CN1315896C - Water soluble C#-[9] petroleum resin terpolymers with scale-inhibiting property and preparation process thereof - Google Patents
Water soluble C#-[9] petroleum resin terpolymers with scale-inhibiting property and preparation process thereof Download PDFInfo
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Abstract
The present invention relates to a water-soluble C9 petroleum resin terpolymer with a scale inhibiting property and a preparation method thereof, which belongs to a water-soluble C9 terpolymer with a scale inhibiting property, which is prepared from byproduct C9 in producing ethene and a preparation method thereof. The present invention has the technical scheme that free radical ternary polymerization is carried out for cheap byproduct C9 in producing ethene with the main components of dicyclopentadiene and the homologous compounds of the dicyclopentadiene, acrylic acid and the homologous compounds of the acrylic acid under the action of chain transfer agents and initiators to prepare practical water-soluble C9 petroleum resin terpolymer. The present invention develops a novel petroleum resin product, the scale inhibitor product has stable and favorable scale inhibiting effect, the scale inhibitor product can be used for industrial circulating water and oilfield flooding water, and the scale inhibiting rate is from 80% to 99%. The preparation method of the present invention has the advantages of simple synthesis technology and low cost in production, a large quantity of byproduct C9 in producing ethene is sufficiently utilized, the application area of the byproduct C9 in producing ethene is widened, and the preparation method has economic and social benefits.
Description
Technical field
The invention belongs to and utilize cheap ethylene production by product C
9(main component is dicyclopentadiene and homologue thereof) synthetic water-soluble C with scale-inhibiting properties
9Petroleum resin terpolymer and preparation method.Be particularly related to ethylene production by product C
9Under chain-transfer agent, initiator effect, take place free-radical polymerizedly, make C with scale-inhibiting properties with maleic anhydride and vinylformic acid or acrylamide
9Water-soluble copolymer and method.
Background technology
Petroleum resin are the by-product C with ethylene unit
5, C
9Cut is a main raw material, polymerization in the presence of catalyzer, or itself and aldehydes, aromatic hydrocarbons, terpene compound carried out copolymerization and the thermoplastic resin that makes.In order to improve constantly the petroleum resin quality, widen its Application Areas, Japan and American-European countries have carried out relevant research one after another, mainly concentrate on petroleum resin modified on.
At present, both at home and abroad to C
9The modification that petroleum resin carry out mainly concentrates on oil soluble C
9On the petroleum resin, limited C
9The Application Areas of petroleum resin.In recent years along with the develop rapidly of domestic ethylene industry, the cracking C of by-product
5, C
9Cut is day by day abundant.National cracking C in 2000
9Stock number be 81.4 ten thousand tons of 51.7 ten thousand tons, calendar year 2001,2002 91.8 ten thousand tons, expect 2005 and will reach 96.7 ten thousand tons, wherein petroleum resin are to cracking C
9Demand will reach 240,000 tons, will account for C
924.8% of resource.C in present China cracking of ethylene
9Cut, major part is used as oil fuel, and resources advantage fails effectively to be brought into play.So exploitation petroleum resin product innovation is necessary greatly.
To C
9The modification of petroleum resin mainly concentrates on oil soluble C at present both at home and abroad
9In the modification of petroleum resin, mainly be: a kind of for introducing polarity group, the consistency with polar compound can improve in petroleum resin introducing polarity group, abroad mainly is under the Friedel-Crafts catalyst action, introduces polar group in the molecule of petroleum resin.For example at cracking C
9Add a small amount of long-chain (C in the fraction oil
8～C
16) unsaturated fatty acids, at BF
3Under the effect, 35 ℃ of reaction 6h; Or reacting but in the still unsegregated mixed system, under 145 ℃, peroxidation, connect the skill copolymerization with above-mentioned unsaturated fatty acids.The products obtained therefrom acid number is 4～12mgKOH/g, and polar group content is less.This modification C
9Petroleum resin are mainly used in printing-ink production.Another kind is the hydrogenation modification of petroleum resin, has just carried out C from the seventies in 20th century abroad
9The hydrogenation modification research of petroleum resin.Main purpose is in order to eliminate C
9The two keys of residual double bonds in the petroleum resin molecule and aromatic ring reduce form and aspect, improve (.C such as Yan Weidong such as consistency, weathering resistance
9Resin modified method [J]. chemistry world, 2000, (6): 327～329).There is the problem of production cost height, complex process in above method of modifying.
