CN102188929A - Carboxylate terpolymer dispersing agent and preparation process thereof - Google Patents
Carboxylate terpolymer dispersing agent and preparation process thereof Download PDFInfo
- Publication number
- CN102188929A CN102188929A CN2011100559267A CN201110055926A CN102188929A CN 102188929 A CN102188929 A CN 102188929A CN 2011100559267 A CN2011100559267 A CN 2011100559267A CN 201110055926 A CN201110055926 A CN 201110055926A CN 102188929 A CN102188929 A CN 102188929A
- Authority
- CN
- China
- Prior art keywords
- parts
- solution
- dispersant
- metal carboxylate
- carboxylate terpolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention relates to a copolymer dispersing agent, namely a carboxylate terpolymer dispersing agent and a preparation process thereof. The prior art has the defects that the molecular weight in the synthetic process is difficult to control and the dispersing effect is undesirable. The carboxylate terpolymer dispersing agent is composed of the following substances in parts by mass: 10-50 parts of styrene, 10-80 parts of methacrylic acid and 10-50 parts of hydroxypropyl acrylate, and the relative number average molecular weight of the terpolymer is 1000-20000. The invention has the advantages that the carboxylate terpolymer dispersing agent containing the methacrylic acid unit has better water solubility and has good adaptability to the pH value of a dispersing system; the dispersing agent has ideal polymerization degree and carboxyl content, and the dispersed substances are stably dispersed by steric hindrance effect and electrostatic repulsion; and the carboxylate terpolymer dispersing agent has the advantages of simple preparation process, short production period, low cost and no environmental pollution, is easy to operate, and is suitable for industrial mass production.
Description
Technical field
The present invention relates to a kind of copolymer dispersant, a kind of specifically metal carboxylate terpolymer dispersants and preparation technology thereof.
Background technology
Dispersant all has important use to played a part dispersion and stable by dispersed substance in industries such as pigment, dyestuff, aqueous solution coal slurry, agricultural chemicals.The shortcoming of the little dispersal agent molecule of tradition is: insecure in solid particles surface absorption, dissociating from the surface easily causes reassembling or precipitating.The metal carboxylate copolymer dispersant can make system stable by sterically hindered effect and electrostatic repulsion effect, has better dispersion effect than little dispersal agent molecule; Compare with traditional lignosulfonates, naphthalenesulfonate formaldehyde condensation compound dispersant, the metal carboxylate copolymer dispersant is insensitive to ion, pH value and the temperature etc. of dispersion, can significantly reduce the viscosity of system.Molecular weight was lower when this analog copolymer was used as dispersant, and generally between several thousand to several ten thousand, the size of molecular weight is most important to the dispersibility of dispersant.Because the polymerization activity of preparation this analog copolymer used monomer is than higher, polymer molecular weight be controlled to key technology for this type of dispersant preparation.The inventor is in the past having done a large amount of work aspect the polymer molecular weight control, as Chinese patent CN200810201806.1, CN200810201805.7, and " the synthetic and dispersive property of acrylic copolymer dispersant " delivered on the process engineering journal.In addition, the method for present technique field inner control polymer molecular weight size also has: use sulfhydryl compound to control polymer molecular weight as chain-transferring agent, EP1304314; Adopt slaine as molecular weight regulator, patent documentation CN1085570; Polymerisation reaches the purpose of control polymer molecular weight in water-isopropyl alcohol mixed solvent, as document US 4301226 or the like.The shortcoming of these methods is: introduced the material of penetrating odor in the product, contaminated environment has increased difficulty of post-processing, and the production cost costliness.
The application of prior art metal carboxylate copolymer dispersant more and more widely is difficult to control, the technical problem that the undesirable grade of dispersion effect is difficult to overcome but the synthesis technique of this class dispersant also exists the molecular weight size.A kind of to have good dispersion stabilization, low, the eco-friendly metal carboxylate terpolymer dispersants of preparation cost and preparation technology thereof be very necessary so invent.
Summary of the invention
The objective of the invention is a kind of have good dispersion stabilization, low, the eco-friendly metal carboxylate terpolymer dispersants of preparation cost and preparation technology thereof.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of metal carboxylate terpolymer dispersants, form than material by following quality:
10～50 parts of styrene
10～80 parts of methacrylic acids
10～50 parts of hydroxypropyl acrylates;
The number average relative molecular weight of terpolymer is 1000～20000.
The preparation technology of metal carboxylate terpolymer dispersants, step is as follows:
A) aqueous solution of a certain amount of distilled water of adding and chain-transferring agent in reaction bulb stirs, is heated to 60～90 ℃;
B) in above-mentioned solution, drip styrene, methacrylic acid, hydroxypropyl acrylate and initiator solution dropwised in 1～5 hour, insulation reaction 2～10 hours;
C) step b gained solution is stirred, is cooled to room temperature, use in the alkali and the carboxylic acid in the system, dosis neutralisata is 50～100% of a carboxyl molal quantity;
D) the metal carboxylate terpolymer solution spray drying with step c preparation makes target dispersant powder.
