CN102731695B - New preparation method for drag reducer polymer - Google Patents
New preparation method for drag reducer polymer Download PDFInfo
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- CN102731695B CN102731695B CN201210203122.1A CN201210203122A CN102731695B CN 102731695 B CN102731695 B CN 102731695B CN 201210203122 A CN201210203122 A CN 201210203122A CN 102731695 B CN102731695 B CN 102731695B
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Abstract
The purpose of the present invention is to overcome problems of difficult material discharging, complex subsequent operations, and the like in the old process. According to the present invention, a new process adopting a small kettle to carry out controllable pre-polymerization is adopted, and is used in production of a HG pipe oil product drag reducer polymer. The preparation method for the drag reducer polymer can comprises the following steps: 1) adding an inert solvent, a small amount of a monomer, an assistant catalyst and a main catalyst to a pre-polymerization autoclave, and carrying out a polymerization reaction at a low temperature, such that the catalyst particles are suspended in the polyolefin solution to form a slurry with moderate viscosity; and 2) adding a monomer, an assistant catalyst, an external electron donor, and the material inside the pre-polymerization autoclave to a small reaction vessel according to a certain amounts, and carrying out polymerization.
Description
Technical field
The present invention relates to a kind of preparation method of high molecular polymer, particularly a kind of preparation method of drag reducer polymerization thing.
Background technology
As the superpolymer of oil phase dra, drag-reduction effect is reasonable is at present mainly alpha-olefin homo and multipolymer thereof.The general polymerization single polymerization monomer adopting is 1-octene, 1-decene, 1-laurylene and 1-hexadecylene etc., and Primary Catalysts adopts solvay-type titanous chloride, and promotor adopts aluminum alkyls.
Olefinic polymerization belongs to the polymerization of coordination ion type, it is a kind of polyreaction of carrying out under complex catalyst effect, conventionally polymerization process is that first complexing occurs for monomer and catalyzer (should be called exactly initiator), through transition state, monomer " insertion ", between living chain and catalyzer, increases living chain.
The current domestic two kinds of production methods that mainly contain.One method adopts monomer and catalyzer prepolymerization in prepolymerization kettle, until catalyzer no longer after sedimentation, divides and installs to little reaction vessel (the domestic plastics bag that is generally) from bleeder valve at the bottom of prepolymerization kettle, then in little reaction vessel, completes polymerization.Specifically can be referring to document " progress of oil product drag reducer " author Zuo Yanmei, Yangzhou Industry Polytechnic College's collection of essay, 01 phase in 2010.But there is obvious defect in the method, mainly: the limited time of (1) discharging.Material in prepolymerization kettle, as do not drained in time within half an hour, exists material viscosity excessive so that stop up the danger of bleeder valve, and operation easier is large; (2) in the arm little reaction vessel, be full of pre-polymerization liquid from bleeder valve, pre-polymerization liquid residual after discharging continues polymerization, causes arm to be stopped up by solid-state flow improver, is difficult to cleaning; (3), in discharging process, temperature of charge may go up to approaching room temperature, cause should low-temp reaction material at room temperature reaction, quality product is defective.
Another kind method is to operate in vacuum glove box, wherein respectively monomer and catalyzer is weighed and is added in little reaction vessel in vacuum glove box, then proceeds to and in refrigeration chamber, carries out polymerization.The method because operate in vacuum glove box, and pump drainage displaced air and handling material are very loaded down with trivial details.
Summary of the invention
the problem that invention will solve
For overcoming aging method discharging difficulty, the problems such as subsequent operations complexity, the inventor proposes to adopt the novel method of the controlled pre-polymerization of little still, is applied to HG drag reduction agent for oil product through pipelines polymer production.
for the scheme of dealing with problems
In order to address the above problem, the invention provides a kind of preparation method of drag reducer polymerization thing, it is characterized in that,
1) monomer, promotor and external electron donor are added in mixing kettle, stir, be cooled to-10 DEG C～10 DEG C;
2) in prepolymerization kettle, add monomer, promotor and the Primary Catalysts of 1 quality % to 5 quality % of inert solvent, inert solvent, carry out polyreaction at-10 DEG C～10 DEG C, form granules of catalyst and be suspended in the slurries of pre-polymer solution;
3) respectively the slurries in the mixture in mixing kettle and prepolymerization kettle are added in little reaction vessel according to the mass ratio of 20:1 to 100:1, then carry out polymerization at-10 DEG C～10 DEG C.
