CN104031258B - Phosphate group containing terpolymer as well as preparation method and application thereof - Google Patents
Phosphate group containing terpolymer as well as preparation method and application thereof Download PDFInfo
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- CN104031258B CN104031258B CN201410260101.2A CN201410260101A CN104031258B CN 104031258 B CN104031258 B CN 104031258B CN 201410260101 A CN201410260101 A CN 201410260101A CN 104031258 B CN104031258 B CN 104031258B
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Abstract
The invention discloses a phosphate group containing terpolymer which can be used as a high-performance dispersing agent for preparing water coal slurry. The phosphate group contained terpolymer has a structure as shown in the formula as the specification, wherein R1=H or CH3, R2=H, CH3 or CH2CH2CH2CH3, R3=PO3Na2, n=45-120, m=15-30, and p=22-50. The phosphate group containing terpolymer contains no sulfur and is incapable of discharging sulfur after combusting so as to be environment-friendly; and in addition, the terpolymer has the advantages of strong coal type adaptability, low dispersant dosage, good dispersibility and stability of prepared slurry, low production cost and the like. The invention also discloses a preparation method of the phosphate group containing terpolymer, and the preparation method is free of concentrated sulfuric acid sulfonation in synthesis and little in equipment corrosion.
Description
Technical field
The present invention relates to a kind of novel phosphorus-containing acidic group terpolymer and its production and use, described phosphorous acidic group terpolymer uses mainly as the dispersion agent of coal water slurry.
Background technology
Coal, with its advantageous natural energy resources, becomes the ground of the competition of countries in the world government Efficient Development and utilization.Especially, in the face of the situation that is becoming tight Global Oil resource day, global scientist will actively probe into economically viable clean coal technology, as one of the important means of the energy-saving and emission-reduction efficiency utilization energy.A large amount of facts have proved in China and foreign countries, coal water slurry (CWM) technology is current technically reliable, economically viable extensive coal utilization means.
CWM is that a kind of coal dust with certain grain size distribution is scattered in the heterogeneous coal/aqueous dispersion of the high density polycomponent made in water medium.Compatible and the stability problem in this coal/water compound system interface, has been acknowledged as an important front edge difficult problem for world CWM engineering so far.CWM additive is requisite auxiliary chemicals in CWM pressurized gasification, burning and conveying engineering, is still the key of CWM progress and advanced technology so far.Desirable CWM has good mobility and the stability of long period, equally store just like petroleum products, transport, and have without pyrophoricity, pollute low advantage, coal for replacing oil clean fuel both economical at present and industrial chemicals, also be at present with the main raw material of coal generating gas liquefaction simultaneously, there is good market outlook and significant social, ecnomics and enviroment benefit.China is the country of an oil starvation, weak breath, rich coal, therefore develops CWM technology to the Energy restructuring of China, promotes the coordinated development of society, ecnomics and enviroment, ensures that national energy security all has very important strategic importance.
The key of preparation coal water slurry is the dispersion agent of coal water slurry.Good coal water slurry dispersing agent must ensure the adaptability to Coal rank simultaneously, good interface compatibility, and the long-term stability of coal slurry and good fluidity, and need take into account production cost and environmental friendliness simultaneously.In the work in early stage, we are design and synthesis molecule novel structure, molecular weight and hydrophilic radical kind, the regulatable tertiary copolymerized high-molecular-weight compound of quantity (ZL97107094.6) once.It is few that this terpolymer has dispersant dosage, the slurry of preparation is dispersed, good stability, the advantages such as low production cost, and to the coal of different areas, different coal-forming time, different interface feature, all there is excellent adaptability, widely use on Weihe River in Shaanxi, Yanzhou, Period In Maoming and other places.
But along with people are to the pay attention to day by day of environmental problem, the pollution of the element sulphur discharged in fuel to air more and more gets more and more people's extensive concerning.The coal water slurry dispersing agent synthesizing not sulfur-bearing is day by day urgent.
Summary of the invention
The object of the invention is to provide a kind of novel phosphorus-containing acidic group terpolymer, not containing element sulphur in described phosphorous acidic group terpolymer, can be used as the high-performance dispersion agent of preparation coal water slurry, and it is strong to have coal adaptability, dispersant dosage is few, the slurry of preparation is dispersed, good stability, the advantages such as low production cost.
