CN101544735B - Three-element comb type copolymer, preparation method and application thereof - Google Patents
Three-element comb type copolymer, preparation method and application thereof Download PDFInfo
- Publication number
- CN101544735B CN101544735B CN2009100491021A CN200910049102A CN101544735B CN 101544735 B CN101544735 B CN 101544735B CN 2009100491021 A CN2009100491021 A CN 2009100491021A CN 200910049102 A CN200910049102 A CN 200910049102A CN 101544735 B CN101544735 B CN 101544735B
- Authority
- CN
- China
- Prior art keywords
- monomer
- comb type
- type copolymer
- element comb
- properties
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a three-element comb type copolymer, a preparation method and application thereof. The preparation method comprises two steps: firstly, copolymerizing alpha-olefin and maleic anhydride monomer by a method of free radical polymerization, adding styrene monomer into the mixture in the polymerizing process to obtain a three-element copolymer of the alpha-olefin, the maleic anhydride and the styrene; and then, adding primary alcohol or primary amine to react with estolide, and obtaining the three-element comb type copolymer which not only contains a nonpolar alkyl lateral chain, but also contains polar carboxylic acid and aromatic group. The hydrophobic degree and size of polarity of the three-element comb type copolymer and the content of the aromatic group in the copolymer can be adjusted respectively by adjusting the alkyl length of the alpha-olefin, the primary alcohol or the primary amine, changing the dosage of the primary alcohol or the primary amine, and changing feed time and dosage of the styrene monomer. Experiment results prove that after the three-element comb type copolymer is added in a plurality of kinds of crude oil, stress yield of the crude oil is significantly reduced at low temperature, wax-crystal dimension is reduced, and the effects of pour point depression and viscosity reduction are obvious.
Description
Technical field
The present invention relates to a kind of polymkeric substance and its production and application, specifically utilize the method for free radical solution polymerization to prepare a kind of three-element comb type copolymer and recover the oil in the pipeline transportation and the deep-sea that are applied to crude oil.
Background technology
Crude oil that China produces is waxy crude oil more than 80%, a considerable amount of waxy crude oil are also arranged in the crude oil that produce countries in the world.The condensation point height of waxy crude oil, rheological complexity (showing the flow characteristics of non-Newtonian fluids such as thixotropy, yielding stress, visco-elasticity and shear history and thermal history dependency at normal temperatures and pressures), bring problems and difficulty for production, storage and the transportation of crude oil, have potential safety hazard etc. as oil transportation energy consumption height, pipeline operation.The petroleum transportation pipeline of especially northerly winter and submarine laying, often because temperature is too low, the wax component in the crude oil is separated out, is deposited, and causes regular line clogging, brings serious puzzlement to petroleum transport.Because the water temperature at deep-sea often has only about 4 ℃, this problem was even more serious when conveying was recovered the oil in the seabed.
Often adopt physical method and chemical process to tackle to deposition of solids plugging problem in the high-wax oil low temperature course of conveying both at home and abroad.Physical method mainly is to heat on the way and mechanical pigging.The former energy consumption is big, latter's investment in machinery and equipment height.Chemical process is the crystal habit that changes wax in the crude oil by additive, as size and shape, makes wax be difficult for forming crosslinked three-dimensional space network structure at low temperatures, to reach pour point depression, to improve the purpose of crude oil low-temperature fluidity.This method has advantage simple to operate, that facility investment is few, and does not need crude oil is carried out aftertreatment, at home and abroad is widely used.