Described chain-transferring agent is sodium hydrogensulfite and isopropyl alcohol, and consumption is 0.5～10% of a monomer gross mass.
Described initator is an ammonium persulfate, and consumption is 2～16% of a monomer gross mass.
Described alkali is one or both in NaOH, potassium hydroxide, ammonia spirit, triethylamine, the triethanolamine.
Main points of the present invention are: with styrene, methacrylic acid, hydroxypropyl acrylate is primary raw material, is auxiliary material with chain-transferring agent, initator, alkali, reacts under 60～90 ℃ of conditions, cools off then, neutralizes with alkali, makes the target dispersant solution; The solid content of dispersant solution is 20～50%, the spray-dried again dispersant powder that makes.
Experiment shows: metal carboxylate terpolymer dispersants of the present invention has good dispersion effect to inorganic particles such as calcium carbonate, zinc oxide, barium sulfate, titanium dioxide and agricultural chemicals; Be widely used in industries such as pesticidal preparations, pigment, dyestuff and aqueous solution coal slurry.
Compared with prior art, beneficial effect of the present invention is as follows:
1, methacrylic acid contains the hydroxy-acid group of functionalization, and the metal carboxylate terpolymer dispersants that therefore contains methacrylic acid unit has aqueous solution dissolubility preferably, and the pH value of dispersion is had good adaptability.
2, metal carboxylate terpolymer dispersants of the present invention has the desirable degree of polymerization and carboxyl-content, makes by the dispersed substance stably dispersing by space steric effect and Coulomb repulsion.
3, simple, the processing ease of metal carboxylate terpolymer dispersants preparation technology, with short production cycle, with low cost, non-environmental-pollution, be suitable for industrial scale production.
The specific embodiment
The present invention is described in further detail and completely below in conjunction with embodiment, but only be to exemplary illustration of the present invention, do not limit the scope of the present invention.
Embodiment 1:
1) preparation of dispersant:
Get 1000 parts of distilled waters, 10 parts of chain-transferring agents, the composition of chain-transferring agent is that 1: 1 sodium hydrogensulfite and isopropanol water solution joins in the four-hole reaction flask, while stirring heating; When the temperature of solution in the reaction bulb rises to 60 ℃, add 100 parts of styrene, 800 parts of methacrylic acids, 100 parts of hydroxypropyl acrylates and 30 parts of initiator solutions and add in 1 hour, 60 ℃ of insulation reaction are 2 hours then; Insulation reaction is reduced to room temperature after finishing while stirring, uses in the sodium hydroxide solution and the carboxylic acid in the system, and dosis neutralisata is 50% of a carboxyl molal quantity, makes the target dispersant solution; This dispersant solution according to existing spray drying process, is made target dispersant powder.
Adopting gel permeation chromatograph (GPC), is the phase that flows with the aqueous solution, and Sodium Polyacrylate is made standard items, and the number average relative molecular weight of measuring prepared metal carboxylate terpolymer dispersants is 15000.
2) dispersant of preparation is measured the dispersiveness of inorganic mineral:
The dispersant and the 50ml distilled water solution that in 100ml tool plug graduated cylinder, add 0.4g step (1) preparation, treat that adding 1.00g again after dispersant 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 thermostatted water solution bath, and static friction is avoided the sunlight direct irradiation, during 30min, extracts upper strata 90ml suspension out with suction pipe, finishes in the 15s.It is m that remaining 10ml suspension is transferred to the quality of having weighed
1Dry culture dish in, and wash graduated cylinder with distilled water solution, guarantee that the precipitum in the graduated cylinder is all transferred in the culture dish, culture dish is put into 80 ℃ of oven dry in the baking oven, m weighs
2, the mass M of calculating insoluble matter, 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 dispersant of 10ml suspension and solid particle, and 1.400 is the gross mass (g) of contained dispersant and solid particle in the 100ml tool plug graduated cylinder.
Press the aforesaid operations step, recording prepared dispersant is 99.00% to the suspensibility of barium sulfate suspension, and prepared dispersant is 95.15% to the suspensibility of tio_2 suspension.
3) described dispersant is measured the dispersiveness of agricultural chemicals:
Prepare agricultural chemicals water dispersion granule (WG) with above-mentioned dispersant, take by weighing this dry WG of 1.0g to beaker, add the 50ml distilled water solution, place 30s, stirring 30s with glass bar makes it to be uniformly dispersed, with distilled water solution this suspension 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 thermostatted water solution bath, and static friction is avoided the sunlight direct irradiation, after leaving standstill 30min, shift out upper strata 90ml suspension with suction pipe, this process makes tip several millimeters places under liquid level, guarantees not shake or stir the precipitum of graduated cylinder bottom.It is m that remaining 10ml suspension is transferred to the quality of having weighed
1Culture dish in, and wash graduated cylinder with distilled water solution, guarantee that the precipitum of graduated cylinder bottom is all transferred in the culture dish, culture dish is put into 80 ℃ of oven dry in the baking oven, m weighs
2, the mass M=(m of calculating insoluble matter
2-m
1), be calculated as follows suspensibility then:
Wherein, 1.00 is the quality of the water dispersion granule of adding; M is the quality of tool plug graduated cylinder bottom precipitum.