Another object of the present invention is also the preparation method and the purposes that provide described phosphorous acidic group terpolymer.
The object of the invention is to be achieved through the following technical solutions:
A kind of phosphorous acidic group terpolymer, its basic structure formula is as follows:
Wherein R
1=H or CH
3; R
2=H, CH
3or CH
2cH
2cH
2cH
3; R
3=PO
4na
2; N=45-120, m=15-30, p=22-50.
The preparation method of phosphorous acidic group terpolymer of the present invention comprises the steps:
(1) by vinylbenzene be selected from the monomer of vinylformic acid, methyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate or butyl methacrylate at 50-70 DEG C, free radical causes copolyreaction, obtained copolymer;
(2) copolymer of step (1) gained is added acid or alkaline catalysts, be heated to 150-170 DEG C, add reacting ethylene oxide, obtained terpolymer;
(3) above-mentioned terpolymer phosphoric acid or polyphosphoric acid are carried out phosphorylation;
(4) be neutralized to weakly alkaline with sodium hydroxide, namely obtain described phosphorous acidic group terpolymer.
In described method, step (1) recommends to adopt persulphate to be radical initiator, also can adopt other known radical initiator, comprise organo-peroxide, as cyclohexanone peroxide, dibenzoyl peroxide, tertbutyl peroxide etc.; Azo-initiator, as Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) etc.
In described method, vinylbenzene is 1:2.5 ~ 1:4 with the mol ratio of the monomer being selected from vinylformic acid, methyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate or butyl methacrylate; The mol ratio of vinylbenzene and oxyethane is 1:1.5 ~ 1:2.
In described method, acid or alkaline catalysts are selected from inorganic acid or alkali, recommend to adopt hydrochloric acid, sulfuric acid, sodium hydroxide or potassium hydroxide etc.
Particularly; optimisation technique scheme of the present invention is: 9.5 ~ 10.5g Sodium dodecylbenzene sulfonate and 500mL water are placed in reactor; logical nitrogen protection; 65 ~ 75g vinylbenzene and 200 ~ 280g methyl methacrylate (or vinylformic acid, methyl acrylate, butyl acrylate, methacrylic acid or butyl methacrylate) is added while stirring at 50 DEG C; drip the persulfate aqueous solution containing 0.7 ~ 0.8g Potassium Persulphate initiator; after reaction 4h, be warming up to 70 DEG C and continue reaction 1h.Be separated, dry.Add sodium hydroxide, after being warming up to 150 DEG C, slowly add oxyethane 40 ~ 45g, after reaction starts, logical water of condensation cooling, by product separation after reaction 1.5h, washing, obtained terpolymer.Add 65 ~ 70g phosphoric acid or tripolyphosphate in described terpolymer, phosphorylation 2h, add sodium hydroxide adjust ph to 7.5-8.5.
The present invention, by redesigning terpolymer, replaces sulfonic group of the prior art as the Core Feature group of dispersion agent using phosphate, and using oxyethane as Third monomer, plays best dispersion effect to coordinate phosphate.Phosphorous acidic group terpolymer of the present invention is not only containing element sulphur, and environment is more friendly; And decrease reactions steps in process of production, reduce production difficulty, eliminate sulfonation reaction, reduce the corrosion to equipment.The consumption that this novel phosphorus-containing acidic group terpolymer not only maintains original terpolymer dispersants is few, and the slurry of preparation is dispersed, good stability, and the advantages such as low production cost, its coal adaptability is better.
The invention still further relates to the purposes of described phosphorous acidic group terpolymer, namely as the application of coal water slurry dispersing agent.
Beneficial effect of the present invention
:phosphorous acidic group terpolymer of the present invention not sulfur-bearing, more friendly to environment; The synthesis step of this terpolymer is simple and without sulfonation process, little to equipment corrosion; This terpolymer has coal adaptability by force when being used for coal water slurry dispersing agent, dispersant dosage is few, and the slurry of preparation is dispersed, good stability, the advantages such as low production cost.This terpolymer not only can be used as the high-performance dispersion agent of preparation coal water slurry, also in cement water reducing agent, emulsifying agent etc., has potential application foreground.
Accompanying drawing explanation
The infrared spectrogram of Fig. 1 phosphorous acidic group terpolymer of the present invention.