The kind of pour point depressant for crude oil is a lot, comprehensive both at home and abroad since 1931 to the research of pour point depressant, wherein to the pour point depression of crude oil effect preferably pour point depressant mainly contain following two types: (1) EVA and modifier thereof.Main the third monomer of utilization carries out modification to EVA by grafting or copolymerization, as vinylbenzene, acrylate, has much room for improvement but shortcoming is a whole structure, needs the collaborative use of composite other kind pour point depressant; (2) poly-(methyl) series of acrylate.Mainly contain compound, (methyl) acrylate and other monomeric multipolymer of poly-(methyl) vinylformic acid C18～22 alkyl esters, (methyl) vinylformic acid C14～22 alkyl esters-olefin copolymer.Its shortcoming is that effect is comparatively single, also needs composite use usually.In addition, some reports about the copolymer-maleic anhydride pour point depressant are arranged also in recent years, but design of the present invention and synthetic ternary comb-shaped copolymer are all different with all in the past reports.
Because the difference in the place of production, the component between the various crude oil differs greatly.But at present commercially available most of polymer pour point depressants are because chemical structure is comparatively single, only be confined to crude oil in the one-component effect, therefore aspect versatility, remain in many defectives.The present invention is by free-radical polymerized method, nonpolar long-chain, polar group and aromatic group have been realized in polymer segment, introducing, these groups are by the assembling under the motivating forces such as hydrophobic association and polar group coupling, with polar compound and the aromatised fraction effect in nonpolar wax component in the crude oil and bituminous matter, the colloid, thereby effectively stop the fusion of wax crystalline substance and bituminous matter, gelationus to condense, improved the versatility of polymer pour point depressant to a great extent.
Summary of the invention
The objective of the invention is to overcome the relatively poor defective of most commercial pour point depressant versatility, work out a kind of applicable to polymer pour point depressant most of crude oil, that versatility is stronger.Through consulting a large amount of documents, and according to the experience of being engaged in pour point depressant for crude oil research for many years, the present invention has developed a kind of novel method of utilizing free-radical polymerized preparation three-element comb type copolymer crude oil low temperature flow ability modifying agent.
The process for preparing described three-element comb type copolymer is as follows:
Wherein, 7＜m＜24,0＜n＜21.
The preparation of this three-element comb type copolymer is divided into two steps, and is specific as follows:
(1) free radical solution polymerization system terpolymer
50ml solvent (dimethylbenzene), first monomer (maleic anhydride), second monomer (alpha-olefin) and initiator (as Diisopropyl azodicarboxylate, benzoyl peroxide) are packed in the 250ml there-necked flask.The first monomeric charging capacity is 0.06mol, and the second monomeric charging capacity is equivalent to first monomeric 100～200mol%, and the charging capacity of initiator is equivalent to first monomeric 1～3mol%.Fully after the dissolving, take out inflated with nitrogen 3～5 times, reaction system is placed under the strict nitrogen protection.After treating that temperature is raised to 100～120 ℃ fast, polyreaction was carried out 0.5～2 hour.System temperature is reduced to 70～90 ℃, slowly adds the 3rd monomer (vinylbenzene), and add a small amount of initiator (as Diisopropyl azodicarboxylate, benzoyl peroxide) and solvent.The 3rd monomeric add-on is equivalent to first monomeric 0～100mol%, and the amount of adding initiator is equivalent to described first monomeric 0.1～0.3mol%, and rate of addition is controlled at 5～10 droplets/minute.Continuation finally can obtain first monomer, second monomer and the 3rd monomeric terpolymer 70～90 ℃ of reactions 4～8 hours.
Because the influence of the reactivity ratio between first monomer and second monomer, the second monomeric charging capacity needs more than the first monomeric charging capacity, otherwise the content of second monomer in multipolymer will reduce, the also corresponding minimizing of the number of its contained nonpolar long-chain side group, finally cause with crude oil in the effect of nonpolar wax component reduce, the pour point depression effect weakens.In addition, the charging capacity of initiator needs moderate, and charging capacity is very few, and then polymerization rate is slow, and polymerization time is long; Charging capacity is too much, and then the molecular weight of multipolymer reduces, and molecular weight distribution broadens.In view of first monomer and the second monomeric copolyreaction have consumed most of initiator, so need add a small amount of initiator when adding the 3rd monomer.It should be noted that in addition, because the 3rd monomer and the first monomeric reactivity ratio are higher than second monomer, therefore the 3rd monomeric charging time is too early unsuitable, and rate of addition is unsuitable too fast, otherwise be easy to get the 3rd monomer and the first monomeric alternating copolymer or the homopolymer of himself.