In order to address the above problem, the invention provides the preparation method of another kind of drag reducer polymerization thing, it is characterized in that,
1) in prepolymerization kettle, add monomer, promotor and the Primary Catalysts of 1 quality % to 5 quality % of inert solvent, inert solvent, carry out polyreaction at-10 DEG C～10 DEG C, form granules of catalyst and be suspended in the slurries of pre-polymer solution;
2) by monomer, promotor and external electron donor, and slurries in prepolymerization kettle add in little reaction vessel, the mass ratio of the slurries in the total mass of described monomer, promotor and the external electron donor wherein adding and the prepolymerization kettle adding is 20:1 to 100:1, then at-10 DEG C～10 DEG C temperature, carries out polymerization.
The preparation method of drag reducer polymerization thing of the present invention, it is characterized in that, in described little reaction vessel, quality based on total material in little reaction vessel before reaction, the concentration range of monomer and prepolymer is 97 quality %～99.8 quality %, the concentration range of Primary Catalysts is 0.005 quality %～0.1 quality %, and the concentration range of promotor is 0.1 quality %～3 quality %, and the concentration range of external electron donor is 0.01 quality %～0.5 quality %.
The preparation method of drag reducer polymerization thing of the present invention, is characterized in that, described Primary Catalysts is titanous chloride or titanium tetrachloride.
The preparation method of drag reducer polymerization thing of the present invention, is characterized in that, described promotor is triethyl aluminum or triisobutyl aluminium.
The preparation method of drag reducer polymerization thing of the present invention, is characterized in that, described external electron donor is diisopropyl dimethoxy silane and the dicyclopentyl dimethoxyl silane of mass ratio 5:1～1:5.
The preparation method of drag reducer polymerization thing of the present invention, is characterized in that, described monomer is C
6～C
20alpha-olefin.
The preparation method of drag reducer polymerization thing of the present invention, is characterized in that, described solvent is normal heptane or octane or normal hexane.
The preparation method of drag reducer polymerization thing of the present invention, is characterized in that, described little reaction vessel is pocket type reaction vessel.
The preparation method of drag reducer polymerization thing of the present invention, is characterized in that, the viscosity of the described slurries that form in prepolymerization kettle is 100mPas to 1000mPas.
the effect of invention
Monomer concentration in control prepolymerization kettle of the present invention keeps lower level, even if the whole polymerizations of the monomer in prepolymerization kettle also can not be solidified.Therefore there is not the danger of line clogging in prepolymerization kettle, and the subsequent operations time is also very abundant.
Embodiment
The present invention has developed a kind of new process for producing of drag reducer polymerization thing, thereby synthetic HG drag reduction agent for oil product through pipelines is applied to long distance oil pipeline, improves pipeline transmission capacity.
The preparation method of drag reducer polymerization thing of the present invention, can comprise the following steps: 1) in prepolymerization kettle, add inert solvent, a small amount of monomer, promotor and Primary Catalysts, carry out at low temperatures polyreaction, formation granules of catalyst is suspended in the slurries of the modest viscosity of polyolefin solution; 2) respectively by monomer, promotor and external electron donor, and material dosing in prepolymerization kettle adds in little reaction vessel, then carries out polymerization.Wherein the 2nd) monomer, promotor and the external electron donor that add in step can be added into respectively little reaction vessel, and also can in mixing kettle, mix in advance, and stirring, be added into together less reaction vessel after cooling.The present invention preferably first mixes monomer, promotor and external electron donor in mixing kettle, cooling.
Little reaction vessel described in the present invention refers to that capacity is the reaction vessel that 1-50 rises, and is preferably pocket type reaction vessel, its capacity is preferably 1 and rises to 10 liters.There is no particular limitation for the material of described little reaction vessel, as long as it is inertia for reaction of the present invention.
Polymerization temperature in prepolymerization kettle is generally-10 DEG C～10 DEG C, is preferably-5 DEG C～5 DEG C.In little reaction vessel, the temperature of polymerization is generally-10 DEG C～10 DEG C, is preferably-5 DEG C～5 DEG C.In mixing kettle, cooling temperature is-10 DEG C～10 DEG C, is preferably-5 DEG C～5 DEG C.
Drag reducer polymerization thing of the present invention comprises the homopolymer of alpha-olefin or the multipolymer of alpha-olefin, or its mixture.The general monomer adopting is C
6～C
20alpha-olefin, be for example 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-hendecene, 1-laurylene and 1-hexadecylene etc., preferably C
8～C
16alpha-olefin.Polymkeric substance can be the homopolymer of alpha-olefin, can be also the multipolymer of two or more alpha-olefin.Preferably use 1-octene, 1-decene and/or 1-laurylene, more preferably use 1-octene, 1-decene and 1-laurylene as comonomer simultaneously.
As Primary Catalysts, can use titanous chloride or titanium tetrachloride, wherein preferred titanous chloride.Promotor can use triethyl aluminum or triisobutyl aluminium, preferably triisobutyl aluminium.
