CN102532393B - Methacrylic acid-styrene copolymer dispersing agent, preparation method and application thereof - Google Patents
Methacrylic acid-styrene copolymer dispersing agent, preparation method and application thereof Download PDFInfo
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Abstract
The present invention relates to a copolymer dispersing agent, and discloses a methacrylic acid-styrene copolymer dispersing agent. According to the dispersing agent, methacrylic acid and styrene are adopted as monomers, a surfactant, an anti-cross-linking agent, a photoinitiator and a neutralization reagent are added, and a photo-initiation method is adopted to prepare the methacrylic acid-styrene copolymer dispersing agent. According to the method, the total activation energy is low, the polymerization can be performed at a low temperature, and advantages of simple process, high product purity, and the like are provided. The obtained dispersing agent provides good dispersing effects for inorganic powder and pesticides, can be used for preparations of aqueous pesticide preparations, and can be widely used in fields of the pesticide preparations and the like. The method of the present invention has characteristics of low cost and no pollution, and is suitable for the large-scale industrial production.
Description
Technical field
The present invention relates to a kind of copolymer dispersant, a kind of metal carboxylate multipolymer, is light-initiated methacrylic acid and styrol copolymer dispersion agent and technology of preparing and purposes specifically.
Background technology
Dispersion agent has important application in industries such as pigment, dyestuff, agricultural chemicals.The shortcoming of tradition small molecules dispersion agent is: insecure in solid particles surface absorption, easily from surface dissociation, cause reassembling or precipitating.Cation dispersing agent is used easily generation precipitation and lost efficacy under hard water condition.Metal carboxylate copolymer dispersant can make stable system by sterically hindered effect and electrostatic repulsion effect, better than small molecules and cation dispersing agent dispersion effect.
This seminar had once synthesized tribasic carboxylic acid salt dispersion agent, and dispersion effect is good.But the shortcomings such as building-up process exists consumed energy large, restive.The present invention uses light initiation polymerization, synthetic take the dicarboxylate base polymer dispersion agent that methacrylic acid and vinylbenzene is monomer.
The fifties in last century, Oster and Shibata did pioneer's work in light-initiated graft polymerization, and light initiation polymerization technology is one of important method of synthesized polymer material.Compare with traditional polymerization process, the total activation energy of light initiation polymerization is low, polymerization at a lower temperature, has that technique is simple, light intensity is easy to measure, product is pure, the reaction times is short, an easy feature such as reproductions of normal-temperature reaction, energy-saving and environmental protection and experimental result, therefore extremely people's attention.But the report there are no light-initiated synthesize methyl acrylic acid and styrol copolymer dispersion agent.
European patent EP 0405872A1 uses as monomer with methacrylic acid and vinylbenzene that suspension polymerization is synthetic has a thermoplastic material, for the moulding such as foaming.This seminar selects methacrylic acid and vinylbenzene as polymerization single polymerization monomer synthetic polymer dispersion agent, and the acid of method synthesize methyl acrylic and styrol copolymer dispersion agent with light initiation polymerization, contain impurity few, narrow molecular weight distribution.Hope can be good to inorganic powder, pesticide dispersion effect, save energy, protection of the environment.
Summary of the invention
The present invention is intended to by light-initiated method, and synthetic a kind of methacrylic acid-styrol copolymer dispersion agent has that good stably dispersing performance, preparation cost are low, environmental friendliness.
The present invention also provides the application of above-mentioned dispersion agent.
For achieving the above object, the technical solution used in the present invention is, a kind of preparation method of methacrylic acid-styrol copolymer dispersion agent, and raw material comprises:
(a) take methacrylic acid and vinylbenzene as monomer, both mass ratioes are 1: 1～9: 1;
(b) tensio-active agent, consumption is monomer total mass 1%～10%; It is sodium lauryl sulphate and the Triton X-100 of 5: 1～1: 5 that tensio-active agent is preferably mass ratio;
(c) anti-linking agent, consumption is 2～16% of monomer total mass; Be selected from thiocarbamide, urea, Resorcinol, O-Phenylene Diamine, Virahol or sodium bisulfite, be preferably thiocarbamide;
(d) light trigger, consumption is 0.1～5% of monomer total mass; Be preferably a kind of in lanthanum nitrate-ITX title complex, lanthanum nitrate-anthraquinone title complex, lanthanum nitrate-benzophenone title complex;
(e) solvent, consumption is 0.8～1.5 times of monomer total mass; Be preferably a kind of in normal hexane, chloroform, ethanol, acetone, epoxy two ethane, tetrahydrofuran (THF) and pimelinketone.
