CN102532393A - 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 specifically metal carboxylate multipolymer is light-initiated methylacrylic acid and styrol copolymer dispersion agent and technology of preparing and purposes.
Background technology
Dispersion agent all has important use in industries such as pigment, dyestuff, agricultural chemicals.The shortcoming of tradition small molecules dispersion agent is: insecure in solid particles surface absorption, dissociating from the surface easily causes reassembling or precipitating.Cation dispersing agent uses generation deposition easily and lost efficacy under the hard water condition.The metal carboxylate copolymer dispersant can make system stable through sterically hindered effect and electrostatic repulsion effect, and is 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 shortcomings such as building-up process exists consumed energy big, and is restive.The present invention uses light initiation polymerization, and synthetic is monomeric dicarboxylate base polymer dispersion agent with methylacrylic acid and vinylbenzene.
The fifties in last century, Oster and Shibata did pioneer's work in light-initiated graft polymerization, and the light initiation polymerization technology is one of important method of synthesized polymer material.Compare with traditional polymerization method; The total activation energy of light initiation polymerization is low; Polymerization at a lower temperature has that technology is simple, light intensity is easy to measure, product is pure, the reaction times is short, normal-temperature reaction, energy-saving and environmental protection and experimental result be prone to characteristics such as reproductions, so extremely people's attention.But do not see the report that light-initiated synthesize methyl acrylic acid and styrol copolymer dispersion agent are arranged.
European patent EP 0405872A1 has thermoplastic material with methylacrylic acid and vinylbenzene as monomer utilization suspension polymerization is synthetic, is used for moulding such as foaming.This seminar selects methylacrylic acid and vinylbenzene as polymerization single polymerization monomer synthetic polymer dispersion agent, and with the acid of method synthesize methyl acrylic and the styrol copolymer dispersion agent of light initiation polymerization, it is few to contain impurity, narrow molecular weight distribution.Hope can be good to inorganic powder, agricultural chemicals dispersion effect, save energy, protection environment.
Summary of the invention
The present invention is intended to through light-initiated method, and synthetic a kind of methylacrylic acid-styrol copolymer dispersion agent has good stably dispersing performance, low, the environmental friendliness of preparation cost.
The present invention also provides the application of above-mentioned dispersion agent.
Be to realize above-mentioned purpose, the technical scheme that the present invention adopts does, the preparation method of a kind of methylacrylic acid-styrol copolymer dispersion agent, and raw material comprises:
(a) be monomer with methylacrylic acid and vinylbenzene, both mass ratioes are 1: 1～9: 1;
(b) tensio-active agent, consumption are monomer total mass 1%～10%; It is 5: 1～1: 5 sodium lauryl sulphate and polyoxyethylene octyl phenyl ether that tensio-active agent is preferably mass ratio;
(c) anti-linking agent, consumption is 2～16% of a monomer total mass; Be selected from thiocarbamide, urea, Resorcinol, O-Phenylene Diamine, Virahol or sodium sulfite anhy 96, be preferably thiocarbamide;
(d) light trigger, consumption are 0.1～5% of monomer total mass; Be preferably a kind of in Lanthanum trinitrate-2-isopropyl thioxanthone title complex, Lanthanum trinitrate-anthraquinone title complex, the Lanthanum trinitrate-UVNUL MS-40 title complex;
(e) solvent, consumption are 0.8～1.5 times of monomer total mass; Be preferably a kind of in normal hexane, chloroform, ethanol, acetone, epoxy two ethane, THF and the pimelinketone.
(f) neutralization reagent, dosis neutralisata are 10%～95% of monomer total amount; Be preferably a kind of in triethylamine, sodium hydroxide, Pottasium Hydroxide, the ammoniacal liquor;
Step comprises: above-mentioned substance (a)-(e) mixed, and exhausted air, and under the condition of secluding air and 15～40 ℃, UV-irradiation 30～150 minutes adds neutralization reagent, sloughs organic solvent; Obtain aqua, perhaps spraying drying obtains the white powder dispersion agent again.
