CN106496400A - A kind of phosphorous terpolymer and preparation method thereof - Google Patents
A kind of phosphorous terpolymer and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/243—Phosphorus-containing polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/38—Esters containing sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/20—Retarders
- C04B2103/22—Set retarders
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/38—Esters containing sulfur
- C08F220/385—Esters containing sulfur and containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
- C08F220/606—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen and containing other heteroatoms
Abstract
The invention discloses a kind of phosphorous terpolymer and preparation method thereof, the copolymer is that copolymerization is obtained in aqueous by phosphorous-containing monomers A, zwitterionic monomer B and unsaturated carboxylic acid monomer C.The present invention is water-soluble polymer, because of performances such as its good wetting, solubilising, scale removal, slow setting and surface-actives, can be used for chemical fibre, plastics, coating, oil, pottery, biological medicine, washing assisant, cement matrix feed additives etc..
Description
Technical field
The present invention relates to one kind is generated by phosphorous-containing monomers unit, zwitterionic monomer unit and unsaturated carboxylic acid monomer unit
Aqueous polymer, and be related to the application of these high molecular polymers.
Background technology
High molecular surfactant is all received much concern all the time, because of its good wetting, dispersion, solubilising, sterilization, is gone
The characteristics such as dirt, slow setting, before all having wide application in chemical fibre, coating, daily use chemicals, pottery, plastics, biological medicine and building materials
Scape.High molecular surfactant can be divided into cationic surface active agent, anionic surface by the difference of its structures alone
Activating agent, nonionic surface active agent and amphoteric ionic surfactant.Wherein amphoteric ionic surfactant due to
Be provided simultaneously with cation and anion in its structure, give its unique performance, such as betaines amphion, acid and
Be respectively provided with excellent stability under alkalescence condition, nontoxic, excitant is little, soluble in water, surface-active is strong, with thickening, sterilization,
Antistatic behaviour, is a kind of good surface activating agent of environmental protection.
In oil-well cement and concrete-containing building material, organic phospho acid reagent is often used as slow setting, corrosion inhibiter, compares traditional Portugal
Grape sodium saccharate, white sugar and citric acid, its high temperature resistant, retarding effect more preferably, but itself is strong to the dispersibility of concrete, uses
Concrete viscous weight is easily caused when measuring big, and dispersiveness is affected substantially, with polycarboxylic acids diminishing in the high glue material of clay content
The compatibility of agent is improved also with consumption and is declined.
Content of the invention
The purpose of the present invention is for the not enough of existing concrete retarder and a kind of phosphorous terpolymer that provides
And preparation method thereof, the construction unit containing phosphate group in the terpolymer, its retarding effect more preferably, consumption less, and
Include both sexes betaine type ion monomer in copolymer, the cation group on its quaternary ammonium salt makes which in the high glue material of clay content
In still have good adaptability, and the phosphoric acid in polymer, sulfonic acid and hydroxy-acid group have good adsorption capacity and point
Scattered ability, water-soluble good and polycarboxylate water-reducer compatibility are good, while with good inhibition, detergency ability.
The object of the present invention is achieved like this：
A kind of phosphorous terpolymer, its feature are that it is based on phosphorous-containing monomers A, zwitterionic monomer B and unsaturation
The copolymer of carboxylic acid monomer C, each monomer account for the percentage of monomer gross mass and are respectively：
Phosphorous-containing monomers A：10-60%
Zwitterionic monomer B：10-60%
Unsaturated carboxylic acid monomer C：10-80%
Wherein：Phosphorous-containing monomers A is by general structure (1) Suo Shi：
In formula (1), X is O, NH, N-R1-Y；R1The alkyl of 1-12 carbon atom is represented, former containing O or N if necessary
Son, when containing O atom, R1It is polyoxyethylene groups, alkylether radicals, containing N atomic time, R1Represent polyvinylamine, polyethyleneimine
Amine, alkylamine etc., its are linear or branch；Y is-N (CH2-PO3M)2、-CH(PO3M)2、-OPHO2M or-PHO3M2；M is
H, Na, K or NH4；
Zwitterionic monomer B is by general structure (2) Suo Shi：
Wherein：R3Represent hydrogen or methyl；W is O, NH or NR4；R4For the alkyl of 1-6 carbon atom, if necessary containing O or
Person's N atoms, which is linear or branch；R5For CH3、CH2CH3、CH2CH2CH3；R6For CH2CH2、CH2CH2CH2Or CH2CH
(OH)CH2；Q is COO, SO3Or PO3；
Unsaturated carboxylic acid monomer C is acrylic acid, methacrylic acid, the one kind in itaconic acid or two kinds of mixing.
