CN1257924C - C9 maleic anhydride copolymer and its preparation method - Google Patents
C9 maleic anhydride copolymer and its preparation method Download PDFInfo
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Abstract
The present invention relates to C9 maleic anhydride copolymer and a preparing method thereof, which belongs to the technical field of organic macromolecular compounds and is used for solving the problem of the utilization of dicyclopentadiene and derivant thereof in C9 distillate. The present invention has the technical scheme that the C9 distillate of polymerization components with double bonds is copolymerized with maleic anhydride. In the copolymer, the weight percentage of the molecule segment of the maleic anhydride is from 40% to 50%, and the molecular weight is from 5000 to 15000. C9-maleic anhydride copolymers are mixed with NaOH according to a proportion of 2: 1, and the distilled water is added to be heated into boil until the solution is clear; thus, water-solubility petroleum resin copolymers are obtained. The prepared resin has the advantages of low price, good water-solubility and high temperature resistance performance, and can be used as a fine chemical product to be used in industries of package, water treatment, construction, printing, paint, traffic and the like; as scale inhibitor, the prepared resin can prevent scale from forming in a composite oil driving system in petroleum production or in the water use of non oil fields.
Description
Technical field
The present invention relates to a kind of water-soluble C
9Petroleum resin and preparation method are particularly by ethylene by-product thing C
9With maleic anhydride synthetic petroleum resin multipolymer and preparation method, belong to the organic high molecular compound technical field.
Background technology
In recent years along with the develop rapidly of ethylene industry, as the cracking C of by-product
9Cut is day by day abundant.C in the present cracking of ethylene
9The cut major part is used as oil fuel, its resources advantage fail be effectively played.If utilize C
9Vinyl active constituent in the cut carries out free radicals copolymerization reaction with maleic anhydride under action of evocating, develop the C with scale inhibition and dispersion performance
9-maleic anhydride water solubility copolymer will have very high economic worth.After nineteen sixties, some countries of the U.S. and West Europe have all set up the device of producing petroleum resin.After 1978, China in Beijing, ground such as Qingdao, Anshan also set up number of C in succession
9The production equipment of petroleum resin, but scale is less, kind is few, and Application Areas remains further to be enlarged.Yet, up to the present domestic and international produce and sell mostly be the oil soluble petroleum resin, this has just limited C
9The application of cut.
U.S. Pat 4539388 discloses C
9Unsaturated polymerizable aromatic component and aromatic carboxylic acid carry out the C that copolymerization obtains modification in the cut under the Friedel-Crafts catalyst action
9Petroleum resin.But the C of these modifications
9Petroleum resin polar group content is low, and skewness, is oil-soluble multipolymer, and its Application Areas is still less.Utilize the C of the rare and derivative of benzene second for main component
9With the maleic anhydride copolymerization, also developed C
9-copolymer-maleic anhydride.Yet since the difference of original place of production and refinery technology, the C of a lot of refinerys
9Main component is based on dicyclopentadiene and derivative thereof, the above-mentioned disclosed method of the copolymerization ratio of this type of cycloolefin and maleic anhydride complexity many.Though disclose C among the Chinese patent literature CN1033814C
9Cut and vinyl polar monomer are produced water-soluble C
9Petroleum resin.Available C wherein
9Cut has also been mentioned dicyclopentadiene, if but the preparation method that it provided is used for the compound of this three-dimensional ring structure of dicyclopentadiene, and then the product yield of Sheng Chaning is low, quality is unstable, far can not satisfy the needs of industrialized mass.So up to now, also do not have both at home and abroad a kind of at being the report of the water-soluble petroleum resin of main material production with dicyclopentadiene and derivative thereof.So, seek a kind of with cheap dicyclopentadiene and derivative thereof be main component, C
9With the maleic anhydride copolymerization, prepare water-soluble C
9The method of-copolymer-maleic anhydride is very important and has realistic meaning.
Summary of the invention
Problem to be solved by this invention is to overcome the prior art defective and provide a kind of to be main copolymer composition, to can be used for preparing the C of Scale inhibitors with dicyclopentadiene and derivative thereof
9-copolymer-maleic anhydride and preparation method.
