CN106117424A - Itaconic acid and 2 acrylamido 2 methyl propane sulfonic acid copolymers and preparation method and application - Google Patents
Itaconic acid and 2 acrylamido 2 methyl propane sulfonic acid copolymers and preparation method and application Download PDFInfo
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- CN106117424A CN106117424A CN201610608241.3A CN201610608241A CN106117424A CN 106117424 A CN106117424 A CN 106117424A CN 201610608241 A CN201610608241 A CN 201610608241A CN 106117424 A CN106117424 A CN 106117424A
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- acid
- acrylamide
- itaconic acid
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- methylpro panesulfonic
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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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
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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
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
Abstract
The present invention relates to itaconic acid copolymer with 2 acrylamido 2 methyl propane sulfonic acids and its preparation method and application.This copolymer is made up of itaconic acid monocarboxylate unit, itaconic acid dicarboxylate unit, 2 acrylamido 2 methyl propane sulfonic acid unit and 2 acrylamido 2 methyl propane sulfonic acid salt unit, the number-average molecular weight of this copolymer is 1,000 5000, and weight average molecular weight is 1,500 6900.This copolymer is brown color or brownish red transparency liquid, biodegradable, belongs to environmentally friendly product.Present copolymer is more suitable for stoping formation and the attachment of the upper calcium carbonate scale of coagulator (temperature is higher) in salt water cooling system, present copolymer as antisludging agent under the conditions of 80 DEG C, compared with poly-itaconic acid, copolymer concentration is reduced to 6mg/L by the 8mg/L in poly-itaconic acid, and scale inhibition performance improves more than 10% than poly-itaconic acid.
Description
Technical field
The present invention relates to water treatment field, especially relate to being total to of itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid
Polymers.This itaconic acid is used as sea water antisludging agent with the copolymer of 2-acrylamide-2-methylpro panesulfonic acid, it is adaptable to high rigidity,
High alkalinity sea water, is more suitable for stoping formation and the attachment of the upper calcium carbonate scale of coagulator (temperature is higher) in salt water cooling system,
It it is a kind of environmentally friendly antisludging agent.The invention still further relates to the copolymer in itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid
Preparation method.
Background technology
Along with people's attention to environmental conservation, the environmental requirement to water treatment agent the most day by day improves, therefore research and develop without phosphorus,
Biodegradable environmentally friendly medicament becomes the important directions of domestic and international water treatment agent research.
Sea water antisludging agent is an important component part of sea water water treatment agent.Although China is in the later stage nineties
The research of environmentally friendly type antisludging agent, but the antisludging agent kind researched and developed of success is few and quality is the most unstable, it is difficult to meet dense
The use requirement of contracting seawater quality, easily causes the organophosphor system antisludging agent of body eutrophication and the most degradable Organic substance scale inhibition
Agent is still the main flow of sea water antisludging agent.In this context, research and development have the sea water antisludging agent of good scale inhibition performance and environment friendly concurrently,
It is to promote China's world-class important opportunity of seawater utilization technology catch-up.
Itaconic acid is a kind of biomass prepared through biological fermentation process by raw materials such as starch, has stronger biodegradable
Ability, is a kind of unsaturated dicarboxylic acid, does not relies on the separation of petroleum chemicals, in the overall background that energy crisis is the most serious
Under, itaconic acid series products constantly demonstrates its superiority in like product.
Summary of the invention
Inventor is by finding the research of inhibitor mechanism, for reaching efficient scale effect, contains only-COOH/-OH etc. weak
Acid and slightly water-wet group polymer is difficult to play good scale inhibition effect, if contain hydrophilic simultaneously in high hardness water
Stronger group is (such as-SO3H), both can effectively prevent slightly water-wet group from generating the calcium sol of indissoluble, and contribute to again dissolving, institute
Should have strong acid and weak acid Liang Zhong functional group with high hardness water treatment agent simultaneously.2-acrylamide-2-methylpro panesulfonic acid
Containing sulfonic group (-SO in molecule3H), the group such as carboxyl, hydroxyl and amide groups, there is strong anionic property, strong solubility, conduction
The characteristics such as property, hydrolytic stability and heat stability.
The present invention, under ensureing the biodegradable premise in poly-itaconic acid, improves the temperature tolerance in poly-itaconic acid, resistance further
Dirt, proposes with itaconic acid as primary raw material, copolymerization a certain amount of 2-acrylamide-2-methylpro panesulfonic acid synthesis itaconic acid and 2-
The copolymer of acrylamide-2-methylpro panesulfonic acid is as environment protecting scale inhibitor.
Present invention firstly provides using the copolymer of itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid as sea water scale inhibition
Agent, raw material itaconic acid is to be prepared through biological fermentation process by starch etc., does not relies on oil product and separates.Itaconic acid and 2-acryloyl
The preparation of the copolymer of amido-2-methyl propane sulfonic acid is with water as medium, with traditional organic solvent and organic initiators of using
Synthetic method is compared, and this technique is simple and safe, and preparation process no waste is discharged, and non-secondary pollution has good commercial Application
Prospect.
Present invention solves the technical problem that and be: overcome the technical problem that poly-itaconic acid temperature tolerance is poor, scale-inhibiting properties is undesirable,
Thering is provided a kind of polymerization time short, preparation technology is simple, the itaconic acid of no waste discharge and 2-acrylamide-2-methylpro panesulfonic acid
Copolymer and preparation method.Present copolymer is more suitable for stoping the upper carbonic acid of coagulator (temperature is higher) in salt water cooling system
The formation of calcium dirt and attachment, present copolymer is as antisludging agent under the conditions of 80 DEG C, and compared with poly-itaconic acid, copolymer uses
Concentration is reduced to 6mg/L by the 8mg/L in poly-itaconic acid, and scale inhibition performance improves more than 10% than poly-itaconic acid.