Embodiment 2:
Get 1000 parts of distilled waters and 80 parts of chain-transferring agents, the composition of chain-transferring agent is 1: 1.2 sodium hydrogensulfite and an isopropanol water solution; Join in the four-hole reaction flask, while stirring heating; When the temperature of solution in the reaction bulb rises to 70 ℃, add 200 parts of styrene, 500 parts of methacrylic acids, 300 parts of hydroxypropyl acrylates and 60 parts of initiator solutions and add in 5 hours, insulation reaction is 3 hours then; Insulation reaction is reduced to room temperature after finishing while stirring, uses in the sodium hydroxide solution and the carboxylic acid in the system, and dosis neutralisata is 80% of a carboxyl molal quantity, makes the target dispersant solution; This dispersant solution spray-drying is promptly got target dispersant powder.
Adopting gel permeation chromatograph, is the phase that flows with the aqueous solution, and Sodium Polyacrylate is made standard items, and the number average relative molecular weight of measuring prepared metal carboxylate terpolymer dispersants is 2500.
Press embodiment 1 described operating procedure, recording above-mentioned dispersant is 98.85% to the suspensibility of barium sulfate suspension, is 96.22% to the suspensibility of tio_2 suspension.
Embodiment 3:
Get 1000 parts of distilled waters and 20 parts of chain-transferring agents, the composition of chain-transferring agent is 1: 0.8 sodium hydrogensulfite and an isopropanol water solution; Join in the four-hole reaction flask, while stirring heating; When the temperature of solution in the reaction bulb rises to 80 ℃, add 200 parts of styrene, 600 parts of methacrylic acids, 200 parts of hydroxypropyl acrylates and 60 parts of initiator solutions and add in 2 hours, insulation reaction is 5 hours then.Insulation reaction is reduced to room temperature after finishing while stirring, uses in the sodium hydroxide solution and the carboxylic acid in the system, and dosis neutralisata is 80% of a carboxyl molal quantity, makes the target dispersant solution; This dispersant solution spray-drying is promptly got target dispersant powder.
Adopting gel permeation chromatograph, is the phase that flows with the aqueous solution, and Sodium Polyacrylate is made standard items, and the number average relative molecular weight of measuring prepared metal carboxylate terpolymer dispersants is 4500.
Press embodiment 1 described operating procedure, recording above-mentioned dispersant is 98.80% to the suspensibility of barium sulfate suspension, is 96.22% to the suspensibility of tio_2 suspension.
Embodiment 4:
Get 1000 parts of distilled waters and 40 parts of chain-transferring agents, the composition of chain-transferring agent is 1: 1 sodium hydrogensulfite and an isopropanol water solution, joins in the four-hole reaction flask, while stirring heating; When the temperature of solution in the reaction bulb rises to 70 ℃, add 100 parts of styrene, 700 parts of methacrylic acids, 200 parts of hydroxypropyl acrylates and 30 parts of initiator solutions and add in 2 hours, insulation reaction is 3 hours then; Insulation reaction is reduced to room temperature after finishing while stirring, uses in the sodium hydroxide solution and the carboxylic acid in the system, and dosis neutralisata is 80% of a carboxyl molal quantity, makes the target dispersant solution; This dispersant solution spray-drying is promptly got target dispersant powder.
Adopting gel permeation chromatograph, is the phase that flows with the aqueous solution, and Sodium Polyacrylate is made standard items, and the number average relative molecular weight of measuring prepared metal carboxylate terpolymer dispersants is 7200.
Press embodiment 1 described operating procedure, recording above-mentioned dispersant is 97.82% to the suspensibility of barium sulfate suspension, is 96.55% to the suspensibility of tio_2 suspension.
Embodiment 5:
Get 1000 parts of distilled waters and 40 parts of chain-transferring agents, the composition of chain-transferring agent is 1: 1 sodium hydrogensulfite and an isopropanol water solution, joins in the four-hole reaction flask, while stirring heating; When the temperature of solution in the reaction bulb rises to 90 ℃, add 400 parts of styrene, 300 parts of methacrylic acids, 300 parts of hydroxypropyl acrylates and 40 parts of initiator solutions and add in 3 hours, insulation reaction is 4 hours then; Insulation reaction is reduced to room temperature after finishing while stirring, uses in the sodium hydroxide solution and the carboxylic acid in the system, and dosis neutralisata is 60% of a carboxyl molal quantity, makes the target dispersant solution; This dispersant solution spray-drying is promptly got target dispersant powder.
Adopting gel permeation chromatograph, is the phase that flows with the aqueous solution, and Sodium Polyacrylate is made standard items, and the number average relative molecular weight of measuring prepared metal carboxylate terpolymer dispersants is 6500.