(f) neutralization reagent, dosis neutralisata is 10%～95% of monomer total amount; Be preferably a kind of in triethylamine, sodium hydroxide, potassium hydroxide, ammoniacal liquor;
Step comprises: above-mentioned substance (a)-(e) mixed, and exhausted air, and under the condition of isolated air and 15～40 ℃, UV-irradiation 30～150 minutes, adds neutralization reagent, sloughs organic solvent; Obtain aqua, or the dry white powder dispersion agent that obtains of spraying again.
Above-mentioned (d) preparation process: take ligand compound (in ITX, anthraquinone, benzophenone a kind of) and rare earth compound lanthanum nitrate, both ratios are 1: 10～10: 1, be dissolved in alcohol, the abundant mixed dissolution of uniform stirring 24h under 20～40 ℃ of conditions, obtains product and retains the filter residue on filter paper with vacuum filtration.With alcohol, adopt and to put at 20～40 ℃ of vacuum drying ovens vacuum-drying after thermal crystallization recrystallization 2～5 times 12 hours～2 days.Take out product, grind to form homogeneous powder powder, obtain light trigger.
Methacrylic acid-styrol copolymer the dispersion agent obtaining by aforesaid method, it is a kind of metal carboxylate multipolymer, average relative molecular mass is between 800～15000, molecular weight distribution is less than 2.5, formulation is aqua or powder, can be for the dispersion of inorganic mineral and the preparation of pesticide water dispersion agent.
Experiment shows: methacrylic acid-styrol copolymer dispersion agent that the light-initiated method of the present invention is prepared, has good dispersion effect to the inorganic powders such as calcium carbonate, zinc oxide, barium sulfate, titanium dioxide and agricultural chemicals; Can be used for preparing pesticide preparation and inorganic powder, be widely used in the industries such as pesticide preparation, inorganic powder.
Compared with prior art, beneficial effect of the present invention is as follows:
1, to have total activation energy low for light initiation polymerization, and product is pure; Polymerization at a lower temperature, energy-saving and environmental protection; Preparation technology is simple, processing ease, with short production cycle; With low cost, non-environmental-pollution, experimental result are easy to reappear; Being suitable for industrial scale produces.
2, the hydroxy-acid group that methacrylic acid contains functionalization, the carboxylic-acid polymeric dispersant that therefore contains methacrylic acid unit has water-soluble preferably, and the pH value of dispersion system is had to good adaptability.
3, metal carboxylate polymeric dispersant of the present invention has the desirable polymerization degree and carboxyl-content, by space steric effect and Coulomb repulsion, makes to be dispersed material stably dispersing.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail and completely.Embodiment is only preference of the present invention, is to exemplary illustration of the present invention, does not limit the scope of the present invention.All within principle of the present invention, to do any modifications and variations, all within protection scope of the present invention.As thiocarbamide, can use urea, Resorcinol, O-Phenylene Diamine, Virahol or sodium bisulfite and replace, effect is identical.
Embodiment 1
1, the preparation of dispersion agent:
Methacrylic acid, vinylbenzene mass ratio are 2: 1, total monomer 20g; The sodium lauryl sulphate that the weight ratio of take is 5: 1, Triton X-100 are tensio-active agent, and consumption is monomer 4%; Thiocarbamide is anti-linking agent, and consumption is monomer 4%; Light trigger consumption is 4% of monomer; The ethanol of take is standby as solvent solution-forming, and solvent load equates with monomer mass.Get 10ml solution in photoresponse pipe, photoresponse pipe is passed into nitrogen exhausted air, cover lid; Then photoresponse pipe is put into 15 ℃ of photoreactors and used ultra violet lamp 50 minutes; Generate faint yellow transparent sticky polymers dispersion agent, add in triethylamine solution with 40%; Slough after organic solvent, aqua dispersion agent, obtains white powder after spraying is dry.