The alleged problem of the present invention is solved by following technical scheme:
A kind of C9-copolymer-maleic anhydride, its special feature is: the C that contains two key polymerizable composition
9Cut and maleic anhydride copolymerization, the molecular formula of multipolymer is:
Wherein R is dicyclopentadiene and derivative thereof, and maleic anhydride weight percent content in molecule segment is 40%～50% in the described copolymer, and molecular weight is 5000～15000, described C
9Cut when cut is 38-120 ℃.
Above-mentioned C9-copolymer-maleic anhydride, described C
9Cut when cut is 38-60 ℃.
Above-mentioned C9-copolymer-maleic anhydride is with described C
9-maleic anhydride copolymer and NaOH press 2: 1 mixed, add distilled water, and ebuillition of heated to the solution clarification, can obtain water miscible C after the hydrolysis
9-maleic anhydride petroleum resin copolymer.
Above-mentioned C9-copolymer-maleic anhydride, described copolymer limiting viscosity is 0.031～0.097dL/g.
Above-mentioned C
9The preparation method of-copolymer-maleic anhydride, it comprises the steps:
A) distillation: with thick C
9Vacuum distilling, and intercept 38-120 ℃ cut;
B) reflux: gold-plating is divided and maleic anhydride heating in water bath and stirring, and adding accounts for reaction monomers total mass 0.6-5% initiator during to 70-80 ℃, constant temperature backflow 6-10 hour, and described initiator is peroxide, azo compound or redox system;
C) precipitation: with reaction product and residual reactant dissolving, add methyl alcohol again precipitation is separated out with butanone; The molar mass of butanone is a reaction monomers molar mass sum; Quantity of methyl alcohol is about the twice of butanone solution volume number.
D) filtering drying: washing and filtering precipitation in 70-80 ℃ of vacuum drying oven vacuum-drying 6-8 hour then, obtains C
9-maleic anhydride copolymer.
Above-mentioned synthetic C
9The preparation method of-copolymer-maleic anhydride is with C
9-maleic anhydride copolymer and NaOH add distilled water by 2: 1 mixed, ebuillition of heated, to the solution clarification, get final product after the hydrolysis water-soluble petroleum resin copolymer.
Above-mentioned synthetic C
9The preparation method of-copolymer-maleic anhydride in described vacuum distilling step, intercepts 38-60 ℃ cut.
Above-mentioned synthetic C
9The preparation method of-copolymer-maleic anhydride, the vacuum tightness of described vacuum distilling is selected in the 0-0.95MPA scope.
The present invention has following advantage: 1, utilize the C of dicyclopentadiene for main component
9With the water-soluble petroleum resin of maleic anhydride copolymerization, some cracking of ethylene C have been solved
9The refinery that cut is mainly dicyclopentadiene and derivative thereof can't make full use of the problem of cracking of ethylene by product, makes the C in the above-mentioned by product
9Cut can be converted into the water-soluble petroleum resin with high added value; 2, product polarity of the present invention is strong, has scale inhibition and dispersion performance, but widespread use is the Scale inhibitors of Treatment of Industrial Water.It is with low cost, and product has very high economic worth; 3, the inventive method agents useful for same is conventional reagent, and preparation process is simple, and the toxicological harmless material produces, its C
9Cut is vacuum distilling in advance, can effectively extract wherein activeconstituents, and conversion rate of products reaches 65-92%.
Embodiment
The invention provides a kind of C
9The preparation method of (main component is dicyclopentadiene and derivative thereof) and copolymer-maleic anhydride.Dicyclopentadiene contains undersaturated carbon-carbon double bond, can with unsaturated compound generation polyaddition reaction such as maleic anhydride, generate the high-molecular weight petroleum resin.But dicyclopentadiene and vinylbenzene difference are them is a spatial polynuclear plane, can regard as on the structure and form by a norbornylene and cyclopentadiene, its double bond position is on polynary carbocyclic ring, the addition polymerization of this compound is more many than the compound addition polymerization difficulty that vinylbenzene etc. contains the chain thiazolinyl, so the present invention requires relatively stricter at aspects such as intercepting cut, reaction conditionss.To make that this petroleum resin have water-soluble because maleic anhydride contains hydrophilic radical, for guaranteeing resin enough wetting abilities arranged, and maleic anhydride should be 40%～50% at the degree of molecule segment.This law make resin price cheap, have good water-solubility and high temperature resistant property, can be used for industries such as packing, water treatment, building, printing, paint, traffic as a kind of fine chemicals.As Scale inhibitors, can be used for the scale inhibition of the complex oil displacing system of oil production, also can be used for the scale inhibition of non-oil field water.Scale inhibition ability to oil-field water is suitable with the polyacrylic polymer Scale inhibitors.And matching effect is preferably arranged, but also has certain surfactivity with the Scale inhibitors of routine.Therefore be expected to become a kind of tensio-active agent that can be used for composite scale inhibitor and reservoir oil displacing system.