Above-mentioned (d) preparation process: take by weighing ligand compound (in 2-isopropyl thioxanthone, anthraquinone, the UVNUL MS-40 a kind of) and rare earth compound Lanthanum trinitrate; Both ratios are 1: 10～10: 1; Be dissolved in the alcohol; Under 20～40 ℃ of conditions, evenly stir the dissolving of 24h thorough mixing, obtain product and keep the filter residue on the filter paper with vacuum filtration.Put into 20～40 ℃ of following vacuum-dryings of vacuum drying oven 12 hours～2 days after adopting thermal crystallization recrystallization 2～5 times with alcohol.Take out product, grind to form the homogeneous powder powder, promptly get light trigger.
Methylacrylic acid-styrol copolymer the dispersion agent that obtains through aforesaid method; It is a kind of metal carboxylate multipolymer; The averagemolecular wt amount is between 800～15000; MWD is less than 2.5, and formulation is aqua or powder, can be used for the dispersion of inorganic mineral and the preparation of agricultural chemicals water dispersant.
Experiment shows: methylacrylic acid-styrol copolymer dispersion agent that the light-initiated method of the present invention is prepared has good dispersion effect to inorganic powders such as lime carbonate, zinc oxide, permanent white, titanium oxide and agricultural chemicals; Can be used for preparing pesticide preparation and inorganic powder, be widely used in industries such as pesticide preparation, inorganic powder.
Compared with prior art, beneficial effect of the present invention is following:
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; Be suitable for industrial scale production.
2, methylacrylic acid contains the hydroxy-acid group of functionalization, and the carboxylic-acid polymeric dispersant that therefore contains methacrylic acid unit has better water solubility, and the pH value of dispersion system is had good flexibility.
3, metal carboxylate polymeric dispersant of the present invention has the ideal polymerization degree and carboxyl-content, makes by the dispersed substance stably dispersing through space steric effect and Coulomb repulsion.
Embodiment
Below in conjunction with embodiment to the present invention do further in detail, intactly explanation.Embodiment is merely 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, any modification and the variation made are all within protection scope of the present invention.Can use urea, Resorcinol, O-Phenylene Diamine, Virahol or sodium sulfite anhy 96 to replace like thiocarbamide, effect is identical.
Embodiment 1
1, the preparation of dispersion agent:
Methylacrylic acid, vinylbenzene mass ratio are 2: 1, total monomer 20g; With weight ratio is that 5: 1 sodium lauryl sulphate, polyoxyethylene octyl phenyl ether is tensio-active agent, and consumption is monomeric 4%; Thiocarbamide is anti-linking agent, and consumption is monomeric 4%; The light trigger consumption is monomeric 4%; With ethanol is that solvent solution-forming is subsequent use, and solvent load equates with monomer mass.Get 10ml solution in the photoresponse pipe, the photoresponse pipe is fed nitrogen exhausted air, cover lid; Then the photoresponse pipe is put into 15 ℃ of photoreactors with ultra violet lamp 50 minutes; Generate faint yellow transparent sticky polymers dispersion agent, add in the triethylamine solution with 40%; After sloughing organic solvent, the aqua dispersion agent obtains white powder after the spraying drying.
Wherein, Light trigger is Lanthanum trinitrate-2-isopropyl thioxanthone title complex, and the preparation method is: Lanthanum trinitrate and 2-isopropyl thioxanthone are mixed by 1: 1 mass ratio and be dissolved in ethanol (reactant is 3: 7 with the weight ratio of alcohol), and 20 ℃ were stirred 16 hours down in electric mantle; Suction filtration is got filter residue; And with ethyl alcohol recrystallization 3 times, 30 ℃ of following vacuum-drying one day is taken out product and is ground to form the homogeneous powder powder.
Adopting gel permeation chromatograph, is moving phase with the aqueous solution, and ZX-I is made standard substance, and the averagemolecular wt amount 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 agricultural chemicals atrazine, is 94.5% to the suspensibility of agricultural chemicals ametryn 80WP.
For prepared dispersion agent, detect following to the suspension and the dispersion effect method of inorganic mineral, agricultural chemicals.