Wherein, light trigger is lanthanum nitrate-ITX title complex, preparation method is: lanthanum nitrate and ITX are mixed by the mass ratio of 1: 1 and be dissolved in ethanol (weight ratio of reactant and alcohol is 3: 7), in electric mantle, at 20 ℃, stir 16 hours, suction filtration is got filter residue, and with ethyl alcohol recrystallization 3 times, vacuum-drying is one day at 30 ℃, takes out product and grinds to form homogeneous powder powder.
Adopt gel permeation chromatograph, take the aqueous solution as moving phase, sodium polyacrylate is made standard substance, and the average relative molecular mass of measuring prepared copolymer dispersant is 2500.
Recording prepared dispersion agent is 99.00% to the suspensibility of barium sulfate suspension, and prepared dispersion agent is 95.15% to the suspensibility of tio_2 suspension.Recording prepared dispersion agent is 90.03% to the suspensibility of Pesticide Atrazine, to the suspensibility of agricultural chemicals ametryn, is 94.5%.
For prepared dispersion agent, detect as follows to the suspension of inorganic mineral, agricultural chemicals and dispersion effect method.
(1) detection dispersion agent is as follows to the dispersed scheme of inorganic mineral:
In 100ml tool plug graduated cylinder, add 0.4g dispersion agent and 50ml distilled water solution, after dispersion agent dissolves, add again the solid particulate that 1.00g is to be disperseed, then add the aqueous solution to 100ml, in 1min, turn upside down 30 times, first put upside down 180 °, returning original position is 1 time.Graduated cylinder is vertically placed in 25 ℃ of super thermostat(t)ed water solution bath, and static friction, avoids sunlight direct irradiation, during 30min, with suction pipe, extracts upper strata 90ml suspension out, in 15s, completes.It is m that remaining 10ml suspension is transferred to the quality of having weighed
1desiccation culture ware in, and rinse graduated cylinder with distilled water solution, guarantee that the sediment in graduated cylinder is all transferred in culture dish, culture dish is put into 80 ℃ of oven dry in baking oven, m weighs
2, the mass M of calculating insolubles, M=m
2-m
1, by following formula, calculate its suspensibility:
Wherein: M is the quality (g) of the 100ml tool plug graduated cylinder bottom contained dispersion agent of 10ml suspension and solid particulate, 1.400 is the total mass (g) of contained dispersion agent and solid particulate in 100ml tool plug graduated cylinder.
(2) prepare water dispersion granule (WG) scheme:
According to formula, make laboratory by oneself polymeric dispersant, former medicine, (NH
4)
2sO
4, Tersperse1004, kaolin etc. take, mix, put into the granulation of tablets press machine by formula after micronizer mill is pulverized; to be dried sieve with standard inspection sieve afterwards; the particle of size in 30-60 order (550 μ m-250 μ m) scope is water dispersible granules sample, fills a prescription as follows:
90% atrazine WDG formula: former medicine 93%, dispersion agent 4.5%, wetting agent Tersperse1004 2.5%.
80% ametryn WDG formula: former medicine 83.3%, dispersion agent 4%-5%, wetting agent Tersperse1004 2%, NNO 3%, and kaolin is supplied.
