CN102492074A - Comb type copolymer with side chains grafted with naphthalene sulfonic acid groups, preparation method thereof and application thereof - Google Patents
Comb type copolymer with side chains grafted with naphthalene sulfonic acid groups, preparation method thereof and application thereof Download PDFInfo
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- CN102492074A CN102492074A CN2011103771572A CN201110377157A CN102492074A CN 102492074 A CN102492074 A CN 102492074A CN 2011103771572 A CN2011103771572 A CN 2011103771572A CN 201110377157 A CN201110377157 A CN 201110377157A CN 102492074 A CN102492074 A CN 102492074A
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Abstract
The invention relates to a comb type copolymer with side chains grafted with naphthalene sulfonic acid groups, a preparation method thereof and an application thereof. The preparation method comprises the following steps: 1, copolymerizing a styrene monomer with a maleic anhydride monomer through a free radical polymerization process to obtain a styrene-maleic anhydride copolymer; and 2, grafting naphthalene sulfonic acid groups to anhydride bonds at the side chains through an amidation reaction to obtain the comb type copolymer with the side chains containing strong polar sulfonic acid groups and non-polar aromatic groups. By adjusting feeding amounts of the styrene monomer and a sulfonic acid group compound, the hydrophobic level, the aromatic group content and the polarity of the comb type copolymer can be respectively adjusted. The comb type copolymer prepared in the invention, which can be used to prepare a high density coal water slurry, can substantially reduce the viscosity of the slurry and greatly improve the fluidity and the stability of the coal water slurry.
Description
Technical field
The present invention relates to a kind of binary comb copolymer that has the naphthene sulfonic acid base side chain; Specifically utilize the method for radical polymerization and grafting and modifying to prepare a kind of comb copolymer, and be applied to the production preparation of coal water slurry and the improvement of rheological property and stability.
Background technology
The energy is the important substance basis of social and economic development, and coal is not inexhaustible as a kind of fossil energy.China's fossil energy is main with coal, and abundant in coal still is a main energy sources reliably and with long-term.Greatly develop clean coal technology, utilize coal resources in China high-efficiency cleaning,, satisfy national economy fast and stable development need, have extremely important strategic importance for promoting the energy and environment coordinated development.Yet traditional coal-fired mode can cause serious topsoil, and coal water slurry is the best achievement of coal liquefaction, also is the most cheap practical technique of coal clean utilization.The coal water slurry conduct can be as oil pumping, atomizing, storage and stable burning for oil fuel, and its calorific value is equivalent to the half the of oil fuel, can replace oil fuel to be used for boiler, power station, industrial furnace and kiln.Also can replace conventional coal to use, have burning high efficiency, load adjustment facility, reduce environmental pollution, improve working conditions and save with advantages such as coals.
In the production process of coal water slurry, higher coal content is the most important condition that coal water slurry becomes high-effect fuel.But particle interphase interaction meeting increases in the high-concentration coal-water slurry pulping process, and this is precipitating generation, thereby gives the stable deleterious impact of coal water slurry.Simultaneously, the increase of coal content also can make slurry viscosity improve, and this also exerts an influence to the pipeline transportation and the pumping energy consumption of meeting coal water slurry.Therefore, find a kind of low-cost method that solves coal water slurry in aspect problems such as preparation and transportations, become the emphasis that current industry member is paid close attention to.The modification of coal microparticle surfaces all is devoted in most studies work now, strengthens coal-water mutual effect to obtain to have the coal water slurry system of low sticking, high coal content and stability.
Slurries additive agent is important auxiliary agent, particularly high density essential in the coal water slurry production process, the preparation of high-stability coal water slurry, and the effect of additive is particularly crucial.For many years, the country of each main developing water coal slurry all drops into the new variety that a large amount of human and material resources are developed additive.The additive that is used for the coal water slurry dispersion system generally is tensio-active agent, inorganic electrolyte and high molecular polymer, and relative molecular mass is bigger, has polarity and nonpolar part in the molecular structure simultaneously.They can be adsorbed onto coal particle surface rapidly in a large number through hydrophobic interaction, thereby non-polar group is wherein navigated to coal particle surface, and polar group then stretches in the water.Additive can make interfacial tension lowering in this adsorption of coal water termination, and owing to the increase of coal space surface steric hindrance and electrostatic repulsion, the reunion of coal particulate also will be hindered simultaneously.
