CN107793525B - A kind of cation type water-soluble polymer polymer - Google Patents
A kind of cation type water-soluble polymer polymer Download PDFInfo
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- CN107793525B CN107793525B CN201710839224.5A CN201710839224A CN107793525B CN 107793525 B CN107793525 B CN 107793525B CN 201710839224 A CN201710839224 A CN 201710839224A CN 107793525 B CN107793525 B CN 107793525B
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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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
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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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/14—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The present invention provides a kind of cation type water-soluble polymer polymer, and the raw material of preparation includes cation type water-soluble acrylic resin and hexamethoxymethyl melamine；The raw material for preparing of the cation type water-soluble acrylic resin includes: monomer, initiator and solvent, and the monomer includes acrylic acid, butyl acrylate, methacrylic acid-beta-hydroxy ethyl ester, methyl methacrylate and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride.Cation type water-soluble polymer polymer prepared by the present invention has preferable flocculating effect.
Description
Technical field
The invention belongs to the technical field of sewage of environmental improvement, and in particular to a kind of cation type water-soluble polymer
Polymer and preparation method thereof.
Background technique
As the enhancing of people's environmental consciousness and the continuous of law perfect, cation type water-soluble polymer is had become at water
Manage the Main way of medicament development.Wherein Key wordscationic polyacrylate resin is because its molecular weight is big, positive charge, adsorptivity, decoloration
The advantages that property, nonstaining property, is widely used in the fields such as flocculant, decolorising agent, chemical industry, environmental protection.General commercially available acroleic acid polymerization
The solvent of object is toluene, dimethylbenzene etc., and since these solvents are containing toxic, when solvent to be removed can cause certain dirt to environment
Dye.
The research and exploration to deepen continuously simultaneously with people to acrylate, and constantly pushing away in application field
Extensively, water soluble acrylate resin's copolymer just gradually replaces the similar resin of solvent type to become the heat subject studied both at home and abroad.
, it can be achieved that adsorptivity, cohesiveness, bridge formation ability, dissolution after the functional groups such as introducing-OH ,-COOH and-CONH- in strand
The performances such as property, decolourising property are more preferably.
CN104817251A discloses a kind of composite high-molecular sludge dehydrating agent and preparation method thereof, be a kind of combination without
Machine-organic polymer flocculation dewatering agent can wrap disclosed in it in scheme and contain acrylic acid as anionic monomer, methyl-prop
E pioic acid methyl ester as non-ionic monomer, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride as cationic monomer and inorganic salts into
Row is mixed to get composite high-molecular sludge dehydrating agent, and inorganic salts include ferric trichloride, ferric sulfate, bodied ferric sulfate, polyaluminium
One or more of iron, polymeric aluminum sulfate iron, alchlor, aluminum sulfate, polyaluminium sulfate and aluminium polychloride.This is multiple
Close high polymer sludge dehydration agent using inorganic, organic dehydrating agent cooperation can effectively save cost, but inorganic salts flocculation dewatering agent
Relative molecular mass and granularity and flocculation bridge formation ability are still more far short of what is expected than organic polymer coargulator, and exist to further water
Solve the instability problem of reaction.Current cation type water-soluble acrylic resin, which exists, is difficult to realize low cost and overpass
The combination of ability, high flocculability.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of cation type water-soluble polymer polymer.
A kind of cation type water-soluble polymer polymer of the invention, the raw material of preparation include cation type water-soluble third
Olefin(e) acid resin and hexamethoxymethyl melamine；
The raw material for preparing of the cation type water-soluble acrylic resin includes: monomer, initiator and solvent, the monomer
Including acrylic acid, butyl acrylate, methacrylic acid-beta-hydroxy ethyl ester, methyl methacrylate and methylacryoyloxyethyl three
Ammonio methacrylate.
Preferably, the weight of the acrylic acid, butyl acrylate, methacrylic acid-beta-hydroxy ethyl ester and methyl methacrylate
Measure ratio are as follows: 1-10:5-20:1-10:1-10.