(3) dispersion agent is measured scheme to the dispersiveness of agricultural chemicals:
With above-mentioned dispersion agent, prepare pesticide water dispersible granule (WG), take this dry WG of 1.4g to beaker, add 50ml distilled water solution, place 30s, with glass stick, stirring 30s makes it to be uniformly dispersed, then with distilled water solution, this suspension is transferred in 100ml tool plug graduated cylinder, adding distil water solution is to 100ml place.Cover stopper, in 1min, tool plug graduated cylinder is turned upside down 30 times, graduated cylinder turns upside down 180 °, and to return original position be 1 time.Graduated cylinder is vertically placed in 30 ℃ of super thermostat(t)ed water solution bath, and static friction, avoids sunlight direct irradiation, after standing 30min, with suction pipe, shift out upper strata 90ml suspension, this process makes tip several millimeters of places under liquid level, to guarantee not shake or stir the sediment of graduated cylinder bottom.It is m that remaining 10ml suspension is transferred to the quality of having weighed
1culture dish in, and rinse graduated cylinder with distilled water solution, guarantee that the sediment of graduated cylinder bottom is all transferred in culture dish, culture dish is put into 80 ℃ of oven dry in baking oven, m weighs
2, the mass M=(m of calculating insolubles
2-m
1), be then calculated as follows suspensibility:
Wherein, 1.400 quality that are the water dispersion granule that adds; M is the quality of tool plug graduated cylinder bottom sediment.
2, after agricultural chemicals heat storage experiment, survey is dispersed
Take 10g pesticide water dispersible granules in ampoule, seal up the mouth of ampoule, ampoule as in 54 degrees Celsius of baking ovens 14 days.Within 14 days, test afterwards the suspensibility of pesticide water dispersible granules.To the suspensibility of Pesticide Atrazine water dispersible granules, being 89.07%, is 90.7% to the suspensibility of agricultural chemicals ametryn water dispersible granules.
Embodiment 2
Methacrylic acid, vinylbenzene mass ratio are 7: 2.5, total monomer 20g; The sodium lauryl sulphate that the weight ratio of take is 4: 1, Triton X-100 are tensio-active agent, and consumption is 5% of monomer total amount; Thiocarbamide is anti-linking agent, and consumption is monomer 9%; Light trigger consumption is 4% of monomer; The chloroform of take is standby as solvent solution-forming, and solvent load equates with monomer mass.Get 10ml solution in photoresponse pipe, photoresponse pipe is passed into nitrogen exhausted air, cover lid; Then photoresponse pipe is put into 15 ℃ of photoreactors and used ultra violet lamp 50 minutes; Generate faint yellow transparent sticky polymers dispersion agent, add in sodium hydroxide solution with 30%.Slough after organic solvent, obtain aqua.
Wherein, light trigger is lanthanum nitrate-anthraquinone title complex, preparation method is: lanthanum nitrate and anthraquinone are mixed by the mass ratio of 1: 2 and be dissolved in ethanol, at 40 ℃, stir 20 hours, suction filtration is got filter residue, and with ethyl alcohol recrystallization 3 times, vacuum-drying is one day at 30 ℃, takes out product and grinds to form homogeneous powder powder.
Adopt gel permeation chromatograph (GPC), take the aqueous solution as moving phase, sodium polyacrylate is made standard substance, and the average relative molecular mass of measuring prepared copolymer dispersant is 15000.
Press operation steps described in embodiment 1, recording above-mentioned dispersion agent is 98.85% to the suspensibility of barium sulfate suspension, to the suspensibility of tio_2 suspension, is 96.22%.To Pesticide Atrazine water dispersion granule suspensibility, be 86.9%, after heat storage, suspensibility is 84.89%; To agricultural chemicals ametryn water dispersible granules suspension, be 92.5%, after heat storage, suspensibility is 90.4%.
Embodiment 3
Methacrylic acid, vinylbenzene mass ratio are 9: 1, total monomer 20g; The sodium lauryl sulphate that the weight ratio of take is 3: 1, Triton X-100 are tensio-active agent, and consumption is monomer 9%; Thiocarbamide is anti-linking agent, and consumption is monomer 7%; Light trigger consumption is 2% of monomer; The acetone of take is standby as solvent solution-forming, and solvent load equates with monomer mass.Get 10ml solution in photoresponse pipe, photoresponse pipe is passed into nitrogen exhausted air, cover lid; Then photoresponse pipe is put into 20 ℃ of photoreactors and used ultra violet lamp 100 minutes; Generate faint yellow transparent sticky polymers dispersion agent, add ammonia neutralization 90%; Slough after organic solvent, obtain aqua, after spraying is dry, obtain white powder.