Described phosphorous terpolymer, its feature be phosphorous-containing monomers A for two methylenephosphonic acid maleic mono-ester of monoethanolamine,
N- (amino-ethyl-phosphate)-maleic acid, N- (2- amino ethoxies ethyl-phosphate)-maleic acid, N- (amino
Hexyl-phosphate)-maleic acid, N- AminomethylphosphoniAcid Acids-maleic acid, N- aminoethyl phosphonic acids-maleic acid, N-
Ethylphosphonic acid-maleimide.
Described phosphorous terpolymer, its feature are zwitterionic monomer B for N, N- dimethyl-N-acryloyl ethoxies
Base-N- (3- sulfopropyls)-ammonium glycine betaine, N, N- dimethyl-N -s acrylamide propyl-N- (sulfopropyl)-ammonium glycine betaine, N, N- bis-
Methyl-N acrylamide propyl group-N- (2- carboxymethyls)-ammonium glycine betaine, N, N- dimethyl-N-acryloyloxyethyl-N- (methylphosphines
Acid)-ammonium glycine betaine.
Described phosphorous terpolymer, its feature are that phosphorous-containing monomers A is N- (amino-ethyl-phosphate)-maleic acid
Acid amides, zwitterionic monomer B be N, N- dimethyl-N -s acryloyloxyethyl-N- (methylphosphonic acid)-ammonium glycine betaine, unsaturated carboxylic
Acid monomers C is acrylic acid.
Described phosphorous terpolymer, its feature are phosphorous-containing monomers A for N- aminoethyl phosphonic acids-maleic acid,
Zwitterionic monomer B be N, N- dimethyl-N -s acrylamide propyl-N- (sulfopropyl)-ammonium glycine betaine, unsaturated carboxylic acid monomer C
For acrylic acid.
Described phosphorous terpolymer, its feature are that phosphorous-containing monomers A is N- (2- amino ethoxies ethyls-phosphoric acid
Ester)-maleic acid, zwitterionic monomer B is N, N- dimethyl-N-acrylamide propyl-N- (2- carboxymethyls)-ammonium beet
Alkali, unsaturated carboxylic acid monomer C are acrylic acid.
A kind of preparation method of phosphorous terpolymer, its feature are that the polymer is by phosphorous-containing monomers A, amphion
Monomer B, unsaturated carboxylic acid monomer C and deionized water are added sequentially in reaction vessel, after stirring heats up, add initiator and chain
Transfer agent, insulation reaction 1-12 hour；Reaction adds 30% NaOH to adjust pH value to 6-8 after terminating, water use regulation was admittedly containing both
Obtain high molecular weight water soluble polymer；Each monomer accounts for the percentage of monomer gross mass and is respectively：Phosphorous-containing monomers A：10-60%；Both sexes
Ion monomer B：10-60%；Unsaturated carboxylic acid monomer C：10-80%；
Wherein：Phosphorous-containing monomers A is by general structure (1) Suo Shi：
In formula (1), X is O, NH, N-R1-Y；R1The alkyl of 1-12 carbon atom is represented, former containing O or N if necessary
Son, its are linear or branch；Y is-N (CH2-PO3M)2、-CH(PO3M)2、-OPHO2M、-OPHO3M2；M be H, Na, K,
NH4；
Zwitterionic monomer B is by general structure (2) Suo Shi：
Wherein：R3Represent hydrogen or methyl；W is O, NH or NR4；R4For the alkyl of 1-6 carbon atom, if necessary containing O or
Person's N atoms, which is linear or branch；R5For CH3、CH2CH3、CH2CH2CH3；R6For CH2CH2、CH2CH2CH2Or CH2CH
(OH)CH2；Q is COO, SO3Or PO3；
Unsaturated carboxylic acid monomer C is acrylic acid, methacrylic acid, the one kind in itaconic acid or two kinds of mixing.
