CN1072681C - Method for preparing poly styrene sulfonate - Google Patents
Method for preparing poly styrene sulfonate Download PDFInfo
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Abstract
The present invention relates to a method for preparing polystyrene sulfonate. Meta-isopropenyl toluene dimer-2, 4-dimetatoly1-4-methyl-1-pentene is used as a chain transferring agent; polystyrene with low molecular weight is prepared by bulk polymerization initiated by heat or suspension polymerization initiated by peroxide; then, the polystyrene is sulfonated and neutralized. The method has the advantages of easy obtainment of raw material, low cost, low requirements of raw material and the purity of reagents, moderate reaction conditions and easy control. The polystyrene sulfonic acid salts prepared by the method can be used as water-reducing agents of concrete, disperser of aqueous coal slurry, etc.
Description
The present invention relates to the preparation method of poly styrene sulfonate, a kind of more precisely preparation method of low-molecular-weight polystyrene sulfonate.
Poly styrene sulfonate is a kind of good water soluble anionic surfactant, can be used as coal water slurry dispersing agent, cement water reducing agent and grout dispersion agent etc.This class dispersion agent has advantages such as the few and mobile hold-time length of addition.
The existing report of the preparation method of poly styrene sulfonate generally is that the low-molecular-weight polystyrene of producing with the ionic polymerization method is a raw material, makes through sulfonation and neutralization procedure.
The flat 3-52902 of JP has proposed a kind of elder generation and has prepared low-molecular-weight polystyrene with cationic polymerization, makes the method for poly styrene sulfonate again through the sulfonation neutralization.
The flat 2-240116 of JP has proposed a kind of preparation method of poly styrene sulfonate, be earlier polystyrene to be dissolved in halohydrocarbon, press styrene monomer: sulphur trioxide=0.8～1.1: 1 mol ratio adds oleum, and sulfonation under＜60 ℃ temperature neutralizes with slaked lime then.
JP flat-224249 has proposed a kind of preparation method of cement dispersants, also is with molecular weight 1,000～100, and 000 commercial polysterol is dissolved in halohydrocarbon, by putting down 2～240116 identical method sulfonation and neutralizations with JP.
EP0253598 disclose a kind ofly contain that molecular weight is 5,000～50,000, sulphonation rate is greater than the cement dispersants of 80% calcium polystyreme sulphonate, this calcium polystyreme sulphonate also neutralizes with the commercial polysterol sulfonation again and obtains.
The low-molecular-weight polystyrene of mentioning in the above-mentioned patent makes by the ionic polymerization method, the working condition of ionic polymer is very harsh, styrene monomer and solvent all need strict purification refine before polymerization, therefore production cost is higher, and this also is one of major reason of applying of restriction poly styrene sulfonate class dispersion agent.
The required polystyrene of poly styrene sulfonate as cement water reducing agent or coal water slurry dispersing agent is the polystyrene of a kind of lower molecular weight, narrow distribution, except above-mentioned ionic polymerization method, also can adopt the method that adds chain-transfer agent to make.
Te Kaiping 3-111405 is with 2, and 4-phenylbenzene-4-methyl-1-pentene is that chain-transfer agent makes low-molecular-weight polystyrene by hot mass polymerization.
JP is flat-and 3-212402 adopts above-mentionedly 2, and 4-phenyl-4-methyl-1-pentene is that chain-transfer agent makes low-molecular-weight polystyrene by suspension polymerization.2,4-phenylbenzene-4-methyl-1-pentene is that the dimerization reaction by alpha-methyl styrene makes.In addition, the spy opens the preparation method that clear 50-76051 discloses unsaturated dimers of alpha-methylstyrenes, is to be catalyzer with the sulfonic acid ion exchange resin, with C
2～C
5Primary alconol be solvent, temperature of reaction is 20～100 ℃.
The objective of the invention is based on prior art, overcome ionic polymerization method technology harshness, the defective that production cost is high provides a kind of by adopting new chain-transfer agent to prepare the method for poly styrene sulfonate.