Preferably, the dosage of the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride accounts for the 10-20% of monomer gross mass.
Preferably, the volume ratio of the cation type water-soluble acrylic resin and hexamethoxymethyl melamine is 80-
100:10-30.
Preferably, the volume ratio of the cation type water-soluble acrylic resin and hexamethoxymethyl melamine is 100:
10-30。
Preferably, the raw material for preparing of the hexamethoxymethyl melamine includes hexamethylolmelamine, formaldehyde, trimerization
Cyanamide and methanol.
Preferably, the molar ratio of the formaldehyde and melamine are as follows: 10:1.
It preferably, further include auxiliary agent, the auxiliary agent is ammonium hydroxide and/or alcamine compound.
Preferably, the initiator is benzoyl peroxide；The solvent is n-butanol.
Preferably, the initiator amount accounts for the 1%-1.5% of monomer gross mass.
The present invention also provides a kind of preparation methods of cation type water-soluble polymer polymer, include the following steps:
(1) synthesizing cationic type water soluble acrylic resin: preparing includes acrylic acid, butyl acrylate, methacrylic acid-
The mixed solution of beta-hydroxy ethyl ester, methyl methacrylate and initiator is spare.10-50 ml solvent is fitted into four-necked bottle, is heated up
To 90 DEG C, then the mixed solution of 10-30% is first added into solvent, after keeping the temperature 30min, then remaining mixed solution is added dropwise, protects
Temperature 2 hours and then addition initiator and 5-30ml solvent, then insulation reaction 2 hours, methacryloxypropyl second is finally added dropwise
Base trimethyl ammonium chloride, and insulation reaction 2 hours, cation type water-soluble acrylic resin is prepared；
(2) hexamethoxymethyl melamine: formalin is added in flask, adjusts pH value to 8-9 with NaOH solution,
It adds melamine, stirs 30min, adjust pH value again, heat up 70-80 DEG C, insulation reaction is to there is white crystalline solid object
Matter is precipitated, cooling after continuing heating reaction 1 hour, separates waste water and free formaldehyde, obtains hexamethylolmelamine, then to
Methanol is added in flask, adjusts pH value to the hexamethylolmelamine between 2-3, being added, heating with 10% HCl
To 45 DEG C, pH value is adjusted, terminates within insulation reaction 1 hour at 45-55 DEG C, hexamethoxymethyl melamine is prepared；
(3) cation type water-soluble polymer polymer: by cation type water-soluble acrylic resin and hexakis-methoxy methyl
Melamine is 80-100:10-30 mixing by volume, and cation type water-soluble polymer polymer is prepared.
Preferably, the time of remaining mixed solution is added dropwise in the step (1) at the uniform velocity as the dropwise addition of completion in 2.5-4 hours.
Preferably, in the step (3), cation type water-soluble acrylic resin and hexamethoxymethyl melamine are mixed
It further include with the water-reducible step of distillation after conjunction.
Cation type water-soluble polymer polymer of the invention has faster flocculating effect.
Specific embodiment
Technical solution of the present invention is described in further detail combined with specific embodiments below, so that the technology of this field
Personnel can better understand the present invention and can be practiced, but illustrated embodiment is not as a limitation of the invention.
The present embodiment provides a kind of cation type water-soluble polymer polymer, a kind of cation type water-soluble polymer is poly-
Close object, which is characterized in that the raw material of preparation includes cation type water-soluble acrylic resin and hexamethoxymethyl melamine；
The raw material for preparing of the cation type water-soluble acrylic resin includes: monomer, initiator and solvent, the monomer
Including acrylic acid, butyl acrylate, methacrylic acid-beta-hydroxy ethyl ester, methyl methacrylate and methylacryoyloxyethyl three
Ammonio methacrylate.
Preferably, the weight of the acrylic acid, butyl acrylate, methacrylic acid-beta-hydroxy ethyl ester and methyl methacrylate
Measure ratio are as follows: 1-10:5-20:1-10:1-10.