(2) chemically modified (esterification or amination) terpolymer prepares three-element comb type copolymer
The terpolymer that the first step obtains can treated purifying taking-up carry out the reaction of second step again, also can directly carry out the reaction of second step.First properties-correcting agent (in lauryl alcohol～stearyl alcohol any) or second properties-correcting agent (in amino dodecane～stearylamine any) are added reaction system, and charging capacity is equivalent to first monomeric 100～200mol%.100～120 ℃ of reactions 8～15 hours, can obtain terpolymer at last, i.e. three-element comb type copolymer through chemically modified (esterification or amination).Can control gamma value or amination degree by the charging capacity of regulating first properties-correcting agent or second properties-correcting agent, thereby can obtain the three-element comb type copolymer of opposed polarity size.
By proton nmr spectra (
1H NMR) chemical structure of three-element comb type copolymer is analyzed, utilized the spectrum peak integrated value of different hydro atom, calculated the gamma value or the amination degree of three-element comb type copolymer.Gamma value here or amination degree are meant that a maleic anhydride group in the polymkeric substance is finally converted into the number of ester group or amide group, and size is between 0～2.Because alkyl end CH
3The chemical shift of last hydrogen atom is at 0.88ppm, and therefore the chemical shift of CH group hydrogen circle can utilize following formula to calculate gamma value or amination degree (f) at 3.28ppm on the maleic anhydride.
The scope of the gamma value that calculates of formula or amination degree is between 1.0～1.3 thus, and general per two the maleic anhydride groups of this explanation have one esterification or amination reaction take place, and have generated an ester group (or amide group) and a hydroxy-acid group.
In addition, also utilize gel permeation chromatography (GPC) that the molecular weight of three-element comb type copolymer is tested, the molecular weight ranges of three-element comb type copolymer is between 5000～20000 gram/moles.
Three-element comb type copolymer is joined in the different crude oils, crude oil as long celebrating oil field, Shengli Oil Field, adopting rheometer test to add their yielding stresses at low temperatures of front and back changes, discovery is behind the three-element comb type copolymer that adds 0.05～0.5wt%, the yielding stress of various crude oil all has tangible reduction, generally can reduce an order of magnitude, the highlyest reduce by four orders of magnitude.With their wax crystalline form looks and distributions at low temperatures of polarized light microscope observing, find that the size of wax crystalline substance obviously diminishes, the dispersed increase, the low-temperature fluidity of crude oil is significantly improved.Its mechanism of action is: nonpolar alkyl group side chain self-assembly nucleation or with crude oil in the wax component produce eutectic, polar compound in polar group and bituminous matter, the colloid interacts and forms micella, and phenyl ring in the polystyrene units and the aromatised fraction effect in the crude oil, thereby stop the brilliant fusion of wax and bituminous matter, gelationus in the crude oil to condense.
Description of drawings
Fig. 1 adds three-element comb type copolymer front and back crude oil yielding stress comparison diagram (0 ℃);
Fig. 2 is the polarizing microscope photo (0 ℃) of crude oil (b part) behind crude oil (a part) and the adding 0.05wt% three-element comb type copolymer.
Embodiment
Below, further specify the present invention with embodiment, but protection scope of the present invention is not limited in embodiment.The variation and the modification of other that those skilled in the art is made in the case of without departing from the spirit and scope of protection of the present invention still are included within the protection domain of the present invention.