The preparation method's of the poly styrene sulfonate that the present invention proposes key problem in technology is to adopt a kind of new chain-transfer agent to control the molecular weight and the molecular weight distribution of polystyrene, promptly with 2, two tolyl-4-methyl-1-pentenes of 4-(calling TUD in the following text) are chain-transfer agent, adopt bulk thermal polymerization or superoxide to cause the suspension polymerization low-molecular-weight polystyrene, make poly styrene sulfonate through sulfonation and neutralization procedure again.Wherein, the method for preparing polystyrene by mass polymerization comprises the steps:
Chain-transfer agent TUD and styrene monomer are mixed by 0.01～0.3: 1, and starvation reacted 1～8 hour the separated product polystyrene down at 100～240 ℃.
Specifically, mass polymerization prepares polystyrene and can implement as follows:
TUD and styrene monomer are mixed by 0.01～0.3: 1 weight ratio, starvation, at 100～240 ℃, 120～200 ℃ of reaction 1～8h down preferably, 2～6h preferably, small-molecule substances such as unreacted monomer are taken out in decompression, promptly get polystyrene.
The molecular weight and the molecular weight distribution of the concentration affects polystyrene of described chain-transfer agent TUD, TUD concentration increases, and the polystyrene molecular weight diminishes, and molecular weight distribution narrows down.The concentration of chain-transfer agent can be determined according to the molecular weight of p-poly-phenyl ethene and the requirement of molecular weight distribution.When the weight ratio of chain-transfer agent and styrene monomer is 0.001～0.25: in the time of 1, weight-average molecular weight is 1,000～120,000, and molecular weight distribution is 1.8～5.5; The weight ratio of chain-transfer agent and styrene monomer is 0.01～0.2: 1 o'clock, and molecular weight is 3,000～50,000, and molecular weight distribution is 1.9～3.5.
The molecular weight and the molecular weight distribution of described reaction temperatures affect speed of response and polystyrene.When other condition was constant, temperature of reaction raise, and speed of response is obviously accelerated, and the molecular weight of polystyrene reduces, and molecular weight distribution broadens.Suitable temperature of reaction is 100～240 ℃, and preferably 120～200 ℃, the suitable reaction times is 1～8h, preferably 2～6h.But in proper extension reaction times when temperature of reaction is low, can suitably shorten the reaction times when temperature of reaction is higher.
Described starvation refers to the oxygen in the eliminating system, prevents reactant oxidation by air at high temperature.Specific practice is with rare gas element such as nitrogen, carbonic acid gas, helium, neon, argon gas etc. and air displacement, or adopts other to keep the method for anoxia condition.
As another kind of embodiment, polystyrene also can prepare by suspension polymerization: promptly, with dispersion agent, chain-transfer agent TUD and the temperature that declined in 10 hours half be 30～90 ℃ peroxide initiator, styrene monomer and water by 0.001～0.005: 0.001～0.2: 0.01～0.05: 1: 2～5 weight ratio is mixed, 40～be lower than under 100 ℃ the temperature and reacted the separated product polystyrene 2～10 hours.
Specifically, suspension polymerization prepares polystyrene can be implemented as follows: dispersion agent, chain-transfer agent TUD, peroxide initiator, vinylbenzene and water are mixed by 0.001～0.005: 0.001～0.2: 0.01～0.05: 1: 2～5 weight ratio, 40～be lower than 100 ℃, preferably react 2～10h under 60～90 ℃ the temperature, behind the reaction product branch vibration layer, small-molecule substances such as unreacted monomer are taken out in decompression, promptly get polystyrene.
Described dispersion agent is the general dispersion agent of suspension polymerization, and as polyvinyl alcohol etc., its consumption can be 0.001～0.005 times of vinylbenzene weight.
Described peroxide initiator can be that the 10h temperature that partly declines is 30～90 ℃ a peroxide initiator; preferably the 10h temperature that partly declines is 40～80 ℃ a peroxide initiator, as benzoyl peroxide, dilauroyl peroxide, acetyl peroxide, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy dicarbonate etc.The too high meeting of the temperature that partly declines of initiator causes speed of response slow, and transformation efficiency is low; On the contrary, the temperature that partly declines is low excessively, and then speed of response is too fast, reacts wayward.Consider the existence of water, temperature of reaction is advisable to be lower than 100 ℃, and preferably 60～90 ℃, and controlling reaction time is 2～10h.Not oxidized in order to ensure reactant, preferably reaction system is placed rare gas element, in nitrogen environment.