The preparation method of described phosphorous terpolymer, its feature be described initiator be thermal decomposition initiating or
Redox initiator；Thermal decomposition initiating is ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, hydrogen peroxide, TBHP
One or more mixing；Redox initiator is collectively constituted using thermal decomposition initiating and reducing agent, is wherein thermally decomposed
One or more mixing of initiator for ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, hydrogen peroxide, TBHP, reduction
Agent is that sodium hydrogensulfite, potassium bisulfite, ferrous sulfate, sodium pyrosulfite, sodium hypophosphite, one or more in sodium formaldehyde sulfoxylate are mixed
Close.
The preparation method of described phosphorous terpolymer, its feature are that the thermal decomposition being added in reaction system causes
0.1%-10.0% of the agent consumption for monomer gross mass, the reducing agent consumption being added in reaction system are monomer gross mass
0%-10%.
The preparation method of described phosphorous terpolymer, its feature are chain-transferring agent used for isopropanol, sulfydryl
One kind in ethanol, TGA, 2 mercaptopropionic acid, 3- mercaptopropionic acids and lauryl mercaptan or two kinds, chain-transferring agent consumption accounts for list
The 0%-6.0% of body gross mass.
The phosphorous terpolymer due to being the water-soluble good high molecular polymer of a class, with dispersion, solubilising, decontamination,
The surface-actives such as slow setting, can be used for chemical fibre, plastics, coating, oil, pottery, biological medicine, washing assisant, cement-based material and add
Plus agent etc..
Description of the drawings
Fig. 1 is hydration heat of cement experimental data comparison diagram.
Specific embodiment
Below with reference to specific embodiment, invention is described further, but any restriction is not caused to invention.
Embodiment 1
In the four-hole boiling flask for being furnished with agitator, thermometer, constant temperature heating device and condenser, the total matter of monomer is sequentially added
The two methylenephosphonic acid maleic mono-ester of monoethanolamine of amount 30%, the N of monomer gross mass 30%, N- dimethyl-N-acryloyloxyethyls-
The deionized water of N- (3- sulfopropyls)-ammonium glycine betaine, the acrylic acid of monomer gross mass 40% and monomer gross mass 60%, stirring rise
To 80 DEG C, the disposable ammonium persulfate for adding monomer gross mass 1%, stirring insulation reaction 6 hours add the hydrogen-oxygen of 30wt% to temperature
Change sodium solution adjust pH value arrive 6-8, water use regulation admittedly contain to 40% obtain phosphorous terpolymer aqueous solution P1.
Embodiment 2
In the four-hole boiling flask for being furnished with agitator, thermometer, constant temperature heating device and condenser, the total matter of monomer is sequentially added
N- (amino-ethyl-the phosphate)-maleic acid of amount 20%, the N of monomer gross mass 40%, N- dimethyl-N-acryloyl second
The deionized water of epoxide-N- (methylphosphonic acid)-ammonium glycine betaine, the acrylic acid of monomer gross mass 40% and monomer gross mass 60%,
Stirring is warming up to 70 DEG C, the disposable ammonium persulfate for adding monomer gross mass 0.8%, is added dropwise and contains monomer gross mass in 1 hour
0.8% aqueous solution of sodium bisulfite, insulation reaction 4 hours after completion of dropwise addition add the sodium hydroxide solution of 30wt% to adjust
PH value to 6-8, water use regulation contain admittedly to 40% phosphorous terpolymer aqueous solution P2.