Below be C
9Material vacuum distillation differing temps and cut:
| Temperature (℃) | 38～60 | 60～75 | 75～92 | 92～120 |
| Cut quantity cut degree (%) mass spectroscopy main component | 143 42.0 dicyclopentadiene and homologue thereof, eneyne homologue | 74 21.8 toluene, ethylbenzene etc., vinylbenzene, the propylene homologue, the trimethylbenzene derivative, vinyl toluene | 47 13.8 indenes, dicyclo alkane and homologue thereof | 76 22.4 durenes and derivative thereof, methyl indenes |
Can find out that by top data 38～120 ℃ vacuum distilling cut substantially all is C
9The polymerizable composition, this also just the present invention select for use 38～120 ℃ the vacuum distilling cut as the preparation raw material reason.Get material like this and both comprised most C
9The polymerizable cut forecloses non-polymerizable composition again to greatest extent.Not only guarantee making full use of of raw material, and reduced the generation of impurity and side reaction.
C
9Can in 1: 0.5～2 scope, select with the mol ratio of maleic anhydride.
Introduce several specific embodiments below:
Embodiment 1
Synthesizing of multipolymer:
Under the room temperature, take by weighing C
9Cut 40g, maleic anhydride 9.643g join in the 100mL there-necked flask that has reflux and thermometer, stir, and heating in water bath to 80 ℃ adds 1.782g benzoyl peroxide (BPO), immediately 80 ℃ of following isothermal reactions 10 hours.Reaction finishes the back and uses the 30g butanone with the reaction product stripping, pours precipitation in the beaker that fills 250mL methyl alcohol, washing into.With behind the sedimentation and filtration in 80 ℃ of vacuum-dryings 6 hours.This copolymerization product transformation efficiency is: 92.0%, and limiting viscosity is: 0.467dL/g.
The hydrolysis of multipolymer
Take by weighing 10gC respectively
9-copolymer-maleic anhydride, 5gNaOH place 500mL to have the distillation beaker of reflux, add 250mL distilled water, are heated to reflux temperature, react about 2 hours transparent to solution.This hydrolyzed copolymer scale inhibition performance is 27.4% (dosage 15mg/L).
Embodiment 2
Synthesizing of multipolymer:
Under the room temperature, take by weighing C
9Cut 30g, maleic anhydride 29.928g join in the 100mL there-necked flask that has reflux and thermometer, stir, and heating in water bath added the 0.494g benzoyl peroxide immediately to 70-80 ℃, 80 ℃ of following isothermal reactions 10 hours.Reaction finishes the back and uses the 30g butanone with the reaction product stripping, pours precipitation in the beaker that fills 250mL methyl alcohol, washing into.With behind the sedimentation and filtration in 80 ℃ of vacuum-dryings 6 hours.This copolymerization product transformation efficiency is: 65.4%, and limiting viscosity is: 0.097dL/g.
The hydrolysis of multipolymer
Take by weighing 10gC respectively
9-copolymer-maleic anhydride, 5gNaOH place 500mL to have the distillation beaker of reflux, add 250mL distilled water, are heated to reflux temperature, react about 2 hours transparent to solution.This hydrolyzed copolymer scale inhibition performance is 72.4% (dosage 15mg/L)
Embodiment 3
Synthesizing of multipolymer:
Under the room temperature, take by weighing C
9Cut 30g, maleic anhydride 29.928g join in the 100mL there-necked flask that has reflux and thermometer, stir, and heating in water bath to 80 ℃ adds the 0.741g benzoyl peroxide, immediately 80 ℃ of following isothermal reactions 10 hours.Reaction finishes the back and uses the 30g butanone with the reaction product stripping, pours precipitation in the beaker that fills 250mL methyl alcohol, washing into.With behind the sedimentation and filtration in 80 ℃ of vacuum-dryings 6 hours.This copolymerization product transformation efficiency is: 67.0%, and limiting viscosity is: 0.087dL/g.