Embodiment 1 free radical solution polymerization prepares three-element comb type copolymer
50ml o-Xylol, 5.96g maleic anhydride, 21.56g octadecylene and 0.25g benzoyl peroxide are packed in the 250ml there-necked flask.Take out inflated with nitrogen 3～5 times, fully after the dissolving, 110 ℃ of reactions 1 one hours.Treat that temperature reduces to 75 ℃ 3.12g vinylbenzene, 0.03g benzoyl peroxide and 15ml o-Xylol slowly be added drop-wise in the reaction system, continue to obtain terpolymer in 8 hours 75 ℃ of reactions.Add the 14.84g amino dodecane at last, can finish amination reaction in 15 hours, finally obtain three-element comb type copolymer 110 ℃ of reactions.
Embodiment 2 free radical solution polymerizations prepare three-element comb type copolymer
50ml o-Xylol, 5.96g maleic anhydride, 19.60g tetradecene and 0.20g benzoyl peroxide are packed in the 250ml there-necked flask.Take out inflated with nitrogen 3～5 times, fully after the dissolving, 120 ℃ of reactions 1 hour.Treat that temperature reduces to 85 ℃ 4.16g vinylbenzene, 0.02g benzoyl peroxide and 15ml o-Xylol slowly be added drop-wise in the reaction system, continue to obtain terpolymer in 6 hours 85 ℃ of reactions.Add the 21.56g stearylamine at last, can finish amination reaction in 8 hours, finally obtain three-element comb type copolymer 120 ℃ of reactions.
Embodiment 3 free radical solution polymerizations prepare three-element comb type copolymer
50ml o-Xylol, 5.96g maleic anhydride, 11.76 laurylenes and 0.25g benzoyl peroxide are packed in the 250ml there-necked flask.Take out inflated with nitrogen 3～5 times, fully after the dissolving, 100 ℃ of reactions 2 hours.Treat that temperature reduces to 75 ℃ 4.16g vinylbenzene, 0.02g benzoyl peroxide and 15ml o-Xylol slowly be added drop-wise in the reaction system, continue to obtain terpolymer in 8 hours 75 ℃ of reactions.Add the 26.57g cetylamine at last, can finish amination reaction in 24 hours, finally obtain three-element comb type copolymer 100 ℃ of reactions.
Claims (3)
1. the preparation method of a three-element comb type copolymer is characterized in that, comprises the steps:
(1) free radical solution polymerization prepares terpolymer:
Add first monomer, second monomer, initiator and solvent in reactor, stirring is fully dissolved it, reacts 0.5～2 hour under nitrogen protection and 100～120 ℃ of conditions; System temperature is reduced to 70～90 ℃, slowly adds the 3rd monomer then, and add a small amount of initiator and solvent, rate of addition is controlled at 5～10 droplets/minute; Continuation finally can obtain terpolymer 70～90 ℃ of reactions 4～8 hours;
Wherein, the consumption mol ratio is first monomer: second monomer: the 3rd monomer: initiator=1: 1～2: 0～1: 0.01～0.03, and the amount of adding initiator is equivalent to described first monomeric 0.1～0.3mol%;
(2) the chemically modified terpolymer prepares three-element comb type copolymer:
With the reaction system of first properties-correcting agent or second properties-correcting agent adding step (1), reacted 8～24 hours down at 100～120 ℃, obtain esterification or aminating terpolymer at last, i.e. three-element comb type copolymer;
Wherein, the consumption of first properties-correcting agent or second properties-correcting agent is equivalent to described first monomeric 100～200mol%;
Described initiator is benzoyl peroxide or Diisopropyl azodicarboxylate, and described solvent is p-Xylol or o-Xylol, and described first monomer is a maleic anhydride, described second monomer is an alpha-olefin, described the 3rd monomer is a vinylbenzene, and described first properties-correcting agent is primary alconol, and described second properties-correcting agent is primary amine;
Described alpha-olefin can be any in laurylene～octadecylene, and used primary alconol or primary amine can be any in lauryl alcohol～stearyl alcohol or the amino dodecane～stearylamine; The molecular weight of described three-element comb type copolymer is 5000～15000, and the gamma value of described terpolymer esterification or aminate or amination degree are 1.0～1.3.