Embodiment 3
In the four-hole boiling flask for being furnished with agitator, thermometer, constant temperature heating device and condenser, the total matter of monomer is sequentially added
N- aminoethyl phosphonic acids-the maleic acid of amount 25%, the N of monomer gross mass 40%, N- dimethyl-N-acrylamide propyl-
The deionized water of N- (sulfopropyl)-ammonium glycine betaine, the acrylic acid of monomer gross mass 35% and monomer gross mass 60%, stirring heat up
To 70 DEG C, the disposable ammonium persulfate for adding monomer gross mass 1%, insulation reaction 6 hours add the NaOH of 30wt% molten
Liquid adjust pH value arrive 6-8, water use regulation admittedly contain to 40% obtain phosphorous terpolymer aqueous solution P3.
Embodiment 4
In the four-hole boiling flask for being furnished with agitator, thermometer, constant temperature heating device and condenser, the total matter of monomer is sequentially added
N- (2- amino ethoxies ethyl-the phosphate)-maleic acid of amount 15%, the N of monomer gross mass 35%, N- dimethyl-N -s
Acrylamide propyl-N- (2- carboxymethyls)-ammonium glycine betaine, the acrylic acid of monomer gross mass 50% and monomer gross mass 60% is gone
Ionized water, stirring are warming up to 70 DEG C, disposably add the ammonium persulfate of monomer gross mass 1% and 0.2% mercaptopropionic acid, insulation
Reaction 6 hours, add 30wt% sodium hydroxide solution adjust pH value arrive 6-8, water use regulation admittedly contain to 40% obtain phosphorous ternary
Aqueous copolymers solution P4.
Embodiment 5
In the four-hole boiling flask for being furnished with agitator, thermometer, constant temperature heating device and condenser, the total matter of monomer is sequentially added
N- (2- amino ethoxies ethyl-the phosphate)-maleic acid of amount 20%, the N of monomer gross mass 15%, N- dimethyl-N -s
Acrylamide propyl-N- (2- carboxymethyls)-ammonium glycine betaine, the acrylic acid of monomer gross mass 65% and monomer gross mass 60% is gone
Ionized water, stirring are warming up to 70 degree, disposably add the ammonium persulfate of monomer gross mass 1% and 0.4% mercaptopropionic acid, insulation
Reaction 4 hours, add 30wt% sodium hydroxide solution adjust pH value arrive 6-8, water use regulation admittedly contain to 40% obtain phosphorous ternary
Aqueous copolymers solution P5.
Embodiment 6
In the four-hole boiling flask for being furnished with agitator, thermometer, constant temperature heating device and condenser, the total matter of monomer is sequentially added
The two methylenephosphonic acid maleic mono-ester of monoethanolamine of amount 20%, the N of monomer gross mass 40%, N- dimethyl-N-methacryl second
The deionization of epoxide-N- (sulfopropyl)-ammonium glycine betaine, the methacrylic acid of monomer gross mass 40% and monomer gross mass 60%
Water, stirring are warming up to 70 degree, disposably add the ammonium persulfate of monomer gross mass 1.2% and 0.15% mercaptopropionic acid, insulation
Reaction 6 hours, add 30wt% sodium hydroxide solution adjust pH value arrive 6-8, water use regulation admittedly contain to 40% obtain phosphorous ternary
Aqueous copolymers solution P6.
Embodiment 7
In the four-hole boiling flask for being furnished with agitator, thermometer, constant temperature heating device and condenser, the total matter of monomer is sequentially added
N- AminomethylphosphoniAcid Acids-the maleic acid of amount 20%, the N of monomer gross mass 40%, N- dimethyl-N-acryloyloxyethyl-N-
The deionized water of (methylphosphonic acid)-ammonium glycine betaine, the methacrylic acid of monomer gross mass 40% and monomer gross mass 60%, stirring
Be warming up to 70 degree, the disposable ammonium persulfate for adding monomer gross mass 2% and 0.3% mercaptopropionic acid, insulation reaction 6 hours,
Add 30wt% sodium hydroxide solution adjust pH value arrive 6-8, water use regulation admittedly contain to 40% obtain phosphorous terpolymer water-soluble
Liquid P7.
