CN104031258A - 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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- CN104031258A CN104031258A CN201410260101.2A CN201410260101A CN104031258A CN 104031258 A CN104031258 A CN 104031258A CN 201410260101 A CN201410260101 A CN 201410260101A CN 104031258 A CN104031258 A CN 104031258A
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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 is used 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 being becoming tight Global Oil resource day, global scientist will actively probe into economically viable clean coal technology, efficiently utilize one of important means of the energy as energy-saving and emission-reduction.A large amount of facts have proved in China and foreign countries, coal water slurry (CWM) technology is that current technology is 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 high density polycomponent of making 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 so far the key of CWM progress and advanced technology.Desirable CWM has good mobility and the stability of long period, just like petroleum products, equally store, transport, and have advantages of without pyrophoricity, pollute low, current both economical coal for replacing oil clean fuel and industrial chemicals, also be the current main raw material with coal generating gas liquefaction, there is good market outlook and significant society, economy and environmental benefit simultaneously.China is the country of an oil starvation, weak breath, rich coal, therefore develops the Energy restructuring of CWM technology to China, promotes the coordinated development of society, economy and environment, 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 guarantee the adaptability to Coal rank simultaneously, good interface compatibility, and long-acting stability and the good fluidity of coal slurry, and need take into account production cost and environmental friendliness simultaneously.In the work in early stage, we once designed and had synthesized molecule novel structure, molecular weight and hydrophilic radical kind, the regulatable tertiary copolymerized high-molecular-weight compound of quantity (ZL97107094.6).It is few that this terpolymer has dispersant dosage, the slurry dispersiveness of preparation, good stability, the advantages such as low production cost, and the coal to different areas, different coal-forming time, different interface features all has good adaptability, on Weihe River in Shaanxi, Yanzhou, Period In Maoming and other places, is widely used.
Yet along with the pay attention to day by day of people to environmental problem, the element sulphur discharging in fuel more and more gets more and more people's extensive concerning to the pollution of atmosphere.The coal water slurry dispersing agent of synthetic 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, in described phosphorous acidic group terpolymer, do not contain element sulphur, 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 dispersiveness of preparation, good stability, the advantages such as low production cost.
Another object of the present invention is also to provide preparation method and the purposes of described phosphorous acidic group terpolymer.
The object of the invention is to be achieved through the following technical solutions:
A phosphorous acidic group terpolymer, its basic structure formula is as follows:
R wherein
1=H or CH
3; R
2=H, CH
3or CH
2cH
2cH
2cH
3; R
3=PO
3na
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 with the monomer that is selected from vinylformic acid, methyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate or butyl methacrylate at 50-70 ℃, free radical causes copolyreaction, makes copolymer;
(2) copolymer of step (1) gained is added to acid or alkaline catalysts, be heated to 150-170 ℃, add reacting ethylene oxide, make terpolymer;
(3) above-mentioned terpolymer is carried out to phosphorylation with phosphoric acid or polyphosphoric acid;
(4) with sodium hydroxide, be neutralized to weakly alkaline, obtain described phosphorous acidic group terpolymer.
In described method, step (1) recommend adoption persulphate is radical initiator, also can adopt other known radical initiator, comprises 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 that is selected from the monomer of 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 adoption 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 to reactor; logical nitrogen protection; at 50 ℃, add while stirring 65～75g vinylbenzene and 200～280g methyl methacrylate (or vinylformic acid, methyl acrylate, butyl acrylate, methacrylic acid or butyl methacrylate); drip the persulfate aqueous solution containing 0.7～0.8g Potassium Persulphate initiator; after reaction 4h, be warming up to 70 ℃ and continue reaction 1h.Separation, dry.Add sodium hydroxide, slowly add oxyethane 40～45g after being warming up to 150 ℃, after reaction starts, logical water of condensation is cooling, and after reaction 1.5h, by product separation, washing, makes terpolymer.In described terpolymer, add 65～70g phosphoric acid or tripolyphosphate, phosphorylation 2h, adds sodium hydroxide to regulate pH value to 7.5-8.5.