The solution using in the present invention comprises normal heptane, octane or normal hexane.Wherein, preferred normal heptane.
In method of the present invention, the external electron donor of use can be diisopropyl dimethoxy silane and dicyclopentyl dimethoxyl silane, and its mass ratio can be 5:1～1:5, and preferably its mass ratio is 2.5:1～1:2.5.
Embodiment
Embodiment 1
(1) triisobutyl aluminium of 1.2 kilograms of the octene of 200 kilograms of the monomers after purifying, the decene of 150 kilograms, the laurylene of 150 kilograms and promotors and external electron donor 65 grams (weight ratio diisopropyl dimethoxy silanes: dicyclopentyl dimethoxyl silane=5:1) are added in mixing kettle and stirred be cooled to-10 DEG C, monomer does not carry out polyreaction;
(2) in prepolymerization kettle, add the normal heptane of 11 kilograms (approximately containing 3 quality % octenes), then add the triisobutyl aluminium of 0.3 kilogram, be cooled to after-10 DEG C, add 100g titanous chloride (titanium content 2.7 quality %) by catalyst charging hole.Under agitation react the slurries that obtain a kind of granules of catalyst for 30 minutes and be suspended in the viscosity 100mPa.s to 1000mPa.s of polyolefin solution.
(3) with peristaltic pump, the material in mixing kettle and prepolymerization kettle is quantitatively added in little reaction vessel according to the weight ratio of 50:1 respectively, then put into freezer-10 DEG C～10 DEG C and carry out polymerization.
Embodiment 2
(1) add the interior also stirring of mixing kettle to be cooled to-10 DEG C the octene of 150 kilograms of the monomers after purifying, the decene of 150 kilograms, the laurylene of 200 kilograms and triisobutyl aluminium and the external electron donor 65 grams (weight ratio diisopropyl dimethoxy silanes: dicyclopentyl dimethoxyl silane=1:5) of promotor 1.3, monomer does not carry out polyreaction;
(2) in prepolymerization kettle, add the solvent of 11 kilograms (approximately containing 3 quality % octenes), then add 0.2 kilogram of triisobutyl aluminium, be cooled to after-5 DEG C, add 100g titanous chloride (titanium content 2.7 quality %) by catalyst charging hole.Under agitation react the slurries that obtain a kind of granules of catalyst for 40 minutes and be suspended in the viscosity 100mPa.s to 1000mPa.s of polyolefin solution.
(3) with peristaltic pump, the material in mixing kettle and prepolymerization kettle is quantitatively added in little reaction vessel according to the weight ratio of 40:1 respectively, then put into freezer-10 DEG C～10 DEG C and carry out polymerization.
Claims (5)
1. a preparation method for drag reducer polymerization thing, is characterized in that,
1) monomer, promotor and external electron donor are added in mixing kettle, stir, be cooled to-10 DEG C～10 DEG C;
2) in prepolymerization kettle, add monomer, promotor and the Primary Catalysts of 1 quality % to 5 quality % of inert solvent, inert solvent, carry out polyreaction at-10 DEG C～10 DEG C, form the slurries that granules of catalyst is suspended in pre-polymer solution, the viscosity of described slurries is 100mPas to 1000mPas;
3) respectively the slurries in the mixture in mixing kettle and prepolymerization kettle are added in little reaction vessel according to the mass ratio of 20:1 to 100:1, then carry out polymerization at-10 DEG C～10 DEG C;
Wherein, described monomer is C
6～C
20alpha-olefin, described Primary Catalysts is titanous chloride or titanium tetrachloride, described promotor is triethyl aluminum or triisobutyl aluminium, described external electron donor is diisopropyl dimethoxy silane and the dicyclopentyl dimethoxyl silane of mass ratio 5:1～1:5.
2. a preparation method for drag reducer polymerization thing, is characterized in that,
1) in prepolymerization kettle, add monomer, promotor and the Primary Catalysts of 1 quality % to 5 quality % of inert solvent, inert solvent, carry out polyreaction at-10 DEG C～10 DEG C, form the slurries that granules of catalyst is suspended in pre-polymer solution, the viscosity of described slurries is 100mPas to 1000mPas;
2) by monomer, promotor and external electron donor, and slurries in prepolymerization kettle add in little reaction vessel, the mass ratio of the slurries in the total mass of described monomer, promotor and the external electron donor wherein adding and the prepolymerization kettle adding is 20:1 to 100:1, then at-10 DEG C～10 DEG C temperature, carries out polymerization;
Wherein, described monomer is C
6～C
20alpha-olefin, described Primary Catalysts is titanous chloride or titanium tetrachloride, described promotor is triethyl aluminum or triisobutyl aluminium, described external electron donor is diisopropyl dimethoxy silane and the dicyclopentyl dimethoxyl silane of mass ratio 5:1～1:5.