Application examples
Terpolymer in embodiment and conventional organic phospho acid retarder 1-hydroxy ethylidene-1,1-diphosphonic acid (abbreviation HEDP) are entered
Gone hydration heat of cement experiment, experimental result as shown in figure 1, from from hydration heat of cement Exotherm Time datagram, with blank water
Mud is compared, and is added the sample hydration exothermic heat appearance time of HEDP to extend, is embodied the deferred action that HEDP delays hydrated cementitious,
Meanwhile, exothermic peak also decreases, each phosphorous terpolymer in embodiment compared with HEDP, when hydration heat peak occurs
Between longer, retarding effect is more preferably obvious, Slow setting time than HEDP extend 1-4.5 hours, effect is significant.
Claims (10)
1. a kind of phosphorous terpolymer, it is characterised in that it is based on phosphorous-containing monomers A, zwitterionic monomer B and unsaturated carboxylic
The copolymer of acid monomers C, each monomer account for the percentage of monomer gross mass and are respectively：
Phosphorous-containing monomers A：10-60%
Zwitterionic monomer B：10-60%
Unsaturated carboxylic acid monomer C：10-80%
Wherein：Phosphorous-containing monomers A is by general structure (1) Suo Shi：
In formula (1), X is O, NH, N-R1-Y；R1The alkyl of 1-12 carbon atom is represented, contains O or N atoms if necessary, its
It is linear or branch；Y is-N (CH2-PO3M)2、-CH(PO3M)2、-OPHO2M or-OPHO3M2；M is H, Na, K or NH4；
Zwitterionic monomer B is by general structure (2) Suo Shi：
Wherein：R3Represent hydrogen or methyl；W is O, NH or NR4；R4For the alkyl of 1-6 carbon atom, contain O or N if necessary
Atom, its are linear or branch；R5For CH3、CH2CH3Or CH2CH2CH3；R6For CH2CH2、CH2CH2CH2Or CH2CH
(OH)CH2；Q is COO, SO3Or PO3；
Unsaturated carboxylic acid monomer C is acrylic acid, methacrylic acid, the one kind in itaconic acid or two kinds of mixing.
2. phosphorous terpolymer according to claim 1, it is characterised in that phosphorous-containing monomers A is two methylenephosphonic acid of monoethanolamine
Maleic mono-ester, N- (amino-ethyl-phosphate)-maleic acid, N- (2- amino ethoxies ethyl-phosphate)-maleic acid
Acid amides, N- (Aminohexyl-phosphate)-maleic acid, N- AminomethylphosphoniAcid Acids-maleic acid, N- aminoethyl phosphonic acids-horse
Come sour acid amides, N- ethylphosphonic acids-maleimide.
3. phosphorous terpolymer according to claim 1, it is characterised in that zwitterionic monomer B is N, N- dimethyl-
N- acryloyloxyethyl-N- (3- sulfopropyls)-ammonium glycine betaine, N, N- dimethyl-N -s acrylamide propyl-N- (sulfopropyl)-ammonium
Glycine betaine, N, N- dimethyl-N-acrylamide propyl-N- (2- carboxymethyls)-ammonium glycine betaine, N, N- dimethyl-N-acryloyl second
Epoxide-N- (methylphosphonic acid)-ammonium glycine betaine.
4. phosphorous terpolymer according to claim 1, it is characterised in that phosphorous-containing monomers A is N- (amino-ethyls-phosphoric acid
Ester)-maleic acid, zwitterionic monomer B is N, N- dimethyl-N -s acryloyloxyethyl-N- (methylphosphonic acid)-ammonium beet
Alkali, unsaturated carboxylic acid monomer C are acrylic acid.
5. phosphorous terpolymer according to claim 1, it is characterised in that phosphorous-containing monomers A is N- aminoethyl phosphonic acids-horse
Carry out sour acid amides, zwitterionic monomer B is N, N- dimethyl-N -s acrylamide propyl-N- (sulfopropyl)-ammonium glycine betaine, unsaturated
Carboxylic acid monomer C is acrylic acid.