Preferably, the dosage of the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride accounts for the 10-20% of monomer gross mass.
Preferably, the volume ratio of the cation type water-soluble acrylic resin and hexamethoxymethyl melamine is 80-
100:10-30.
Preferably, the volume ratio of the cation type water-soluble acrylic resin and hexamethoxymethyl melamine is 100:
10-30。
Preferably, the raw material for preparing of the hexamethoxymethyl melamine includes hexamethylolmelamine, formaldehyde, trimerization
Cyanamide and methanol.
Preferably, the molar ratio of the formaldehyde and melamine are as follows: 10:1, lower content of formaldehyde can preferably guarantee
The synthesis of hexamethoxymethyl melamine.
It preferably, further include auxiliary agent, the auxiliary agent is ammonium hydroxide and/or alcamine compound.
Preferably, the initiator is benzoyl peroxide；The solvent is n-butanol.
Preferably, the initiator amount accounts for the 1%-1.5% of monomer gross mass, and the reasonable dosage of initiator can make whole
The conversion ratio of a reaction all reaches 90% or more, and the viscosity downward trend of the resin prepared is gentle.
The present invention also provides a kind of preparation methods of cation type water-soluble polymer polymer, include the following steps:
(1) synthesizing cationic type water soluble acrylic resin: preparing includes acrylic acid, butyl acrylate, methacrylic acid-
The mixed solution of beta-hydroxy ethyl ester, methyl methacrylate and initiator is spare.10-50 ml solvent is fitted into four-necked bottle, is heated up
To 90 DEG C, then the mixed solution of 10-30% is first added into solvent, after keeping the temperature 30min, then remaining mixed solution is added dropwise, protects
Temperature 2 hours and then addition initiator and 5-30ml solvent, then insulation reaction 2 hours, methacryloxypropyl second is finally added dropwise
Base trimethyl ammonium chloride, and insulation reaction 2 hours, cation type water-soluble acrylic resin is prepared；
(2) hexamethoxymethyl melamine: formalin is added in flask, adjusts pH value to 8-9 with NaOH solution,
It adds melamine, stirs 30min, adjust pH value again, heat up 70-80 DEG C, insulation reaction is to there is white crystalline solid object
Matter is precipitated, cooling after continuing heating reaction 1 hour, separates waste water and free formaldehyde, obtains hexamethylolmelamine, then to
Methanol is added in flask, adjusts pH value to the hexamethylolmelamine between 2-3, being added, heating with 10% HCl
To 45 DEG C, pH value is adjusted, terminates within insulation reaction 1 hour at 45-55 DEG C, hexamethoxymethyl melamine is prepared；
(3) cation type water-soluble polymer polymer: by cation type water-soluble acrylic resin and hexakis-methoxy methyl
Melamine is 80-100:10-30 mixing by volume, and cation type water-soluble polymer polymer is prepared.
Preferably, the time of remaining mixed solution is added dropwise in the step (1) at the uniform velocity as the dropwise addition of completion in 2.5-4 hours.
Preferably, in the step (3), cation type water-soluble acrylic resin and hexamethoxymethyl melamine are mixed
It further include with the water-reducible step of distillation after conjunction.
The present embodiment also provides a kind of preparation method of cation type water-soluble polymer polymer, includes the following steps:
(1) synthesizing cationic type water soluble acrylic resin: preparing includes acrylic acid, butyl acrylate, methacrylic acid-
The mixed solution of beta-hydroxy ethyl ester, methyl methacrylate and initiator is spare.10-50 ml solvent is fitted into four-necked bottle, is heated up
To 90 DEG C, then the mixed solution of 10-30% is first added into solvent, after keeping the temperature 30min, then remaining mixed solution is added dropwise, protects
Temperature 2 hours and then addition initiator and 5-30ml solvent, then insulation reaction 2 hours, methacryloxypropyl second is finally added dropwise
Base trimethyl ammonium chloride, and insulation reaction 2 hours, cation type water-soluble acrylic resin, reaction temperature 90 is prepared
DEG C, be conducive to increase resin of the reaction rate to which high conversion must be beaten, if reaction temperature is lower than 90 DEG C, reaction is slow, preparation
Resin molecular weight it is high, viscosity is larger；Weak reaction temperature is higher than 90 DEG C, and viscosity is smaller, and the degree of polymerization reduces.