Described five kinds of reactive components are dispersion agent, chain-transfer agent, peroxide initiator, vinylbenzene and water when mixing, order in no particular order, but consider water yield maximum, other four kinds of components can be added in the entry so that operation.Dispersion effect can add dispersion agent earlier in the entry in order to reach preferably, is mixed with the aqueous solution, other three kinds of components is joined in the aqueous solution again.In addition, also initiator can be added in reaction process several times,, make the molecular weight ratio of product more even so that initiator concentration keeps relative stability in the reaction process.If initiator adds several times, then preferably it is dissolved in the part styrene monomer, so that operation.After all adding, preferably continues by initiator reaction 1～2h again.
Among the preparation method of poly styrene sulfonate provided by the invention, chain-transfer agent 2, two tolyl-4-methyl-1-pentenes of 4-(TUD) can be opened clear 50-76051 disclosed method preparation according to existing document such as spy, also can prepare: promptly according to following method, isopropenyl toluene and acidic white earth mix by 1: 0.03～0.3 weight ratio between inciting somebody to action, after reacting 2～10 hours under 80～140 ℃, under 5～50mmHg, collect 120～220 ℃ cut then, can obtain content greater than 90% product TUD.The structural formula of TUD is:
If described acidic white earth spent glycol is before use handled, can further improve its selectivity to TUD.Concrete grammar is to be that 0.5～2: 1 ethylene glycol and carclazyte mix with weight ratio, and decompress filter then, filter residue are with isopropenyl toluene washing between monomer, and suction filtration promptly makes ethylene glycol/clay catalyst again.
Between the weight ratio of isopropenyl toluene and acidic white earth can be 1: 0.03～0.3, preferably 1: 0.1～0.2.Temperature of reaction can be 80～140 ℃, preferably 95～125 ℃.Reaction times can be 2～10h, preferably 4～8h.Under so preferred time and temperature, the transformation efficiency of reaction is not necessarily the highest, but selectivity is good, the productive rate height of purpose product TUD.Reaction removes by filter impurity with product, then underpressure distillation after finishing.Between two kinds of isomer that boiling point is close are arranged in the dimerisation products of isopropenyl toluene, promptly the purpose product 2, two tolyl-4-methyl-1-pentenes of 4-(TUD) and 2, two tolyls of 4--4-methyl-2-amylene (TUD2).The existence of TUD2 can prolong the initiation reaction time, and is unfavorable to polyreaction.But when its content less than 10% the time, little to the polyreaction influence.
Among the preparation method of poly styrene sulfonate provided by the invention, sulfonation and neutralization procedure are routine techniques, can carry out as follows:
Polystyrene and halogenated hydrocarbon solvent are mixed by 1: 1～10 weight ratio, by free SO
3: styrene units=0.8～1.3: 1 mol ratio, preferably 0.9～1.2: 1 mol ratio adds sulphonating agent, react 0.5～3h down at 20～60 ℃, after reaction finishes, add moisture and remove the upper strata solvent, add the slaked lime PH=8 that neutralizes in lower floor's sulfonic acid aqueous solution, the elimination precipitation can obtain calcium polystyreme sulphonate after concentrating filter liquor, the drying.In addition, in above-mentioned filtrate, add carbonic acid metal salt, can obtain different poly styrene sulfonates.For example, according to yellow soda ash: the mol ratio of calcium polystyreme sulphonate=0.5 adds yellow soda ash in above-mentioned filtrate, the elimination precipitation of calcium carbonate is concentrated, dry with filtrate, can obtain sodium polystyrene sulfonate.
Described halohydrocarbon is this area general solvent for being used for dissolved polystyrene, can be selected from ethylene dichloride, ethylene dibromide etc.Sulphonating agent can be oleum or liquid sulphur trioxide.The add-on of sulphonating agent is with contained free SO in the sulphonating agent
3Calculate generally free SO
3With the mol ratio of styrene units in the polystyrene is 0.8～1.3 to be advisable, preferably 0.9～1.2.In such scope, can guarantee that sulphonation rate is more than 80%.Sulphonation rate is too low if ratio is too small, and multidigit sulfonation even rearrangement reaction take place on the part phenyl ring the too high oversulfonate that then causes of ratio, influence quality product.In addition, in reaction system, be uniformly dispersed, can take the mode of repeatedly sulfonation or dropping sulphonating agent in order to make product.If the latter after dropwising, should continue to react 1～2h.