Present domestic utilization is the cracking of ethylene by-product C of main component with vinylbenzene and homologue thereof
9C has been developed in cut and maleic anhydride copolymerization
9-MA multipolymer (Yan Weidong, Xiao Cuiling, Liu Lixin .C
9The water-soluble petroleum resin evaluation of antisludging performance of-MA [J]. Speciality Petrochemicals, 1998, (3): 7～10), yet this water-soluble petroleum resin copolymer shows certain deficiency on as Scale inhibitors, show that mainly functional group is more single, thereby influence the performance and the stability of its scale inhibition.
Up to now, still there is not employing with cheap ethylene production by product C
9(main component is dicyclopentadiene and homologue thereof) and the vinyl active ingredient that has functional group, as maleic anhydride, vinylformic acid or acrylamide terpolymer, preparation has the C of scale-inhibiting properties
9The report of water-soluble petroleum resin terpolymer.
Summary of the invention
At above-mentioned situation, the invention solves the current cheap ethylene production by product C that still is difficult
9With the problem of maleic anhydride and vinylformic acid or acrylamide terpolymer, the product innovation that a kind of stable performance is provided and has had the efficient scale performance---water-soluble C
9The petroleum resin terpolymer.
Technical scheme of the present invention:
Water-soluble C with scale-inhibiting properties
9The petroleum resin terpolymer is to utilize the ethylene production by product C of main component for dicyclopentadiene and homologue thereof
9Cut, synthetic water-soluble C with scale-inhibiting properties
9Petroleum resin terpolymer, this terpolymer are following composition:
With
Mixture;
This mixture has C
9Cut and R
1, R
2The terpolymer of alternating structure;
Wherein: R is C
9In contain the active ingredient of vinyl double bond, as dicyclopentadiene and homologue, indenes and homologue thereof, vinylbenzene and homologue thereof etc.;
R
1, R
2Be two kinds of different monomers in vinylformic acid and the derivative thereof, as be selected from maleic anhydride, vinylformic acid, the acrylamide 2 kinds.
Main performance index: the terpolymer limiting viscosity is 0.01～0.10dL/g;
The multipolymer productive rate is 80～90%.
Water-soluble C with scale-inhibiting properties
9The preparation method of petroleum resin terpolymer is to utilize azo class or peroxide initiator, is the ethylene production by product C of dicyclopentadiene and homologue thereof with the main component
9Cut and vinylformic acid and derivative thereof, (2 kinds of monomer polymerizations in maleic anhydride, vinylformic acid and the acrylamide) generate has C
9The terpolymer of cut and vinylformic acid and derivative alternating structure thereof, and regulate the multipolymer limiting viscosity by adding chain-transfer agent, chain-transfer agent adopts thio-alcohol or mercaptan carboxylic acid's class, and is above-mentioned raw materials used and the consumption prescription is as follows:
Three kinds of polymerization single polymerization monomers are ethylene production by product C
92 kinds of monomer mole ratios in cut and maleic anhydride, vinylformic acid, the acrylamide are 1: 1: 1; Other material composition add-on is:
Material composition accounts for reaction monomers total mass number per-cent
Chain-transfer agent 1～10%
Initiator 1～10%
Organic solvent 100%
Its concrete preparation process is as follows:
Underpressure distillation; With C
9Oil is ethylene production by product C
9Oil, underpressure distillation intercepts 38～120 ℃ of cuts.
Multipolymer is synthetic: cut, vinylformic acid and derivative thereof, the chain-transfer agent of underpressure distillation are joined in the band cooling and reflux device container according to above-mentioned formula rate, and heated and stirred after 70 ℃, adds initiator, isothermal reaction 4～10 hours;
Termination reaction: reaction finishes the back and adds stopper.
Washing and filtering: with reacted copolymerization product and residuum, pour in the beaker that the precipitation agent sherwood oil is housed, be settled out multipolymer.With multipolymer vacuum-drying 6h in 80 ℃ of vacuum drying ovens again, obtain C
9The petroleum resin terpolymer.
Multipolymer hydrolysis: in multipolymer and 2: 1 ratio of NaOH mass ratio, multipolymer and NaOH are joined in the container of taking back stream, add distilled water, the terpolymer of the above-mentioned preparation of hydrolysis under the distilled water boiling temperature, until aqueous solution clarification, can obtain water-soluble C
9The petroleum resin terpolymer.
Need to prove:
Ethylene production by product C
9Oil, through underpressure distillation, 38～120 ℃ of cuts of intercepting intercepting, the quality percentage composition of its polymerizable composition is: 68%, bromine number is: 160.81.