(2) hexamethoxymethyl melamine: formalin is added in flask, adjusts pH value to 7.5- with NaOH solution
9, it adds melamine, stirs 30min, adjust pH value again and keep 7.5-9, heat up 70-80 DEG C, insulation reaction is to there is white
Crystalline solid material is precipitated, cooling after continuing heating reaction 1 hour, separates waste water and free formaldehyde, obtains hexamethylol trimerization
Then methanol is added in cyanamide into flask, adjust pH value between 2-3 with 10% HCl, hexamethylolmelamine is added,
45 DEG C are warming up to, pH value is adjusted, terminates within insulation reaction 1 hour at 45-55 DEG C, hexamethoxymethyl melamine is prepared.
It reacts during hydroxymethylation early period there is there are polycondensation reactions in polycondensation reaction, when pH value is less than 7.5, generation
Polycondensation easily occurs between methylol, therefore can only obtain its copolymer；When pH value is greater than 9, it is not susceptible to polycondensation, but be catalyzed
Agent concentration is high, and reaction speed is too fast, and reaction is difficult to carry out completely, and the hexamethoxymethyl melamine generated is easy agglomeration, therefore
Early period, the pH value of reaction should be controlled in 7.5-9, in further preferred embodiments, it should which control is in 8-9.It is anti-to react later period etherificate
For general control pH value between 2-3, etherificate speed is moderate during answering.When pH value between 1 and 2 when, catalyst concn is higher,
Reaction is excessively fierce, and etherificate speed is too fast；When pH value is between 4-5, etherificate speed is excessively slow.
The structural formula of hexamethoxymethyl melamine such as formula 1:
(3) cation type water-soluble polymer polymer: by cation type water-soluble acrylic resin and hexakis-methoxy methyl
Melamine is 80-100:10-30 mixing by volume, and cation type water-soluble polymer polymer is prepared.Hexakis-methoxy
Methyl melamine is as crosslinking agent, and when its dosage is less, a part of hydroxyl and carboxyl are not crosslinked reaction；When its dosage mistake
When more, remaining activity after the hydroxyl in active group and acrylic resin and carboxyl crosslinking in hexamethoxymethyl melamine
Cross-linking reaction has occurred for itself in group, and product viscosity is caused to increase, and density increases, the decline of property stability, and flocculating effect is bad.
In a preferred embodiment, the time that remaining mixed solution is at the uniform velocity added dropwise in step (1) is to complete for 2.5-4 hours
It is added dropwise.
In a preferred embodiment, in step (3), by cation type water-soluble acrylic resin and hexakis-methoxy methyl melamine
It further include auxiliary agent being added and with the water-reducible step of distillation after amine mixing.In further preferred embodiments, auxiliary agent includes ammonia
One or both of water and alcamines.
In a preferred embodiment, the mass percent of NaOH solution is 10%.
The cation type water-soluble polymer polymer that the present embodiment obtains can be used as flocculant, decolorising agent etc., at waste water
In reason field.The present embodiment is preferably applied in the processing of wastewater from chemical industry, coking wastewater and dyeing waste water.
In order to have further understanding and understanding to technical solution of the present invention, several preferred embodiments pair are now enumerated
It is described in further details.
Embodiment 1
Synthesizing cationic type water soluble acrylic resin: by methyl methacrylate 5.5mL, methacrylic acid-β-hydroxyl second
Ester 3.5mL, acrylic acid 2mL, butyl acrylate 16mL and initiator benzoyl peroxide (BPO) are mixed to get mixed solution.