(1) the detection dispersion agent is following to the dispersed scheme of inorganic mineral:
In 100ml tool plug graduated cylinder, add 0.4g dispersion agent and 50ml distilled water solution; Treat that adding 1.00g again after dispersion agent dissolves treats the dispersed solids particle, add the aqueous solution then, in 1min, turn upside down 30 times to 100ml; Put upside down 180 ° earlier, returning original position is 1 time.Graduated cylinder vertically is placed in 25 ℃ of super thermostat(t)ed water solution bath, and static friction is avoided the sunlight direct irradiation, during 30min, extracts upper strata 90ml suspension-s out with suction pipe, accomplishes in the 15s.It is m that remaining 10ml suspension-s is transferred to the quality of having weighed
1Dry petridish in, and wash graduated cylinder with distilled water solution, guarantee that the sediment in the graduated cylinder is all transferred in the petridish, petridish is put into 80 ℃ of oven dry in the baking oven, m weighs
2, the mass M of calculating insolubles, M=m
2-m
1, calculate its suspensibility by following formula:
Wherein: M is the quality (g) of 100ml tool plug graduated cylinder bottom contained dispersion agent of 10ml suspension-s and solid particulate, and 1.400 is the total mass (g) of contained dispersion agent and solid particulate in the 100ml tool plug graduated cylinder.
(2) preparation water dispersion granule (WG) scheme:
Make the laboratory by oneself polymeric dispersant, former medicine, (NH according to prescription
4)
2SO
4, Tersperse1004, kaolin etc. take by weighing, mixing, put into the granulation of tablets press machine by prescription after micronizer mill is pulverized; Sieve with standard test back to be dried; The particle of size in 30-60 order (550 μ m-250 μ m) scope is the water dispersible granules sample, fills a prescription as follows:
90% atrazine WDG prescription: former medicine 93%, dispersion agent 4.5%, wetting agent Tersperse1004 2.5%.
80% ametryn 80WP WDG prescription: 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:
Prepare agricultural chemicals water dispersion granule (WG) with above-mentioned dispersion agent; Take by weighing this exsiccant of 1.4g WG to beaker; Add the 50ml distilled water solution, place 30s, stir 30s with glass stick and make it to be uniformly dispersed; With distilled water solution this suspension-s is transferred in the 100ml tool plug graduated cylinder then, adding distil water solution is to the 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 vertically is placed in 30 ℃ of super thermostat(t)ed water solution bath, and static friction is avoided the sunlight direct irradiation; After leaving standstill 30min; Shift out upper strata 90ml suspension-s with suction pipe, this process makes tip several millimeters places under liquid level, to guarantee not shake or stir the sediment of graduated cylinder bottom.It is m that remaining 10ml suspension-s is transferred to the quality of having weighed
1Petridish in, and wash graduated cylinder with distilled water solution, guarantee that the sediment of graduated cylinder bottom is all transferred in the petridish, petridish is put into 80 ℃ of oven dry in the baking oven, m weighs
2, the mass M=(m of calculating insolubles
2-m
1), be calculated as follows suspensibility then:
Wherein, 1.400 is the quality of the water dispersion granule of adding; M is the quality of tool plug graduated cylinder bottom sediment.
2, agricultural chemicals heat storage experiment back is surveyed dispersed
Take by weighing the 10g pesticide water dispersible granules in ampoule, seal up the mouth of ampoule, ampoule as in 54 degrees centigrade of baking ovens 14 days.The suspensibility of test pesticide water dispersible granules after 14 days.Suspensibility to the agricultural chemicals atrazine water dispersible granule is 89.07%, is 90.7% to the suspensibility of agricultural chemicals ametryn 80WP water dispersible granules.
Embodiment 2
Methylacrylic acid, vinylbenzene mass ratio are 7: 2.5, total monomer 20g; With weight ratio is that 4: 1 sodium lauryl sulphate, polyoxyethylene octyl phenyl ether is tensio-active agent, and consumption is 5% of a monomer total amount; Thiocarbamide is anti-linking agent, and consumption is monomeric 9%; The light trigger consumption is monomeric 4%; With the chloroform is that solvent solution-forming is subsequent use, and solvent load equates with monomer mass.Get 10ml solution in the photoresponse pipe, the photoresponse pipe is fed nitrogen exhausted air, cover lid; Then the photoresponse pipe is put into 15 ℃ of photoreactors with ultra violet lamp 50 minutes; Generate faint yellow transparent sticky polymers dispersion agent, add in the sodium hydroxide solution with 30%.After sloughing organic solvent, obtain aqua.