In order to solve above-mentioned technical problem, first aspect, the present invention provides a kind of itaconic acid and 2-acrylamido-2-first
The copolymer of base propane sulfonic acid, it is by itaconic acid monocarboxylate unit, itaconic acid dicarboxylate unit, 2-acrylamido-2-first
Base propane sulfonic acid unit and 2-acrylamide-2-methylpro panesulfonic acid salt unit are constituted.
Preferably, the number-average molecular weight of described copolymer is 1000-5000, and weight average molecular weight is 1500-6900, preferably
, number-average molecular weight is 2500-4000, and weight average molecular weight is 3200-5600.
Preferably, itaconic acid monocarboxylate unit and itaconic acid dicarboxylate unit sum, with 2-acrylamido-2-first
The ratio of the molar fraction of base propane sulfonic acid unit and 2-acrylamide-2-methylpro panesulfonic acid salt unit sum is 14.1:1.
Preferably, the ratio of the molar fraction of itaconic acid dicarboxylate unit and itaconic acid monocarboxylate unit is 1:1；2-third
The ratio of the molar fraction of acrylamide base-2-methyl propane sulfonic acid unit and 2-acrylamide-2-methylpro panesulfonic acid salt unit sum
For 1:3.
Second aspect, the present invention provides the thing in a kind of itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid.
This copolymer is by construction unitAnd construction unitConstitute,
R represents M or H, but in this copolymer, R is not all M or is not all H.
This copolymer preparation process is as follows:
Wherein, wherein M represents alkali metal or alkaline-earth metal, and M (OH) L is monoacidic base or diacidic base, the preferred hydrogen-oxygen of monoacidic base
Change sodium, potassium hydroxide, diacidic base preferably calcium hydroxide；L represents alkali-metal quantivalence, is 1 or 2.
The number-average molecular weight of this copolymer is 1000-5000, and weight average molecular weight is 1500-6900, it is preferred that this copolymer
Number-average molecular weight be 2500-4000, weight average molecular weight is 3200-5600.
Preferably, itaconic acid monocarboxylate unit and itaconic acid dicarboxylate unit sum, with 2-acrylamido-2-first
The ratio of the molar fraction of base propane sulfonic acid and 2-acrylamide-2-methylpro panesulfonic acid salt unit sum is 14.1:1.
The third aspect, the present invention provides the copolymer in a kind of itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid, its by
Itaconic acid monocarboxylate unit, itaconic acid dicarboxylate unit, 2-acrylamide-2-methylpro panesulfonic acid and 2-acrylamide
Base-2-methyl propane sulfonic acid salt unit is constituted, and it is prepared by following method:
A itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid are reacted by () respectively with water soluble alkali, preparation part neutralizes
Itaconic acid monomer and part neutralize 2-acrylamide-2-methylpro panesulfonic acid monomer；Then itaconic acid part neutralized
The 2-acrylamide-2-methylpro panesulfonic acid monomer mixing that monomer and part neutralize, obtains monomer mixture；
B () by radical initiator, makes monomer mixture be polymerized in aqueous phase, obtain itaconic acid and 2-acrylamido-
The copolymer of 2-methyl propane sulfonic acid.
Fourth aspect, the present invention provides the preparation in a kind of itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid copolymer
Method, prepared copolymer is by itaconic acid monocarboxylate unit, itaconic acid dicarboxylate unit, 2-acrylamido-2-first
Base propane sulfonic acid and 2-acrylamide-2-methylpro panesulfonic acid salt unit are constituted, employing following steps:
A itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid are reacted by () respectively with water soluble alkali, preparation part neutralizes
Itaconic acid monomer and part neutralize 2-acrylamide-2-methylpro panesulfonic acid monomer, then will part neutralize itaconic acid
The 2-acrylamide-2-methylpro panesulfonic acid monomer mixing neutralized with part, obtains monomer mixture；With itaconic acid and 2-propylene
On the basis of the quality sum of amide groups-2-methyl propane sulfonic acid, the addition of 2-acrylamide-2-methylpro panesulfonic acid is 10wt%
～50wt%；
B () by radical initiator, makes monomer mixture be polymerized in aqueous phase, and obtain itaconic acid and 2-acrylamide
The copolymer of base-2-methyl propane sulfonic acid.
Preferably, the monomer mixture that part neutralizes is adding during initiator, as a kind of solution, with
Initiator is simultaneously added dropwise in reactor.
Preferably, course of reaction keeps reaction temperature between 70 DEG C～110 DEG C.
Preferably, in step (a), in itaconic acid and sulfonic acid on the basis of the amount of the material of carboxyl, the degree of neutralization of carboxyl
It is 40%～75%, preferably 75%；Water soluble alkali is monoacidic base, preferably sodium hydroxide, potassium hydroxide；Or diacidic base, preferably hydrogen
Calcium oxide.
Preferably, on the basis of the quality of monomer, initiator addition is 5wt%～7.5wt%；Below initiator is selected
Any one material: potassium peroxydisulfate, sodium peroxydisulfate and Ammonium persulfate., initiator system of ammonium persulfate.