In the four-necked bottle equipped with blender, thermometer, the low liquid funnel of constant pressure and condenser pipe, 20ml butanol solution is added, unlatching is stirred
It mixes, water bath with thermostatic control is warming up to 90 DEG C, and 20% mixed solution is first added dropwise, and after keeping the temperature 30min, then residue 80% is at the uniform velocity added dropwise
Mixed solution is added dropwise to complete for 2.5-4 hours, is kept the temperature 2 hours and then is added a certain amount of benzoyl peroxide (BPO) and 5ml
N-butanol, the dosage of BPO account for the 1.25% of monomer gross mass.Last insulation reaction 2 hours, methylacryoyloxyethyl is added dropwise afterwards
Trimethyl ammonium chloride, dosage account for the 18% of monomer gross mass, and insulation reaction 2 hours, and reaction terminates.
Synthetic cross-linking agent-hexamethoxymethyl melamine: (water-bath) heater, blender and temperature are loaded on three-necked flask
Degree meter, excessive formalin is added in flask, adjusts pH value to 8-9 with the NaOH solution that mass percent is 10%, then
The molar ratio of addition 63g melamine, formaldehyde and melamine is 10:1, stirs 30min, adjusts pH value again, is heated up
70-80 DEG C, to there is the precipitation of white crystalline solid substance, stops stirring, cooling after continuing heating standing reaction 1 hour, separates waste water
And free formaldehyde, obtain hexamethylolmelamine.Then, excessive methanol is added into flask, stirs, with 10% HCl tune
PH value is saved to hexamethylolmelamine between 2-3, is added, 45 DEG C is warming up under stirring condition, to sufficiently dissolve, adjusts pH
Value, terminates for insulation reaction 1 hour at 45-55 DEG C.
Cation type water-soluble polymer polymer: by cation type water-soluble acrylic resin and hexakis-methoxy methyl trimerization
Cyanamide is uniformly mixed by volume for 100:20, and required viscosity is diluted to distilled water.It is water-soluble that cationic is prepared
Property high molecular polymer.
Embodiment 2
Synthesizing cationic type water soluble acrylic resin: by methyl methacrylate 5.5mL, methacrylic acid-β-hydroxyl second
Ester 4.5mL, acrylic acid 5mL, butyl acrylate 12mL and initiator benzoyl peroxide (BPO) are mixed to get mixed solution.
In the four-necked bottle equipped with blender, thermometer, the low liquid funnel of constant pressure and condenser pipe, 45ml butanol solution is added, unlatching is stirred
It mixes, water bath with thermostatic control is warming up to 90 DEG C, and 10% mixed solution is first added dropwise, and after keeping the temperature 30min, then residue 90% is at the uniform velocity added dropwise
Mixed solution is added dropwise to complete for 3 hours, is kept the temperature 2 hours and then is added a certain amount of benzoyl peroxide (BPO) and 14ml just
Butanol, the dosage of BPO account for the 1.25% of monomer gross mass.It is last insulation reaction 2 hours, rear that methylacryoyloxyethyl three is added dropwise
Ammonio methacrylate, dosage account for the 15% of monomer gross mass, and insulation reaction 2 hours, and reaction terminates.
Synthetic cross-linking agent-hexamethoxymethyl melamine: (water-bath) heater, blender and temperature are loaded on three-necked flask
Degree meter, excessive formalin is added in flask, adjusts pH value to 8-9 with the NaOH solution that mass percent is 10%, then
The molar ratio of addition 63g melamine, formaldehyde and melamine is 10:1, stirs 30min, adjusts pH value again, is heated up
70-80 DEG C, to there is the precipitation of white crystalline solid substance, stops stirring, cooling after continuing heating standing reaction 1 hour, separates waste water
And free formaldehyde, obtain hexamethylolmelamine.Then, excessive methanol is added into flask, stirs, with 10% HCl tune
PH value is saved to hexamethylolmelamine between 2-3, is added, 45 DEG C is warming up under stirring condition, to sufficiently dissolve, adjusts pH
Value, terminates for insulation reaction 1 hour at 45-55 DEG C.