Azo-initiator such as Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile); Peroxide initiator such as benzoyl peroxide or dilauroyl peroxide.
It is thio-alcohol or mercaptan carboxylic acid's class that institute adds chain-transfer agent.Chain-transfer agent adopts thio-alcohol such as lauryl mercaptan, n-butyl mercaptan etc.; Chain-transfer agent adopts mercaptan carboxylic acid's class such as thiohydracrylic acid, Thiovanic acid etc.
Initiator adding mode has two kinds, a kind of is to take the dropping mode to add, its concrete grammar is: a kind of monomer in cut, vinylformic acid and the derivative thereof of underpressure distillation, chain-transfer agent are joined in the band cooling and reflux device container according to above-mentioned formula rate, heated and stirred, to 70 ℃ of temperature, dropping is with the another kind of monomeric solution in solvent, initiator and vinylformic acid and the derivative thereof, and the control dropping time was at 0.5～2 hour; Another kind takes disposable adding mode to add, and is about to three kinds of polymerization single polymerization monomers and chain-transfer agent according to above-mentioned formula ratio, joins in the band cooling and reflux device container, after the heated and stirred to 70 ℃, adds superoxide or azo-initiator rapidly.
Water-soluble C with scale-inhibiting properties
9The purposes of petroleum resin terpolymer is to do Scale inhibitors, and its use range is in 15～80 ℃, the industrial circulating water or oil-field flooding of pH=6.0～8.0, when add-on is the water-soluble C of 5mg/L～30mg/L
9During the petroleum resin terpolymer, its scale inhibition performance can reach 80%～99%.
Beneficial effect:
The present invention has developed a petroleum resin product innovation.It is with cheap ethylene production by product C
9Oil makes the water-soluble C with scale-inhibiting properties
9The petroleum resin terpolymer.This Scale inhibitors has stable, good scale inhibition effect, has very high value.Scale inhibition performance can reach 80%～99%.Preparation method of the present invention has the synthesis technique production advantage simple, with low cost, and makes a large amount of ethylene production by product C
9Oil is fully utilized, and has expanded ethylene production by product C
9Application Areas both had an economic benefit, and social benefit is arranged again.
Embodiment:
Table 1C
9Raw material
1.Its temperature of underpressure distillation and cut information slip
| Temperature (℃) | 38～60 | 60～75 | 75～92 | 92～120 |
| Cut quantity (mL) | 143 | 74 | 47 | 76 |
| Shared cut per-cent (%) | 42.0 | 21.8 | 13.8 | 22.4 |
| The mass spectroscopy main component | Dicyclopentadiene and homologue eneyne homologue thereof | Vinylbenzene such as toluene, ethylbenzene, propyl benzene homologue vinyl toluene, trimethylbenzene derivative | Indenes, dicyclo alkane and homologue thereof | Durene and derivative thereof, methyl indenes |
Annotate: 1. C
9Raw material is taken from the ethylene production by product C of Yanshan Petro-Chemical Industry Corporation
9Oil
Table 2 dicyclopentadiene different concns
1.The bromine number contrast table
| Concentration % | 40 | 50 | 60 | 70 | 80 | 90 | 100 |
| Bromine number | 109.57 | 126.54 | 147.12 | 163.01 | 183.55 | 202.59 | 221.38 |
Annotate: 1. the dicyclopentadiene of above each concentration is to be the solvent configuration with the tetracol phenixin
Different polymerizing condition polymerization results of table 3 embodiment 1-10 and scale-inhibiting properties table
| Embodiment | Mol ratio ① | The chain-transfer agent kind | Chain-transfer agent % | Initiator type | Initiator percentage composition % | Polymerization time h | Transformation efficiency % | Limiting viscosity dL/g | Scale inhibitors dosage mg/L | Scale inhibition performance ② ％ |