At present, slurries additive agent both domestic and external mainly contains high condensation degree naphthalenesulfonate, vinylformic acid and other Acrylic Acid Monomer multipolymers, polyolefine, sulfonated lignin, carboxylic acid and phosphoric acid salt, humic acids and sulfonated humic acid, and non-ionic dispersing agent etc.Wherein, naphthalenesulfonate condensation compound and poly styrene sulfonate are to use two types of coal water slurry dispersing agents the most widely.Japan Ljon company develops the slurries additive agent that is the basis with Lewatit (PSSNa); Its average weight-molecular mass is 1.5 ten thousand～2.0 ten thousand; Add-on is few; Its dispersiveness, stable more superior than methylene radical sulphonate traditional dispersion agents such as (NSF), but dependency is arranged to being suitable for coal.U.S. Nat Distillers chemical company has reported that a kind of non-ionic dispersing agent is as slurries additive agent; Its water-wet side is a high molecular polymer; Can be affine well with water; The coal grain is dispersed in the water, form stable dispersion system, but higher production cost has limited its industrial application.Zeki Akta etc. has studied the viscosity influence of non-ionics Triton X-405 (to uncle's polyoxyethylene octylphenol ether) to high-concentration coal-water slurry.The result shows, in the presence of Triton X-405, can prepare the low ash content coal water slurry with suitable viscosity, and it is nearly 60% that its concentration can reach, but shortcoming is that cost is higher equally.
Summary of the invention
The slurries additive agent that the present invention seeks to develop a kind of low cost and have good versatility makes it be applicable to most of coals, and effectively improves the rheological property and the stability of coal water slurry.
The present invention synthesizes the comb copolymer coal water slurry properties-correcting agent that side chain contains the naphthene sulfonic acid group through the method for radical polymerization and the chemically modified of side chain naphthene sulfonic acid base.Concrete scheme is following:
The sulfonic comb copolymer of a kind of side chain graft has following structural formula:
Wherein, m, n are integer, and 7 < m < 24,7 < n < 24.
The amidation degree of said comb copolymer is 0.4～1.3.
The preparation method of said comb copolymer comprises the steps:
(1) free radical solution polymerization prepares comb copolymer:
The maleic anhydride and first solvent are joined in the reactor drum, and stirring is fully dissolved it; The vinylbenzene and first initiator fully are dissolved in first solvent; Splash into said reactor drum with constant pressure funnel; Under nitrogen protection and 60～110 ℃ of conditions, reacted 1～5 hour; Obtain the copolymer of relative molecular weight at 2000～10000 gram/moles, wherein the x of maleic anhydride is 42～50%;
Wherein, reactant consumption mol ratio is a maleic anhydride: vinylbenzene: first initiator=1:1～2:0.005～0.02;
Said first initiator is Diisopropyl azodicarboxylate or Lucidol, and said first solvent is YLENE, toluene, butanone, pimelinketone or ethylene dichloride etc.;
(2) amidation graft modification comb copolymer:
The copolymer in the step (1) and second solvent are joined in the reaction flask, and stirring is fully dissolved it; Amidation reagent fully is dissolved in the 3rd solvent, splashes into said reaction flask, reacted 6～24 hours down, obtain amidation grafted multipolymer, i.e. comb copolymer at 40～60 ℃ with constant pressure funnel;
Wherein, the first contained monomer mole ratio is 0.5～1.5:1 in the middle copolymer of amidation reagent and step (1);
Said second solvent is acetone, THF, methyl-sulphoxide or N, and said amidation reagent is a napthylamine sulfonic acid, and said the 3rd solvent is that massfraction is 1～2% sodium hydroxide solution.
Side chain of the present invention contains the comb copolymer coal water slurry properties-correcting agent of naphthene sulfonic acid base, is used to prepare high-concentration coal-water slurry, and the pumping of coal water slurry is stored with stable.Comb copolymer is joined in the coal water slurry by different coal preparations; Adopt rheometer test to add the viscosity of front and back slurry and the variation of yielding stress; After finding to add the comb copolymer of massfraction 0.2～1.0% (with respect to dry coal), various viscosity of coal-water slurry and yielding stress all have obvious reduction.
Styrene-maleic anhydride copolymer described in the preparation method of the present invention can pass through the method preparation of step (1), also can select the like product of selling on the market for use.
Through proton nmr spectra (
1H NMR) chemical structure of comb copolymer is analyzed, utilized spectrum peak integrating meter to calculate the amidation degree of comb copolymer.The amidation degree here is meant that a maleic anhydride group in the polymkeric substance is finally converted into the number of amido linkage, and size is between 0～2.Through calculating, the amidation degree of this comb copolymer is 0.4～1.3.
In addition, also utilize gel permeation chromatography (GPC) that the molecular weight of comb copolymer is tested, the molecular weight of comb copolymer is 2000～10000.
Description of drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of comb-shaped polymer;
Fig. 2 adds comb copolymer front and back viscosity in aqueous coal slurries test pattern (25 ℃);
Fig. 3 adds comb copolymer front and back coal water slurry yielding stress variation diagram (25 ℃).