2. the three-element comb type copolymer that obtains of the preparation method of claim 1.
3. the application of the three-element comb type copolymer of claim 2 is characterized in that, recovers the oil in the pipeline transportation or the deep-sea that are used for crude oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100491021A CN101544735B (en) | 2009-04-10 | 2009-04-10 | Three-element comb type copolymer, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100491021A CN101544735B (en) | 2009-04-10 | 2009-04-10 | Three-element comb type copolymer, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101544735A CN101544735A (en) | 2009-09-30 |
| CN101544735B true CN101544735B (en) | 2011-12-28 |
Family
ID=41192128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100491021A Expired - Fee Related CN101544735B (en) | 2009-04-10 | 2009-04-10 | Three-element comb type copolymer, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101544735B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870750A (en) * | 2010-06-02 | 2010-10-27 | 华东理工大学 | Comb copolymer, preparation method and application thereof |
| CN101921377B (en) * | 2010-08-17 | 2012-06-27 | 浙江大学 | Anhydride amidated block comb copolymer as well as preparation method and application thereof as pour-point depressing and viscosity reducing agent of crude oil |
| CN101942067B (en) * | 2010-08-17 | 2013-03-13 | 浙江大学 | Anhydride esterification segmented pectinate copolymer, preparation method thereof and application for serving as crude oil pour point depressants and viscosity reducer |
| CN102492074A (en) * | 2011-11-24 | 2012-06-13 | 华东理工大学 | Comb type copolymer with side chains grafted with naphthalene sulfonic acid groups, preparation method thereof and application thereof |
| CN105175629B (en) * | 2015-07-20 | 2018-08-14 | 山东大学 | A kind of high wax viscous crude pour-point depressant and preparation method thereof |
| CN108730770A (en) | 2017-04-13 | 2018-11-02 | 通用电气公司 | The method that oil generates wax deposit is reduced for the wax-proofing agent of oil and with wax-proofing agent |
| CN108410443A (en) * | 2018-04-04 | 2018-08-17 | 青岛艾尔乐新材料有限公司 | Efficient thick-oil thinner |
| CN114644724B (en) * | 2020-12-21 | 2024-01-26 | 中国石油化工股份有限公司 | Polymeric asphaltene precipitation inhibitor and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6174843B1 (en) * | 1990-08-13 | 2001-01-16 | Nalco Chemical Company | Composition and method for lubricant wax dispersant and pour point improver |
| CN1968976A (en) * | 2004-04-19 | 2007-05-23 | 卢布里佐尔公司 | Dispersant viscosity modifiers based on maleic anhydride-styrene copolymers |
| US20070219100A1 (en) * | 2003-10-22 | 2007-09-20 | Taeubert Hiltrud | Additive Mixture As Component Of A Mineral Oil Composition |
| CN101386659A (en) * | 2008-11-05 | 2009-03-18 | 中国海洋石油总公司 | Method for preparing oil soluble crude oil improved flowable agent |
-
2009
- 2009-04-10 CN CN2009100491021A patent/CN101544735B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6174843B1 (en) * | 1990-08-13 | 2001-01-16 | Nalco Chemical Company | Composition and method for lubricant wax dispersant and pour point improver |
| US20070219100A1 (en) * | 2003-10-22 | 2007-09-20 | Taeubert Hiltrud | Additive Mixture As Component Of A Mineral Oil Composition |
| CN1968976A (en) * | 2004-04-19 | 2007-05-23 | 卢布里佐尔公司 | Dispersant viscosity modifiers based on maleic anhydride-styrene copolymers |
| CN101386659A (en) * | 2008-11-05 | 2009-03-18 | 中国海洋石油总公司 | Method for preparing oil soluble crude oil improved flowable agent |
Non-Patent Citations (4)
| Title |
|---|
| 刘公召等.柴油低温流动改性剂的合成与使用效果研究.《石油与天然气化工》.2001,第30卷(第3期),第130-131页. * |