Embodiment
Embodiment 1:
9.5g Sodium dodecylbenzene sulfonate and 500mL water are placed in reactor; logical nitrogen protection, adds 65g vinylbenzene and 250g methyl methacrylate while stirring at 50 DEG C, drip the persulfate aqueous solution containing 0.7g Potassium Persulphate initiator; after reaction 4h, be warming up to 70 DEG C and continue reaction 1h.Be separated, dry.Add sodium hydroxide, after being warming up to 150 DEG C, slowly add oxyethane 40g, after reaction starts, logical water of condensation cooling, by product separation after reaction 1.5h, washing, obtained terpolymer.Add 65g tripolyphosphate in described terpolymer, phosphorylation 2h, add sodium hydroxide adjust ph to 7.5-8.5.
Obtained phosphorous acidic group terpolymer VPO method records its number-average molecular weight and is about 13600.
Embodiment 2:
9.5g Sodium dodecylbenzene sulfonate and 500mL water are placed in reactor; logical nitrogen protection, adds 65g vinylbenzene and 280g butyl methacrylate while stirring at 50 DEG C, drip the persulfate aqueous solution containing 0.7g Potassium Persulphate initiator; after reaction 4h, be warming up to 70 DEG C and continue reaction 1h.Be separated, dry.Add sodium hydroxide, after being warming up to 150 DEG C, slowly add oxyethane 40g, after reaction starts, logical water of condensation cooling, by product separation after reaction 1.5h, washing, obtained terpolymer.Add 70g phosphoric acid in described terpolymer, phosphorylation 2h, add sodium hydroxide adjust ph to 7.5-8.5.
Embodiment 3:
10.5g Sodium dodecylbenzene sulfonate and 500mL water are placed in reactor; logical nitrogen protection, adds 75g vinylbenzene and 200g vinylformic acid while stirring at 50 DEG C, drip the persulfate aqueous solution containing 0.8g Potassium Persulphate initiator; after reaction 4h, be warming up to 70 DEG C and continue reaction 1h.Be separated, dry.Add sodium hydroxide, after being warming up to 150 DEG C, slowly add oxyethane 45g, after reaction starts, logical water of condensation cooling, by product separation after reaction 1.5h, washing, obtained terpolymer.Add 70g phosphoric acid in described terpolymer, phosphorylation 2h, add sodium hydroxide adjust ph to 7.5-8.5.
Embodiment 4:
10.0g Sodium dodecylbenzene sulfonate and 500mL water are placed in reactor; logical nitrogen protection, adds 75g vinylbenzene and 260g methyl acrylate while stirring at 50 DEG C, drip the persulfate aqueous solution containing 0.8g Potassium Persulphate initiator; after reaction 4h, be warming up to 70 DEG C and continue reaction 1h.Be separated, dry.Add sodium hydroxide, after being warming up to 150 DEG C, slowly add oxyethane 45g, after reaction starts, logical water of condensation cooling, by product separation after reaction 1.5h, washing, obtained terpolymer.Add 65g tripolyphosphate in described terpolymer, phosphorylation 2h, add sodium hydroxide adjust ph to 7.5-8.5.
Embodiment 5:
9.5g Sodium dodecylbenzene sulfonate and 500mL water are placed in reactor; logical nitrogen protection, adds 65g vinylbenzene and 280g butyl acrylate while stirring at 50 DEG C, drip the persulfate aqueous solution containing 0.7g Potassium Persulphate initiator; after reaction 4h, be warming up to 70 DEG C and continue reaction 1h.Be separated, dry.Add sodium hydroxide, after being warming up to 150 DEG C, slowly add oxyethane 40g, after reaction starts, logical water of condensation cooling, by product separation after reaction 1.5h, washing, obtained terpolymer.Add 65g tripolyphosphate in described terpolymer, phosphorylation 2h, add sodium hydroxide adjust ph to 7.5-8.5.