Press embodiment 1 described operating procedure, recording above-mentioned dispersant is 97.99% to the suspensibility of barium sulfate suspension, is 95.05% to the suspensibility of tio_2 suspension.
Embodiment 6:
Get 1000 parts of distilled waters and 80 parts of chain-transferring agents, the composition of chain-transferring agent is 1: 1 sodium hydrogensulfite and an isopropanol water solution, joins in the four-hole reaction flask, while stirring heating; When the temperature of solution in the reaction bulb rises to 80 ℃, add 400 parts of styrene, 200 parts of methacrylic acids, 400 parts of hydroxypropyl acrylates and 60 parts of initiator solutions and add in 4 hours, insulation reaction is 5 hours then; Insulation reaction is reduced to room temperature after finishing while stirring, uses in the sodium hydroxide solution and the carboxylic acid in the system, and dosis neutralisata is 90% of a carboxyl molal quantity, makes the target dispersant solution; This dispersant solution spray-drying is promptly got target dispersant powder.
Adopting gel permeation chromatograph, is the phase that flows with the aqueous solution, and Sodium Polyacrylate is made standard items, and the number average relative molecular weight of measuring prepared metal carboxylate terpolymer dispersants is 2500.
Press embodiment 1 described operating procedure, recording above-mentioned dispersant is 98.86% to the suspensibility of barium sulfate suspension, is 97.05% to the suspensibility of tio_2 suspension.
Embodiment 7:
Get 1000 parts of alcoholic solutions and 100 parts of chain-transferring agents, the composition of chain-transferring agent is 1: 1 sodium hydrogensulfite and an isopropanol water solution, joins in the four-hole reaction flask, while stirring heating; When the temperature of solution in the reaction bulb rises to 70 ℃, add 200 parts of styrene, 200 parts of methacrylic acids, 600 parts of hydroxypropyl acrylates and 30 parts of initiator solutions and add in 3 hours, insulation reaction is 1 hour then; Insulation reaction is reduced to room temperature after finishing while stirring, uses in the sodium hydroxide solution and the carboxylic acid in the system, and dosis neutralisata is 90% of a carboxyl molal quantity, makes the target dispersant solution; This dispersant solution spray-drying is promptly got target dispersant powder.
Adopting gel permeation chromatograph, is the phase that flows with the aqueous solution, and Sodium Polyacrylate is made standard items, and the number average relative molecular weight of measuring prepared metal carboxylate terpolymer dispersants is 5300.
Press embodiment 1 described operating procedure, recording above-mentioned dispersant is 96.60% to the suspensibility of barium sulfate suspension, is 93.35% to the suspensibility of tio_2 suspension.
Embodiment 8:
Get 1000 parts of alcoholic solutions and 60 parts of chain-transferring agents, the composition of chain-transferring agent is 1: 1 sodium hydrogensulfite and an isopropanol water solution, joins in the four-hole reaction flask, while stirring heating; When the temperature of solution in the reaction bulb rises to 60 ℃, add 300 parts of styrene, 500 parts of methacrylic acids, 200 parts of hydroxypropyl acrylates and 160 parts of initiator solutions and add in 3 hours, insulation reaction is 3 hours then; Insulation reaction is reduced to room temperature after finishing while stirring, uses in the sodium hydroxide solution and the carboxylic acid in the system, and dosis neutralisata is 80% of a carboxyl molal quantity, makes the target dispersant solution; This dispersant solution spray-drying is promptly got target dispersant powder.
Adopting gel permeation chromatograph, is the phase that flows with the aqueous solution, and Sodium Polyacrylate is made standard items, and the number average relative molecular weight of measuring prepared metal carboxylate terpolymer dispersants is 1800.
Press embodiment 1 described operating procedure, recording above-mentioned dispersant is 98.60% to the suspensibility of barium sulfate suspension, is 95.82% to the suspensibility of tio_2 suspension.
Embodiment 9:
Get 1000 parts of distilled waters and 80 parts of chain-transferring agents, the composition of chain-transferring agent is 1: 1 sodium hydrogensulfite and an isopropanol water solution, joins in the four-hole reaction flask, while stirring heating; When the temperature of solution in the reaction bulb rises to 80 ℃, add 400 parts of styrene, 500 parts of methacrylic acids, 100 parts of hydroxypropyl acrylates and 80 parts of initiator solutions and add in 2 hours, insulation reaction is 3 hours then; Insulation reaction is reduced to room temperature after finishing while stirring, uses in the sodium hydroxide solution and the carboxylic acid in the system, and dosis neutralisata is 70% of a carboxyl molal quantity, makes the target dispersant solution; This dispersant solution spray-drying is promptly got target dispersant powder.
Adopting gel permeation chromatograph, is the phase that flows with the aqueous solution, and Sodium Polyacrylate is made standard items, and the number average relative molecular weight of measuring prepared metal carboxylate terpolymer dispersants is 3300.