Preferably, the feed time of monomer solution and initiator is 1.0～3.0 hours, preferably 1.0 hours.
Preferably, course of reaction temperature controls at 80-90 DEG C, preferably 80 DEG C.
Preferably, after monomer and initiator dropping, continuation polymerase 10 .5～5 hours, preferably 1.0 hours.
5th aspect, the present invention provides the copolymerization in any of the above-described kind of itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid
Thing application in antisludging agent.
Preferably, described antisludging agent is sea water antisludging agent.
Preferably, under the conditions of antisludging agent application temperature 60 C-80 DEG C, the application concentration of described copolymer is less than being equal to
6mg/L。
6th aspect, the present invention provides a kind of water treatment agent, including any of the above-described kind of itaconic acid and 2-acrylamido-2-
The copolymer of methyl propane sulfonic acid is as antisludging agent.
The present invention with itaconic acid, 2-acrylamide-2-methylpro panesulfonic acid monomer as raw material, draw through free radical in aqueous phase
Send out agent initiation and aggregate into itaconic acid and the copolymer of 2-acrylamide-2-methylpro panesulfonic acid.In particular, by with solvable
Property alkali react, obtain part neutralize itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid monomer, at initiator system
Lower aqueous polymerization obtains itaconic acid and the copolymer of 2-acrylamide-2-methylpro panesulfonic acid.The present invention is prepared with water as medium,
Technique is simple and safe, and polymerization time is short, and energy consumption is low, and preparation process no waste is discharged, non-secondary pollution.The clothing health obtained by this method
The copolymer temperature tolerance of acid and 2-acrylamide-2-methylpro panesulfonic acid is good, can effectively stop sea water cooling system as antisludging agent
The formation of the upper calcium carbonate scale of coagulator (temperature is higher, 60 DEG C-80 DEG C) in system, is a kind of green, highly effective sea-water antisludging agent.
Accompanying drawing explanation
Fig. 1 is itaconic acid and the infrared spectrum of 2-acrylamide-2-methylpro panesulfonic acid copolymer of the present invention.
Fig. 2 is itaconic acid and the nuclear magnetic spectrogram of 2-acrylamide-2-methylpro panesulfonic acid copolymer.
Detailed description of the invention
Specifically, the preparation method of the copolymer of the itaconic acid of the present invention and 2-acrylamide-2-methylpro panesulfonic acid,
Use following steps: add water in reaction unit, be heated to uniform temperature (between 70 DEG C～110 DEG C), the most slowly drip
Add itaconic acid, 2-acrylamide-2-methylpro panesulfonic acid monomer solution and initiator solution that part neutralizes in reaction unit.
Wherein, when the itaconic acid of preparation part neutralization and 2-acrylamide-2-methylpro panesulfonic acid monomer are as monomer solution, it is with clothing
In health acid and 2-acrylamide-2-methylpro panesulfonic acid monomer on the basis of the amount of the material of carboxyl, add a certain amount of solubility
Alkali, the degree of neutralization of carboxyl is 40%～75%, preferably 75%.Water soluble alkali can be that monoacidic base is (such as sodium hydroxide, potassium hydroxide
Deng), it is also possible to being diacidic base (such as calcium hydroxide etc.), the concentration of alkali is 40%～50% (mass percent).
When carrying out polyreaction, initiator addition is (with itaconic acid and the matter of 2-acrylamide-2-methylpro panesulfonic acid
On the basis of amount) 3.5%～15%, preferably 5%～10%, more preferably 7.5%, gained itaconic acid and 2-acrylamido-2-
Methyl propane sulfonic acid copolymer anti-scale best results.Initiator selection any one material following: potassium peroxydisulfate, sodium peroxydisulfate, over cure
Acid ammonium, initiator system of ammonium persulfate.The feed time of monomer solution and initiator solution is 1.0～3.0 hours, monomer solution and/or
After initiator solution dropping, continuation polymerase 10 .5～8.0 hours, preferably 1 hour.In polymerization process, temperature controls at 70 DEG C
～between 110 DEG C, preferably 70～80 DEG C, resulting polymers scale inhibition effect is optimal.
Final products solid content of the present invention, between 30wt%～32wt%, can obtain brown color or palm fibre under different polymerizing conditions
Red, transparent liquid.
Itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid copolymer are as sea water antisludging agent, and it passes through standard polyoxy
Change ethylene (PEO) be 1000～5000 by the number-average molecular weight that chromatograph of gel permeation measures, weight average molecular weight be 1500～
6900.Preferred number average molecular weight is 2500～4000, and weight average molecular weight is 3200～5600, and scale inhibition effect is more preferably.
End product itaconic acid prepared by the present invention and 2-acrylamide-2-methylpro panesulfonic acid copolymer, by structure
UnitAnd construction unit
R represents alkali metal, alkaline-earth metal or H, and R is not all alkali and alkaline earth metal ions, or H.Alkali metal source is in one
Unit alkali, preferably sodium hydroxide, potassium hydroxide；Alkaline-earth metal derives from diacidic base, preferably calcium hydroxide.
The itaconic acid of the present invention and 2-acrylamide-2-methylpro panesulfonic acid copolymer environmental friendliness, preparation method is simple,
Polymerization time is short, and energy consumption is low, no waste discharge.Itaconic acid-the sulfonic acid copolymer obtained by preparation method of the present invention is more applicable
In stoping formation and the attachment of (temperature is at 60 DEG C-80 DEG C) calcium carbonate scale on salt water cooling system coagulator, can follow as sea water
Dirt dispersion agent in ring cooling system, it is possible to as Scale inhibitor for sea water desalination, detergent additives, chelating agen etc..