| 1 | C9∶MA ③∶AA ④＝1∶1∶1 | Lauryl mercaptan | 1 | Diisopropyl azodicarboxylate | 3.0 | 10 | 68.9 | 0.084 | 5 | 83.2 |
| 2 | C 9∶MA∶AA＝1∶1∶1 | N-butyl mercaptan | 2 | Diisopropyl azodicarboxylate | 4.0 | 6 | 79.2 | 0.082 | 10 | 93.7 |
| 3 | C 9∶MA∶AA＝1∶1∶1 | Lauryl mercaptan | 9 | Diisopropyl azodicarboxylate | 5.0 | 6 | 89.2 | 0.014 | 10 | 96.5 |
| 4 | C 9∶MA∶AA＝1∶1∶1 | Thiohydracrylic acid | 2 | Benzoyl peroxide | 3.0 | 10 | 74.6 | 0.091 | 15 | 91.7 |
| 5 | C 9∶MA∶AA＝1∶1∶1 | Thiohydracrylic acid | 3 | Benzoyl peroxide | 5.0 | 6 | 89.7 | 0.0521 | 30 | 99.7 |
| 6 | C 9∶AA∶AM ⑤＝1∶1∶1 | Thiovanic acid | 1 | Diisopropyl azodicarboxylate | 10 | 4 | 66.7 | 0.076 | 10 | 91.4 |
| 7 | C 9∶MA∶AM＝1∶1∶1 | Thiohydracrylic acid | 2 | Diisopropyl azodicarboxylate | 4.0 | 6 | 74.5 | 0.046 | 10 | 94.6 |
| 8 | C 9∶MA∶AM＝1∶1∶1 | Lauryl mercaptan | 3 | Diisopropyl azodicarboxylate | 5.0 | 6 | 87.4 | 0.043 | 10 | 97.4 |
| 9 | C 9∶MA∶AM＝1∶1∶1 | Lauryl mercaptan | 2 | Benzoyl peroxide | 4.0 | 6 | 76.1 | 0.052 | 10 | 95.6 |
| 10 | C 9∶MA∶AM＝1∶1∶1 | Thiohydracrylic acid | 3 | Benzoyl peroxide | 5.0 | 6 | 87.8 | 0.048 | 10 | 97.3 |
Annotate: 1. above experiment C
9Bromine number is 160.81 to be equivalent to 68% dicyclopentadiene, and molar mass is calculated by 68% dicyclopentadiene;
2. adopt the mensuration-man standard test of tosca France of GB/T 16632-1996 water conditioner scale-inhibiting properties:
3. maleic anhydride;
4. vinylformic acid;
5. acrylamide;
Embodiment specifies as follows:
Embodiment 1:
With C
9Oil is ethylene production by product C
9Oil, underpressure distillation intercepts 38～120 ℃ of cuts.
Synthesizing of multipolymer
Under the room temperature, take by weighing C
9Cut 22.010g, maleic anhydride 11.126g, chain-transfer agent lauryl mercaptan 0.343g join in the 100mL four-hole bottle that has reflux and thermometer, stir, heating in water bath to 70 ℃.8.176g vinylformic acid, 34.302g solvent butanone, 1.029g initiator Diisopropyl azodicarboxylate are joined in the 100mL dropping funnel, dropwise join in the four-hole bottle, control the dropping time, dropwise in 2 hours.70 ℃ of following isothermal reactions 10 hours.Pour reaction product into precipitation in the beaker that fills precipitation agent 250mL sherwood oil, washing after reacting end.Throw out is filtered the back in 80 ℃ of vacuum-dryings 6 hours.
This copolymerization product transformation efficiency is: 68.9%, and limiting viscosity is: 0.084dL/g.
The multipolymer hydrolysis
Take by weighing 10g terpolymer, 5g NaOH respectively and place 500mL to have the distilling flask of reflux, add 250mL distilled water, be heated to reflux temperature, react about 2 hours transparent to solution, off-test.
Application test: at 500mL, in 70 ℃, the industrial circulating water of pH=7.0, add the above-mentioned Scale inhibitors of 2.5mg, this hydrolyzed copolymer scale inhibition performance is 83.2%.
Embodiment 2:
Synthesizing of multipolymer
Under the room temperature, take by weighing C
9Cut 22.010g, maleic anhydride 11.126g, n-butyl mercaptan 0.686g join in the 100mL four-hole bottle that has reflux and thermometer, stir, heating in water bath to 70 ℃.8.176g vinylformic acid, 34.302g butanone, 1.372g initiator Diisopropyl azodicarboxylate are joined in the 100mL dropping funnel, dropwise join in the four-hole bottle, the control dropping time, in 40 minutes, dropwise.70 ℃ of following isothermal reactions 6 hours.Pour reaction product into precipitation in the beaker that fills the 250mL sherwood oil, washing after reacting end.Throw out is filtered the back in 80 ℃ of vacuum-dryings 6 hours.
This copolymerization product transformation efficiency is: 79.2%, and limiting viscosity is: 0.082dL/g.