Wherein, light trigger is lanthanum nitrate-benzophenone title complex, preparation method is: lanthanum nitrate and benzophenone are mixed by the mass ratio of 2: 1 and be dissolved in ethanol, at 25 ℃, stir 20 hours, suction filtration is got filter residue, and with ethyl alcohol recrystallization 3 times, vacuum-drying is one day at 30 ℃, takes out product and grinds to form homogeneous powder powder.
Adopt gel permeation chromatograph, take the aqueous solution as moving phase, sodium polyacrylate is made standard substance, and the average relative molecular mass of measuring prepared metal carboxylate copolymer dispersant is 4500.
Recording above-mentioned dispersion agent is 98.80% to the suspensibility of barium sulfate suspension, to the suspensibility of tio_2 suspension, is 96.22%.To Pesticide Atrazine water dispersion granule suspensibility, be 90.8%, after heat storage, suspensibility is 84.89%; To agricultural chemicals ametryn water dispersible granules suspension, be 96.5%, after heat storage, suspensibility is 93.4%.
Embodiment 4
Methacrylic acid, vinylbenzene mass ratio are 4: 1, total monomer 20g; The sodium lauryl sulphate that the weight ratio of take is 1: 5, Triton X-100 are tensio-active agent, and consumption is monomer 4%; Thiocarbamide is anti-linking agent, and consumption is monomer 8%; Light trigger consumption is 1% of monomer; The tetrahydrofuran (THF) of take is standby as solvent solution-forming, and solvent load equates with monomer mass.Get 10ml solution in photoresponse pipe, after photoresponse pipe is put into ultrasonic cleaner and vibrated 10 minutes, take out; Pass into nitrogen exhausted air, cover lid; Then photoresponse pipe is put into 20 ℃ of photoreactors and used ultra violet lamp 150 minutes; Generate faint yellow transparent sticky polymers dispersion agent, add ammonia neutralization 60%; Slough after organic solvent, obtain aqua, after spraying is dry, obtain white powder.
Wherein, light trigger is lanthanum nitrate-benzophenone title complex, preparation method is: lanthanum nitrate and benzophenone are mixed by the mass ratio of 1: 2 and be dissolved in ethanol, at 20 ℃, stir 26 hours, suction filtration is got filter residue, and with ethyl alcohol recrystallization 3 times, vacuum-drying is one day at 30 ℃, takes out product and grinds to form homogeneous powder powder.
Adopt gel permeation chromatograph, take the aqueous solution as moving phase, sodium polyacrylate is made standard substance, and the average relative molecular mass of measuring prepared carboxylic acid copolymer dispersion agent is 7200.
Recording above-mentioned dispersion agent is 97.82% to the suspensibility of barium sulfate suspension, to the suspensibility of tio_2 suspension, is 96.55%.To Pesticide Atrazine water dispersion granule suspensibility, be 94.9%, after heat storage, suspensibility is 89.89%; To agricultural chemicals ametryn water dispersible granules suspension, be 93.34%, after heat storage, suspensibility is 94.87%.
Embodiment 5
Methacrylic acid, vinylbenzene mass ratio are 7: 3, total monomer 20g; The sodium lauryl sulphate that the weight ratio of take is 1: 4, Triton X-100 are tensio-active agent, and consumption is monomer 1%; Thiocarbamide is anti-linking agent, and consumption is monomer 13%; Adding light trigger consumption is 0.5% of monomer; The pimelinketone of take is standby as solvent solution-forming, and solvent load equates with monomer mass.Get 10ml solution in photoresponse pipe, after photoresponse pipe is put into ultrasonic cleaner and vibrated 10 minutes, take out; Pass into nitrogen exhausted air, cover lid; Then photoresponse pipe is put into 30 ℃ of photoreactors and used ultra violet lamp 150 minutes; Generate faint yellow transparent sticky polymers dispersion agent, add ammonia neutralization 90%; After sloughing organic solvent, obtain aqua.
