CN103420495A - Preparation method for antisludging agent of central air-conditioning circulating water and application thereof - Google Patents
Preparation method for antisludging agent of central air-conditioning circulating water and application thereof Download PDFInfo
- Publication number
- CN103420495A CN103420495A CN2013101927621A CN201310192762A CN103420495A CN 103420495 A CN103420495 A CN 103420495A CN 2013101927621 A CN2013101927621 A CN 2013101927621A CN 201310192762 A CN201310192762 A CN 201310192762A CN 103420495 A CN103420495 A CN 103420495A
- Authority
- CN
- China
- Prior art keywords
- group
- alkyl
- oxyalkylene
- carbon atom
- representative
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention provides a preparation method for an antisludging agent of central air-conditioning circulating water and application thereof. A copolymer (A), a copolymer (B) or a copolymer (C), which is used as a necessary component of the antisludging agent of the central air-conditioning circulating water, is a copolymer having certain weight-average molecular weight, and is gained by polymerizing certain mass of alkyl glycol ether, maleic anhydride and other monomers capable of being copolymerized. The antisludging property of the central air-conditioning circulating water can be provided by copolymer (A), copolymer (B) or copolymer (C) individually, and when the copolymer (A), copolymer (B) or copolymer (C) is in combined utilization, the antisludging property can be improved to a certain extent. The antisludging agent can enable the air-conditioning circulating water to be good in water quality stability property under the condition of air conditioning running temperature, and the acquired stable property cannot be lost along with time within a longer time.
Description
Background technology
The present invention relates to a kind of center air-condition circle water water conditioning chemicals production methods and applications.Be that the present invention is Scale inhibitors production method and the application thereof in a kind of concrete center air-condition circle water Water Treatment Chemicals, the metal ion that this Scale inhibitors can produce incrustation scale in water is combined and is formed water miscible material, this water-soluble substances can long-term stability exist under the operation of air conditioner temperature condition, make air-conditioner circulating water under this condition there is the character of good water conditioning, and the stability property obtained can not passed in time and lose within the longer time.
The fouling of central air-conditioning water quality is air conditioner industry problem in the urgent need to address now, and it is basic Scale inhibitors that existing many suggestions adopt carboxylate salts.But prolongation in time of the carboxylate metal salt-stable of its generation and descending, can separate out the precipitation fouling gradually, and air-conditioning water quality is produced to detrimentally affect.Therefore the purpose of this invention is to provide a kind of air-conditioner circulating water efficient scale performance and prevent scale-inhibiting properties from passing in time and production method and the application of the Scale inhibitors that lowers.
Summary of the invention
Below given concrete multipolymer (A), (B) or a kind of good Scale inhibitors of center air-condition circle water (C) can be provided, it has efficient low temperature scale-inhibiting properties and can prevent from it and can produce the formed dissolved matter stability of incrustation ion increasing in time and decomposing, the character that stops its stability to reduce, when multipolymer (A), (B) or (C), combine while using, its scale-inhibiting properties can have the raising of certain amplitude.
The above-mentioned multipolymer (A) as the necessary component of center air-condition circle water Scale inhibitors is that a kind of weight-average molecular weight is the multipolymer in 5000 to 100000 scopes, the toxilic acid that its method for making is is polymerization single polymerization monomer (I) (meaning with following general formula 1), 50% to 1% (quality) by the alkyl glycol ether of 50% to 99% (quality) be polymerization single polymerization monomer (II) (meaning with following general formula 2) and 0～49% (quality) but other monomer (III) of copolymerization carries out polymerization, (I), the total amount of (II), (III) is 100%.
R
1-C(R
3)＝C(R
2)-R
4-O(R
5O)
PR
6 (1)
R wherein
1, R
2And R
3Represent methylidene group and hydrogen atom separately, R
1, R
2And R
3Can not be methyl group simultaneously, R
4Representative-CH
2-, C (CH
3)-, R
1, R
2, R
3And R
4The total number of carbon atoms be 3, R
5O represents the oxyalkylene group of 2～4 carbon atoms or the mixture of two or more oxyalkylene groups, R
6Representative element hydrogen or the alkyl group that contains 1～20 carbon atom, phenyl group or alkyl phenyl group (alkyl group in the alkyl phenyl group contains 1～20 carbon atom), p is the average addition mole number of oxyalkylene group group, and it represents an integer between 1～85.