Embodiment
The present invention is described in detail below by embodiment.In all embodiments, with reference to GB/T16632-2008 " at water
The mensuration tosca method of reason agent scale-inhibiting properties ", tested by static-state scale inhibition, evaluation itaconic acid and 2-acrylamido-2-
Methyl propane sulfonic acid copolymer is as the antisludging agent scale inhibition effect to high rigidity sea water.Seawater quality situation used by appraisal of scale mitigating effect
Following Table A.
Table A
Evaluation of antisludging performance seawater quality such as Table A, cycles of concentration is constant temperature 24 hours at 2.0,80 DEG C, medicament (clothing health
Acid and 2-acrylamide-2-methylpro panesulfonic acid copolymer) concentration is 6mg/L (in terms of valid density), titrates with EDTA
Calcium ion content in filtrate, calculates scale inhibition performance.Scale inhibition performance (η %) is calculated by following equation:
C in formula2For with water treatment agent (i.e. the itaconic acid of the present invention and 2-acrylamide-2-methylpro panesulfonic acid copolymer)
Calcium ion concentration after sample experiment, c1For with the calcium ion concentration after water treatment agent sample experiment, c0For former sea water calcium from
Sub-concentration.
Embodiment 1
The itaconic acid of preparation part neutralization, 2-acrylamide-2-methylpro panesulfonic acid monomer solution, weigh 40.0g clothing health
Acid, is dissolved in 25g water, is slowly added dropwise the sodium hydroxide solution containing 37g (weight/mass percentage composition is 50%), the degree of neutralization of carboxyl
It is 75%.Weigh 4.5g 2-acrylamide-2-methylpro panesulfonic acid monomer, be dissolved in 5g water, be then slowly added dropwise containing 1.3g's
Sodium hydroxide solution (weight/mass percentage composition is 50%), the degree of neutralization of carboxyl is 75%, then by two kinds of monomer mixing, obtains list
Liquid solution.Preparation is containing 2.3g Ammonium persulfate. and the initiator solution of 10g deionized water.
30g water is added in four mouthfuls of reaction bulbs equipped with thermometer, two Dropping funnels, reflux condenser and agitator,
Flask is heated to 70 DEG C～80 DEG C.Being slowly added dropwise monomer and initiator solution, dropping in 1 hour is complete simultaneously.Meanwhile protect
Hold reaction bulb temperature (as shown in table 1,70 DEG C～110 DEG C).Drip complete, insulation reaction 1.0 hours.It is cooled to room temperature discharging,
Obtaining itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid copolymer, product appearance is brown color or brown-red solution.
Table 1: reaction temperature is on itaconic acid and the impact of 2-acrylamide-2-methylpro panesulfonic acid copolymer anti-scale rate
Above-described embodiment can be seen that, when itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid degree of neutralization 75%, initiator
2.3g, reaction temperature 80 DEG C, polymerization time 1.0h, gained itaconic acid and the resistance of 2-acrylamide-2-methylpro panesulfonic acid copolymer
Dirt best results, scale inhibition performance reaches 78.1%.Resulting polymers number all (Mn) molecular weight are 3426, and weight average molecular weight (Mw) is
3857.As can be seen here, although polymer concentration is reduced to 6mg/L by the present invention, scale inhibition performance still can be up to 78.1%.
Molecular weight is measured by standard polyethylene glycol oxide (PEO) chromatograph of gel permeation, gel infiltration color used
Spectrometer is produced by VISCOTEK company of the U.S., and model is M302, and flowing is PBS (pH=7.0) aqueous solution of 0.1M mutually, and flow velocity is
1.0mL/min。
Wherein, in the present invention, in embodiment 1 and latter embodiments, itaconic acid, 2-acrylamido-2-methyl-prop sulphur
Acid monomers degree of neutralization refers both to, in itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid on the basis of the amount of the material of carboxyl, and clothing
The degree of neutralization of carboxyl in health acid and 2-acrylamide-2-methylpro panesulfonic acid monomer；Its raw material initially added by reaction, clothing
In health acid and 2-acrylamide-2-methylpro panesulfonic acid monomer, the amount of the material of carboxyl is come with the ratio of the amount of the material of hydroxyl in alkali
Determine.
80 DEG C of gained itaconic acids of reaction temperature and 2-acrylamide-2-methylpro panesulfonic acid copolymer are carried out infrared survey
Examination, copolymer sample and potassium bromide mixed pressuring plate, use Nicolet 6700 infrared spectrometer to carry out IR spectrum scanning, wave number
Scope is 400-4000cm-1.Fig. 1 is the FT-IR spectrum of gained itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid copolymer
Figure.By this figure it can be seen that in 3450cm-1Place observes a big broad peak, is the stretching vibration peak of carboxyl.At 2953cm-1
The peak that place occurs, represents the asymmetrical stretching vibration peak of saturated methylene.1720cm-1The spike at place, is the stretching vibration of carbonyl
Peak.1561cm-1Place occurs in that the blended absorbent peak representing N-H bending vibration and C-N stretching vibration.The appearance of these characteristic peaks
Prove successfully synthesis itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid copolymer.