Press embodiment 1 described operating procedure, recording above-mentioned dispersant is 95.82% to the suspensibility of barium sulfate suspension, is 93.35% to the suspensibility of tio_2 suspension.
Embodiment 10:
Get 1000 parts of distilled waters and 100 parts of chain-transferring agents, the composition of chain-transferring agent is 1: 1 sodium hydrogensulfite and an isopropanol water solution, joins in the four-hole reaction flask, while stirring heating; When the temperature of solution in the reaction bulb rises to 90 ℃, add 100 parts of styrene, 700 parts of methacrylic acids, 200 parts of hydroxypropyl acrylates and 50 parts of initiator solutions and add in 1 hour, insulation reaction is 4 hours then; Insulation reaction is reduced to room temperature after finishing while stirring, uses in the sodium hydroxide solution and the carboxylic acid in the system, and dosis neutralisata is 70% of a carboxyl molal quantity, makes the target dispersant solution; This dispersant solution spray-drying is promptly got target dispersant powder.
Adopting gel permeation chromatograph, is the phase that flows with the aqueous solution, and Sodium Polyacrylate is made standard items, and the number average relative molecular weight of measuring prepared metal carboxylate terpolymer dispersants is 5600.
Press embodiment 1 described operating procedure, recording above-mentioned dispersant is 91.60% to the suspensibility of barium sulfate suspension, is 90.06% to the suspensibility of tio_2 suspension.
Embodiment 11:
Get 1000 parts of distilled waters and 10 parts of chain-transferring agents, the composition of chain-transferring agent is 1: 1 sodium hydrogensulfite and an isopropanol water solution, joins in the four-hole reaction flask, while stirring heating; When the temperature of solution in the reaction bulb rises to 80 ℃, add 200 parts of styrene, 700 parts of methacrylic acids, 100 parts of hydroxypropyl acrylates and 20 parts of initiator solutions and add in 1 hour, insulation reaction is 2 hours then; Insulation reaction is reduced to room temperature after finishing while stirring, uses in the sodium hydroxide solution and the carboxylic acid in the system, and dosis neutralisata is 80% of a carboxyl molal quantity, makes the target dispersant solution; This dispersant solution spray-drying is promptly got target dispersant powder.
Adopting gel permeation chromatograph, is the phase that flows with the aqueous solution, and Sodium Polyacrylate is made standard items, and the number average relative molecular weight of measuring prepared metal carboxylate terpolymer dispersants is 19500.
Press embodiment 1 described operating procedure, recording above-mentioned dispersant is 96.80% to the suspensibility of barium sulfate suspension, is 93.26% to the suspensibility of tio_2 suspension.
Embodiment 12:
Get 1000 parts of distilled waters and 50 parts of chain-transferring agents, the composition of chain-transferring agent is 1: 1 sodium hydrogensulfite and an isopropanol water solution, joins in the four-hole reaction flask, while stirring heating; When the temperature of solution in the reaction bulb rises to 60 ℃, add 300 parts of styrene, 600 parts of methacrylic acids, 100 parts of hydroxypropyl acrylates and 30 parts of initiator solutions and add in 2 hours, insulation reaction is 4 hours then; Insulation reaction is reduced to room temperature after finishing while stirring, uses in the sodium hydroxide solution and the carboxylic acid in the system, and dosis neutralisata is 100% of a carboxyl molal quantity, makes the target dispersant solution; This dispersant solution spray-drying is promptly got target dispersant powder.
Adopting gel permeation chromatograph, is the phase that flows with the aqueous solution, and Sodium Polyacrylate is made standard items, and the number average relative molecular weight of measuring prepared metal carboxylate terpolymer dispersants is 15000.
Press embodiment 1 described operating procedure, recording above-mentioned dispersant is 90.00% to the suspensibility of barium sulfate suspension, is 95.24% to the suspensibility of tio_2 suspension.
Embodiment 13:
Get 1000 parts of distilled waters and 50 parts of chain-transferring agents, the composition of chain-transferring agent is 1: 1 sodium hydrogensulfite and an isopropanol water solution, joins in the four-hole reaction flask, while stirring heating; When the temperature of solution in the reaction bulb rises to 70 ℃, add 400 parts of styrene, 500 parts of methacrylic acids, 100 parts of hydroxypropyl acrylates and 100 parts of initiator solutions and add in 4 hours, insulation reaction is 4 hours then; Insulation reaction is reduced to room temperature after finishing while stirring, uses in the sodium hydroxide solution and the carboxylic acid in the system, and dosis neutralisata is 90% of a carboxyl molal quantity, makes the target dispersant solution; This dispersant solution spray-drying is promptly got target dispersant powder.
Adopting gel permeation chromatograph, is the phase that flows with the aqueous solution, and Sodium Polyacrylate is made standard items, and the number average relative molecular weight of measuring prepared metal carboxylate terpolymer dispersants is 4200.