The hydrolysis of multipolymer
Take by weighing 10gC respectively
9-copolymer-maleic anhydride, 5gNaOH place 500mL to have the distillation beaker of reflux, add 250mL distilled water, are heated to reflux temperature, react about 2 hours transparent to solution.This hydrolyzed copolymer scale inhibition performance is 68.5% (dosage 15mg/L).
Embodiment 4
Synthesizing of multipolymer:
Under the room temperature, take by weighing C
9Cut 30g, maleic anhydride 29.928g join in the 100mL there-necked flask that has reflux and thermometer, stir, and heating in water bath to 80 ℃ adds the 0.989g benzoyl peroxide, immediately 80 ℃ of following isothermal reactions 10 hours.Reaction finishes the back and uses the 30g butanone with the reaction product stripping, pours precipitation in the beaker that fills 250mL methyl alcohol, washing into.With behind the sedimentation and filtration in 80 ℃ of vacuum-dryings 6 hours.This copolymerization product transformation efficiency is: 84.0%, and limiting viscosity is: 0.079dL/g.
The hydrolysis of multipolymer
Take by weighing 10gC respectively
9-copolymer-maleic anhydride, 5gNaOH place 500mL to have the distillation beaker of reflux, add 250mL distilled water, are heated to reflux temperature, react about 2 hours transparent to solution.This hydrolyzed copolymer scale inhibition performance is 73.4% (dosage 15mg/L).
Embodiment 5
Synthesizing of multipolymer:
Under the room temperature, take by weighing C
9Cut 30g, maleic anhydride 29.928g join in the 100mL there-necked flask that has reflux and thermometer, stir, and heating in water bath to 80 ℃ adds the 1.483g benzoyl peroxide, immediately 80 ℃ of following isothermal reactions 10 hours.Reaction finishes the back and uses the 30g butanone with the reaction product stripping, pours precipitation in the beaker that fills 250mL methyl alcohol, washing into.With behind the sedimentation and filtration in 80 ℃ of vacuum-dryings 6 hours.This copolymerization product transformation efficiency is: 86.4%, and limiting viscosity is: 0.064dL/g.
The hydrolysis of multipolymer
Take by weighing 10gC respectively
9-copolymer-maleic anhydride, 5gNaOH place 500mL to have the distillation beaker of reflux, add 250mL distilled water, are heated to reflux temperature, react about 2 hours transparent to solution.This hydrolyzed copolymer scale inhibition performance is 81.6% (dosage 15mg/L).
Embodiment 6
Synthesizing of multipolymer:
Under the room temperature, take by weighing C
9Cut 40g, maleic anhydride 19.286g join in the 100mL there-necked flask that has reflux and thermometer, stir, and heating in water bath to 80 ℃ adds 0.453g azo compound initiator, immediately 80 ℃ of following isothermal reactions 10 hours.Reaction finishes the back and uses the 30g butanone with the reaction product stripping, pours precipitation in the beaker that fills 250mL methyl alcohol, washing into.With behind the sedimentation and filtration in 80 ℃ of vacuum-dryings 6 hours.This copolymerization product transformation efficiency is: 67.3%, and limiting viscosity is: 0.084dL/g.Azo compound is peroxidation two acyls or dilauroyl peroxide.
The hydrolysis of multipolymer
Take by weighing 10gC respectively
9-copolymer-maleic anhydride, 5gNaOH place 500mL to have the distillation beaker of reflux, add 250mL distilled water, are heated to reflux temperature, react about 2 hours transparent to solution.This hydrolyzed copolymer scale inhibition performance is 34.1% (dosage 15mg/L).
Embodiment 7
Synthesizing of multipolymer:
Under the room temperature, take by weighing C
9Cut 40g, maleic anhydride 19.286g join in the 100mL there-necked flask that has reflux and thermometer, stir, and heating in water bath to 80 ℃ adds 0.906g azo compound initiator, immediately 80 ℃ of following isothermal reactions 10 hours.Reaction finishes the back and uses the 30g butanone with the reaction product stripping, pours precipitation in the beaker that fills 250mL methyl alcohol, washing into.With behind the sedimentation and filtration in 80 ℃ of vacuum-dryings 6 hours.This copolymerization product transformation efficiency is: 68.5%, and limiting viscosity is: 0.076dL/g.Azo compound is peroxidation two acyls or dilauroyl peroxide.