HC(COOM
1)＝CH-COX (2)
X representative-OM in formula
2Or-Y-(R
7O) qR
8, and represent hydrogen, M
1And M
2Represent separately monovalent metallic ion, divalent-metal ion, ammonium ion or organic amine, Y representative-O-or-NH-, R
7O represents oxyalkylene group or two kinds and a multiple oxyalkylene group mixture that 2～4 carbon atoms are arranged, R
8The alkyl group of representative element hydrogen or 1～20 carbon atom, phenyl group, alkyl phenyl group, aminoalkyl groups or hydroxyalkyl group (alkyl phenyl group, aminoalkyl groups or hydroxyalkyl group contain 1～20 carbon atom), q is the average addition mole number of oxyalkylene group, it represents an integer of 0～200 ,-COOM
1And-can form an anhydride group between carbon atom that the COX group connects respectively.
Center air-condition circle water Scale inhibitors component copolymers (B) comprises that unit (∏ ') (meaning with general formula 4) that the unit (I ') that the unit alkyl diol ether of repetition is base (meaning with following general formula 3) and dicarboxylic acid are base is as its repeating unit.
R in formula
1To R
3Represent methylidene group and protium separately, R
5O represents that one has the oxyalkylene group of 2～4 carbon Sauerstoffatoms or the mixture of two or more oxyalkylene groups, R
6Representative element hydrogen, the alkyl group that contains 1～20 carbon atom, phenyl group or alkyl phenyl group (alkyl group in the alkyl phenyl group contains 1～20 carbon atom), R
4Representative-(CH
2)
2-or-C (CH
3)
2-, p is the average addition mole number of oxyalkylene group group, it is an integer of 1～200.
-[HC(COOM
1)-CH-COX
1]- (4)
X in formula
1Representative-OM
2Or-Y-(R
7O) qR
8, M
1And `M
2Representative element hydrogen, monovalent metallic ion, divalent-metal ion, ammonium or organic amine separately, Y representative-O-or-NH-, R
7O represents that one has the oxyalkylene group of 2-4 carbon atom or the mixture of two or more oxyalkylene groups, R
8Representative element hydrogen, a 1-20 carbon atom alkyl group, phenyl group, alkyl phenyl group, aminoalkyl groups or hydroxyalkyl group (alkyl group in alkyl group, aminoalkyl group and hydroxyalkyl group contains 1～20 carbon atom), q is the average addition mole number of oxyalkylene group group, it represents an integer of 0～200 ,-COOM
1With-COX
1Can form (CO-O-CO-) group between the carbon atom that group connects respectively.
Above-mentioned multipolymer (C) comprises that unit that alkyl diol ether is base is shown in that the unit that following general formula (5) and dicarboxylic acid are base is shown in that following general formula (6) is as its repeating unit.
R in formula
10O represents that one has the oxyalkylene group of 2～4 carbon atoms or the mixture of two or more oxyalkylene groups, when its can block during for mixture or random state add, R
9Representative-(CH
2)
2-or-C (CH
3)
2-, r is the average addition mole number of oxyalkylene group, it represents an integer between 1～200.
-[CH(COOM
3)-CH(COX
2)]- (6)
X in formula
2Representative-OM
4Or-Z-(R
11O)
sR
12, M
3And M
4Representative element hydrogen, monovalent metallic ion, divalent-metal ion, ammonium or organic amine separately, Z representative-O-or-NH-, R
11O represents oxyalkylene group or two or more oxyalkylene group mixtures of 2～4 carbon atoms, when its can block during for mixture or random state add, R
12Represent hydrogen, alkyl group, phenyl group, alkyl phenyl group, aminoalkyl groups or the hydroxyalkyl group (alkyl group in alkyl group, aminoalkyl group and hydroxyalkyl group contains 1～20 carbon atom) of 1～20 carbon atom are arranged, s is the average addition mole number of oxyalkylene group, it represents an integer of 0～200 ,-COOM
3With-COX
2Can form an anhydride group (CO-O-CO-) between the carbon atom that group connects respectively.