Press embodiment 1 described operating procedure, recording above-mentioned dispersant is 93.00% to the suspensibility of barium sulfate suspension, is 94.07% to the suspensibility of tio_2 suspension.
Embodiment 14:
Get 1000 parts of distilled waters and 50 parts of chain-transferring agents, the composition of chain-transferring agent is 1: 1 sodium hydrogensulfite and an isopropanol water solution, joins in the four-hole reaction flask, while stirring heating; When the temperature of solution in the reaction bulb rises to 60 ℃, add 400 parts of styrene, 200 parts of methacrylic acids, 400 parts of hydroxypropyl acrylates and 120 parts of initiator solutions and add in 4 hours, insulation reaction is 3 hours then; Insulation reaction is reduced to room temperature after finishing while stirring, uses in the sodium hydroxide solution and the carboxylic acid in the system, and dosis neutralisata is 70% of a carboxyl molal quantity, makes the target dispersant solution; This dispersant solution spray-drying is promptly got target dispersant powder.
Adopting gel permeation chromatograph, is the phase that flows with the aqueous solution, and Sodium Polyacrylate is made standard items, and the number average relative molecular weight of measuring prepared metal carboxylate terpolymer dispersants is 4000.
Press embodiment 1 described operating procedure, recording above-mentioned dispersant is 97.80% to the suspensibility of barium sulfate suspension, is 96.56% to the suspensibility of tio_2 suspension.
Embodiment 15:
Get 1000 parts of distilled waters and 30 parts of chain-transferring agents, the composition of chain-transferring agent is 1: 1 sodium hydrogensulfite and an isopropanol water solution, joins in the four-hole reaction flask, while stirring heating; When the temperature of solution in the reaction bulb rises to 60 ℃, add 400 parts of styrene, 100 parts of methacrylic acids, 500 parts of hydroxypropyl acrylates and 60 parts of initiator solutions and add in 2 hours, insulation reaction is 5 hours then; Insulation reaction is reduced to room temperature after finishing while stirring, uses in the sodium hydroxide solution and the carboxylic acid in the system, and dosis neutralisata is 60% of a carboxyl molal quantity, makes the target dispersant solution; This dispersant solution spray-drying is promptly got target dispersant powder.
Adopting gel permeation chromatograph, is the phase that flows with the aqueous solution, and Sodium Polyacrylate is made standard items, and the number average relative molecular weight of measuring prepared metal carboxylate terpolymer dispersants is 6700.
Press embodiment 1 described operating procedure, recording above-mentioned dispersant is 92.84% to the suspensibility of barium sulfate suspension, is 93.28% to the suspensibility of tio_2 suspension.
Embodiment 16:
Get 1000 parts of distilled waters and 80 parts of chain-transferring agents, the composition of chain-transferring agent is 1: 1 sodium hydrogensulfite and an isopropanol water solution, joins in the four-hole reaction flask, while stirring heating; When the temperature of solution in the reaction bulb rises to 80 ℃, add 400 parts of styrene, 300 parts of methacrylic acids, 300 parts of hydroxypropyl acrylates and 10 parts of initiator solutions and add in 1 hour, insulation reaction is 2 hours then; Insulation reaction is reduced to room temperature after finishing while stirring, uses in the sodium hydroxide solution and the carboxylic acid in the system, and dosis neutralisata is 50% of a carboxyl molal quantity, makes the target dispersant solution; This dispersant solution spray-drying is promptly got target dispersant powder.
Adopting gel permeation chromatograph, is the phase that flows with the aqueous solution, and Sodium Polyacrylate is made standard items, and the number average relative molecular weight of measuring prepared metal carboxylate terpolymer dispersants is 18800.
Press embodiment 1 described operating procedure, recording above-mentioned dispersant is 92.85% to the suspensibility of barium sulfate suspension, is 93.29% to the suspensibility of tio_2 suspension.
Embodiment 17:
Get 1000 parts of distilled waters and 100 parts of chain-transferring agents, the composition of chain-transferring agent is 1: 1 sodium hydrogensulfite and an isopropanol water solution, joins in the four-hole reaction flask, while stirring heating; When the temperature of solution in the reaction bulb rises to 90 ℃, add 200 parts of styrene, 200 parts of methacrylic acids, 600 parts of hydroxypropyl acrylates and 20 parts of initiator solutions and add in 3 hours, insulation reaction is 3 hours then; Insulation reaction is reduced to room temperature after finishing while stirring, uses in the sodium hydroxide solution and the carboxylic acid in the system, and dosis neutralisata is 70% of a carboxyl molal quantity, makes the target dispersant solution; This dispersant solution spray-drying is promptly got target dispersant powder.
Adopting gel permeation chromatograph, is the phase that flows with the aqueous solution, and Sodium Polyacrylate is made standard items, and the number average relative molecular weight of measuring prepared metal carboxylate terpolymer dispersants is 16500.
Press embodiment 1 described operating procedure, recording above-mentioned dispersant is 90.81% to the suspensibility of barium sulfate suspension, is 89.82% to the suspensibility of tio_2 suspension.