The present invention is by redesigning terpolymer, and the phosphate of usining replaces sulfonic group of the prior art as the Core Feature group of dispersion agent, and usings oxyethane as the 3rd monomer, to coordinate phosphate to bring into play best dispersion effect.Phosphorous acidic group terpolymer of the present invention is not only containing element sulphur, and environment is more friendly; And reduced in process of production reactions steps, reduced production difficulty, removed sulfonation reaction, reduced the corrosion to equipment.This novel phosphorus-containing acidic group terpolymer has not only kept the consumption of original terpolymer dispersants few, the slurry dispersiveness of preparation, 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, as the application of coal water slurry dispersing agent.
Beneficial effect of the present invention
:phosphorous acidic group terpolymer of the present invention is sulfur-bearing not, more friendly to environment; The synthesis step of this terpolymer is simple and without sulfonation process, little to equipment corrosion; It is strong that this terpolymer has coal adaptability while being used for coal water slurry dispersing agent, and dispersant dosage is few, the slurry dispersiveness of preparation, 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 at aspects such as cement water reducing agent, emulsifying agents, 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 to reactor; logical nitrogen protection, adds 65g vinylbenzene and 250g methyl methacrylate at 50 ℃ while stirring, drips the persulfate aqueous solution containing 0.7g Potassium Persulphate initiator; after reaction 4h, be warming up to 70 ℃ and continue reaction 1h.Separation, dry.Add sodium hydroxide, slowly add oxyethane 40g after being warming up to 150 ℃, after reaction starts, logical water of condensation is cooling, and after reaction 1.5h, by product separation, washing, makes terpolymer.In described terpolymer, add 65g tripolyphosphate, phosphorylation 2h, adds sodium hydroxide to regulate pH value to 7.5-8.5.
The phosphorous acidic group terpolymer VPO method making records its number-average molecular weight and is about 13600.
Embodiment 2:
9.5g Sodium dodecylbenzene sulfonate and 500mL water are placed in to reactor; logical nitrogen protection, adds 65g vinylbenzene and 280g butyl methacrylate at 50 ℃ while stirring, drips the persulfate aqueous solution containing 0.7g Potassium Persulphate initiator; after reaction 4h, be warming up to 70 ℃ and continue reaction 1h.Separation, dry.Add sodium hydroxide, slowly add oxyethane 40g after being warming up to 150 ℃, after reaction starts, logical water of condensation is cooling, and after reaction 1.5h, by product separation, washing, makes terpolymer.In described terpolymer, add 70g phosphoric acid, phosphorylation 2h, adds sodium hydroxide to regulate pH value to 7.5-8.5.
Embodiment 3:
10.5g Sodium dodecylbenzene sulfonate and 500mL water are placed in to reactor; logical nitrogen protection, adds 75g vinylbenzene and 200g vinylformic acid at 50 ℃ while stirring, drips the persulfate aqueous solution containing 0.8g Potassium Persulphate initiator; after reaction 4h, be warming up to 70 ℃ and continue reaction 1h.Separation, dry.Add sodium hydroxide, slowly add oxyethane 45g after being warming up to 150 ℃, after reaction starts, logical water of condensation is cooling, and after reaction 1.5h, by product separation, washing, makes terpolymer.In described terpolymer, add 70g phosphoric acid, phosphorylation 2h, adds sodium hydroxide to regulate pH value to 7.5-8.5.
Embodiment 4:
10.0g Sodium dodecylbenzene sulfonate and 500mL water are placed in to reactor; logical nitrogen protection, adds 75g vinylbenzene and 260g methyl acrylate at 50 ℃ while stirring, drips the persulfate aqueous solution containing 0.8g Potassium Persulphate initiator; after reaction 4h, be warming up to 70 ℃ and continue reaction 1h.Separation, dry.Add sodium hydroxide, slowly add oxyethane 45g after being warming up to 150 ℃, after reaction starts, logical water of condensation is cooling, and after reaction 1.5h, by product separation, washing, makes terpolymer.In described terpolymer, add 65g tripolyphosphate, phosphorylation 2h, adds sodium hydroxide to regulate pH value to 7.5-8.5.