80 DEG C of gained itaconic acids of reaction temperature and 2-acrylamide-2-methylpro panesulfonic acid copolymer are carried out nuclear-magnetism survey
Examination, nuclear magnetic resonance, NMR chromatograph used is the 400M nuclear-magnetism of Varian company, and model is UNITY-plus, and reagent is D2O.Fig. 2 institute
Show it is this polymer1H NMR spectra.Peak (d) 5.5, at 6.0ppm represent in copolymer solution on unreacted monomer with
The characteristic peak of the H that double bond is connected.The chemical shift of other hydrogen in itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid copolymer
As follows:1H NMR(D2O, ppm): a, δ=1.2 (-C (CH3)2), b, 1.4～3.3 (-COCH2、-COCHCH2), c, 3.6 (-
CH2SO3R)。
Embodiment 2
The itaconic acid of preparation part neutralization, 2-acrylamide-2-methylpro panesulfonic acid monomer solution, weigh 40.0g clothing health
Acid, is dissolved in 25g water, is slowly added dropwise the sodium hydroxide solution containing 37g (weight/mass percentage composition is 50%), the degree of neutralization of carboxyl
It is 75%.Weigh 4.5g 2-acrylamide-2-methylpro panesulfonic acid monomer, be dissolved in 5g water, be then slowly added dropwise containing 1.3g's
Sodium hydroxide solution (weight/mass percentage composition is 50%), the degree of neutralization of carboxyl is 75%, then by two kinds of monomer mixing, obtains list
Liquid solution.Preparation is containing a certain amount of Ammonium persulfate. and the initiator solution of 10g deionized water again, and initiator addition is shown in Table 2.
30g water is added in four mouthfuls of reaction bulbs equipped with thermometer, two Dropping funnels, reflux condenser and agitator,
Flask is heated to 70 DEG C～80 DEG C.Being slowly added dropwise monomer and initiator solution, dropping in 1 hour is complete simultaneously.Meanwhile protect
Holding reaction bulb temperature is 80 DEG C.Drip complete, insulation reaction 1.0 hours.It is cooled to room temperature discharging, obtains itaconic acid and 2-acryloyl
Amido-2-methyl propane sulfonic acid copolymer, product appearance is brown color or brown liquid.
Table 2: initiator addition is to itaconic acid-and the shadow of 2-acrylamide-2-methylpro panesulfonic acid copolymer anti-scale rate
Ring
Above-described embodiment can be seen that, when itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid copolymer degree of neutralization 75%,
Initiator 3.4g, reaction temperature 80 DEG C, polymerization time 1 hour, gained itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid are altogether
Polymers scale inhibition effect is optimal, reaches 86.9%, and resulting polymers number all (Mn) molecular weight are 2684, and weight average molecular weight (Mw) is
3526.As can be seen here, although polymer concentration is reduced to 6mg/L by the present invention, scale inhibition performance still can be up to 86.9%.
Embodiment 3
The itaconic acid of preparation part neutralization, 2-acrylamide-2-methylpro panesulfonic acid monomer solution, weigh 40.0g clothing health
Acid, is dissolved in 25g water, is slowly added dropwise the sodium hydroxide solution containing 37g (weight/mass percentage composition is 50%), the degree of neutralization of carboxyl
It is 75%.Weigh a certain amount of 2-acrylamide-2-methylpro panesulfonic acid monomer (being specifically shown in Table 3), be dissolved in water, the most slowly drip
Hydro-oxidation sodium solution (weight/mass percentage composition is 50%) is 75% to the degree of neutralization of carboxyl, then by two kinds of monomer mixing,
To monomer solution.Preparation is containing 3.4g Ammonium persulfate. and the initiator solution of 10g deionized water again.
30g water is added in four mouthfuls of reaction bulbs equipped with thermometer, two Dropping funnels, reflux condenser and agitator,
Flask is heated to 70 DEG C～80 DEG C.Being slowly added dropwise monomer and initiator solution, dropping in 1 hour is complete simultaneously.Meanwhile protect
Holding reaction bulb temperature is 80 DEG C.Drip complete, insulation reaction 1.0 hours.It is cooled to room temperature discharging, obtains itaconic acid and 2-acryloyl
Amido-2-methyl propane sulfonic acid copolymer, product appearance is brown color or brown liquid.
Table 3:2-acrylamide-2-methylpro panesulfonic acid content of monomer is to itaconic acid and 2-acrylamido-2-methyl-prop
The impact of sulfonic acid copolymer scale inhibition performance.
Above-described embodiment can be seen that, when itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid copolymer degree of neutralization 75%,
Initiator 3.4g, 2-acrylamide-2-methylpro panesulfonic acid monomer 40g, reaction temperature 80 DEG C, polymerization time 1.0 hours, gained
Itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid copolymer anti-scale best results, biological degradation rate is minimum；2-acrylamide
Base-2-methyl propane sulfonic acid content of monomer 4.5g, gained itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid copolymer biology fall
Solution rate is the highest.For having good scale inhibition performance and biological degradability concurrently, select 2-acrylamide-2-methylpro panesulfonic acid monomer addition
For 4.5g.
Biological degradation rate measures with reference to GB/T20778-2006 " water treatment agent biodegradable performance evaluation methodology-CO2Raw
Become mensuration ".Use the activated sludge of sewage treatment plant as inoculum, 25 DEG C, under lucifuge, stirring, be passed through removal CO continuously2's
Air, absorbs, with barium hydroxide, the CO that reaction generates2, obtain CO by hydrochloric acid standard solution titration2Growing amount.By itaconic acid
The CO generated with 2-acrylamide-2-methylpro panesulfonic acid copolymer2Amount deduction blank, is calculated itaconic acid and 2-acryloyl
The biological degradation rate of amido-2-methyl propane sulfonic acid copolymer.