Embodiment 6:
9.5g Sodium dodecylbenzene sulfonate and 500mL water are placed in reactor; logical nitrogen protection, adds 65g vinylbenzene and 260g methacrylic acid while stirring at 50 DEG C, drip the persulfate aqueous solution containing 0.8g Potassium Persulphate initiator; after reaction 4h, be warming up to 70 DEG C and continue reaction 1h.Be separated, dry.Add sodium hydroxide, after being warming up to 150 DEG C, slowly add oxyethane 40g, after reaction starts, logical water of condensation cooling, by product separation after reaction 1.5h, washing, obtained terpolymer.Add 65g tripolyphosphate in described terpolymer, phosphorylation 2h, add sodium hydroxide adjust ph to 7.5-8.5.
Embodiment 7:
Adopt phosphorous acidic group terpolymer (phosphate dispersion agent) of the present invention as dispersion agent preparation coal water slurry, compare with tertiary copolymerized high-molecular-weight compound disclosed in ZL97107094.6 (original dispersion agent) under the same terms, its result is as shown in the table.
From table 1, not only dispersant dosage is few for phosphorous acidic group terpolymer of the present invention, and coal adaptability is strong, and over-all properties is slightly excellent.Phosphorous acidic group terpolymer of the present invention not sulfur-bearing, more friendly to environment.
Claims (6)
1. a phosphorous acidic group terpolymer, is characterized in that, described terpolymer has the structural formula that is shown below:
Wherein R
1=H or CH
3; R
2=H, CH
3or CH
2cH
2cH
2cH
3; R
3=PO
4na
2; N=45-120, m=15-30, p=22-50.
2. a preparation method for phosphorous acidic group terpolymer according to claim 1, comprises the steps:
(1) by vinylbenzene be selected from the monomer of vinylformic acid, methyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate or butyl methacrylate at 50-70 DEG C, free radical causes copolyreaction, obtained copolymer;
(2) copolymer of step (1) gained is added acid or alkaline catalysts, be heated to 150-170 DEG C, add reacting ethylene oxide, obtained terpolymer;
(3) above-mentioned terpolymer phosphoric acid or polyphosphoric acid are carried out phosphorylation;
(4) be neutralized to weakly alkaline with sodium hydroxide, namely obtain described phosphorous acidic group terpolymer.
3. the preparation method of phosphorous acidic group terpolymer according to claim 2, it is characterized in that, in described method, vinylbenzene is 1:2.5 ~ 1:4 with the mol ratio of the monomer being selected from vinylformic acid, methyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate or butyl methacrylate; The mol ratio of vinylbenzene and oxyethane is 1:1.5 ~ 1:2.
4. the preparation method of phosphorous acidic group terpolymer according to claim 2, is characterized in that, step (1) adopts persulphate to be radical initiator.
5. the preparation method of phosphorous acidic group terpolymer according to claim 2, it is characterized in that, described method is, 9.5 ~ 10.5g Sodium dodecylbenzene sulfonate and 500mL water are placed in reactor, logical nitrogen protection, 65 ~ 75g vinylbenzene and 200 ~ 280g vinylformic acid, methyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate or butyl methacrylate is added while stirring at 50 DEG C, drip the persulfate aqueous solution containing 0.7 ~ 0.8g Potassium Persulphate initiator, after reaction 4h, be warming up to 70 DEG C and continue reaction 1h, be separated, dry; Add sodium hydroxide, after being warming up to 150 DEG C, slowly add oxyethane 40 ~ 45g, after reaction starts, logical water of condensation cooling, by product separation after reaction 1.5h, washing, obtained terpolymer; Add 65 ~ 70g phosphoric acid or tripolyphosphate in described terpolymer, phosphorylation 2h, add sodium hydroxide adjust ph to 7.5-8.5.
6. phosphorous acidic group terpolymer according to claim 1 is as the application of coal water slurry dispersing agent.
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| CN108410310B (en) * | 2018-03-27 | 2020-02-21 | 湖南智涂环保科技有限公司 | Coating film forming material and preparation method and application thereof |
| CN111727964A (en) * | 2020-06-01 | 2020-10-02 | 南京师范大学 | Avermectin nano slow-release pesticide preparation and preparation method thereof |
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| CN101570696B (en) * | 2008-04-30 | 2012-07-18 | 中国石油天然气股份有限公司 | Demulsifier for ternary combination flooding produced fluid and preparation method thereof |
| CN101368117A (en) * | 2008-07-03 | 2009-02-18 | 中国矿业大学(北京) | Preparation and application of polyacrylic acid system slurries additive |
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