Wherein, Light trigger is Lanthanum trinitrate-anthraquinone title complex, and the preparation method is: Lanthanum trinitrate and anthraquinone are mixed by 1: 2 mass ratio and be dissolved in ethanol, and 40 ℃ were stirred 20 hours down; Suction filtration is got filter residue; And with ethyl alcohol recrystallization 3 times, 30 ℃ of following vacuum-drying one day is taken out product and is ground to form the homogeneous powder powder.
Adopting gel permeation chromatograph (GPC), is moving phase with the aqueous solution, and ZX-I is made standard substance, and the averagemolecular wt amount of measuring prepared copolymer dispersant is 15000.
Press embodiment 1 said operation steps, recording above-mentioned dispersion agent is 98.85% to the suspensibility of barium sulfate suspension, is 96.22% to the suspensibility of tio_2 suspension.To agricultural chemicals atrazine water dispersion granule suspensibility is 86.9%, and heat storage back suspensibility is 84.89%; To agricultural chemicals ametryn 80WP water dispersible granules suspension is 92.5%, and heat storage back suspensibility is 90.4%.
Embodiment 3
Methylacrylic acid, vinylbenzene mass ratio are 9: 1, total monomer 20g; With weight ratio is that 3: 1 sodium lauryl sulphate, polyoxyethylene octyl phenyl ether is tensio-active agent, and consumption is monomeric 9%; Thiocarbamide is anti-linking agent, and consumption is monomeric 7%; The light trigger consumption is monomeric 2%; With acetone is that solvent solution-forming is subsequent use, and solvent load equates with monomer mass.Get 10ml solution in the photoresponse pipe, the photoresponse pipe is fed nitrogen exhausted air, cover lid; Then the photoresponse pipe is put into 20 ℃ of photoreactors with ultra violet lamp 100 minutes; Generate faint yellow transparent sticky polymers dispersion agent, add in the ammoniacal liquor with 90%; After sloughing organic solvent, obtain aqua, obtain white powder after the spraying drying.
Wherein, Light trigger is Lanthanum trinitrate-UVNUL MS-40 title complex, and the preparation method is: Lanthanum trinitrate and UVNUL MS-40 are mixed by 2: 1 mass ratio and be dissolved in ethanol, and 25 ℃ were stirred 20 hours down; Suction filtration is got filter residue; And with ethyl alcohol recrystallization 3 times, 30 ℃ of following vacuum-drying one day is taken out product and is ground to form the homogeneous powder powder.
Adopting gel permeation chromatograph, is moving phase with the aqueous solution, and ZX-I is made standard substance, and the averagemolecular wt amount of measuring prepared metal carboxylate copolymer dispersant is 4500.
Recording above-mentioned dispersion agent is 98.80% to the suspensibility of barium sulfate suspension, is 96.22% to the suspensibility of tio_2 suspension.To agricultural chemicals atrazine water dispersion granule suspensibility is 90.8%, and heat storage back suspensibility is 84.89%; To agricultural chemicals ametryn 80WP water dispersible granules suspension is 96.5%, and heat storage back suspensibility is 93.4%.
Embodiment 4
Methylacrylic acid, vinylbenzene mass ratio are 4: 1, total monomer 20g; With weight ratio is that 1: 5 sodium lauryl sulphate, polyoxyethylene octyl phenyl ether is tensio-active agent, and consumption is monomeric 4%; Thiocarbamide is anti-linking agent, and consumption is monomeric 8%; The light trigger consumption is monomeric 1%; With the THF is that solvent solution-forming is subsequent use, and solvent load equates with monomer mass.Get 10ml solution in the photoresponse pipe, the photoresponse pipe is put into the ultrasonic cleaner vibration take out after 10 minutes; Feed the nitrogen exhausted air, cover lid; Then the photoresponse pipe is put into 20 ℃ of photoreactors with ultra violet lamp 150 minutes; Generate faint yellow transparent sticky polymers dispersion agent, add in the ammoniacal liquor with 60%; After sloughing organic solvent, obtain aqua, after the spraying drying, obtain white powder.