Cation type water-soluble polymer polymer: by cation type water-soluble acrylic resin and hexakis-methoxy methyl trimerization
Cyanamide is uniformly mixed by volume for 100:18, and required viscosity is diluted to distilled water.
Embodiment 3
Synthesizing cationic type water soluble acrylic resin: by methyl methacrylate 6mL, methacrylic acid-beta-hydroxy ethyl ester
5.5mL, acrylic acid 2mL, butyl acrylate 8mL and initiator benzoyl peroxide (BPO) are mixed to get mixed solution.It is filling
In the four-necked bottle for having the low liquid funnel of blender, thermometer, constant pressure and condenser pipe, 40ml butanol solution is added, opens stirring, it is permanent
Tepidarium is warming up to 90 DEG C, and 25% mixed solution is first added dropwise, and after keeping the temperature 30min, then the mixing of at the uniform velocity dropwise addition residue 75% is molten
Liquid is added dropwise to complete for 2.5 hours, is kept the temperature 2 hours and then is added a certain amount of benzoyl peroxide (BPO) and the positive fourth of 20ml
Alcohol, the dosage of BPO account for the 1.25% of monomer gross mass.It is last insulation reaction 2 hours, rear that methylacryoyloxyethyl front three is added dropwise
Ammonium chloride, dosage account for the 10% of monomer gross mass, and insulation reaction 2 hours, and reaction terminates.
Synthetic cross-linking agent-hexamethoxymethyl melamine: (water-bath) heater, blender and temperature are loaded on three-necked flask
Degree meter, excessive formalin is added in flask, adjusts pH value to 8-9 with the NaOH solution that mass percent is 10%, then
The molar ratio of addition 63g melamine, formaldehyde and melamine is 10:1, stirs 30min, adjusts pH value again, is heated up
70-80 DEG C, to there is the precipitation of white crystalline solid substance, stops stirring, cooling after continuing heating standing reaction 1 hour, separates waste water
And free formaldehyde, obtain hexamethylolmelamine.Then, excessive methanol is added into flask, stirs, with 10% HCl tune
PH value is saved to hexamethylolmelamine between 2-3, is added, 45 DEG C is warming up under stirring condition, to sufficiently dissolve, adjusts pH
Value, terminates for insulation reaction 1 hour at 45-55 DEG C.
Cation type water-soluble polymer polymer: by cation type water-soluble acrylic resin and hexakis-methoxy methyl trimerization
Cyanamide is uniformly mixed by volume for 100:28, and required viscosity is diluted to distilled water.It is water-soluble that cationic is prepared
Property high molecular polymer.
Embodiment 4
Synthesizing cationic type water soluble acrylic resin: by methyl methacrylate 6mL, methacrylic acid-beta-hydroxy ethyl ester
5.5mL, acrylic acid 7mL, butyl acrylate 14mL and initiator benzoyl peroxide (BPO) are mixed to get mixed solution.In
In four-necked bottle equipped with blender, thermometer, the low liquid funnel of constant pressure and condenser pipe, 35ml butanol solution is added, opens stirring,
Water bath with thermostatic control is warming up to 90 DEG C, and 15% mixed solution is first added dropwise, and after keeping the temperature 30min, then the mixing of residue 85% is at the uniform velocity added dropwise
Solution is added dropwise to complete for 2.5 hours, is kept the temperature 2 hours and then is added a certain amount of benzoyl peroxide (BPO) and the positive fourth of 10ml
Alcohol, the dosage of BPO account for the 1.25% of monomer gross mass.It is last insulation reaction 2 hours, rear that methylacryoyloxyethyl front three is added dropwise
Ammonium chloride, dosage account for the 12% of monomer gross mass, and insulation reaction 2 hours, and reaction terminates.