Embodiment 4
The itaconic acid of preparation part neutralization, 2-acrylamide-2-methylpro panesulfonic acid monomer solution, weigh 40.0g clothing health
Acid, is dissolved in 25g water, is slowly added dropwise the sodium hydroxide solution containing 37g (weight/mass percentage composition is 50%), the degree of neutralization of carboxyl
It is 75%.Weigh 4.5g 2-acrylamide-2-methylpro panesulfonic acid monomer, be dissolved in 5g water, be then slowly added dropwise containing 1.3g's
Sodium hydroxide solution (weight/mass percentage composition is 50%), the degree of neutralization of carboxyl is 75%, then by two kinds of monomer mixing, obtains list
Liquid solution.Preparation is containing 3.4g Ammonium persulfate. and the initiator solution of 10g deionized water again.
Equipped with four mouthfuls of reaction bulbs of thermometer, two Dropping funnels, reflux condenser and agitator add 30g water, will
Flask is heated to 80 DEG C.Dropping monomer and initiator solution the most slowly, dropping in 1 hour is complete.Meanwhile keep reaction
Bottle temperature is 80 DEG C.Dripping complete, continue insulation reaction certain time, the response time is shown in Table 4.It is cooled to room temperature discharging, to obtain final product
To itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid copolymer, product appearance is brown color liquid or brown liquid.
Table 4: the insulation reaction time is on itaconic acid and the impact of 2-acrylamide-2-methylpro panesulfonic acid copolymer anti-scale rate
Above-described embodiment can be seen that, when itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid copolymer degree of neutralization 75%,
Initiator 3.4g, reaction temperature 80 DEG C, polymerization time is to itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid copolymer molecule
Amount and scale inhibition performance impact are inconspicuous, it is contemplated that save the energy, and selecting polymerization time is 1.0 hours.
Embodiment 5
In four mouthfuls of reaction bulbs equipped with thermometer, two Dropping funnels, reflux condenser and agitator, add 40g clothing health
Acid, 4.5g 2-acrylamide-2-methylpro panesulfonic acid monomer and 60g water, flask is heated to 80 DEG C.It is slowly added dropwise simultaneously
38.3g concentration is sodium hydroxide solution and the Ammonium persulfate. Han 3.4g of 50%, the initiator solution of 10g deionized water, within 1 hour, drips
Add complete.Keeping reaction bulb temperature is 80 DEG C.Drip complete, continue reaction 1.0 hours.It is cooled to room temperature discharging, obtains clothing health
Acid and 2-acrylamide-2-methylpro panesulfonic acid copolymer, product appearance is brown liquid.
Gained itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid copolymer number all (Mn) molecular weight are 1235, weight average
Molecular weight (Mw) is 1621, and scale inhibition performance is 21.5%.
By the experimental result of above-described embodiment 5 it can be seen that preparing itaconic acid and 2-acrylamido-2-methyl-prop sulphur
During acid copolymer, neutralize clothing health with obtaining part by itaconic acid, 2-acrylamide-2-methylpro panesulfonic acid monomer with alkali reaction
Acid and 2-acrylamide-2-methylpro panesulfonic acid monomer solution, then it is slowly added dropwise being polymerized of addition reactor with initiator simultaneously
Method (embodiment 1～4) is compared, and alkali liquor and initiator solution are slowly added in itaconic acid monomer solution and gather by this
The method closed, the itaconic acid obtained and 2-acrylamide-2-methylpro panesulfonic acid molecular weight of copolymer are relatively low, for the resistance of sea water
During dirt experiment, scale inhibition performance is relatively low.
Embodiment 6
Equipped with four mouthfuls of reaction bulbs of thermometer, two Dropping funnels, reflux condenser and agitator add 40g clothing health
Acid, 4.5g 2-acrylamide-2-methylpro panesulfonic acid monomer and 60g water, flask is heated to 80 DEG C.In reaction bulb slowly
Dropping is containing 3.4g Ammonium persulfate. and the initiator solution of 10g deionized water, and dropping in 1 hour is complete, meanwhile keeps reaction bulb
Temperature is 80 DEG C.Drip complete, continue reaction 1.0 hours.It is cooled to room temperature discharging, i.e. obtains itaconic acid and 2-acrylamide
Base-2-methyl propane sulfonic acid copolymer polymer, product appearance is brown color liquid.
Gained itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid copolymer number all (Mn) molecular weight are 1167, weight average
Molecular weight (Mw) is 1356, and scale inhibition performance is 16.8%.
By the experimental result of above-described embodiment 6 it can be seen that preparing itaconic acid and 2-acrylamido-2-methyl-prop sulphur
During acid copolymer, neutralize clothing health with obtaining part by itaconic acid, 2-acrylamide-2-methylpro panesulfonic acid monomer with alkali reaction
Acid, 2-acrylamide-2-methylpro panesulfonic acid monomer solution, then it is slowly added dropwise the side of polymerization adding reactor with initiator simultaneously
Method (embodiment 1～4) is compared, should be direct without itaconic acid, the neutralization of 2-acrylamide-2-methylpro panesulfonic acid monomer and alkali
Initiator solution is slowly added to the side carrying out being polymerized in itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid monomer solution
Method, the itaconic acid obtained and 2-acrylamide-2-methylpro panesulfonic acid molecular weight of copolymer are relatively low, and scale inhibition performance is relatively low.