Embodiment 5:
9.5g Sodium dodecylbenzene sulfonate and 500mL water are placed in to reactor; logical nitrogen protection, adds 65g vinylbenzene and 280g butyl acrylate at 50 ℃ while stirring, drips the persulfate aqueous solution containing 0.7g Potassium Persulphate initiator; after reaction 4h, be warming up to 70 ℃ and continue reaction 1h.Separation, dry.Add sodium hydroxide, slowly add oxyethane 40g after being warming up to 150 ℃, after reaction starts, logical water of condensation is cooling, and after reaction 1.5h, by product separation, washing, makes terpolymer.In described terpolymer, add 65g tripolyphosphate, phosphorylation 2h, adds sodium hydroxide to regulate pH value to 7.5-8.5.
Embodiment 6:
9.5g Sodium dodecylbenzene sulfonate and 500mL water are placed in to reactor; logical nitrogen protection, adds 65g vinylbenzene and 260g methacrylic acid at 50 ℃ while stirring, drips the persulfate aqueous solution containing 0.8g Potassium Persulphate initiator; after reaction 4h, be warming up to 70 ℃ and continue reaction 1h.Separation, dry.Add sodium hydroxide, slowly add oxyethane 40g after being warming up to 150 ℃, after reaction starts, logical water of condensation is cooling, and after reaction 1.5h, by product separation, washing, makes terpolymer.In described terpolymer, add 65g tripolyphosphate, phosphorylation 2h, adds sodium hydroxide to regulate pH value to 7.5-8.5.
Embodiment 7:
Adopt phosphorous acidic group terpolymer of the present invention (phosphate dispersion agent) as dispersion agent preparation coal water slurry, under the same terms, compare with the disclosed tertiary copolymerized high-molecular-weight compound of ZL97107094.6 (original dispersion agent), 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 is sulfur-bearing not, more friendly to environment.
Claims (6)
1. a phosphorous acidic group terpolymer, is characterized in that, described terpolymer has the structural formula of being shown below:
R wherein
1=H or CH
3; R
2=H, CH
3or CH
2cH
2cH
2cH
3; R
3=PO
3na
2; N=45-120, m=15-30, p=22-50.
2. a preparation method for phosphorous acidic group terpolymer claimed in claim 1, comprises the steps:
(1) by vinylbenzene with the monomer that is selected from vinylformic acid, methyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate or butyl methacrylate at 50-70 ℃, free radical causes copolyreaction, makes copolymer;
(2) copolymer of step (1) gained is added to acid or alkaline catalysts, be heated to 150-170 ℃, add reacting ethylene oxide, make terpolymer;
(3) above-mentioned terpolymer is carried out to phosphorylation with phosphoric acid or polyphosphoric acid;
(4) with sodium hydroxide, be neutralized to weakly alkaline, 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 that is selected from the monomer of 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, it is radical initiator that step (1) adopts persulphate.
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 to reactor, logical nitrogen protection, at 50 ℃, add while stirring 65～75g vinylbenzene and 200～280g vinylformic acid, methyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate or butyl methacrylate, drip the persulfate aqueous solution containing 0.7～0.8g Potassium Persulphate initiator, after reaction 4h, be warming up to 70 ℃ and continue reaction 1h, separation, dry; Add sodium hydroxide, slowly add oxyethane 40～45g after being warming up to 150 ℃, after reaction starts, logical water of condensation is cooling, and after reaction 1.5h, by product separation, washing, makes terpolymer; In described terpolymer, add 65～70g phosphoric acid or tripolyphosphate, phosphorylation 2h, adds sodium hydroxide to regulate pH value to 7.5-8.5.
6. phosphorous acidic group terpolymer claimed in claim 1 is as the application of coal water slurry dispersing agent.
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Cited By (4)
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| WO2017113992A1 (en) * | 2015-12-31 | 2017-07-06 | 江苏苏博特新材料股份有限公司 | Phosphorylated polycondensate as high efficiency water reducing agent and preparation method thereof |
| CN108410310A (en) * | 2018-03-27 | 2018-08-17 | 湖南智涂环保科技有限公司 | A kind of coating film forming matter and its preparation method and application |
| CN111587890A (en) * | 2020-06-01 | 2020-08-28 | 南京师范大学 | Methylamino abamectin benzoate nano slow-release pesticide preparation and preparation method 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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| 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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