The necessary component copolymers A of center air-condition circle water Scale inhibitors can be by production method preparation in the following example.The method is under a kind of transformation period of radical polymerization initiator is 1.5～300 hours and certain temperature, monomer component is carried out to aqueous solution polymerization, this monomer component comprises unsaturated alkyl glycol ethers polymerization single polymerization monomer (meaning with following general formula 1), 50～1% (quality) toxilic acid polymerization single polymerization monomer (meaning with general formula 2) and polymerisable other monomer of 0～49 (quality) of 50～99% (quality), and three kinds of monomer total amount quality are 100%.
R
1-C(R
3)＝C(R
2)-R
4-O(R
5O)
PR
6 (1)
R wherein
1, R
2And R
3Represent separately protium and methyl group, R
1, R
2And R
3Can not be methyl group simultaneously, R
4Representative-CH
2-,-(CH
2)-, C (CH
3)-, R
1, R
2, R
3And R
4The total number of carbon atoms be 3, R
5O represents the oxyalkylene group of 2～4 carbon atoms or the mixture of two or more oxyalkylene groups, R
6Representative element hydrogen, contain 1～20 carbon atom alkyl group, phenyl group or alkyl phenyl group (alkyl phenyl group in alkyl group contain 1～20 carbon atom), p is the average addition mole number of oxyalkylene group group, and it represents an integer between 1～200.
HC(COOM
1)＝CH-COX (2)
X representative-OM in formula
1Or-Y-(R
7O) qR
8, also can represent hydrogen, M
rMonovalent metallic ion, ammonium ion or organic amine, Y representative-O-or-NH-, R
7O represents oxyalkylene group or two kinds and a multiple oxyalkylene group mixture that 2～4 carbon atoms are arranged, R
8The alkyl group of representative element hydrogen or 1～20 carbon atom, phenyl group, alkyl phenyl group, aminoalkyl groups or hydroxyalkyl group (alkyl phenyl group, aminoalkyl groups or hydroxyalkyl group contain 1～20 carbon atom), q is the average addition mole number of oxyalkylene group, it represents an integer of 0～200 ,-COOM
1And-can form an anhydride group (CO-O-CO-) between carbon atom that the COX group connects respectively.
Entreat aborning in the method for the necessary component copolymers A of air-conditioner circulating water Scale inhibitors 30～85% (quality) of total raw material used when the total amount of monomer used for example can be polymerization.
Entreat aborning in the method for the necessary component copolymers A of air-conditioner circulating water Scale inhibitors, method is the initiator as polyreaction with a kind of persulphate preferably, and the temperature of polyreaction can be at 40-70 ℃, and the total amount of monomer can in above-mentioned scope.
Above-mentioned general formula (1) expression for necessary repeating unit (I '), the monomer (I) that the unsaturated alkyl glycol ethers of for example using above-mentioned general formula (1) to mean is base can be used as the monomer that this repeating unit is provided.The example of monomer (I) has, and for example, by the oxyalkylene group by 1～200 mole, adds to a kind of unsaturated alcohol some compounds as obtained in 3-methyl-3-butene-1-alcohol, 3-M2BOL or 2-M3BOL.These compounds can be used separately wherein one or more mixing to use.
For obtaining the center air-condition circle water efficient scale inhibitor, utilizing the average addition mole number of oxyalkylene group by repeating unit (I ') alkyl diol chain is that to make polymer dissolution be very crucial to 1～200 caused wetting ability in water.Therefore, must in alkyl diol ether chain, will introduce a large amount of oxyalkylene groups, and the use polyglycol chain is best.From polymerizable and wetting ability, have in mind, in the alkyl diol chain, the average addition mole number of addition polymerization oxyalkylene group is 5～100th, more suitable.
(I ") means with general formula (2) necessary repeating unit.For example, the toxilic acid polymerization single polymerization monomer (II) meaned with above-mentioned general formula (2) can be used as the monomer that this repeating unit is provided.The example of monomer (II) has, for example, toxilic acid, maleic anhydride, the half ester of toxilic acid and the alcohol that contains 1～12 carbon atom, the half amide of toxilic acid and the amine that contains 1～twelve carbon atom, half amide and the half ester of toxilic acid and the amino alcohol that contains 1～20 carbon atom, toxilic acid and add to the half ester of the compound (G) of making in alcohol by the oxyalkylene that contains 2～4 carbon atoms by 1～200 mole, the oh group of toxilic acid and the end by compound (G) changes the half amide of the compound that amino group makes into, toxilic acid and the dibasic alcohol that contains 2～4 carbon atoms or enter the half ester of polyalkylene glycol prepared by 2～100 moles of dibasic alcohol by addition, toxilic acid and the dibasic alcohol that contains 2～4 carbon atoms or enter the half amide of the polyalkylene glycol that 2～100 moles of dibasic alcohol prepare by addition, and univalent metal salt divalent metal salt, ammonium salt and organic amine etc.They can use separately or mix use.