Embodiment 7
The itaconic acid of preparation part neutralization, 2-acrylamide-2-methylpro panesulfonic acid monomer solution, weigh 40.0g clothing health
Acid, is dissolved in 25g water, is slowly added dropwise the sodium hydroxide solution containing 37g (weight/mass percentage composition is 50%), the degree of neutralization of carboxyl
It is 75%.Weigh 4.5g 2-acrylamide-2-methylpro panesulfonic acid monomer, be dissolved in 5g water, be then slowly added dropwise containing 1.3g's
Sodium hydroxide solution (weight/mass percentage composition is 50%), the degree of neutralization of carboxyl is 75%, then by two kinds of monomer mixing, obtains list
Liquid solution.Itaconic acid, 2-acrylamide-2-methylpro panesulfonic acid monomer solution after neutralizing respectively join equipped with temperature
In four mouthfuls of reaction bulbs of meter, two Dropping funnels, reflux condenser and agitator, heating flask is to 80 DEG C.Preparation mistake Han 3.4g
Ammonium sulfate and the initiator solution of 10g deionized water.It is slowly added dropwise initiator solution to equipped with the itaconic acid partly neutralized, 2-third
In the reaction bulb of acrylamide base-2-methyl propane sulfonic acid monomer solution, dropping in 1 hour is complete.Meanwhile keep reaction bulb temperature
It it is 80 DEG C.Drip complete, continue reaction 1.0 hours.It is cooled to room temperature discharging, i.e. obtains itaconic acid and 2-acrylamido-2-
Methyl propane sulfonic acid copolymer polymer, product appearance is brown liquid.
Gained itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid copolymer number all (Mn) molecular weight, for for 1573, weigh
Average molecular weight (Mw) is 1834, and scale inhibition performance is 35.2%.
By the experimental result of above-described embodiment 7 it can be seen that preparing itaconic acid and 2-acrylamido-2-methyl-prop sulphur
During acid copolymer, initiator solution is individually slowly dropped to itaconic acid and the 2-acrylamido-2-methyl that part neutralizes by this
The method carrying out in sulphonic acid copolymer monomer solution being polymerized, compared with embodiment 5 and embodiment 6, itaconic acid and 2-acryloyl
Amido-2-methyl propane sulfonic acid copolymer is when the scale inhibition experiment of sea water, and scale inhibition performance increases；But with embodiment 1～4 phase
Ratio, i.e. with will the itaconic acid that neutralizes of part and 2-acrylamide-2-methylpro panesulfonic acid monomer solution and initiator solution simultaneously
The polymerization being slowly added into reactor is compared, the itaconic acid obtained and 2-acrylamide-2-methylpro panesulfonic acid copolymer
The scale inhibition effect of sea water there is certain gap.
Embodiment 8
30g water is added in four mouthfuls of reaction bulbs equipped with thermometer, two Dropping funnels, reflux condenser and agitator,
Flask is heated to 70 DEG C～80 DEG C.The itaconic acid monomer solution that preparation part neutralizes, weighs 45.5g itaconic acid, is dissolved in 30g
Water, is then slowly added dropwise 42.0g sodium hydroxide (weight/mass percentage composition is 50%) solution, and the degree of neutralization of carboxyl is 75%, obtains
Monomer solution.Preparation is containing 2.3g Ammonium persulfate. and the initiator solution of 10g deionized water.It is slowly added dropwise monomer and initiator simultaneously
Solution, dropping in 1 hour is complete.Meanwhile keep reaction bulb temperature 70 C.Drip complete, insulation reaction 1.0 hours.It is cooled to
Room temperature discharging, obtains poly-itaconic acid, and product appearance is light yellow or dark red solution.
Number all (Mn) molecular weight in gained poly-itaconic acid are 2926, and weight average molecular weight (Mw) is 3657.When the conduct of poly-itaconic acid
Antisludging agent, concentration is 6mg/mL, and scale inhibition performance is 44.2%；Concentration is 8mg/mL, and scale inhibition performance is 61.3%
Present copolymer is more suitable for stoping the shape of the upper calcium carbonate scale of coagulator (temperature is higher) in salt water cooling system
Becoming and attachment, present copolymer is as antisludging agent under the conditions of 80 DEG C, and compared with poly-itaconic acid, copolymer concentration is by gathering
8mg/L in itaconic acid is reduced to 6mg/L, and scale inhibition performance improves more than 10% than poly-itaconic acid.
Claims (17)
1. an itaconic acid and the copolymer of 2-acrylamide-2-methylpro panesulfonic acid, it is characterised in that it is by itaconic acid list carboxylic
Acid salt units, itaconic acid dicarboxylate unit, 2-acrylamide-2-methylpro panesulfonic acid unit and 2-acrylamido-2-first
Base propane sulfonic acid salt unit is constituted.
Itaconic acid the most according to claim 1 and the copolymer of 2-acrylamide-2-methylpro panesulfonic acid, its feature exists
In, the number-average molecular weight of described copolymer is 1000-5000, and weight average molecular weight is 1500-6900, it is preferred that number-average molecular weight
For 2500-4000, weight average molecular weight is 3200-5600.
Itaconic acid the most according to claim 1 and 2 and the copolymer of 2-acrylamide-2-methylpro panesulfonic acid, its feature
Being, itaconic acid monocarboxylate unit and itaconic acid dicarboxylate unit sum, with 2-acrylamide-2-methylpro panesulfonic acid list
The ratio of the molar fraction of unit and 2-acrylamide-2-methylpro panesulfonic acid salt unit sum is 1.6-14.1:1.