The multipolymer hydrolysis
Take by weighing 10g terpolymer, 5g NaOH respectively and place 500mL to have the distilling flask of reflux, add 250mL distilled water, be heated to reflux temperature, react about 2 hours transparent to solution, off-test.
Application test: 15 ℃, the oil-field flooding of pH=6.0,500mL, add the above-mentioned Scale inhibitors of 5mg, this hydrolyzed copolymer scale inhibition performance is 93.7%.
Other is with embodiment 1.
Embodiment 3:
Synthesizing of multipolymer
Under the room temperature, take by weighing C
9Cut 22.010g, maleic anhydride 11.126g, chain-transfer agent lauryl mercaptan 3.087g join in the 100mL four-hole bottle that has reflux and thermometer, stir, heating in water bath to 70 ℃.8.176g vinylformic acid, 34.302g butanone, 1.715g initiator Diisopropyl azodicarboxylate are joined in the 100mL dropping funnel, dropwise join in the four-hole bottle, the control dropping time, in 40 minutes, dropwise.70 ℃ of following isothermal reactions 6 hours.Pour reaction product into precipitation in the beaker that fills the 250mL sherwood oil, washing after reacting end.Throw out is filtered the back in 80 ℃ of vacuum-dryings 6 hours.
This copolymerization product transformation efficiency is: 89.2%, and limiting viscosity is: 0.014dL/g.
The multipolymer hydrolysis
Take by weighing 10g terpolymer, 5g NaOH respectively and place 500mL to have the distilling flask of reflux, add 250mL distilled water, be heated to reflux temperature, react about 2 hours transparent to solution, off-test.
Add the above-mentioned Scale inhibitors of 5mg, other is with embodiment 1, and this hydrolyzed copolymer scale inhibition performance is 96.5%.
Embodiment 4:
Synthesizing of multipolymer
Under the room temperature, take by weighing C
9Cut 22.010g, maleic anhydride 11.126g, chain-transfer agent thiohydracrylic acid 0.686g join in the 100mL four-hole bottle that has reflux and thermometer, stir, heating in water bath to 70 ℃.8.176g vinylformic acid, 34.302g butanone, 1.029g initiator benzoyl peroxide are joined in the 100mL dropping funnel, dropwise join in the four-hole bottle, the control dropping time, in two hours, dropwise.70 ℃ of following isothermal reactions 10 hours.Pour reaction product into precipitation in the beaker that fills the 250mL sherwood oil, washing after reacting end.Throw out is filtered the back in 80 ℃ of vacuum-dryings 6 hours.
This copolymerization product transformation efficiency is: 74.6%, and limiting viscosity is: 0.091dL/g.
The multipolymer hydrolysis
Take by weighing 10g terpolymer, 5g NaOH respectively and place 500mL to have the distilling flask of reflux, add 250mL distilled water, be heated to reflux temperature, react about 2 hours transparent to solution, off-test.
Add the above-mentioned Scale inhibitors of 7.5mg, other is with embodiment 1, and this hydrolyzed copolymer scale inhibition performance is 91.7%.
Other is with embodiment 1.
Embodiment 5:
Synthesizing of multipolymer
Under the room temperature, take by weighing C
9Cut 22.010g, maleic anhydride 11.126g, chain-transfer agent thiohydracrylic acid 1.029g join in the 100mL four-hole bottle that has reflux and thermometer, stir, heating in water bath to 70 ℃.8.176g vinylformic acid, 34.302g butanone, 1.715g initiator benzoyl peroxide are joined in the 100mL dropping funnel, dropwise join in the four-hole bottle, the control dropping time, in 40 minutes, dropwise.70 ℃ of following isothermal reactions 6 hours.Pour reaction product into precipitation in the beaker that fills the 250mL sherwood oil, washing after reacting end.Throw out is filtered the back in 80 ℃ of vacuum-dryings 6 hours.
This copolymerization product transformation efficiency is: 89.7%, and limiting viscosity is: 0.052dL/g.
The multipolymer hydrolysis
Take by weighing 10g terpolymer, 5g NaOH respectively and place 500mL to have the distilling flask of reflux, add 250mL distilled water, be heated to reflux temperature, react about 2 hours transparent to solution, off-test.
Add the above-mentioned Scale inhibitors of 15mg, other is with embodiment 1, and this hydrolyzed copolymer scale inhibition performance is 99.7%.