When being sulphonating agent with the oleum, free SO
3Content can be 10～50%, preferably 20～30%.SO in the oleum
3Too high levels can reduce the dissemination of the vitriol oil to product, thereby reduces sulphonation rate.With the oleum is sulphonating agent, and required quantity of solvent is little, and the sulphonation rate height also can reduce the generation of by products such as sulfone, oxide compound.
When being sulphonating agent with the liquid sulphur trioxide, preferably control reaction temperature is lower than 35 ℃, to prevent side reaction.In the process that adds sulphur trioxide, sulphonation rate improves constantly, partly sulfonated polystyrene becomes water-soluble gradually from oil soluble, from organic solvent, separate out, make reaction system be heterogeneous, the sulphur trioxide that continues to add is difficult to contact with partly sulfonated polystyrene, causes the product sulphonation rate low.For improving the sulfonation effect, initial reaction stage need strengthen quantity of solvent, is increased to 5～10 times of polystyrene weight.In the sulfonation reaction system, add dispersion agent (as alkyl benzene sulphonate (ABS), methylcellulose gum etc.) or improve stir speed (S.S.) and can improve sulphonation rate.
The weight-average molecular weight of the poly styrene sulfonate that makes with method provided by the invention is generally 2 times of weight-average molecular weight of described polystyrene, and promptly 2000～240,000.
The preparation method of poly styrene sulfonate provided by the invention is that first dimer with an isopropenyl toluene is that chain-transfer agent prepares low-molecular-weight polystyrene, again poly styrene sulfonate is made in polystyrene sulfonation, neutralization.This preparation method has following advantage:
(1). described stock yard isopropenyl toluene can directly be taken from by the cymene oxidation style and produce isopropenyl toluene between the by product of cresols and acetone process, thereby raw material be easy to get, with low cost.
(2). compare with the ionic polymerization method, preparation method provided by the invention is not high to the purity requirement of raw material and reagent, needn't be strict refining, the reaction conditions gentleness, technology and equipment are simple, are easy to realize suitability for industrialized production.
(3). preparation method provided by the invention can obtain the poly styrene sulfonate product of the poly styrene sulfonate product, particularly narrow distribution of different molecular weight and molecular weight distribution by the add-on of Quality Initiative transfer agent.According to needed molecular weight and range of molecular weight distributions, can be used as cement water reducing agent, cement dispersants, coal water slurry dispersing agent etc.For example, be 2,000～120 with weight-average molecular weight, 000, preferably 5,000～60,000, molecular weight distribution be 1.8～3.0 calcium polystyreme sulphonate or sodium polystyrene sulfonate as cement water reducing agent, can obviously improve concrete flowing property, improve water-reducing rate, water-reducing rate is reached more than 14%, also can delay loss of slump, improve ultimate compression strength, make the ultimate compression strength of 7 days and 28 days obviously be better than the effect that commercially available water reducer reaches.And for example, with weight-average molecular weight is 5,000～120,000, preferably molecular weight is 10,000～80,000, molecular weight distribution is that 1.8～3.0 sodium polystyrene sulfonate is as coal water slurry dispersing agent, can significantly reduce viscosity of coal-water slurry, improve the flowing property of coal water slurry, compare, can make viscosity in aqueous coal slurries further reduce about 40～90mPa.s with the coal water slurry dispersing agent naphthalenesulfonic acid-formaldehyde condensate that commercially available effect is best.
Accompanying drawing 1 is TUD's
1The H-NMR spectrogram.
Accompanying drawing 2 is TUD's
13The C-NMR spectrogram.
The invention will be further described below by embodiment.
Example 1～3 is the preparation of chain-transfer agent.