Itaconic acid the most according to claim 3 and the copolymer of 2-acrylamide-2-methylpro panesulfonic acid, its feature exists
In, the ratio of the molar fraction of itaconic acid dicarboxylate unit and itaconic acid monocarboxylate unit is 0-1:1；2-acrylamido-
The ratio of the molar fraction of 2-methyl propane sulfonic acid unit and 2-acrylamide-2-methylpro panesulfonic acid salt unit is 2-6:9.
5. an itaconic acid and the copolymer of 2-acrylamide-2-methylpro panesulfonic acid, it is characterised in that it is by itaconic acid list carboxylic
Acid salt units, itaconic acid dicarboxylate unit, 2-acrylamide-2-methylpro panesulfonic acid and 2-acrylamido-2-methyl-prop
Sulfonate salt units is constituted, and its preparation method comprises the steps:
A itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid are reacted by () respectively with water soluble alkali, the clothing that preparation part neutralizes
The 2-acrylamide-2-methylpro panesulfonic acid monomer that health acid monomers and part neutralize；Then itaconic acid monomer part neutralized
The 2-acrylamide-2-methylpro panesulfonic acid monomer mixing neutralized with part, obtains monomer mixture；
B () by radical initiator, makes monomer mixture be polymerized in aqueous phase, obtain itaconic acid and 2-acrylamido-2-first
The copolymer of base propane sulfonic acid.
6. a preparation method for itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid copolymer, prepared copolymer by
Itaconic acid monocarboxylate unit, itaconic acid dicarboxylate unit, 2-acrylamide-2-methylpro panesulfonic acid and 2-acrylamide
Base-2-methyl propane sulfonic acid salt unit is constituted, it is characterised in that its preparation method comprises the following steps:
A itaconic acid and 2-acrylamide-2-methylpro panesulfonic acid are reacted by () respectively with water soluble alkali, the clothing that preparation part neutralizes
The 2-acrylamide-2-methylpro panesulfonic acid monomer that health acid monomers and part neutralize, the itaconic acid then part neutralized and portion
Divide the 2-acrylamide-2-methylpro panesulfonic acid monomer mixing neutralized, obtain monomer mixture；With itaconic acid and 2-acrylamide
On the basis of the quality sum of base-2-methyl propane sulfonic acid, the addition of 2-acrylamide-2-methylpro panesulfonic acid be 10wt%～
50wt%；
B () by radical initiator, makes monomer mixture be polymerized in aqueous phase, and obtain itaconic acid and 2-acrylamido-2-
The copolymer of methyl propane sulfonic acid.
Preparation method the most according to claim 6, it is characterised in that the monomer mixture that part neutralizes is adding initiator
During, as a kind of solution, it is simultaneously added dropwise in reactor with initiator.
8. according to the preparation method described in claim 6 or 7, it is characterised in that course of reaction keep reaction temperature at 70 DEG C～
Between 110 DEG C.
9. according to the system in itaconic acid described in any one of claim 6-8 Yu the copolymer of 2-acrylamide-2-methylpro panesulfonic acid
Preparation Method, it is characterised in that in step (a), in itaconic acid and sulfonic acid on the basis of the amount of the material of carboxyl, the neutralization of carboxyl
Degree is 40%～75%, preferably 75%；Water soluble alkali is monoacidic base, preferably sodium hydroxide, potassium hydroxide；Or diacidic base, preferably
Calcium hydroxide.
10. according to the system in itaconic acid described in any one of claim 6-9 Yu the copolymer of 2-acrylamide-2-methylpro panesulfonic acid
Preparation Method, it is characterised in that on the basis of the quality of monomer, initiator addition is 5wt%～7.5wt%；Initiator is selected
Any one material below: potassium peroxydisulfate, sodium peroxydisulfate and Ammonium persulfate., initiator system of ammonium persulfate.
11. according to the copolymer of itaconic acid described in any one of claim 6-10 and 2-acrylamide-2-methylpro panesulfonic acid
Preparation method, it is characterised in that the feed time of monomer solution and initiator is 1.0～3.0 hours, preferably 1.0 hours.
12. according to the preparation method in itaconic acid described in claim 11 Yu the copolymer of 2-acrylamide-2-methylpro panesulfonic acid,
It is characterized in that, course of reaction temperature controls at 80-90 DEG C, preferably 80 DEG C.
13. according to the copolymer in itaconic acid described in any one of claim 6-12 Yu 2-acrylamide-2-methylpro panesulfonic acid, its
It is characterised by, after monomer and initiator dropping, continuation polymerase 10 .5～5 hours, preferably 1.0 hours.
Itaconic acid described in 14. any one of claim 1-4 or claim 5 is total to 2-acrylamide-2-methylpro panesulfonic acid
Polymers application in antisludging agent.
15. application according to claim 14, it is characterised in that described antisludging agent is sea water antisludging agent.
16. application according to claim 15, it is characterised in that under the conditions of antisludging agent application temperature 60 C-80 DEG C, institute
The application concentration stating copolymer is less than equal to 6mg/L.
17. 1 kinds of water treatment agents, including itaconic acid described in any one of claim 1-4 or claim 5 and 2-acrylamido-
The copolymer of 2-methyl propane sulfonic acid is as antisludging agent.
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