(I ") means with above-mentioned general formula (5) above-mentioned repeating unit.Provide repeating unit (examples of monomers of I ") comprises, for example by the oxyalkylene addition by 1～200 mole, enters the unsaturated alcohol in monomer (I), for example, the system in 3-methyl 3-butene-1-ol and methallyl alcohol compound.They can a kind of independent use or two or more mixing uses.
Above-mentioned repeating unit
With general formula (6), mean.This repeating unit is provided
Examples of monomers comprise, for example, the toxilic acid in monomer (II) and monovalent metal salt, divalent metal salt, ammonium salt, organic amine salt and maleic anhydride.They can use separately or two or more mixing or use successively.
For obtaining each component copolymers of center air-condition circle water Scale inhibitors of the present invention (A) (B), in the method for (C), with a kind of initiator, cause above-mentioned those monomer component generation copolyreaction.Copolyreaction can be undertaken by record method, as solution polymerization or mass polymerization etc.
Preparing the necessary component copolymers converging operationJu Hecaozuo of center air-condition circle water Scale inhibitors can take mode in batches or continuously to carry out.Solvent for solution polymerization can be water, methyl alcohol, ethanol and Virahol, the benzene,toluene,xylene of aromatics, straight chain hexanaphthene, normal hexane, the ethyl acetate of ester class, Isoamyl Acetate FCC, ethyl propionate, the acetone of ketone, butanone, pimelinketone etc.From the solubleness of the polymkeric substance of starting monomer and acquisition, have in mind, preferably at least adopting a kind of solvent is the component of the low-carbon alcohol of water and 1～4 carbon atom as solvent.Optimum solvent is water, because can save the removal of solvents operation sequence like this.
In the necessary component copolymers preparation method of center air-condition circle water Scale inhibitors, aqueous solution polymerization has environmental effect and relative cheap cost and the schedule of operation of simplification preferably relatively, when carrying out the aqueous solution polymerization reaction, used water soluble polymeric reaction initiator is as the initiator of reaction, and for example the water-soluble polymeric reaction initiator is by the persulfuric acid salt: ammonium persulphate, Potassium Persulphate or sodium sulfate; Peroxide: hydrogen peroxide, benzoyl peroxide, cyclohexanone peroxide; Azo: azo is two-2-methyl propionyl amidine hydrochloride.These all can be used as the aqueous solution polymerization initiator.Aqueous solution polymerization also can be used promotor as sodium bisulfite, S-WAT, Sodium Pyrosulfite, sodium hypophosphite etc.In this case, promotor should be combined with above-mentioned initiators for polymerization to cause better and control the initiation of polyreaction and control polymerization rate and degree.
As adopt mass polymerization; polyreaction is carried out at 50～200 ℃ of temperature; as use superoxide as hydrogen peroxide, benzoyl peroxide or the azobis isobutyronitrile initiator as polyreaction; sodium hypophosphite is promotor; the multipolymer (A) that polymerization obtains like this (B), (C) can be directly as the main ingredient of central air-conditioning water Scale inhibitors, also can to it, be neutralized with a kind of alkaline matter.Alkaline matter comprises mineral alkali preferably, and as monovalence or divalent metal oxyhydroxide, carbonate, ammoniacal liquor etc., and organic bases is as organic amine etc., and neutralizing treatment can not reduce the relevant art index and often have positive effect.
The repeating unit mass ratio of the component copolymers of center air-condition circle water Scale inhibitors (B) is (I '): (I "): (I " ')=1-99: 99-1: 0-50, optimum proportion is: 60-90: 40-5: 0-10.The repeating unit mass ratio of multipolymer (C) be (I "):
: (III ")=1-99: 99-1: 0-50, optimum proportion is 70-95: 30-5: 0-10.Multipolymer (B) and weight-average molecular weight (C) are 5000 to 100000, and the best is 20000 to 60000.If mass ratio and weight-average molecular weight surpass above-mentioned scope, scale inhibition efficiency will reduce in various degree, can not obtain the center air-condition circle water Scale inhibitors that scale-inhibiting properties is good.