Embodiment 18:
Get 1000 parts of distilled waters and 80 parts of chain-transferring agents, the composition of chain-transferring agent is 1: 1 sodium hydrogensulfite and an isopropanol water solution, joins in the four-hole reaction flask, while stirring heating; When the temperature of solution in the reaction bulb rises to 70 ℃, add 100 parts of styrene, 300 parts of methacrylic acids, 600 parts of hydroxypropyl acrylates and 80 parts of initiator solutions and add in 2 hours, insulation reaction is 2 hours then; Insulation reaction is reduced to room temperature after finishing while stirring, uses in the sodium hydroxide solution and the carboxylic acid in the system, and dosis neutralisata is 80% of a carboxyl molal quantity, makes the target dispersant solution; This dispersant solution spray-drying is promptly got target dispersant powder.
Adopting gel permeation chromatograph, is the phase that flows with the aqueous solution, and Sodium Polyacrylate is made standard items, and the number average relative molecular weight of measuring prepared metal carboxylate terpolymer dispersants is 5500.
Press embodiment 1 described operating procedure, recording above-mentioned dispersant is 98.85% to the suspensibility of barium sulfate suspension, is 97.28% to the suspensibility of tio_2 suspension.
The foregoing description only is a preference of the present invention, is not used for limiting the present invention, and all within principle of the present invention, any modifications and variations of being done are all within protection scope of the present invention.
Claims (5)
1. metal carboxylate terpolymer dispersants, form than material by following quality:
10～50 parts of styrene
10～80 parts of methacrylic acids
10～50 parts of hydroxypropyl acrylates;
The number average relative molecular weight of terpolymer is 1000～20000.
2. the preparation technology of a metal carboxylate terpolymer dispersants, step is as follows:
A) aqueous solution of adding distilled water and chain-transferring agent in reaction bulb stirs, heats 60～90 ℃;
B) in above-mentioned solution, drip styrene, methacrylic acid, hydroxypropyl acrylate and initiator solution dropwised in 1～5 hour, insulation reaction 2～10 hours;
C) step b gained solution is stirred, is cooled to room temperature, use in the alkali and the carboxylic acid in the system, dosis neutralisata is 50～100% of a carboxyl molal quantity;
D) the metal carboxylate terpolymer solution spray drying with step c preparation makes target dispersant powder.
3. the preparation technology of metal carboxylate terpolymer dispersants according to claim 2 is characterized in that: described chain-transferring agent is sodium hydrogensulfite and isopropyl alcohol, and consumption is 0.5～10% of a monomer gross mass.
4. the preparation technology of metal carboxylate terpolymer dispersants according to claim 2 is characterized in that: described initator is an ammonium persulfate, and consumption is 2～16% of a monomer gross mass.
5. the preparation technology of metal carboxylate terpolymer dispersants according to claim 2 is characterized in that: described alkali is one or both in NaOH, potassium hydroxide, ammonia spirit, triethylamine, the triethanolamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110055926.7A CN102188929B (en) | 2011-03-09 | 2011-03-09 | Carboxylate terpolymer dispersing agent and preparation process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110055926.7A CN102188929B (en) | 2011-03-09 | 2011-03-09 | Carboxylate terpolymer dispersing agent and preparation process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102188929A true CN102188929A (en) | 2011-09-21 |
| CN102188929B CN102188929B (en) | 2014-05-28 |
Family
ID=44598333
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110055926.7A Active CN102188929B (en) | 2011-03-09 | 2011-03-09 | Carboxylate terpolymer dispersing agent and preparation process thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102188929B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102689992A (en) * | 2012-02-22 | 2012-09-26 | 浙江省海洋开发研究院 | Terpolymer antisludging agent and preparation process thereof |
| CN104031259A (en) * | 2014-06-12 | 2014-09-10 | 南京师范大学 | Multiple-carboxyl terpolymer as well as preparation method and application thereof |
| CN104031258A (en) * | 2014-06-12 | 2014-09-10 | 南京师范大学 | Phosphate group containing terpolymer as well as preparation method and application thereof |
| CN104722241A (en) * | 2013-12-19 | 2015-06-24 | 上海师范大学 | Carboxylate-sulfonate terpolymer dispersant and preparation process thereof |
| CN105983372A (en) * | 2015-03-06 | 2016-10-05 | 上海师范大学 | Carboxylates terpolymer dispersing agent and preparing process thereof |
| CN106582438A (en) * | 2015-10-14 | 2017-04-26 | 上海师范大学 | Multipolymer surfactant and preparing technology thereof |
| CN115403692A (en) * | 2022-06-14 | 2022-11-29 | 上海启璇化工科技有限公司 | Powdery polycarboxylate polymer dispersant, and preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106758391B (en) * | 2016-12-22 | 2018-02-13 | 绍兴海成化工有限公司 | Multifunctional dyeing auxiliary agent and the dyeing using the multifunctional dyeing auxiliary agent |