Adopt gel permeation chromatograph, take the aqueous solution as moving phase, sodium polyacrylate is made standard substance, measures prepared carboxylic acid
the average relative molecular mass of analog copolymer dispersion agent is 6500.
Light trigger is lanthanum nitrate-benzophenone title complex, preparation method is: lanthanum nitrate and benzophenone are mixed by the mass ratio of 2: 1 and be dissolved in ethanol, at 26 ℃, stir 19 hours, suction filtration is got filter residue, and with ethyl alcohol recrystallization 3 times, at 30 ℃, vacuum-drying is one day, takes out product and grinds to form homogeneous powder powder.
Recording above-mentioned dispersion agent is 97.99% to the suspensibility of barium sulfate suspension, to the suspensibility of tio_2 suspension, is 95.05%.To Pesticide Atrazine water dispersion granule suspensibility, be 90.78%, after heat storage, suspensibility is 87.65%; To agricultural chemicals ametryn water dispersible granules suspension, be 96.56%, after heat storage, suspensibility is 92.34%.
Embodiment 6
Methacrylic acid, vinylbenzene mass ratio are 1.5: 1, total monomer 20g; The sodium lauryl sulphate that the weight ratio of take is 1: 2, Triton X-100 are tensio-active agent, and consumption is monomer 7%; Thiocarbamide is anti-linking agent, and consumption is monomer 14%; Light trigger consumption is 2% of monomer; Epoxy two hexanes of take are standby as solvent solution-forming, and solvent load equates with monomer mass.Get 10ml solution in photoresponse pipe, after photoresponse pipe is put into ultrasonic cleaner and vibrated 10 minutes, take out; Pass into nitrogen exhausted air, cover lid; Then photoresponse pipe is put into 30 ℃ of photoreactors and used ultra violet lamp 80 minutes; Generate faint yellow transparent sticky polymers dispersion agent.Add ammonia neutralization 60%, obtain aqua after sloughing organic solvent, after spraying is dry, obtain white powder.
Light trigger is lanthanum nitrate-ITX title complex, and preparation method is with embodiment 1.
Adopt gel permeation chromatograph, take the aqueous solution as moving phase, sodium polyacrylate is made standard substance, and the average relative molecular mass of measuring prepared carboxylic acid copolymer dispersion agent is 2500.
Recording above-mentioned dispersion agent is 98.86% to the suspensibility of barium sulfate suspension, to the suspensibility of tio_2 suspension, is 97.05%.To Pesticide Atrazine water dispersion granule suspensibility, be 93.84%, after heat storage, suspensibility is 92.69%; To agricultural chemicals ametryn water dispersible granules suspension, be 96.59%, after heat storage, suspensibility is 93.74%.
Embodiment 7
Methacrylic acid, vinylbenzene mass ratio are 1: 1, total monomer 20g; The sodium lauryl sulphate that the weight ratio of take is 1: 4, Triton X-100 are tensio-active agent, and consumption is monomer 10%; Thiocarbamide is anti-linking agent, and consumption is monomer 16%; Light trigger consumption is 1% of monomer; The acetone of take is standby as solvent solution-forming, and solvent load equates with monomer mass.Get 10ml solution in photoresponse pipe, after photoresponse pipe is put into ultrasonic cleaner and vibrated 10 minutes, take out; Pass into nitrogen exhausted air, cover lid; Then photoresponse pipe is put into 15 ℃ of photoreactors and used ultra violet lamp 70 minutes; Generate faint yellow transparent sticky polymers dispersion agent, add in potassium hydroxide with 70%; After sloughing organic solvent, obtain aqua, after spraying is dry, obtain white powder.
Light trigger is lanthanum nitrate-ITX title complex, and preparation method is with embodiment 1.
Adopt gel permeation chromatograph, take the aqueous solution as moving phase, sodium polyacrylate is made standard substance, and the average relative molecular mass of measuring prepared carboxylic acid copolymer dispersion agent is 5300.