6. phosphorous terpolymer according to claim 1, it is characterised in that phosphorous-containing monomers A is N- (2- amino ethoxy second
Base-phosphate)-maleic acid, zwitterionic monomer B be N, N- dimethyl-N-acrylamide propyl-N- (2- carboxymethyls)-
Ammonium glycine betaine, unsaturated carboxylic acid monomer C are acrylic acid.
7. the preparation method of phosphorous terpolymer described in a kind of claim 1, it is characterised in that the polymer is by phosphorous list
Body A, zwitterionic monomer B, unsaturated carboxylic acid monomer C and deionized water are added sequentially in reaction vessel, after stirring heats up, plus
Enter initiator and chain-transferring agent, insulation reaction 1-12 hour；Reaction adds 30% NaOH to adjust pH value to 6-8 after terminating, use
Water is adjusted and both obtain high molecular weight water soluble polymer；Each monomer accounts for the percentage of monomer gross mass and is respectively：Phosphorous-containing monomers A：
10-60%；Zwitterionic monomer B：10-60%；Unsaturated carboxylic acid monomer C：10-80%；
Wherein：Phosphorous-containing monomers A is by general structure (1) Suo Shi：
In formula (1), X is O, NH, N-R1-Y；R1The alkyl of 1-12 carbon atom is represented, contains O or N atoms if necessary, its
It is linear or branch；Y is-N (CH2-PO3M)2、-CH(PO3M)2、-OPHO2M or-PHO3M2；M is H, Na, K or NH4；
Zwitterionic monomer B is by general structure (2) Suo Shi：
Wherein：R3Represent hydrogen or methyl；W is O, NH or NR4；R4For the alkyl of 1-6 carbon atom, contain O or N if necessary
Atom, its are linear or branch；R5For CH3、CH2CH3Or CH2CH2CH3；R6For CH2CH2、CH2CH2CH2Or CH2CH
(OH)CH2；Q is COO, SO3Or PO3；
Unsaturated carboxylic acid monomer C is acrylic acid, methacrylic acid, the one kind in itaconic acid or two kinds of mixing.
8. the preparation method of phosphorous terpolymer according to claim 7, it is characterised in that described initiator is heat point
Solution initiator or redox initiator；Thermal decomposition initiating is ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, hydrogen peroxide, tertiary fourth
One or more mixing of base hydrogen peroxide；Redox initiator is collectively constituted using thermal decomposition initiating and reducing agent,
Wherein thermal decomposition initiating is ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, hydrogen peroxide, one kind of TBHP or many
Kind of mixing, reducing agent be sodium hydrogensulfite, potassium bisulfite, ferrous sulfate, sodium pyrosulfite, sodium hypophosphite, in sodium formaldehyde sulfoxylate
One or more mixing.
9. the preparation method of phosphorous terpolymer according to claim 8, it is characterised in that be added in reaction system
0.1%-10.0% of the thermal decomposition initiating consumption for monomer gross mass, the reducing agent consumption being added in reaction system are monomer
The 0%-10% of gross mass.
10. the preparation method of phosphorous terpolymer according to claim 7, it is characterised in that chain-transferring agent used is different
Propyl alcohol, the one kind in mercaptoethanol, TGA, 2 mercaptopropionic acid, 3- mercaptopropionic acids and lauryl mercaptan or two kinds, chain-transferring agent
Consumption accounts for the 0%-6.0% of monomer gross mass.
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| CN109776742A (en) * | 2019-02-14 | 2019-05-21 | 江西省建筑材料工业科学研究设计院 | A kind of anti-chamotte mould polycarboxylate water-reducer of phosphate ester-containing and preparation method thereof |
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| WO2021160788A1 (en) * | 2020-02-12 | 2021-08-19 | Solvay Sa | Methods for reducing or preventing colloids adhesion and/or fouling on different substrates, compositions, and copolymers useful therefor |
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