Following example will give further instruction to method provided by the invention, but therefore the present invention is not subjected to any restriction.
Handled olefin polymer all is to be C with the carbon number in the example
6-C
30Soap wax destructive distillation mixed olefins and/or pure alpha-olefin (containing two keys or a plurality of pairs of keys) be raw material, at Z-N TiCl
3/ Al (i-C
4H
9)
3The olefin polymer that polymerization obtains under the effect of catalyzer and the mixture of Ziegler-Natta catalyst.
The silicon sol that used silicate gelling agent is produced for the water glass plant, Tianjin in the example.Used low mass molecule alcohol is the ethanol of concentration 95%, and used low molecular acid is a Glacial acetic acid, is the Beijing Chemical Plant and produces.
Embodiment 1
It with molecular weight 600,000 100g olefin polymer is made olefin polymer with the dilution of 100g xylene soluble xylene solution.In the 500ML there-necked flask, adding 3g modulus is 2.2 silicon sol and 100g water, stirs 20 minutes down at 85-90 ℃.In speed is the xylene solution that adds olefin polymer under 700 rev/mins brute force stirs gradually, holding temperature 85-90 ℃, and powerful the stirring 40 minutes.Add 1.5g ethanol down at 65 ℃ then, continue to stir 30 minutes.Standing demix is removed lower layer of water suspension, and the hot water that adds one times of amount is washed oil phase 1 time, removes lower floor's water.Upper oil phase is filtered, steam at last and remove unreacted reactant and dimethylbenzene, obtain the polyolefine behind the purifying.The content of metal Ti, Al and ash in test underlying condition and the polyolefine sees Table 1.
Embodiment 2-8
Test underlying condition sees Table 1, and all the other steps are with example 1.Obtain the polyolefine behind the purifying.The content of the metal Ti in the polyolefine, Al and ash sees Table 1.
Comparative Examples 1
With molecular weight is that 310,000 200g olefin polymer places the 500ML there-necked flask, adds 10g concentration and be 95% ethanol under nitrogen protection, is heated to 65 ℃, stirs, and makes its esterification, generates water-soluble titanium and/or aluminic acid ester; After adding the dilution of 100g kerosene, use tap water, extremely neutral at 85 ℃ of following agitator treatings.Use 100g150SN turbine oil (production of Dalian oil seven factories) dilution again, steam then and remove unreacted reactant and kerosene, obtain the polyolefine pour point depressant behind the purifying.The content of its metal Ti, Al and ash sees Table 1.
Comparative Examples 2
With molecular weight is that 310,000 100g olefin polymer places the 500ML there-necked flask, adding 7g modulus is 2.8 silicon sol, common stirring is 40 minutes under 75 ℃, the ethanol that adds 2g concentration 95% again continues to stir 10 minutes, the centrifugal slag that takes off, steam to remove unreacted alkene, obtain the polyolefine pour point depressant behind the purifying.The content of reaction conditions and metal Ti, Al and ash sees Table 1.
Claims (10)
1. a method that removes catalyst impurities from olefin polymer may further comprise the steps, and the add-on of each material is a benchmark with the weight of olefin polymer:
(1) the silicate gelling agent with 1-10 weight % is diluted with water to silicate solutions A, and the water yield is 10-20 a times of silicate gelling agent weight,
(2) olefin polymer is formed solution B with 0-3 organic solvent diluting doubly,
(3) under 700-1200 rev/min brute force stirring, solution B is added in the solution A, forms solution C,
(4) in solution C, add 0.5-4 weight % condensing agent and fully stirring,
(5) layering is filtered, and removes impurity, obtains purified olefin polymer.
2. according to the described method that removes catalyst impurities of claim 1, the molecular weight that it is characterized in that described olefin polymer is 10-300 ten thousand.
3. according to the described method that removes catalyst impurities of claim 1, it is characterized in that described olefin polymer is is C with the carbon number
6-C
30Soap wax destructive distillation mixed olefins and/or pure alpha-olefin be raw material, at Z-N TiCl
3/ Al (i-C
4H
9)
3The olefin polymer that polymerization obtains under the effect of catalyzer.
4. according to the described method that removes catalyst impurities of claim 1, it is characterized in that described silicate gelling agent is that modulus is water glass or the silicon sol of 1-4.
5. according to the described method that removes catalyst impurities of claim 4, it is characterized in that described silicate gelling agent is that modulus is water glass or the silicon sol of 2-3.
6. according to the described method that removes catalyst impurities of claim 1, it is characterized in that described silicate gelling agent consumption is 3-7 weight %.
7. according to the described method that removes catalyst impurities of claim 1, it is characterized in that described organic solvent is selected from alkanes, olefines, aromatic hydrocarbons, or their mixture, or the solvent of other energy dissolved olefin polymkeric substance.
8. according to the described method that removes catalyst impurities of claim 1, it is characterized in that described condensing agent is methyl alcohol or ethanol.
9. according to the described method that removes catalyst impurities of claim 1, it is characterized in that described condensing agent is acetic acid, oxalic acid or sulfuric acid.
10. according to the described method that removes catalyst impurities of claim 1, it is characterized in that described condensing agent consumption is 1-2 weight %.
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| CN2005101054315A CN1939935B (en) | 2005-09-28 | 2005-09-28 | Removal of catalyst impurities from olefine polymer |
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| CN2005101054315A CN1939935B (en) | 2005-09-28 | 2005-09-28 | Removal of catalyst impurities from olefine polymer |
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| CN1939935B true CN1939935B (en) | 2010-04-14 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977230B (en) * | 2011-09-05 | 2015-07-01 | 中国石油化工股份有限公司 | Method for removing hydrogenation catalyst in polymer solution |
| CN108219034B (en) * | 2016-12-09 | 2020-02-18 | 中国石油化工股份有限公司 | Catalyst removal method of ethylene propylene rubber liquid containing vanadium catalyst, ethylene propylene rubber and preparation method thereof |
| CN116253825A (en) * | 2021-12-09 | 2023-06-13 | 乐凯化学材料有限公司 | Method for removing small molecules in maleic anhydride/alpha-olefin copolymer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1520513A1 (en) * | 1961-12-05 | 1969-04-10 | Polymer Corp | Process for the treatment of polymer solutions |
| US4770782A (en) * | 1985-02-22 | 1988-09-13 | Exxon Chemical Patents Inc. | Method for preventing gel/emulsion formation |
| CN1058351A (en) * | 1990-07-23 | 1992-02-05 | 中国石油化工总公司石油化工科学研究院 | From olefin polymer or mink cell focus, remove the method for impurity |
-
2005
- 2005-09-28 CN CN2005101054315A patent/CN1939935B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1520513A1 (en) * | 1961-12-05 | 1969-04-10 | Polymer Corp | Process for the treatment of polymer solutions |
| US4770782A (en) * | 1985-02-22 | 1988-09-13 | Exxon Chemical Patents Inc. | Method for preventing gel/emulsion formation |
| CN1058351A (en) * | 1990-07-23 | 1992-02-05 | 中国石油化工总公司石油化工科学研究院 | From olefin polymer or mink cell focus, remove the method for impurity |
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