The optimized method for production of producing center air-condition circle water Scale inhibitors, particularly multipolymer of the present invention (A) is as follows:
Initiator with a kind of persulphate as polyreaction, the transformation period of solution polymerization initiator is 1.5 to 300h, and the temperature of aqueous solution polymerization reaction is 40～70 ℃, and the monomer total amount is total raw material used 40～70%.
Wishing to get the present invention has the polymer antisludging agent of certain molecular weight, and polyreaction must be 1.5～300h in half-lives of initiators, the best be 5 to 250h and the certain temperature condition under carry out.For example, when with persulphate, making initiator, polyreaction must be carried out under 40 to 70 ℃, the temperature condition that the best is 50 to 65 ℃.The initiator of polyreaction also can dropwise join reactor in Ah in can when starting, adding reactor, and these methods can combine use on demand.The time of polyreaction is 3 to 7h better, 4 to 5h the bests.Exceed above-mentioned scope, polyreaction degree or productive rate have impact in various degree.The monomer total amount is 40 to 70% of material total amount, and the best is 50 to 60%.Exceed above-mentioned scope, the degree of polyreaction or productive rate have disadvantageous effect in various degree.Monomer (I) is preferably in before reaction starts and adds reactor, monomer (II) and (III) can when the reaction beginning, add and also can dropwise join reactor.Perhaps two kinds of methods are combined to use.In addition, monomer (II) and if ratio (III) be 0～70% to be greater than 70%, the scale-inhibiting properties of polymkeric substance has reduction.After polyreaction finishes, it is necessary being hydrolyzed on demand with neutralization operation.
Multipolymer (A) can be directly as the main component of high-temperature water Scale inhibitors, or also can with alkaline matter, neutralize on demand.As use basic metal or alkaline earth metal hydroxides, as alkaline matters such as sodium hydroxide, potassium hydroxide.
In the various polyreactions of the necessary component copolymers of above-mentioned center air-condition circle water Scale inhibitors, can use on demand one or more chain-transfer agents, as thioglycol, thioglycerol, ethyl thioglycollic acid, 2-ethyl thioglycollic acid, 3-coloured glaze base propionic acid, 2-coloured glaze base ethane sulfonic acid etc.
The necessary component copolymers (A) of center air-condition circle water Scale inhibitors, (B) and mixture (C) or be dissolved in water after making the aqueous solution and be added to the water the direct main ingredient as the center air-condition circle water Scale inhibitors, also can be combined with other water conditioner.These water conditioners comprise conventional inhibiter, tensio-active agent, oxygen scavenger etc.
Multipolymer (A), (B) and (C) add-on be 0.015% to 1.2% of center air-condition circle water quality, preferred range is 0.02%～0.6%.Adding of they can produce many obvious scale effects.If lower than 0.015%, the Scale inhibitors added can not obtain gratifying performance.Be greater than 1.2%, performance can not be further improved and be inappropriate economically.
When central air-conditioner circulating water water conditioner contains multipolymer (A), (B) and (C) and during other components outside multipolymer, multipolymer and other components can add respectively, also can add, and can not affect the stabilizing water quality effect simultaneously.
Center air-condition circle water Scale inhibitors of the present invention is not subject to the restriction of above-mentioned thinking.
The necessary component copolymers of center air-condition circle water Scale inhibitors of the present invention (A) is as main component, and because multipolymer (A) monomer whose ratio and weight-average molecular weight limit, therefore adopt Scale inhibitors of the present invention can produce very high scale inhibition effect and can prevent along with the deteriorated consequence of the prolongation scale inhibition effect of time, thereby overcoming the product dirt problem often occurred in center air-condition circle water.
Center air-condition circle water Scale inhibitors of the present invention can obtain high scale inhibition performance, can prevent that scale inhibition performance from reducing in time, this is because the center air-condition circle water Scale inhibitors comprises multipolymer (B) and the active principle of increase soluble substance stability such as (C).Therefore, when adopting this Scale inhibitors combination, just can make the efficient scale rate can be provided Scale inhibitors for center air-condition circle water.