Wherein, Light trigger is Lanthanum trinitrate-UVNUL MS-40 title complex, and the preparation method is: Lanthanum trinitrate and UVNUL MS-40 are mixed by 1: 2 mass ratio and be dissolved in ethanol, and 20 ℃ were stirred 26 hours down; Suction filtration is got filter residue; And with ethyl alcohol recrystallization 3 times, 30 ℃ of following vacuum-drying one day is taken out product and is ground to form the homogeneous powder powder.
Adopting gel permeation chromatograph, is moving phase with the aqueous solution, and ZX-I is made standard substance, and the averagemolecular wt amount 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, is 96.55% to the suspensibility of tio_2 suspension.To agricultural chemicals atrazine water dispersion granule suspensibility is 94.9%, and heat storage back suspensibility is 89.89%; To agricultural chemicals ametryn 80WP water dispersible granules suspension is 93.34%, and heat storage back suspensibility is 94.87%.
Embodiment 5
Methylacrylic acid, vinylbenzene mass ratio are 7: 3, total monomer 20g; With weight ratio is that 1: 4 sodium lauryl sulphate, polyoxyethylene octyl phenyl ether is tensio-active agent, and consumption is monomeric 1%; Thiocarbamide is anti-linking agent, and consumption is monomeric 13%; Adding the light trigger consumption is monomeric 0.5%; With the pimelinketone is that solvent solution-forming is subsequent use, and solvent load equates with monomer mass.Get 10ml solution in the photoresponse pipe, the photoresponse pipe is put into the ultrasonic cleaner vibration take out after 10 minutes; Feed the nitrogen exhausted air, cover lid; Then the photoresponse pipe is put into 30 ℃ of photoreactors with ultra violet lamp 150 minutes; Generate faint yellow transparent sticky polymers dispersion agent, add in the ammoniacal liquor with 90%; Obtain aqua after sloughing organic solvent.
Adopt gel permeation chromatograph; With the aqueous solution is moving phase; ZX-I is made standard substance, and the averagemolecular wt amount of measuring prepared carboxylic acid
analog copolymer dispersion agent is 6500.
Light trigger is Lanthanum trinitrate-UVNUL MS-40 title complex; The preparation method is: Lanthanum trinitrate and UVNUL MS-40 are mixed by 2: 1 mass ratio and be dissolved in ethanol; 26 ℃ were stirred 19 hours down, and suction filtration is got filter residue, and with ethyl alcohol recrystallization 3 times; 30 ℃ of following vacuum-drying one day is taken out product and is ground to form the homogeneous powder powder.
Recording above-mentioned dispersion agent is 97.99% to the suspensibility of barium sulfate suspension, is 95.05% to the suspensibility of tio_2 suspension.To agricultural chemicals atrazine water dispersion granule suspensibility is 90.78%, and heat storage back suspensibility is 87.65%; To agricultural chemicals ametryn 80WP water dispersible granules suspension is 96.56%, and heat storage back suspensibility is 92.34%.
Embodiment 6
Methylacrylic acid, vinylbenzene mass ratio are 1.5: 1, total monomer 20g; With weight ratio is that 1: 2 sodium lauryl sulphate, polyoxyethylene octyl phenyl ether is tensio-active agent, and consumption is monomeric 7%; Thiocarbamide is anti-linking agent, and consumption is monomeric 14%; The light trigger consumption is monomeric 2%; With epoxy two hexanes is that solvent solution-forming is subsequent use, and solvent load equates with monomer mass.Get 10ml solution in the photoresponse pipe, the photoresponse pipe is put into the ultrasonic cleaner vibration take out after 10 minutes; Feed the nitrogen exhausted air, cover lid; Then the photoresponse pipe is put into 30 ℃ of photoreactors with ultra violet lamp 80 minutes; Generate faint yellow transparent sticky polymers dispersion agent.Add in the ammoniacal liquor with 60%, obtain aqua after sloughing organic solvent, obtain white powder after the spraying drying.