Example 1
With acidic white earth (Fushun Petrochemical Company chemical plastic factory product, technical grade) and ethylene glycol mix by 1: 1 weight ratio, decompress filter, (Yanshan Petrochemical company wins the by product that good chemical plant cymene oxidation style is produced cresols to isopropenyl toluene between filter cake is used, purity＞90%) washing, suction filtration makes weight ratio and is ethylene glycol/clay catalyst of 0.3/1.Will between isopropenyl toluene monomer 50 gram and ethylene glycol/clay catalyst 10 grams mix, at 110 ℃ of reaction 6h, the elimination carclazyte, filtrate decompression is distilled, and collects 196～198 ℃ of cuts under 34mmHg, obtains TUD.Transformation efficiency 90% according to gas chromatographic analysis, records TUD/TUD2=20.
Example 2
Acidic white earth and ethylene glycol are mixed by 1: 1.5 weight ratio, press the method processing of example 1, make weight ratio and be ethylene glycol/clay catalyst of 0.5/1.Will between isopropenyl toluene monomer 50 gram and ethylene glycol/clay catalyst 12 grams mix, at 100 ℃ of reaction 7h, the elimination carclazyte, filtrate decompression is distilled, and collects 160～162 ℃ of cuts under 8.5mmHg, obtains TUD.Transformation efficiency 80% according to gas chromatographic analysis, records TUD/TUD2=26.
Example 3
Carclazyte and ethylene glycol are mixed by 1: 0.7 weight ratio, press the method processing of example 1, make weight ratio and be ethylene glycol/clay catalyst of 0.2/1.Will between isopropenyl toluene monomer 50 gram and ethanol/clay catalyst 5 grams mix, at 95 ℃ of reaction 4h, the elimination carclazyte, filtrate decompression is distilled, and obtains TUD.Transformation efficiency 68% according to gas chromatographic analysis, records TUD/TUD2=15.
Example 4～9 is the preparation of polystyrene.
Example 4
This example is mass polymerization.
TUD 1 gram and 15 gram styrene monomers (Yanshan Mountain chemical industry two factory's products, chemical pure) that example 1 is made mix, and reactor is sealed after with nitrogen replacement, and at 130 ℃ of reaction 6h down, small-molecule substances such as unreacted monomer are taken out in decompression, polystyrene 14.1 restrains.Gel permeation chromatography (GPC) records weight-average molecular weight Mw=20, and 200, molecular weight distribution mw/mn=2.1.
Example 5
This example is mass polymerization.
TUD 1.2 grams and 20 gram styrene monomers that example 1 is made mix, and reactor is sealed after with nitrogen replacement, and at 160 ℃ of reaction 4h down, small-molecule substances such as unreacted monomer are taken out in decompression, polystyrene 18.8 restrains.The GPC method records weight-average molecular weight Mw=15, and 000, molecular weight distribution mw/mn=2.0.
Example 6
This example is mass polymerization.
TUD 5 grams and 20 gram styrene monomers that example 1 is made mix, and reactor is sealed after with nitrogen replacement, and at 200 ℃ of reaction 2h down, small-molecule substances such as unreacted monomer are taken out in decompression, polystyrene 19.1 restrains.The GPC method records weight-average molecular weight Mw=2, and 900, molecular weight distribution mw/mn=1.9.
Example 7
This example is suspension polymerization.
In the 500ml four-hole bottle that connects reflux condensing tube, agitator, thermometer and dropping funnel; TUD 13 grams that the polyvinyl alcohol water solution of adding 200 grams 0.05% and example 2 make and 60 gram styrene monomers; under nitrogen protection; be warming up to 90 ℃; 40 gram styrene monomers and 4 gram benzoyl peroxides (Beijing chemical reagent factory, analytical pure) mixing are placed dropping funnel, and every interval 10min drips once to reactor; 2h drips off, and continues reaction 2h then.Reaction product leaves standstill branch vibration layer earlier, and small-molecule substances such as unreacted monomer are taken out in decompression again, gets polystyrene 80 grams, and the GPC method records weight-average molecular weight Mw=6, and 600, molecular weight distribution mw/mn=1.9.
Example 8
This example is suspension polymerization.