The hydrolysis of multipolymer
Take by weighing 10gC respectively
9-copolymer-maleic anhydride, 5gNaOH place 500mL to have the distillation beaker of reflux, add 250mL distilled water, are heated to reflux temperature, react about 2 hours transparent to solution.This hydrolyzed copolymer scale inhibition performance is 41.8% (dosage 15mg/L).
Embodiment 8
Synthesizing of multipolymer:
Under the room temperature, take by weighing C
9Cut 40g, maleic anhydride 19.286g join in the 100mL there-necked flask that has reflux and thermometer, stir, and heating in water bath to 80 ℃ adds 1.359g azo compound initiator, immediately 80 ℃ of following isothermal reactions 10 hours.Reaction finishes the back and uses the 30g butanone with the reaction product stripping, pours precipitation in the beaker that fills 250mL methyl alcohol, washing into.With behind the sedimentation and filtration in 80 ℃ of vacuum-dryings 6 hours.This copolymerization product transformation efficiency is: 74.0%, and limiting viscosity is: 0.064dL/g.Azo compound is peroxidation two acyls or dilauroyl peroxide.
The hydrolysis of multipolymer
Take by weighing 10gC respectively
9-copolymer-maleic anhydride, 5gNaOH place 500mL to have the distillation beaker of reflux, add 250mL distilled water, are heated to reflux temperature, react about 2 hours transparent to solution.This hydrolyzed copolymer scale inhibition performance is 76.2% (dosage 15mg/L).
Embodiment 9
Synthesizing of multipolymer:
Under the room temperature, take by weighing C
9Cut 40g, maleic anhydride 19.286g join in the 100mL there-necked flask that has reflux and thermometer, stir, and heating in water bath to 80 ℃ adds 1.811g azo compound initiator, immediately 80 ℃ of following isothermal reactions 10 hours.Reaction finishes the back and uses the 30g butanone with the reaction product stripping, pours precipitation in the beaker that fills 250mL methyl alcohol, washing into.With behind the sedimentation and filtration in 80 ℃ of vacuum-dryings 6 hours.This copolymerization product transformation efficiency is: 89.7%, and limiting viscosity is: 0.032dL/g.Azo compound is peroxidation two acyls or dilauroyl peroxide.
The hydrolysis of multipolymer
Take by weighing 10gC respectively
9-copolymer-maleic anhydride, 5gNaOH place 500mL to have the distillation beaker of reflux, add 250mL distilled water, are heated to reflux temperature, react about 2 hours transparent to solution.This hydrolyzed copolymer scale inhibition performance is 87.6% (dosage 15mg/L).
Embodiment 10
Synthesizing of multipolymer:
Under the room temperature, take by weighing C
9Cut 40g, maleic anhydride 19.286g join in the 100mL there-necked flask that has reflux and thermometer, stir, and heating in water bath to 80 ℃ adds the 2.264g benzoyl peroxide, immediately 80 ℃ of following isothermal reactions 10 hours.Reaction finishes the back and uses the 30g butanone with the reaction product stripping, pours precipitation in the beaker that fills 250mL methyl alcohol, washing into.With behind the sedimentation and filtration in 80 ℃ of vacuum-dryings 6 hours.This copolymerization product transformation efficiency is: 90.1%, and limiting viscosity is: 0.031dL/g.
The hydrolysis of multipolymer
Take by weighing 10gC respectively
9-copolymer-maleic anhydride, 5gNaOH place 500mL to have the distillation beaker of reflux, add 250mL distilled water, are heated to reflux temperature, react about 2 hours transparent to solution.This hydrolyzed copolymer scale inhibition performance is 92.4% (dosage 15mg/L).
Embodiment 11
Synthesizing of multipolymer:
Under the room temperature, take by weighing C
9Cut 30g, maleic anhydride 22.594g join in the 100mL there-necked flask that has reflux and thermometer, stir, and heating in water bath to 80 ℃ adds the 0.316g benzoyl peroxide, immediately 80 ℃ of following isothermal reactions 6 hours.Reaction after finishing steams unreacted monomer.This copolymerization product transformation efficiency is 67.2%, and limiting viscosity is 0.054dL/g.