Embodiment 6:
Synthesizing of multipolymer
Under the room temperature, take by weighing C
9Cut 22.010g, vinylformic acid 8.179g, chain-transfer agent Thiovanic acid 0.312g join in the 100mL four-hole bottle that has reflux and thermometer, stir, heating in water bath to 70 ℃.8.065g acrylamide, 31.2g butanone, 3.124g initiator Diisopropyl azodicarboxylate are joined in the 100mL dropping funnel, dropwise join in the four-hole bottle, the control dropping time, in 30 minutes, dropwise.70 ℃ of following isothermal reactions 4 hours.Pour reaction product into precipitation in the beaker that fills the 250mL sherwood oil, washing after reacting end.Throw out is filtered the back in 80 ℃ of vacuum-dryings 6 hours.
This copolymerization product transformation efficiency is: 66.7%, and limiting viscosity is: 0.076dL/g.
The multipolymer hydrolysis
Take by weighing 10g terpolymer, 5g NaOH respectively and place 500mL to have the distilling flask of reflux, add 250mL distilled water, be heated to reflux temperature, react about 2 hours transparent to solution, off-test.
Add the above-mentioned Scale inhibitors of 5mg, other is with embodiment 1, and this hydrolyzed copolymer scale inhibition performance is 91.4%.
Embodiment 7:
Synthesizing of multipolymer
Under the room temperature, take by weighing C
9Cut 22.010g, maleic anhydride 11.126g, chain-transfer agent thiohydracrylic acid 0.686g join in the 100mL four-hole bottle that has reflux and thermometer, stir, heating in water bath to 70 ℃.8.065g acrylamide, 34.302g butanone, 1.372g initiator Diisopropyl azodicarboxylate are joined in the 100mL dropping funnel, dropwise join in the four-hole bottle, the control dropping time, in 40 minutes, dropwise.70 ℃ of following isothermal reactions 6 hours.Pour reaction product into precipitation in the beaker that fills the 250mL sherwood oil, washing after reacting end.Throw out is filtered the back in 80 ℃ of vacuum-dryings 6 hours.
This copolymerization product transformation efficiency is: 74.5%, and limiting viscosity is: 0.046dL/g.
The multipolymer hydrolysis
Take by weighing 10g C respectively
9-MA multipolymer, 5g NaOH place 500mL to have the distilling flask of reflux, add 250mL distilled water, are heated to reflux temperature, react about 2 hours transparent to solution, off-test.
Add the above-mentioned Scale inhibitors of 5mg, other is with embodiment 1, and this hydrolyzed copolymer scale inhibition performance is 94.6%.
Other is with embodiment 1.
Embodiment 8:
Synthesizing of multipolymer
Under the room temperature, take by weighing C
9Cut 22.010g, maleic anhydride 11.126g, chain-transfer agent lauryl mercaptan 1.029g, acrylamide 8.065g, butanone 34.302g join in the 100mL four-hole bottle that has reflux and thermometer, stir, behind the heating in water bath to 70 ℃, add initiator Diisopropyl azodicarboxylate 1.715g immediately.70 ℃ of following isothermal reactions 6 hours.Pour reaction product into precipitation in the beaker that fills the 250mL sherwood oil, washing after reacting end.Throw out is filtered the back in 80 ℃ of vacuum-dryings 6 hours.
This copolymerization product transformation efficiency is: 87.4%, and limiting viscosity is: 0.043dL/g.
The multipolymer hydrolysis
Take by weighing 10g terpolymer, 5g NaOH respectively and place 500mL to have the distilling flask of reflux, add 250mL distilled water, be heated to reflux temperature, react about 2 hours transparent to solution, off-test.
Add the above-mentioned Scale inhibitors of 5mg, other is with embodiment 1, and this hydrolyzed copolymer scale inhibition performance is 97.4%.
Other is with embodiment 1.
Embodiment 9:
Synthesizing of multipolymer
Under the room temperature, take by weighing C
9Cut 22.010g, maleic anhydride 11.126g, chain-transfer agent lauryl mercaptan 0.686g join in the 100mL four-hole bottle that has reflux and thermometer, stir, heating in water bath to 70 ℃.8.065g acrylamide, 34.302g butanone, 1.372g initiator benzoyl peroxide are joined in the 100mL dropping funnel, dropwise join in the four-hole bottle, the control dropping time, in two hours, dropwise.70 ℃ of following isothermal reactions 10 hours.Pour reaction product into precipitation in the beaker that fills the 250mL sherwood oil, washing after reacting end.Throw out is filtered the back in 80 ℃ of vacuum-dryings 6 hours.