Light trigger is Lanthanum trinitrate-2-isopropyl thioxanthone title complex, and the preparation method is with embodiment 1.
Adopting gel permeation chromatograph, is moving phase with the aqueous solution, and ZX-I is made standard substance, and the averagemolecular wt amount 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, is 97.05% to the suspensibility of tio_2 suspension.To agricultural chemicals atrazine water dispersion granule suspensibility is 93.84%, and heat storage back suspensibility is 92.69%; To agricultural chemicals ametryn 80WP water dispersible granules suspension is 96.59%, and heat storage back suspensibility is 93.74%.
Embodiment 7
Methylacrylic acid, vinylbenzene mass ratio are 1: 1, total monomer 20g; With weight ratio is that 1: 4 sodium lauryl sulphate, polyoxyethylene octyl phenyl ether is tensio-active agent, and consumption is monomeric 10%; Thiocarbamide is anti-linking agent, and consumption is monomeric 16%; The light trigger consumption is monomeric 1%; With acetone is that solvent solution-forming is subsequent use, and solvent load equates with monomer mass.Get 10ml solution in the photoresponse pipe, the photoresponse pipe is put into the ultrasonic cleaner vibration take out after 10 minutes; Feed the nitrogen exhausted air, cover lid; Then the photoresponse pipe is put into 15 ℃ of photoreactors with ultra violet lamp 70 minutes; Generate faint yellow transparent sticky polymers dispersion agent, add in the Pottasium Hydroxide with 70%; Obtain aqua after sloughing organic solvent, obtain white powder after the spraying drying.
Light trigger is Lanthanum trinitrate-2-isopropyl thioxanthone title complex, and the preparation method is with embodiment 1.
Adopting gel permeation chromatograph, is moving phase with the aqueous solution, and ZX-I is made standard substance, and the averagemolecular wt amount 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, is 93.35% to the suspensibility of tio_2 suspension.To agricultural chemicals atrazine water dispersion granule suspensibility is 95.46%, and heat storage back suspensibility is 91.87%; To agricultural chemicals ametryn 80WP water dispersible granules suspension is 95.29%, and heat storage back suspensibility is 90.78%.
Embodiment 8
Methylacrylic acid, vinylbenzene mass ratio are 1.5: 1, total monomer 20g; With weight ratio is that 1: 1 sodium lauryl sulphate, polyoxyethylene octyl phenyl ether is tensio-active agent, and consumption is monomeric 7%; Thiocarbamide is anti-linking agent, and consumption is monomeric 11%; The light trigger consumption is monomeric 2%; With the normal hexane is that solvent solution-forming is subsequent use, and solvent load equates with monomer mass.Get 10ml solution in the photoresponse pipe, the photoresponse pipe is put into the ultrasonic cleaner vibration take out after 10 minutes; Feed the nitrogen exhausted air, cover lid; Then the photoresponse pipe is put into 40 ℃ of photoreactors with ultra violet lamp 50 minutes; Generate faint yellow transparent sticky polymers dispersion agent, add in the ammoniacal liquor with 30%; Obtain aqua after sloughing solvent.
Light trigger is Lanthanum trinitrate-2-isopropyl thioxanthone title complex, and the preparation method is with embodiment 1.
Adopting gel permeation chromatograph, is moving phase with the aqueous solution, and ZX-I is made standard substance, and the averagemolecular wt amount 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, is 95.82% to the suspensibility of tio_2 suspension.To agricultural chemicals atrazine water dispersion granule suspensibility is 92.89%, and heat storage back suspensibility is 92.23%; To agricultural chemicals ametryn 80WP water dispersible granules suspension is 92.76%, and heat storage back suspensibility is 90.09%.