Recording above-mentioned dispersion agent is 96.60% to the suspensibility of barium sulfate suspension, to the suspensibility of tio_2 suspension, is 93.35%.To Pesticide Atrazine water dispersion granule suspensibility, be 95.46%, after heat storage, suspensibility is 91.87%; To agricultural chemicals ametryn water dispersible granules suspension, be 95.29%, after heat storage, suspensibility is 90.78%.
Embodiment 8
Methacrylic acid, vinylbenzene mass ratio are 1.5: 1, total monomer 20g; The sodium lauryl sulphate that the weight ratio of take is 1: 1, Triton X-100 are tensio-active agent, and consumption is monomer 7%; Thiocarbamide is anti-linking agent, and consumption is monomer 11%; Light trigger consumption is 2% of monomer; The normal hexane of take is standby as solvent solution-forming, and solvent load equates with monomer mass.Get 10ml solution in photoresponse pipe, after photoresponse pipe is put into ultrasonic cleaner and vibrated 10 minutes, take out; Pass into nitrogen exhausted air, cover lid; Then photoresponse pipe is put into 40 ℃ of photoreactors and used ultra violet lamp 50 minutes; Generate faint yellow transparent sticky polymers dispersion agent, add ammonia neutralization 30%; After sloughing solvent, obtain aqua.
Light trigger is lanthanum nitrate-ITX title complex, and preparation method is with embodiment 1.
Adopt gel permeation chromatograph, take the aqueous solution as moving phase, sodium polyacrylate is made standard substance, and the average relative molecular mass of measuring prepared carboxylic acid copolymer dispersion agent is 800.
Recording above-mentioned dispersion agent is 98.60% to the suspensibility of barium sulfate suspension, to the suspensibility of tio_2 suspension, is 95.82%.To Pesticide Atrazine water dispersion granule suspensibility, be 92.89%, after heat storage, suspensibility is 92.23%; To agricultural chemicals ametryn water dispersible granules suspension, be 92.76%, after heat storage, suspensibility is 90.09%.
Embodiment 9
Methacrylic acid, vinylbenzene mass ratio are 4: 1, total monomer 20g; The sodium lauryl sulphate that the weight ratio of take is 5: 1, Triton X-100 are tensio-active agent, and consumption is monomer 8%; Thiocarbamide is anti-linking agent, and consumption is monomer 10%; Light trigger consumption is 3% of monomer; The normal hexane of take is standby as solvent solution-forming, and solvent load equates with monomer mass.Get 10ml solution in photoresponse pipe, after photoresponse pipe is put into ultrasonic cleaner and vibrated 10 minutes, take out; Pass into nitrogen exhausted air, cover lid; Then photoresponse pipe is put into 20 ℃ of photoreactors and used ultra violet lamp 90 minutes; Generate faint yellow transparent sticky polymers dispersion agent, add in sodium hydroxide with 30%; After sloughing solvent, obtain aqua, after spraying is dry, obtain white powder dispersion agent.
Light trigger is lanthanum nitrate-ITX title complex, and preparation method is with embodiment 1.
Adopt gel permeation chromatograph, take the aqueous solution as moving phase, sodium polyacrylate is made standard substance, and the average relative molecular mass of measuring prepared carboxylic acid copolymer dispersion agent is 3300.
Recording above-mentioned dispersion agent is 95.82% to the suspensibility of barium sulfate suspension, to the suspensibility of tio_2 suspension, is 93.35%.To Pesticide Atrazine water dispersion granule suspensibility, be 97.96%, after heat storage, suspensibility is 92.59%; To agricultural chemicals ametryn water dispersible granules suspension, be 93.35%, after heat storage, suspensibility is 93.13%.
Embodiment 10
Methacrylic acid, vinylbenzene mass ratio are 7: 3, total monomer 20g; The sodium lauryl sulphate that the weight ratio of take is 1: 5, Triton X-100 are tensio-active agent, and consumption is monomer 10%; Thiocarbamide is anti-linking agent, and consumption is monomer 5%; Light trigger consumption is 2% of monomer; The chloroform of take is standby as solvent solution-forming, and solvent load equates with monomer mass.Get 10ml solution in photoresponse pipe, after photoresponse pipe is put into ultrasonic cleaner and vibrated 10 minutes, take out; Pass into nitrogen exhausted air, cover lid; Then photoresponse pipe is put into 15 ℃ of photoreactors and used ultra violet lamp 150 minutes; Generate faint yellow transparent thickness water-soluble polymer dispersant, add in potassium hydroxide with 50%; Slough after organic solvent, obtain aqua.