Embodiment
The necessary component copolymers preparation of following center air-condition circle water Scale inhibitors and Application Example can further illustrate the present invention.But the present invention is not limited by these.In following these embodiment, if no special instructions, " % " refers to mass percent, and " umber " refers to mass percent.
Embodiment 1: the production of center air-condition circle water Scale inhibitors X
In 1 ton of enamel reaction still, add 50kg distilled water, 350kg by unsaturated alcohol, 200kg maleic anhydride that 35 moles of ethylene oxide and the addition reaction of 3-methyl-3-butene-1-alcohol are made, the temperature of reactor is increased to 60 ℃.The 25kg distilled water solution that will dissolve the 1.0kg Sodium Persulfate in 240min is added dropwise in reactor.Make the interior temperature of reactor maintain the 60min polyreaction under 60 ℃ of conditions and complete, obtain the aqueous solution that a kind of polymkeric substance is the center air-condition circle water Scale inhibitors, the weight-average molecular weight of this polymkeric substance is 35000.
Embodiment 2: the production of center air-condition circle water Scale inhibitors Y
In one ton of reactor, add 130kg ion exchanged water, 400kg by unsaturated alcohol, 220kg maleic anhydride that 35 moles of ethylene oxide and the addition reaction of 3-methyl-3-butene-1-alcohol are made, the temperature of reactor is increased to 65 ℃.The 50kg ion-exchange aqueous solution that will dissolve the Sodium Persulfate of 1.0kg in 200min is added dropwise in reactor.Make the interior temperature of reactor maintain the 60min polyreaction under 65 ℃ of conditions and complete, obtain the aqueous solution that a kind of polymkeric substance is the center air-condition circle water Scale inhibitors, the weight-average molecular weight of this polymkeric substance is 25000.
Embodiment 3: test medium: 80 ℃ of tap water and preparation water: the pH value of with NaOH and HCl, regulating the aqueous solution; Use analytical pure CaCl
2Ca in regulator solution
2+Content.The chemical composition of tap water is: pH7.6, Ca
2+67mg/L, Mg
2+28mg/L, Cl-15mg/L,
SiO
218mg/L.
The Scale inhibitors scale inhibition effect relatively
Adopt the static-state scale inhibition method to study X, two kinds of high temperature Scale inhibitorss of Y under working concentration 5mg/L, the scale inhibition effect in the tap water of 70 ℃ and preparation water, the results are shown in Table 1.
Scale inhibition performance/the % of table 1 Scale inhibitors in 100 ℃ of water
By table 1, found out, in tap water and preparation water, the scale inhibition performance of X is better than Y.This is because the high-temperature stability of Y complex compound not as X unboiled water solution occurred frequently, makes its scale inhibition ability reduce.
And X not only has higher high temperature resistant property, and also contain the amino groups beyond carboxyl in molecule, therefore have and suppress preferably CaCO
3The ability that dirt forms.
Claims (6)
1. a center air-condition circle water Scale inhibitors, comprise multipolymer (A), (B) or (C), as multipolymer (A), (B) or (C) combine while using and have to a certain degree synergistic effect, its scale-inhibiting properties can have the raising of certain amplitude, wherein the multipolymer of main ingredient (A) is that a kind of weight-average molecular weight is the multipolymer in 5000 to 100000 scopes, its method for making is to be polymerization single polymerization monomer (I) (meaning with following general formula 1) by the alkyl glycol ether of 50 to 99% (quality), the toxilic acid of 50 to 1% (quality) be polymerization single polymerization monomer (II) (meaning with following general formula 2) and 0～49% (quality) but other monomer (III) of copolymerization carries out polymerization, (I), (II), (III) total amount is 100%.
R
1-C(R
3)＝C(R
2)-R
4-O(R
5O)
pR
6
(1)
R wherein
1, R
2And R
3Represent methylidene group and hydrogen atom separately, R
1, R
2And R
3Can not be methyl group simultaneously, R
4Representative-CH
2-, C (CH
3)-, R
1, R
2, R
3And R
4The total number of carbon atoms be 3, R
5O represents the oxyalkylene group of 2～4 carbon atoms or the mixture of two or more oxyalkylene groups, R
6Representative element hydrogen or the alkyl group that contains 1～20 carbon atom, phenyl group or alkyl phenyl group (alkyl group in the alkyl phenyl group contains 1～20 carbon atom), p is the average addition mole number of oxyalkylene group group, and it represents an integer between 1～85.