TUD 1 gram that the polyvinyl alcohol water solution of adding 200 grams 0.03% and example 1 make in example 7 described reactors and 60 gram styrene monomers; under nitrogen protection; be warming up to 70 ℃; with 40 gram styrene monomers and 3 gram lauroyl peroxide (Tianjin organic chemical industry two factory's products; analytical pure) mixing places dropping funnel; every interval 10min drips once to reactor, and 2h drips off, and continues reaction 3h then.All the other operations are with example 7.Get polystyrene 81 grams at last, the GPC method records weight-average molecular weight Mw=28, and 000, molecular weight distribution mw/mn=2.4.
Example 9
This example is suspension polymerization.
TUD 0.7 gram that the polyvinyl alcohol water solution of adding 200 grams 0.08% and example 3 make in example 7 described reactors and 60 gram styrene monomers; under nitrogen protection; be warming up to 80 ℃; 40 gram styrene monomers and 6 gram benzoyl peroxides mixing are placed dropping funnel; every interval 10min drips once to reactor; 2h drips off, and continues reaction 3h then.All the other operations are with example 7.Get polystyrene 91 grams at last, the GPC method records weight-average molecular weight Mw=36, and 300, molecular weight distribution mw/mn=3.0.
Example 10～example 15 is the preparation of poly styrene sulfonate.
Example 10
The polystyrene that 40 grams are made by example 6 is dissolved in the 48 gram ethylene dichloride, under 50 ℃ according to free SO3: styrene units=mol ratio of 1: 1 drips the oleum of 123 grams 25%, dripped off in 1 hour.Dropwise and continue reaction 1 hour, reaction product is poured in the water, remove organic layer, water layer is with the slaked lime PH=8 that neutralizes, the elimination precipitation, with the filtrate drying, calcium polystyreme sulphonate product 78 grams, weight-average molecular weight is 5,600, sulphonation rate is 92%.Sulphonation rate by
1H-NMR determination of quantitative analysis (with reference to EP0253598), calculation formula is as follows:
Sulphonation rate=100% * (5-3 I
a/ I
b)
I in the formula
aBe the spectral strength of hydrogen atom on the phenyl ring in the polystyrene, I
bBe hydrogen atom (CH on the polystyrene main chain
2-CH-) spectral strength.
Example 11
The polystyrene that 40 grams are made by example 5 is dissolved in the 150 gram ethylene dichloride, adds 1 gram alkyl benzene sulphonate (ABS) dispersion agent (Jinzhou additive factory, chemical pure), under 30 ℃, according to SO
3: the mol ratio of styrene units=1.2: 1 drips 30 gram liquid sulphur trioxides, dropwises and continues reaction 1 hour, and all the other are operated with example 10.Get calcium polystyreme sulphonate 73 grams at last, weight-average molecular weight is 27,000, and sulphonation rate is 82%.
Example 12
The polystyrene that 40 grams are made by example 8 is dissolved in the 48 gram ethylene dichloride, under 50 ℃ according to free SO
3: styrene units=mol ratio of 1.2: 1 drips the oleum of 123 grams 30%, dripped off in 0.5 hour.Dropwise and continue reaction 1 hour, all the other are operated with example 10.Get calcium polystyreme sulphonate 81 grams at last, weight-average molecular weight is 53,000, and sulphonation rate is 95%.
Example 13
The polystyrene that 40 grams are made by example 4 is dissolved in the 48 gram ethylene dichloride, and step sulfonation, neutralization, the filtration of pressing example 9 add 20 gram yellow soda ash in filtrate, the elimination throw out, the filtrate drying gets sodium polystyrene sulfonate 76 grams, weight-average molecular weight is 39,000, and sulphonation rate is 93%.
Example 14
The polystyrene that 40 grams are made by example 9 is dissolved in the 48 gram ethylene dichloride, and all the other conditions make sodium polystyrene sulfonate 78 grams with example 13, and weight-average molecular weight is 68,000, and sulphonation rate is 87%.
Example 15
The polystyrene that 40 grams are made by example 7 is dissolved in the 48 gram ethylene dichloride, and all the other conditions make sodium polystyrene sulfonate 76 grams with example 13, and weight-average molecular weight is 12,800, and sulphonation rate is 94%.
Example 16
This example illustrates that poly styrene sulfonate provided by the invention is to concrete water reducer performance.