Embodiment
Further specify the present invention with embodiment below, but protection scope of the present invention is not limited in embodiment.The variation and the modification of other that those skilled in the art is made under the situation that does not deviate from spirit of the present invention and protection domain still are included within the protection domain of the present invention.
Reaction scheme is exemplified below among the embodiment:
The preparation of embodiment 1 styrene-maleic anhydride copolymer
2.94g maleic anhydride and 30ml o-Xylol are joined in the there-necked flask, and stirring is fully dissolved maleic anhydride, takes out inflated with nitrogen 3～5 times, is warming up to 80 ℃ gradually.6.24g vinylbenzene and 0.04g Lucidol fully are dissolved in the 50ml o-Xylol, splash into there-necked flask with constant pressure funnel.Reaction system was reacted under nitrogen protection after 4 hours, and termination reaction slowly is added drop-wise to reaction solution in a large amount of methyl alcohol of quick stirring; It is fully precipitated; Suction filtration and vacuum-drying obtain Zelan 338, and wherein the maleic anhydride x is 42%.
The preparation of embodiment 2 comb copolymers
The preparation of styrene-maleic anhydride copolymer joins 6g styrene-maleic anhydride copolymer and 30ml acetone in the there-necked flask with embodiment 1, stirs it is fully dissolved, and is warming up to 50 ℃ gradually.It is in 2% the aqueous sodium hydroxide solution that the 8.78g napthylamine sulfonic acid fully is dissolved in the 150ml massfraction; Splash into there-necked flask with constant pressure funnel; Reacted 6 hours, and obtained the Zelan 338 that the side chain napthylamine sulfonic acid is modified, i.e. comb copolymer; The hydrogen nuclear magnetic resonance spectrogram of product is as shown in Figure 1, and the molecular weight that its gel permeation chromatography records is about 4700～25000.
Embodiment 3
The preparation of styrene-maleic anhydride copolymer joins 6g multipolymer and 30ml THF in the there-necked flask with embodiment 1, stirs it is fully dissolved, and is warming up to 60 ℃ gradually.It is in 1% the aqueous sodium hydroxide solution that the 2.93g napthylamine sulfonic acid fully is dissolved in the 50ml massfraction; Splash into there-necked flask with constant pressure funnel; Reacted 6 hours; Obtain the Zelan 338 that the side chain napthylamine sulfonic acid is modified, i.e. comb copolymer, the molecular weight that its gel permeation chromatography records is about 2400～15000.
Embodiment 4
Get commercially available maleic anhydride x and be 43.5% styrene-maleic anhydride copolymer 6g and 30ml acetone and join in the there-necked flask, stir it is fully dissolved, be warming up to 50 ℃ gradually.It is in 2% the aqueous sodium hydroxide solution that the 5.85g napthylamine sulfonic acid fully is dissolved in the 100ml massfraction; Splash into there-necked flask with constant pressure funnel; Reacted 6 hours; Obtain the Zelan 338 that the side chain napthylamine sulfonic acid is modified, i.e. comb copolymer, the molecular weight that its gel permeation chromatography records is about 3000～20000.
Fig. 2 is a viscosity in aqueous coal slurries test pattern (25 ℃) before and after the comb copolymer that adds among the embodiment 4 of massfraction 1% (to dry coal); Fig. 3 is a coal water slurry yielding stress variation diagram (25 ℃) before and after the comb copolymer that adds among the embodiment 4 of different mass mark (to dry coal); Can find out that behind the adding comb-shaped polymer, viscosity of coal-water slurry significantly reduces; Simultaneously, the adding of comb-shaped polymer can also make the yielding stress of coal water slurry decline to a great extent, and seldom can reach this effect under the condition of (about 0.2%) at comb-shaped polymer content.Above-mentioned phenomenon shows that the adding of comb-shaped polymer can significantly improve the flowability of coal water slurry, thereby is convenient to the pumping and the pipeline transportation of coal water slurry, cuts down the consumption of energy, and has also kept the good static stability of coal water slurry simultaneously, prevents its sedimentation in storage process.
Claims (4)
1. sulfonic comb copolymer of side chain graft is characterized in that said comb copolymer has following structural formula:
Wherein, m, n are integer, and 7 < m < 24,7 < n < 24.
2. comb copolymer according to claim 1 is characterized in that, the amidation degree of said comb copolymer is 0.4～1.3.