Embodiment 9
Methylacrylic acid, vinylbenzene mass ratio are 4: 1, total monomer 20g; With weight ratio is that 5: 1 sodium lauryl sulphate, polyoxyethylene octyl phenyl ether is tensio-active agent, and consumption is monomeric 8%; Thiocarbamide is anti-linking agent, and consumption is monomeric 10%; The light trigger consumption is monomeric 3%; With the normal hexane is that solvent solution-forming is subsequent use, and solvent load equates with monomer mass.Get 10ml solution in the photoresponse pipe, the photoresponse pipe is put into the ultrasonic cleaner vibration take out after 10 minutes; Feed the nitrogen exhausted air, cover lid; Then the photoresponse pipe is put into 20 ℃ of photoreactors with ultra violet lamp 90 minutes; Generate faint yellow transparent sticky polymers dispersion agent, add in the sodium hydroxide with 30%; Obtain aqua after sloughing solvent, obtain the white powder dispersion agent after the spraying drying.
Light trigger is Lanthanum trinitrate-2-isopropyl thioxanthone title complex, and the preparation method is with embodiment 1.
Adopting gel permeation chromatograph, is moving phase with the aqueous solution, and ZX-I is made standard substance, and the averagemolecular wt amount 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, is 93.35% to the suspensibility of tio_2 suspension.To agricultural chemicals atrazine water dispersion granule suspensibility is 97.96%, and heat storage back suspensibility is 92.59%; To agricultural chemicals ametryn 80WP water dispersible granules suspension is 93.35%, and heat storage back suspensibility is 93.13%.
Embodiment 10
Methylacrylic acid, vinylbenzene mass ratio are 7: 3, total monomer 20g; With weight ratio is that 1: 5 sodium lauryl sulphate, polyoxyethylene octyl phenyl ether is tensio-active agent, and consumption is monomeric 10%; Thiocarbamide is anti-linking agent, and consumption is monomeric 5%; The light trigger consumption is monomeric 2%; With the chloroform is that solvent solution-forming is subsequent use, and solvent load equates with monomer mass.Get 10ml solution in the photoresponse pipe, the photoresponse pipe is put into the ultrasonic cleaner vibration take out after 10 minutes; Feed the nitrogen exhausted air, cover lid; Then the photoresponse pipe is put into 15 ℃ of photoreactors with ultra violet lamp 150 minutes; Generate faint yellow transparent thickness water-soluble polymer dispersant, add in the Pottasium Hydroxide with 50%; After sloughing organic solvent, obtain aqua.
Light trigger is Lanthanum trinitrate-2-isopropyl thioxanthone title complex, and the preparation method is with embodiment 1.
Adopting gel permeation chromatograph, is moving phase with the aqueous solution, and ZX-I is made standard substance, and the averagemolecular wt amount 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, is 90.06% to the suspensibility of tio_2 suspension.To agricultural chemicals atrazine water dispersion granule suspensibility is 94.47%, and heat storage back suspensibility is 91.62%; To agricultural chemicals ametryn 80WP water dispersible granules suspension is 95.25%, and heat storage back suspensibility is 90.44%.
Claims (10)
1. the preparation method of methylacrylic acid-styrol copolymer dispersion agent is characterized in that, raw material comprises following material:
(a) be monomer with methylacrylic acid and vinylbenzene, both mass ratioes are 1: 1～9: 1;
(b) tensio-active agent, consumption are monomer total mass 1%～10%;
(c) anti-dosage of crosslinking agent is 2～16% of a monomer total mass;
(d) light trigger, consumption are 0.1～5% of monomer total mass;
(e) solvent, consumption are 0.8～1.5 times of monomer total mass;
(f) neutralization reagent, dosis neutralisata are 10%～95% of monomer total amount;
Step comprises: above-mentioned substance (a)-(e) is mixed exhausted air and under the condition of secluding air and 15～40 ℃, UV-irradiation 30～150 minutes; Add (f) and remove solvent.
2. the preparation method of the said methylacrylic acid of claim 1-styrol copolymer dispersion agent is characterized in that, said tensio-active agent is that mass ratio is 5: 1～1: 5 sodium lauryl sulphate and a polyoxyethylene octyl phenyl ether.
3. the preparation method of the said methylacrylic acid of claim 1-styrol copolymer dispersion agent is characterized in that, said anti-linking agent is thiocarbamide, urea, Resorcinol, O-Phenylene Diamine, Virahol or sodium sulfite anhy 96.