Take by weighing cement 300 grams, add entry 87 grams and be selected from poly styrene sulfonate 1.5 grams that example 10～15 makes, press the GB-8077-87 method and measure flowing degree of net paste of cement, press the GB8076-87 method and measure water-reducing rate and concrete crushing strength, test result sees Table 1.Degree of mobilization, water-reducing rate and compressive strength rate are big more, and performance is good more.
Example 17
This example illustrates the dispersing property of poly styrene sulfonate provided by the invention to coal water slurry.
Take by weighing 68 gram coal dust (Datong District, the place of production,＜200 purpose coal dusts 70%, 60～100 purpose coal dusts 30%), add poly styrene sulfonate 0.27 gram that entry 32 restrained and be selected from example 9～14, after stirring 10min, with Brookfield viscometer test water viscosity of coal slurry (12rpm, No. 3 rotors), measurement result sees Table 2.Viscosity is more little, and dispersion effect is good more.Testing method is with reference to " Petroleum Association of Japan's will ", and 39 roll up 129-136 page or leaf (1996).
Comparative Examples 1
Method according to example 16, with toluene sulfonic acide formaldehyde condensation products (Jiangsu Jiangdu County water reducer factory product), carbolineum sulfonate and formaldehyde condenses (coke-oven plant, Beijing product), naphthalenesulfonate formaldehyde condensation compound (Zhanjiang, Guangdong admixture factory product) as cement water reducing agent, measure water-reducing rate and ultimate compression strength, test result is seen and is listed table 1 in the lump in.
Comparative Examples 2
Method according to example 17, with calcium lignin sulphonate (Jilin cut into a mountain village chemical fibre mill product), mahogany acid formaldehyde condensation products (swallowization new and high technology company limited), naphthalenesulfonate formaldehyde condensation compound as coal water slurry dispersing agent, measure viscosity in aqueous coal slurries, test result is listed table 2 in the lump in.
By contrast as can be known, as cement water reducing agent or coal water slurry dispersing agent, its effect is better than at present the generally commercially available product of use with the poly styrene sulfonate of method provided by the invention preparation.
Table 1
| The water reducer source | Molecular weight (Mw) | Degree of mobilization, mm | Water-reducing rate, % | Compressive strength rate, % | |||
| 1 day | 3 days | 7 days | 28 days | ||||
| Example 10 | 5600 | 200 | 12 | 145 | 140 | 159 | 132 |
| Example 11 | 27000 | 220 | 14 | 150 | 144 | 172 | 141 |
| Example 12 | 53000 | 230 | 15 | 142 | 148 | 158 | 132 |
| Example 13 | 39000 | 230 | 14 | 148 | 140 | 142 | 131 |
| Example 14 | 12800 | 220 | 14 | 148 | 147 | 138 | 134 |
| FDN* | ---- | 185 | 12 | 1 58 | 148 | 131 | 125 |
| MF* | ---- | 110 | 12 | 147 | 146 | 130 | 121 |
| AF* | ---- | 120 | 12 | 149 | 142 | 128 | 113 |
* FDN: naphthalenesulfonate formaldehyde condensation compound
MF: toluene sulfonic acide formaldehyde condensation products
AF: carbolineum sulfonate and formaldehyde condenses
Table 2
| The dispersion agent source | Molecular weight (Mw) | Addition, % | Viscosity in aqueous coal slurries, mPa.s |
| Example 13 | 39,000 | 0.4 | 670 |
| Example 14 | 68,000 | 0.4 | 720 |
| Example 15 | 12,800 | 0.4 | 700 |
| Wood calcium * | ---- | 0.4 | 1270 |
| PF* | ---- | 0.4 | 780 |
| FDN | ---- | 0.4 | 760 |
* wooden calcium: calcium lignin sulphonate
PF: mahogany acid formaldehyde condensation products
Claims (10)
1. the preparation method of a poly styrene sulfonate is that polystyrene and halogenated hydrocarbon solvent are mixed by 1: 1～10 weight ratio, by free SO
3: styrene units=0.8～1.3: 1 mol ratio adds sulphonating agent, react 0.5～3h down at 20～60 ℃, neutralization again after the sulfonation, it is characterized in that polystyrene prepares as follows: with chain-transfer agent 2, two tolyl-4-methyl-1-pentenes of 4-and vinylbenzene mix by 0.01～0.3: 1 weight ratio, starvation reacts 1～8h, the separated product polystyrene under 100～240 ℃ of temperature.