| 廖克俭等.EsMOVS 柴油降凝剂的研制.《精细化工》.1996,第13卷(第5期),第19页. * |
| 成广兴.三元共聚衍生物类低温流动改进剂应用研究.《菏泽师专学报》.1997,第19卷(第4期),第55-58页. * |
| 薛兆民.MOAS-a降凝助滤剂的合成、表征及应用性能.《山东教育学院学报》.2003,(第4期),第60页实验部分1.1-1.2. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101544735A (en) | 2009-09-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101544735B (en) | Three-element comb type copolymer, preparation method and application thereof | |
| CN101870750A (en) | Comb copolymer, preparation method and application thereof | |
| CN103184043A (en) | Crude oil pour point depressant and preparation method thereof | |
| El-Ghazawy et al. | Modified maleic anhydride-co-octadecene copolymers as flow improver for waxy Egyptian crude oil | |
| CN102510878B (en) | Improve the composition of oil fuel cold flow properties | |
| AU2013361819B2 (en) | Polymer compositions of ethylene-vinyl ester copolymers and alkyl(meth)acrylates, method for the production thereof and use thereof as pour-point depressants for crude oils, mineral oils or mineral oil products | |
| Yang et al. | Influence of polar groups on the depressive effects of polymethacrylate polymers as cold flow improvers for diesel fuel | |
| CN102050917A (en) | Macromolecular compound containing aliphatic tertiary amine group as well as preparation method thereof and application in oil displacement agent | |
| CN101899162A (en) | Comb-shaped polymer and preparation method and application thereof | |
| Moriceau et al. | Well-defined alkyl functional poly (styrene-co-maleic anhydride) architectures as pour point and viscosity modifiers for lubricating oil | |
| CN108456279B (en) | Crude oil pour point depressant, and preparation method and application thereof | |
| CN104837871A (en) | Polymer formulations in solvents with a high flash point, method for the production thereof and use thereof as pour-point depressants for crude oils, mineral oils or mineral oil products | |
| Jukic et al. | Alkyl methacrylate and styrene terpolymers as lubricating oil viscosity index improvers | |
| CN106188362B (en) | One kind has the preparation method of the imidazoline polymer of inhibition and viscosity reduction effect concurrently | |
| CN104356296B (en) | A kind of aminolysis type polymer and preparation method thereof and application | |
| US20100175310A1 (en) | Acrylic polymer low temperature flow modifiers in bio-derived fuels | |
| CN102453478A (en) | Temperature-resistance salt-tolerance macromolecular surfactant for oil field, preparation method and application thereof | |
| Xue et al. | Effect of methacrylate-methacrylamide copolymers with various polar pendants on the cold flow properties of diesel fuels | |
| Lomège et al. | Fatty acid-based methacrylate polymers as viscosity modifiers for mineral oils | |
| Zhang et al. | Synthesis of comb bipolymers and their pour point depressing properties | |
| CN105199699B (en) | A kind of inexpensive oil-soluble viscosity reducer and preparation method for reducing thick oil viscosity | |
| Zhang et al. | Terpene resin prepared from renewable turpentine oil as a new type of cold flow improver for soybean biodiesel-diesel blends | |
| CN110093193B (en) | Compound diesel pour point depressant and preparation method and application thereof | |
| CN104710560B (en) | A kind of dicyclopentadiene and Long Chain Alkyl Acrylate polymer pour point depressant for crude oil | |
| CN110564459A (en) | Diesel oil pour point depressant containing nonionic surfactant and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20111228 Termination date: 20150410 |
|
| EXPY | Termination of patent right or utility model |