Light trigger is lanthanum nitrate-ITX title complex, and preparation method is with embodiment 1.
Adopt gel permeation chromatograph, take the aqueous solution as moving phase, sodium polyacrylate is made standard substance, and the average relative molecular mass of measuring prepared carboxylic acid copolymer dispersion agent is 5600.
Recording above-mentioned dispersion agent is 91.60% to the suspensibility of barium sulfate suspension, to the suspensibility of tio_2 suspension, is 90.06%.To Pesticide Atrazine water dispersion granule suspensibility, be 94.47%, after heat storage, suspensibility is 91.62%; To agricultural chemicals ametryn water dispersible granules suspension, be 95.25%, after heat storage, suspensibility is 90.44%.
Claims (6)
1. the preparation method of methacrylic acid-styrol copolymer dispersion agent, is characterized in that, raw material comprises following material:
(a) take methacrylic acid and vinylbenzene as monomer, both mass ratioes are 1:1～9:1;
(b) tensio-active agent, consumption is monomer total mass 1%～10%;
(c) anti-dosage of crosslinking agent is 2～16% of monomer total mass;
(d) light trigger, consumption is 0.1～5% of monomer total mass;
(e) solvent, consumption is 0.8～1.5 times of monomer total mass;
(f) neutralization reagent, dosis neutralisata is 10%～95% of monomer total amount;
Step comprises: above-mentioned substance (a)-(e) is mixed to exhausted air under the condition of isolated air and 15～40 ℃, UV-irradiation 30～150 minutes; Add (f) desolvation;
Described tensio-active agent is that mass ratio is sodium lauryl sulphate and the Triton X-100 of 5:1～1:5; Described anti-linking agent is thiocarbamide, urea, Resorcinol, O-Phenylene Diamine, Virahol or sodium bisulfite;
Described light trigger is a kind of in lanthanum nitrate-ITX title complex, lanthanum nitrate-anthraquinone title complex, lanthanum nitrate-benzophenone title complex, preparation method comprises the following steps: lanthanum nitrate and title complex are dissolved in to alcohol, stir 16～30 hours at 20～40 ℃; Suction filtration is got filter residue, and uses alcohol recrystallization;
Lanthanum nitrate and title complex mass ratio 1:10～10:1; Described title complex is a kind of in ITX, anthraquinone, benzophenone.
2. the preparation method of methacrylic acid-styrol copolymer dispersion agent described in claim 1, is characterized in that, described solvent is a kind of in normal hexane, chloroform, ethanol, acetone, epoxy two ethane, tetrahydrofuran (THF) and pimelinketone.
3. the preparation method of methacrylic acid-styrol copolymer dispersion agent described in claim 1, is characterized in that, described neutralization reagent is a kind of in triethylamine, ammoniacal liquor, sodium hydroxide, potassium hydroxide.
4. methacrylic acid-styrol copolymer dispersion agent, is characterized in that, by the method described in claim 1～3 any one, prepares, and average relative molecular mass is 800～15000, and distribution coefficient is less than 2.5.
5. methacrylic acid-styrol copolymer dispersion agent described in claim 4, is characterized in that, its formulation is aqua product or powder.
Described in claim 4 or 5 methacrylic acid-styrol copolymer dispersion agent in the application of preparing aspect pesticide preparation and inorganic powder.
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| CN102532393B true CN102532393B (en) | 2014-02-26 |
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Application publication date: 20120704 Assignee: Nanjing Jian Qiang polymer materials Co., Ltd. Assignor: Shanghai Normal University Contract record no.: 2016310000035 Denomination of invention: Methacrylic acid-styrene copolymer dispersing agent, preparation method and application thereof Granted publication date: 20140226 License type: Common License Record date: 20160804 |
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