2. according to the described preparation method of claim 1, it is characterized in that said temperature of reaction is 120～200 ℃.
3. according to the described preparation method of claim 1, it is characterized in that the said reaction times is 2～6h.
4. according to the described preparation method of claim 1, it is characterized in that said chain-transfer agent 2, two tolyl-4-methyl-1-pentenes of 4-prepare as follows: isopropenyl toluene and acidic white earth mix by 1: 0.03～0.3 weight ratio between inciting somebody to action, react 2～10h, separated product down at 80～140 ℃.
5. according to the described preparation method of claim 4, the weight ratio that it is characterized in that said isopropenyl toluene and acidic white earth is 1: 0.1～0.2.
6. according to the described preparation method of claim 4, it is characterized in that said acidic white earth is the acidic white earth of handling through ethylene glycol.
7. according to the described preparation method of claim 4, it is characterized in that said temperature of reaction is 95～125 ℃.
8. according to the described preparation method of claim 4, it is characterized in that the said reaction times is 4～8h.
9. according to the described preparation method of claim 1, it is characterized in that sulfonation reaction finishes after, add moisture and remove the upper strata solvent, in lower floor's sulfonic acid aqueous solution, add the slaked lime pH=8 that neutralizes, filter, with the filtrate concentrate drying, can obtain calcium polystyreme sulphonate.
10. according to the described preparation method of claim 1, after it is characterized in that sulfonation reaction finishes, add moisture and remove the upper strata solvent, in lower floor's sulfonic acid aqueous solution, add the slaked lime pH=8 that neutralizes, filter, according to yellow soda ash: the mol ratio of calcium polystyreme sulphonate=0.5 adds yellow soda ash in filtrate, the elimination precipitation, filtrate is concentrated, dry, can obtain sodium polystyrene sulfonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98101648 CN1072681C (en) | 1998-04-24 | 1998-04-24 | Method for preparing poly styrene sulfonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98101648 CN1072681C (en) | 1998-04-24 | 1998-04-24 | Method for preparing poly styrene sulfonate |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00124447 Division CN1125093C (en) | 2000-09-07 | 2000-09-07 | Process for preparing polystyrene sulfonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1233618A CN1233618A (en) | 1999-11-03 |
| CN1072681C true CN1072681C (en) | 2001-10-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98101648 Expired - Fee Related CN1072681C (en) | 1998-04-24 | 1998-04-24 | Method for preparing poly styrene sulfonate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10287522B2 (en) | 2013-01-31 | 2019-05-14 | General Electric Company | System and method for preparing coal water slurry |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108822900A (en) * | 2018-06-15 | 2018-11-16 | 广西隆昌德民生态农业发展有限公司 | A kind of compound alcohol fuel that can be burnt sufficiently and mitigate tail gas pollution discharge |
| CN108822906B (en) * | 2018-06-22 | 2021-07-09 | 义乌市牛尔科技有限公司 | Modified waste polystyrene foam coal water slurry additive and preparation method thereof |
| CN108865303B (en) * | 2018-06-22 | 2021-07-06 | 义乌市牛尔科技有限公司 | Coal water slurry additive containing sulfonic acid group and preparation method thereof |
| CN108707490B (en) * | 2018-06-22 | 2021-07-06 | 义乌市牛尔科技有限公司 | Coal water slurry additive and production process thereof |
| CN108841371B (en) * | 2018-06-27 | 2020-07-31 | 长江大学 | Composite pulverized coal suspending agent for coal bed gas fracturing and preparation method thereof |
| WO2020246718A1 (en) * | 2019-06-05 | 2020-12-10 | 주식회사 실크로드시앤티 | Preparation method for admixture for plasterboard, admixture prepared thereby, and composition for forming plasterboard comprising same |
-
1998
- 1998-04-24 CN CN 98101648 patent/CN1072681C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10287522B2 (en) | 2013-01-31 | 2019-05-14 | General Electric Company | System and method for preparing coal water slurry |
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| Publication number | Publication date |
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| CN1233618A (en) | 1999-11-03 |
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