-
2011
- 2011-03-09 CN CN201110055926.7A patent/CN102188929B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| 舒绪刚等: "聚丙烯酸-苯乙烯分散剂的合成及其对纳米二氧化锆分散性能的影响", 《精细石油化工》 * |
| 陈军等: "丙烯酸类共聚物分散剂的合成及其分散性能", 《过程工程学报》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102689992A (en) * | 2012-02-22 | 2012-09-26 | 浙江省海洋开发研究院 | Terpolymer antisludging agent and preparation process thereof |
| CN104722241A (en) * | 2013-12-19 | 2015-06-24 | 上海师范大学 | Carboxylate-sulfonate terpolymer dispersant and preparation process thereof |
| CN104031259A (en) * | 2014-06-12 | 2014-09-10 | 南京师范大学 | Multiple-carboxyl terpolymer as well as preparation method and application thereof |
| CN104031258A (en) * | 2014-06-12 | 2014-09-10 | 南京师范大学 | Phosphate group containing terpolymer as well as preparation method and application thereof |
| CN105983372A (en) * | 2015-03-06 | 2016-10-05 | 上海师范大学 | Carboxylates terpolymer dispersing agent and preparing process thereof |
| CN106582438A (en) * | 2015-10-14 | 2017-04-26 | 上海师范大学 | Multipolymer surfactant and preparing technology thereof |
| CN106582438B (en) * | 2015-10-14 | 2019-08-20 | 上海师范大学 | A kind of multiple copolymer surfactant and its preparation process |
| CN115403692A (en) * | 2022-06-14 | 2022-11-29 | 上海启璇化工科技有限公司 | Powdery polycarboxylate polymer dispersant, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102188929B (en) | 2014-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102188929B (en) | Carboxylate terpolymer dispersing agent and preparation process thereof | |
| CN101391194B (en) | Terpolymer dispersants and preparation technique and use thereof | |
| CN104725576A (en) | Carboxylate quadripolymer dispersant and preparation technology thereof | |
| CN104587891A (en) | Comb type carboxylate ternary copolymer and preparation technology thereof | |
| CN103992421B (en) | The preparation method of Pickering acrylate polymer emulsions | |
| CN102585082B (en) | Methacrylic acid-styrene-hydroxyethyl acrylate copolymer dispersant and preparation method and application thereof | |
| CN103468028B (en) | A kind of Efficient calcium slurry dispersant and preparation method thereof | |
| CN110387017A (en) | Combed polycarboxylate salt dispersant containing polyether lateral chain and preparation method thereof | |
| CA2861443A1 (en) | A process for lime slurry production | |
| CN106582430A (en) | Novel carboxylate phosphate ternary polymerization dispersing agent and preparation process thereof | |
| CN110316939A (en) | A kind of novel composite flocculating agent improves the process of sewage treatment plant excess sludge dewatering | |
| CN103506050A (en) | Universal agricultural polymer dispersant and preparation method thereof | |
| CN104722241A (en) | Carboxylate-sulfonate terpolymer dispersant and preparation process thereof | |
| CN103432960B (en) | A kind of agricultural anti-hard water type macromolecule dispersing agent and preparation method thereof | |
| CN106582438B (en) | A kind of multiple copolymer surfactant and its preparation process | |
| CN101391193A (en) | Acrylics polymeric dispersant and preparation technique and use thereof | |
| CN108047373A (en) | Water-soluble polymer dispersant and preparation method thereof and pyraclostrobin aqueous suspension | |
| CN108017163B (en) | The processing method of non-Phosphorus composite anti incrustation eorrosion snhibiter and its application and recirculated cooling water | |
| CN106478872B (en) | A kind of copolymer and the preparation method and application thereof | |
| CN102532393B (en) | Methacrylic acid-styrene copolymer dispersing agent, preparation method and application thereof | |
| CN105983372A (en) | Carboxylates terpolymer dispersing agent and preparing process thereof | |
| CN101391195A (en) | Rosin graft copolymer dispersant and preparation technique and use thereof | |
| CN102558424B (en) | Terpolymer dispersing agent, and preparation method and application thereof | |
| CN106582436B (en) | A kind of terpolymer dispersants and its preparation process | |
| CN104971660A (en) | Carboxylate terpolymer dispersing agent and preparation process thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Jingjiang Kaiyuan Chemical Material Co.,Ltd. Assignor: Shanghai Normal University Contract record no.: 2012310000003 Denomination of invention: Carboxylate terpolymer dispersing agent and preparation process thereof License type: Common License Open date: 20110921 Record date: 20120109 |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230111 Address after: 032100 No. 189, Baijinbao Industrial Park, Wenshui Economic Development Zone, Wenshui County, Luliang City, Shanxi Province Patentee after: Wenshui County is Big Polymer Material Co.,Ltd. Address before: 200234 No. 100, Xuhui District, Shanghai, Guilin Road Patentee before: SHANGHAI NORMAL University |
|
| TR01 | Transfer of patent right |