Synthetic cross-linking agent-hexamethoxymethyl melamine: (water-bath) heater, blender and temperature are loaded on three-necked flask
Degree meter, excessive formalin is added in flask, adjusts pH value to 8-9 with the NaOH solution that mass percent is 10%, then
The molar ratio of addition 63g melamine, formaldehyde and melamine is 10:1, stirs 30min, adjusts pH value again, and heat up 70-
80 DEG C, to there is the precipitation of white crystalline solid substance, stop stirring, continue it is cooling after heating stands reaction 1 hour, separate waste water and
Free formaldehyde obtains hexamethylolmelamine.Then, excessive methanol is added into flask, stirs, is adjusted with 10% HCl
PH value is warming up to 45 DEG C under stirring condition to hexamethylolmelamine between 2-3, is added, and to sufficiently dissolve, adjusts pH value,
Terminate within insulation reaction 1 hour at 45-55 DEG C.
Cation type water-soluble polymer polymer: by cation type water-soluble acrylic resin and hexakis-methoxy methyl trimerization
Cyanamide is uniformly mixed by volume for 100:25, and required viscosity is diluted to distilled water.It is water-soluble that cationic is prepared
Property high molecular polymer.
Comparative example 1
Compared with Example 2, in comparative example 1, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride dosage accounts for monomer gross mass
20%, remaining compositing formula ratio and preparation method condition are same as Example 2.
Comparative example 2
Compared with Example 2, in comparative example 2, cation type water-soluble acrylic resin and hexamethoxymethyl melamine
It is by volume 100:35, remaining compositing formula ratio and preparation method condition are same as Example 2.
Effect example
1. chemical wastewater treatment: taking the waste water in certain chemical plant: 1000ppm embodiment 1-4 and comparative example 1-2 preparation is added
Cation type water-soluble polymer polymer is as Coagulation and Adsorption agent, and COD (mg/L) and suspended matter before and after test processes
(mg/L).Concrete outcome is shown in Table 1.
Table 1
2. be used for treatment of dyeing wastewater: take 6 parts of 500mL dye house effluents (pH=7.4~7.9 of dyeing waste water, it is turbid
Degree 120~140NTU, 1112~1340mg/l of COD) it is respectively placed in the beaker of 800ml, it is then molten with hydrochloric acid and sodium hydroxide
Liquid adjusts the pH of dyeing waste water, then adds embodiment 1-4 and comparative example into each beaker in such a way that dosage is 80mg/L
The cation type water-soluble polymer polymer of 1-2 preparation tests cation type water-soluble as coagulant, and with national standard method
The turbidity and COD of waste water solution, calculate its turbidity removal rate and COD removal rate, and take 6 before and after high molecular polymer flocculation sedimentation
The average value record of group.Test result is as shown in table 2:
Table 2
3. being used for Treatment of Coking Effluent: taking the bio-chemical effluent of certain coke-oven plant, 800-1000ppm is added under stirring
The cation type water-soluble polymer polymer of embodiment 1-4 and comparative example 1-2 preparation is protected as coking wastewater coagulation release agent
It holds and stirs evenly, after standing sedimentation 1min, take supernatant measurement COD and coloration, test result as shown in table 3:
Table 3
It can be seen that the Ionic water-soluble high molecular polymer conduct that embodiment 1-4 is prepared from the data of table 1-3
Flocculant has better effects relative to comparative example 1-2 in the processing of wastewater from chemical industry, dyeing waste water and coking wastewater.
In comparative example 1, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride dosage accounts for the 20% of monomer gross mass, obtained sun
Ionic water-soluble high molecular polymer illustrates this in the effect of wastewater from chemical industry, dyeing waste water and Treatment of Coking Effluent and bad
Invention MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride dosage rationally realizes preferable effect.