This copolymerization product transformation efficiency is: 76.1%, and limiting viscosity is: 0.052dL/g.
The multipolymer hydrolysis
Take by weighing 10g terpolymer, 5g NaOH respectively and place 500mL to have the distilling flask of reflux, add 250mL distilled water, be heated to reflux temperature, react about 2 hours transparent to solution, off-test.
Add the above-mentioned Scale inhibitors of 5mg, other is with embodiment 1, and this hydrolyzed copolymer scale inhibition performance is 95.6%.
Other is with embodiment 1.
Embodiment 10:
Synthesizing of multipolymer
Under the room temperature, take by weighing C
9Cut 22.010g, maleic anhydride 11.126g, chain-transfer agent thiohydracrylic acid 1.029g join in the 100mL four-hole bottle that has reflux and thermometer, stir, heating in water bath to 70 ℃.8.065g acrylamide, 34.302g butanone, 1.715g initiator benzoyl peroxide are joined in the 100mL dropping funnel, dropwise join in the four-hole bottle, the control dropping time, in 40 minutes, dropwise.70 ℃ of following isothermal reactions 6 hours.Pour reaction product into precipitation in the beaker that fills the 250mL sherwood oil, washing after reacting end.Throw out is filtered the back in 80 ℃ of vacuum-dryings 6 hours.
This copolymerization product transformation efficiency is: 87.8%, and limiting viscosity is: 0.048dL/g.
The multipolymer hydrolysis
Take by weighing 10g terpolymer, 5g NaOH respectively and place 500mL to have the distilling flask of reflux, add 250mL distilled water, be heated to reflux temperature, react about 2 hours transparent to solution, off-test.
Add the above-mentioned Scale inhibitors of 5mg, other is with embodiment 1, and this hydrolyzed copolymer scale inhibition performance is 97.3%.
Other is with embodiment 1.
Claims (9)
1. the water-soluble C that has scale-inhibiting properties
9The petroleum resin terpolymer is characterized in that it being to utilize the ethylene production by product C of main component for dicyclopentadiene and homologue thereof
9Cut, synthetic water-soluble C with scale-inhibiting properties
9Petroleum resin terpolymer, this terpolymer are following composition:
This mixture has C
9Cut and R
1, R
2The terpolymer of alternating structure;
Wherein: R is C
9In contain the active ingredient of vinyl double bond;
R
1, R
2Be two kinds of different monomers in vinylformic acid and the derivative thereof;
Three kinds of polymerization single polymerization monomer mol ratios are 1: 1: 1;
Main performance index: the terpolymer limiting viscosity is 0.01～0.10dL/g;
The multipolymer productive rate is 80～90%.
2. the water-soluble C with scale-inhibiting properties according to claim 1
9The petroleum resin terpolymer is characterized in that R is dicyclopentadiene and homologue, indenes and homologue thereof, vinylbenzene and homologue thereof; Vinylformic acid and derivative thereof are selected from maleic anhydride, vinylformic acid and acrylamide.
3. the described water-soluble C of claim 1 with scale-inhibiting properties
9The preparation method of petroleum resin terpolymer is characterized in that utilizing azo class or peroxide initiator, is the ethylene production by product C of dicyclopentadiene and derivative thereof with the main component
92 kinds of monomer polymerizations in cut and vinylformic acid and derivative maleic anhydride thereof, vinylformic acid, the acrylamide, generation has C
9The terpolymer of cut and vinylformic acid and derivative alternating structure thereof, and regulate the multipolymer limiting viscosity by adding chain-transfer agent, chain-transfer agent adopts thio-alcohol or mercaptan carboxylic acid's class, and is above-mentioned raw materials used and the consumption prescription is as follows:
The ratio of three kinds of polymerization single polymerization monomers, i.e. ethylene production by product C
92 kinds of monomer mole ratios in cut and maleic anhydride, vinylformic acid, the acrylamide are 1: 1: 1; Other material composition add-on is:
Material composition accounts for reaction monomers total mass number per-cent
Chain-transfer agent 1～10%
Initiator 1～10%
Organic solvent 100%
Its concrete preparation method is as follows:
Underpressure distillation; With C
9Oil is ethylene production by product C
9Oil, underpressure distillation intercepts 38～120 ℃ of cuts.