4. the preparation method of the said methylacrylic acid of claim 1-styrol copolymer dispersion agent is characterized in that, said light trigger is a kind of in Lanthanum trinitrate-2-isopropyl thioxanthone title complex, Lanthanum trinitrate-anthraquinone title complex, the Lanthanum trinitrate-UVNUL MS-40 title complex.
5. the preparation method of the said methylacrylic acid of claim 4-styrol copolymer dispersion agent is characterized in that the preparation method of said light trigger may further comprise the steps: Lanthanum trinitrate and title complex are dissolved in alcohol, 20～40 ℃ of following stirrings 16～30 hours; Suction filtration is got filter residue, and uses pure recrystallization;
Lanthanum trinitrate and title complex mass ratio 1: 10～10: 1; Said title complex is a kind of in 2-isopropyl thioxanthone, anthraquinone, the UVNUL MS-40.
6. the preparation method of the said methylacrylic acid of claim 1-styrol copolymer dispersion agent is characterized in that, said organic solvent is a kind of in normal hexane, chloroform, ethanol, acetone, epoxy two ethane, THF and the pimelinketone.
7. the preparation method of the said methylacrylic acid of claim 1-styrol copolymer dispersion agent is characterized in that, said neutralization reagent is a kind of in triethylamine, ammoniacal liquor, sodium hydroxide, the Pottasium Hydroxide.
8. methylacrylic acid-styrol copolymer dispersion agent is characterized in that, through each described method preparation of claim 1～6, the averagemolecular wt amount is 800～15000, and distribution coefficient is less than 2.5.
9. the said methylacrylic acid of claim 8-styrol copolymer dispersion agent is characterized in that, its formulation is aqua product or powder.
10. claim 8 or the 9 said methylacrylic acid-styrol copolymer dispersion agents application aspect preparation pesticide preparation and inorganic powder.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103553148A (en) * | 2013-11-15 | 2014-02-05 | 湖南科技大学 | Preparation method of cobalt chromium green pigment |
| CN103601243A (en) * | 2013-11-15 | 2014-02-26 | 湖南科技大学 | Sol-gel self-propagating combustion method for preparing copper chrome black pigment |
| CN111704701A (en) * | 2020-07-15 | 2020-09-25 | 北京理工大学 | Unsaturated carboxylic acid/styrene monomer/methoxy polyethylene glycol carboxylate copolymer, preparation method, aqueous suspending agent and application |
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| EP0405872A1 (en) * | 1989-06-30 | 1991-01-02 | Arco Chemical Technology, Inc. | Suspension polymerization of styrene and methacrylic acid |
| CN101279215A (en) * | 2008-01-02 | 2008-10-08 | 沈阳化工学院 | Stable low molecular weight dispersing agent |
| CN101601381A (en) * | 2009-07-17 | 2009-12-16 | 扬州斯培德化工有限公司 | A kind of polycarboxylate polymeric dispersant and preparation method thereof and application |
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| EP0405872A1 (en) * | 1989-06-30 | 1991-01-02 | Arco Chemical Technology, Inc. | Suspension polymerization of styrene and methacrylic acid |
| CN101279215A (en) * | 2008-01-02 | 2008-10-08 | 沈阳化工学院 | Stable low molecular weight dispersing agent |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103553148A (en) * | 2013-11-15 | 2014-02-05 | 湖南科技大学 | Preparation method of cobalt chromium green pigment |
| CN103601243A (en) * | 2013-11-15 | 2014-02-26 | 湖南科技大学 | Sol-gel self-propagating combustion method for preparing copper chrome black pigment |
| CN111704701A (en) * | 2020-07-15 | 2020-09-25 | 北京理工大学 | Unsaturated carboxylic acid/styrene monomer/methoxy polyethylene glycol carboxylate copolymer, preparation method, aqueous suspending agent and application |
| CN111704701B (en) * | 2020-07-15 | 2021-11-16 | 北京理工大学 | Unsaturated carboxylic acid/styrene monomer/methoxy polyethylene glycol carboxylate copolymer, preparation method, aqueous suspending agent and application |
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