The hydrolysis of multipolymer
Take by weighing 10gC respectively
9-copolymer-maleic anhydride, 5gNaOH place 500mL to have the distillation beaker of reflux, add 250mL distilled water, are heated to reflux temperature, react about 2 hours transparent to solution.This hydrolyzed copolymer scale inhibition performance is 30.7% (dosage 20mg/L).
Above-mentioned peroxide initiator is selected dibenzoyl peroxide (BPO), benzoyl peroxide or t-butylperoxyl benzoate etc. for use; Azo compound is selected Diisopropyl azodicarboxylate, azo two cyclohexane nitriles, peroxidation two acyls or dilauroyl peroxide or the like for use.
Claims (6)
1. C9-copolymer-maleic anhydride is characterized in that: it is to contain the C of two key polymerizable composition
9Cut and maleic anhydride copolymerization, the fraction of multipolymer is:
Wherein R is dicyclopentadiene and derivative thereof, and maleic anhydride weight percent content in molecule segment is 40%～50% in the described copolymer, and molecular weight is 5000～15000, described C
9Cut when cut is 38-120 ℃.
2. C9-copolymer-maleic anhydride according to claim 1 is characterized in that, described C
9Cut when cut is 38-60 ℃.
3. C9-copolymer-maleic anhydride according to claim 1 and 2 is characterized in that, described copolymer limiting viscosity is 0.031～0.097dL/g.
4. one kind according to claim 1,2 or 3 described C
9The preparation method of-copolymer-maleic anhydride is characterized in that it comprises the steps:
A. distillation: with thick C
9Vacuum distilling, and intercept 38-120 ℃ cut;
B. reflux: with cut and maleic anhydride heating in water bath and stir, adding accounts for reaction monomers total mass 0.6-5% initiator during to 70-80 ℃, constant temperature backflow 6-10 hour, and described initiator is peroxide, azo compound or redox system;
C. precipitate: with reaction product and residual reactant dissolving, add methyl alcohol again precipitation is separated out with butanone; The molar mass of butanone is a reaction monomers molar mass sum; Quantity of methyl alcohol is the twice of butanone solution volume number,
D. filtering drying: the washing and filtering precipitation in 70-80 ℃ of vacuum drying oven vacuum-drying 6-8 hour then, obtains C
9-maleic anhydride copolymer.
5. according to the described C of claim 4
9The preparation method of-copolymer-maleic anhydride is characterized in that, in described vacuum distilling step, intercepts 38-60 ℃ cut.
6. according to the described C of claim 5
9The preparation method of-copolymer-maleic anhydride is characterized in that, the vacuum tightness of described vacuum distilling is selected in the 0-0.95MPA scope.
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| CN102731720B (en) * | 2011-04-07 | 2014-07-16 | 王晟航 | Preparation method of chain ring-like biopolymer environmentally-friendly corrosion-inhibition scale inhibitor |
| CN102212166B (en) * | 2011-05-05 | 2013-07-03 | 北京化工大学 | Novel method for performing copolymerization reaction of dicyclopentadiene and maleic anhydride |
| CN102153710B (en) * | 2011-05-06 | 2012-11-07 | 上虞市佳华高分子材料有限公司 | Preparation method of modified petroleum resin |
| CN105949388B (en) * | 2016-05-23 | 2019-03-29 | 北京化工大学 | A kind of functional copolymer directly prepared by higher carbon number hydrocarbon class mixture and preparation method |
| CN110563875B (en) * | 2019-09-20 | 2021-12-21 | 宁波甬华树脂有限公司 | Preparation method of modified aromatic hydrocarbon petroleum resin |
| CN114437275B (en) * | 2020-11-05 | 2023-10-20 | 万华化学集团股份有限公司 | High specific surface area adsorption resin and application thereof in removing dinotefuran residues |
| CN112661905B (en) * | 2020-12-24 | 2023-05-16 | 广东新华粤石化集团股份公司 | C9 petroleum resin and preparation method thereof |
| CN115717053B (en) * | 2022-12-05 | 2024-05-17 | 芜湖徽氏新材料科技有限公司 | High-initial-adhesion corrosion-resistant kneading insulating tape, adhesive and preparation method thereof |
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