In comparative example 2, cation type water-soluble acrylic resin and hexamethoxymethyl melamine are 100 by volume:
35, obtained Ionic water-soluble high molecular polymer wastewater from chemical industry, dyeing waste water and Treatment of Coking Effluent effect not
It is good, illustrate that the proportion of cation type water-soluble acrylic resin and hexamethoxymethyl melamine will affect cation type water-soluble
The flocculating effect of high molecular polymer.The hydroxyl and carboxylic in active group and acrylic resin in hexamethoxymethyl melamine
Cross-linking reaction has occurred for itself in remaining active group after base crosslinking, and product viscosity is caused to increase, and density increases, property stability
Decline, flocculating effect are bad.
The above description is only a preferred embodiment of the present invention, is not intended to limit the scope of the invention, all utilizations
Equivalent structure or equivalent flow shift made by present specification is applied directly or indirectly in other relevant technologies
Field is included within the scope of the present invention.
Claims (7)
1. a kind of cation type water-soluble polymer polymer, which is characterized in that the raw material of preparation includes cation type water-soluble
Acrylic resin and hexamethoxymethyl melamine；
The raw material for preparing of the cation type water-soluble acrylic resin includes: monomer, initiator and solvent, and the monomer includes
Acrylic acid, butyl acrylate, methacrylic acid-beta-hydroxy ethyl ester, methyl methacrylate and methylacryoyloxyethyl trimethyl
Ammonium chloride；
The volume ratio of the cation type water-soluble acrylic resin and hexamethoxymethyl melamine is 100:10-30；
The dosage of the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride accounts for the 10-18% of monomer gross mass.
2. cation type water-soluble polymer polymer as described in claim 1, which is characterized in that the acrylic acid, propylene
The weight ratio of acid butyl ester, methacrylic acid-beta-hydroxy ethyl ester and methyl methacrylate are as follows: 1-10:5-20:1-10:1-10.
3. cation type water-soluble polymer polymer as described in claim 1, which is characterized in that the hexakis-methoxy methyl three
The raw material for preparing of poly cyanamid includes hexamethylolmelamine, formaldehyde, melamine and methanol.
4. cation type water-soluble polymer polymer as claimed in claim 3, which is characterized in that the formaldehyde and melamine
The molar ratio of amine are as follows: 10:1.
5. cation type water-soluble polymer polymer as described in claim 1, which is characterized in that the raw material of preparation further includes
Auxiliary agent, the auxiliary agent are ammonium hydroxide and/or alcamine compound.
6. cation type water-soluble polymer polymer as described in claim 1, which is characterized in that the initiator is peroxide
Change benzoyl；The solvent is n-butanol.
7. cation type water-soluble polymer polymer as described in claim 1, which is characterized in that the initiator amount accounts for
The 1%-1.5% of monomer gross mass.
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| CN101333198A (en) * | 2008-07-02 | 2008-12-31 | 张家港顺昌化工有限公司 | Method for preparing HMMM resin |
| CN104073117A (en) * | 2014-06-23 | 2014-10-01 | 无锡市崇安区科技创业服务中心 | Water-soluble acrylic resin coating and preparation method thereof |
| CN105366789A (en) * | 2015-11-10 | 2016-03-02 | 陕西科技大学 | Multifunctional amphoteric polymer flocculant and preparation method thereof |
| CN105504163A (en) * | 2016-01-20 | 2016-04-20 | 广东溢达纺织有限公司 | Cationic flocculant and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101333198A (en) * | 2008-07-02 | 2008-12-31 | 张家港顺昌化工有限公司 | Method for preparing HMMM resin |
| CN104073117A (en) * | 2014-06-23 | 2014-10-01 | 无锡市崇安区科技创业服务中心 | Water-soluble acrylic resin coating and preparation method thereof |
| CN105366789A (en) * | 2015-11-10 | 2016-03-02 | 陕西科技大学 | Multifunctional amphoteric polymer flocculant and preparation method thereof |
| CN105504163A (en) * | 2016-01-20 | 2016-04-20 | 广东溢达纺织有限公司 | Cationic flocculant and preparation method thereof |
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