Multipolymer is synthetic: cut, vinylformic acid and derivative thereof, the chain-transfer agent of underpressure distillation are joined in the band cooling and reflux device container according to above-mentioned prescription, and heated and stirred after 70 ℃, adds initiator, isothermal reaction 4～10 hours;
Termination reaction: reaction finishes the back and adds stopper such as Resorcinol;
Washing and filtering: with reacted copolymerization product and residuum, pour in the beaker that precipitation agent such as sherwood oil are housed, be settled out multipolymer, will fall multipolymer vacuum-drying 6h in 80 ℃ of vacuum drying ovens again, obtain C
9The petroleum resin terpolymer;
Multipolymer hydrolysis: in multipolymer and 2: 1 ratio of NaOH mass ratio, multipolymer and NaOH are joined in the container of taking back stream, add distilled water, the terpolymer of the above-mentioned preparation of hydrolysis under the distilled water boiling temperature, until aqueous solution clarification, can obtain water-soluble C
9The petroleum resin terpolymer.
4. the water-soluble C with scale-inhibiting properties according to claim 3
9The preparation method of petroleum resin terpolymer is characterized in that the quality percentage composition of polymerizable composition is: 68%, and bromine number is: 160.81.
5. according to the described water-soluble C of claim 3 with scale-inhibiting properties
9The preparation method of petroleum resin terpolymer is characterized in that, azo-initiator is selected from Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile); The peroxide initiator is selected from benzoyl peroxide or dilauroyl peroxide.
6. according to the described water-soluble C of claim 3 with scale-inhibiting properties
9The preparation method of petroleum resin terpolymer is characterized in that, chain-transfer agent adopts the thio-alcohol chain to be selected from lauryl mercaptan or n-butyl mercaptan.
7. according to the described water-soluble C of claim 3 with scale-inhibiting properties
9The preparation method of petroleum resin terpolymer is characterized in that, chain-transfer agent adopts mercaptan carboxylic acid's class selected from mercapto propionic acid or Thiovanic acid.
8. according to the described water-soluble C of claim 3 with scale-inhibiting properties
9The petroleum resin terpolymer the preparation method, it is characterized in that initiator takes the dropping mode to add, be about to the cut C of underpressure distillation
9, a kind of monomer, chain-transfer agent in vinylformic acid and the derivative thereof join in the band cooling and reflux device container according to above-mentioned formula rate, heated and stirred, after 70 ℃, dropping is the solution of solute with the another kind of monomer in solvent, initiator and the acrylic acid derivative, and the control dropping time was at 0.5～2 hour.
9. the described water-soluble C of claim 1 with scale-inhibiting properties
9The purposes of petroleum resin terpolymer is characterized in that, as Scale inhibitors, its use range is to be that add-on is the water-soluble C of 5mg/L～30mg/L in 15～80 ℃, the industrial circulating water or oil-field flooding of pH=6.0～8.0
9During the petroleum resin terpolymer, its scale inhibition performance can reach 80%～99%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100197590A CN1315896C (en) | 2004-06-28 | 2004-06-28 | Water soluble C#-[9] petroleum resin terpolymers with scale-inhibiting property and preparation process thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100197590A CN1315896C (en) | 2004-06-28 | 2004-06-28 | Water soluble C#-[9] petroleum resin terpolymers with scale-inhibiting property and preparation process thereof |
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| CN1594383A CN1594383A (en) | 2005-03-16 |
| CN1315896C true CN1315896C (en) | 2007-05-16 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN102898574B (en) * | 2012-10-25 | 2014-06-25 | 南京大地冷冻食品有限公司 | Preparation method of novel environment-friendly high-efficiency detergent |
| CN106905481B (en) * | 2015-12-22 | 2019-03-12 | 中国石油天然气股份有限公司 | Method for preparing functionalized DCPD petroleum resin |
| CN106565903A (en) * | 2016-11-14 | 2017-04-19 | 武汉宜田科技发展有限公司 | Preparation method of novel scale-inhibiting terpolymer used in strongly acidic environment |
| KR102640216B1 (en) * | 2020-11-20 | 2024-02-27 | 코오롱인더스트리 주식회사 | A resin composition, method of preparing the same, and rubber composition including the same |
| KR102614617B1 (en) * | 2020-11-20 | 2023-12-19 | 코오롱인더스트리 주식회사 | A resin composition, method of preparing the same, and paint composition including the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091751A (en) * | 1993-07-06 | 1994-09-07 | 大庆石油学院 | Water-soluble carbon pellet petroleum resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091751A (en) * | 1993-07-06 | 1994-09-07 | 大庆石油学院 | Water-soluble carbon pellet petroleum resin |
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