3. according to the preparation method of the drag reducer polymerization thing of claim 1 or 2, it is characterized in that, in described little reaction vessel, quality based on total material in little reaction vessel before reaction, the concentration range of monomer and prepolymer is 97 quality %～99.8 quality %, and the concentration range of Primary Catalysts is 0.005 quality %～0.1 quality %, and the concentration range of promotor is 0.1 quality %～3 quality %, the concentration range of external electron donor is 0.01 quality %～0.5 quality %, and surplus is solvent.
4. according to the preparation method of the drag reducer polymerization thing of claim 1 or 2, it is characterized in that, described solvent is normal heptane, octane or normal hexane.
5. according to the preparation method of the drag reducer polymerization thing of claim 1 or 2, it is characterized in that, described little reaction vessel is pocket type reaction vessel.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103936900B (en) * | 2013-01-17 | 2016-03-16 | 中国石油化工股份有限公司 | A kind of flow improver and preparation method thereof |
| CN103936897B (en) * | 2013-01-17 | 2016-03-23 | 中国石油化工股份有限公司 | A kind of drag reducer and preparation method thereof |
| GB201901499D0 (en) | 2019-02-04 | 2019-03-27 | Innospec Ltd | Polymeric materials |
| GB201901496D0 (en) | 2019-02-04 | 2019-03-27 | Innospec Ltd | Chemical reactions |
| GB201901494D0 (en) | 2019-02-04 | 2019-03-27 | Innospec Ltd | Polymeric materials |
| GB201901503D0 (en) | 2019-02-04 | 2019-03-27 | Innospec Ltd | Chemical reactions |
| CN111217953A (en) * | 2019-10-30 | 2020-06-02 | 中国石油化工股份有限公司 | A kind of low crystallinity high molecular weight polyolefin and its synthesis and application |
| MX2023007518A (en) * | 2020-12-23 | 2023-09-14 | Liquidpower Specialty Products Inc | Rapid dissolution of drag-reducing agents at low temperatures. |
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| CN101735366A (en) * | 2009-12-17 | 2010-06-16 | 中国石油化工股份有限公司 | Complex electron donor for drag reducer polymerization |
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| CN101735366A (en) * | 2009-12-17 | 2010-06-16 | 中国石油化工股份有限公司 | Complex electron donor for drag reducer polymerization |
Non-Patent Citations (2)
| Title |
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| 正交试验在预聚合法合成减阻剂中的应用;苏张教等;《当代化工》;20090630;第38卷(第3期);第218-221，225页 * |
| 苏张教等.正交试验在预聚合法合成减阻剂中的应用.《当代化工》.2009,第38卷(第3期),第218-221,225页. |
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Inventor after: Zhang Ning Inventor after: Su Hang Inventor after: Yin Shoucheng Inventor after: Ni Guangdi Inventor after: Jia Banglong Inventor after: Zu Haiyan Inventor after: Zhuang Jun Inventor after: Yang Hui Inventor after: Cui Di Inventor after: Wang Yiran Inventor after: Zhao Liang Inventor after: Cao Danfu Inventor after: Zhang Yiding Inventor after: Jiang Hesheng Inventor after: Fan Junzhong Inventor after: Jia Baofang Inventor after: Cheng Xuxia Inventor after: Wu Jie Inventor after: Wang Dezhi Inventor after: Li Hao Inventor before: Zhang Ning Inventor before: Cao Danfu Inventor before: Jiang Hesheng Inventor before: Fan Junzhong Inventor before: Jia Baofang |
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Free format text: CORRECT: INVENTOR; FROM: ZHANG NING CAO DANFU JIANG HESHENG FAN JUNZHONG JIA BAOFANG TO: ZHANG NING CAO DANFU JIANG HESHENG FAN JUNZHONG JIA BAOFANG CHENG XUXIA WU JIE WANG DEZHI LI HAO SU HANG YIN SHOUCHENG NI GUANGDI JIA BANGLONG ZU HAIYAN ZHUANG JUN YANG HUI CUI DI WANG YIRAN ZHAO LIANG ZHANG YIDING |
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Effective date of registration: 20220211 Address after: 100029 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: State pipe network group east crude oil storage and Transportation Co.,Ltd. Patentee after: XUZHOU JINQIAO PETROCHEMICAL PIPELINE TRANSPORTATION TECHNOLOGY CO.,LTD. Address before: 100029 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: PIPELINE STORAGE AND TRANSPORT BRANCH OF CHINA PETROLEUM & CHEMICAL Corp. Patentee before: XUZHOU JINQIAO PETROCHEMICAL PIPELINE TRANSPORTATION TECHNOLOGY CO.,LTD. |
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