3. the preparation method of claim 1 or 2 described comb copolymers is characterized in that, comprises the steps:
(1) free radical solution polymerization prepares comb copolymer:
The maleic anhydride and first solvent are joined in the reactor drum, and stirring is fully dissolved it; The vinylbenzene and first initiator fully are dissolved in first solvent; Splash into said reactor drum with constant pressure funnel; Under nitrogen protection and 60～110 ℃ of conditions, reacted 1～5 hour; Obtain the copolymer of relative molecular weight at 2000～10000 gram/moles, wherein the x of maleic anhydride is 42～50%;
Wherein, reactant consumption mol ratio is a maleic anhydride: vinylbenzene: first initiator=1:1～2:0.005～0.02;
Said first initiator is Diisopropyl azodicarboxylate or Lucidol, and said first solvent is YLENE, toluene, butanone, pimelinketone or ethylene dichloride etc.;
(2) amidation graft modification comb copolymer:
The copolymer in the step (1) and second solvent are joined in the reaction flask, and stirring is fully dissolved it; Amidation reagent fully is dissolved in the 3rd solvent, splashes into said reaction flask, reacted 6～24 hours down, obtain amidation grafted multipolymer, i.e. comb copolymer at 40～60 ℃ with constant pressure funnel;
Wherein, the first contained monomer mole ratio is 0.5～1.5:1 in the middle copolymer of amidation reagent and step (1);
Said second solvent is acetone, THF, methyl-sulphoxide or N, and said amidation reagent is a napthylamine sulfonic acid, and said the 3rd solvent is that massfraction is 1～2% sodium hydroxide solution.
4. the application of claim 1 or 2 described comb copolymers is characterized in that, is used for producing the preparation coal water slurry, and the pumping of coal water slurry is stored with stable.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936314A (en) * | 2012-12-04 | 2013-02-20 | 华东理工大学 | Comb type copolymer with polyfunctional group grafted on side chain and preparation method and application thereof |
| CN104593103A (en) * | 2014-12-29 | 2015-05-06 | 上海海乔化工有限公司 | Additive for water coal slurry |
| CN106478855A (en) * | 2015-08-31 | 2017-03-08 | 华东理工大学 | A kind of bipolymer slurries additive agent of side chain graft benzenesulfonic acid base |
| CN108530639A (en) * | 2018-04-04 | 2018-09-14 | 青岛艾尔乐新材料有限公司 | Efficient water-coal-slurry thinner |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08231256A (en) * | 1995-02-28 | 1996-09-10 | Dai Ichi Kogyo Seiyaku Co Ltd | Cement dispersing agent |
| WO2006016499A1 (en) * | 2004-08-09 | 2006-02-16 | Hagihara Industries Inc. | Thermoplastic resin fibers for the reinforcement of cement |
| CN101544735A (en) * | 2009-04-10 | 2009-09-30 | 华东理工大学 | Three-element comb type copolymer, preparation method and application thereof |
| CN101870750A (en) * | 2010-06-02 | 2010-10-27 | 华东理工大学 | Comb copolymer, preparation method and application thereof |
| CN101899162A (en) * | 2010-07-16 | 2010-12-01 | 华东理工大学 | Comb-shaped polymer and preparation method and application thereof |
-
2011
- 2011-11-24 CN CN2011103771572A patent/CN102492074A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08231256A (en) * | 1995-02-28 | 1996-09-10 | Dai Ichi Kogyo Seiyaku Co Ltd | Cement dispersing agent |
| WO2006016499A1 (en) * | 2004-08-09 | 2006-02-16 | Hagihara Industries Inc. | Thermoplastic resin fibers for the reinforcement of cement |
| CN101544735A (en) * | 2009-04-10 | 2009-09-30 | 华东理工大学 | Three-element comb type copolymer, preparation method and application thereof |
| CN101870750A (en) * | 2010-06-02 | 2010-10-27 | 华东理工大学 | Comb copolymer, preparation method and application thereof |
| CN101899162A (en) * | 2010-07-16 | 2010-12-01 | 华东理工大学 | Comb-shaped polymer and preparation method and application thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936314A (en) * | 2012-12-04 | 2013-02-20 | 华东理工大学 | Comb type copolymer with polyfunctional group grafted on side chain and preparation method and application thereof |
| CN104593103A (en) * | 2014-12-29 | 2015-05-06 | 上海海乔化工有限公司 | Additive for water coal slurry |
| CN104593103B (en) * | 2014-12-29 | 2016-04-20 | 上海海乔化工有限公司 | A kind of additive for coal water slurry |
| CN106478855A (en) * | 2015-08-31 | 2017-03-08 | 华东理工大学 | A kind of bipolymer slurries additive agent of side chain graft benzenesulfonic acid base |
| CN108530639A (en) * | 2018-04-04 | 2018-09-14 | 青岛艾尔乐新材料有限公司 | Efficient water-coal-slurry thinner |
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Application publication date: 20120613 |