HC(COOM
1)＝CH-COX
(2)
X representative-OM in formula
2Or-Y-(R
7O) qR
8, x represents hydrogen, M
1And M
2Represent separately monovalent metallic ion, divalent-metal ion, ammonium ion or organic amine, Y representative-O-or-NH-, R
7O represents oxyalkylene group or two kinds and a multiple oxyalkylene group mixture that 2～4 carbon atoms are arranged, R
8The alkyl group of representative element hydrogen or 1～20 carbon atom, phenyl group, alkyl phenyl group, aminoalkyl groups or hydroxyalkyl group (alkyl phenyl group, aminoalkyl groups or hydroxyalkyl group contain 1～20 carbon atom), q is the average addition mole number of oxyalkylene group, it represents an integer of 0～200 ,-COOM
1And-can form an anhydride group between carbon atom that the COX group connects respectively.
2. a center air-condition circle water Scale inhibitors component copolymers (B) comprises that unit (∏ ') (meaning with general formula 4) that the unit (I ') that the unit alkyl diol ether of repetition is base (meaning with following general formula 3) and dicarboxylic acid are base is as its repeating unit.
R in formula
1To R
3Represent methylidene group and protium separately, R
5O represents that one has the oxyalkylene group of 2～4 carbon Sauerstoffatoms or the mixture of two or more oxyalkylene groups, R
6Representative element hydrogen, the alkyl group that contains 1～20 carbon atom, phenyl group or alkyl phenyl group (alkyl group in the alkyl phenyl group contains 1～20 carbon atom), R
4Representative-(CH
2)
2-or-C (CH
3)
2-, p is the average addition mole number of oxyalkylene group group, it is an integer of 1～200.
X in formula
1Representative-OM
2Or-Y-(R
7O) qR
8, M
1And `M
2Representative element hydrogen, monovalent metallic ion, divalent-metal ion, ammonium or organic amine separately, Y representative-O-or-NH-, R
7O represents that one has the oxyalkylene group of 2-4 carbon atom or the mixture of two or more oxyalkylene groups, R
8Representative element hydrogen, a 1-20 carbon atom alkyl group, phenyl group, alkyl phenyl group, aminoalkyl groups or hydroxyalkyl group (alkyl group in alkyl group, aminoalkyl group and hydroxyalkyl group contains 1～20 carbon atom), q is the average addition mole number of oxyalkylene group group, it represents an integer of 0～200 ,-COOM
1With-COX
1Can form an anhydride group between the carbon atom that group connects respectively.
3. a center air-condition circle water Scale inhibitors component copolymers (C) comprises that unit that alkyl diol ether is base is shown in that the unit that following general formula (5) and dicarboxylic acid are base is shown in that following general formula (6) is as its repeating unit.
R in formula
10O represents that one has the oxyalkylene group of 2～4 carbon atoms or the mixture of two or more oxyalkylene groups, when its can block during for mixture or random state add, R
9Representative-(CH
2)
2-or-C (CH
3)
2-, r is the average addition mole number of oxyalkylene group, it represents an integer between 1～200.
X in formula
2Representative-OM
4Or-Z-(R
11O)
sR
12, M
3And M
4Representative element hydrogen, monovalent metallic ion, divalent-metal ion, ammonium or organic amine separately, Z representative-O-or-NH-, R
11O represents oxyalkylene group or two or more oxyalkylene group mixtures of 2～4 carbon atoms, when its can block during for mixture or random state add, R
12Represent hydrogen, alkyl group, phenyl group, alkyl phenyl group, aminoalkyl groups or the hydroxyalkyl group (alkyl group in alkyl group, aminoalkyl group and hydroxyalkyl group contains 1～20 carbon atom) of 1～20 carbon atom are arranged, s is the average addition mole number of oxyalkylene group, it represents an integer of 0～200 ,-COOM
3With-COX
2Can form an anhydride group (CO-O-CO-) between the carbon atom that group connects respectively.
4. a production method of producing multipolymer claimed in claim 1 (A).The necessary component copolymers A of center air-condition circle water Scale inhibitors production method is under a kind of transformation period of radical polymerization initiator is 1.5～300 hours and certain temperature, monomer component is carried out to aqueous solution polymerization, the temperature of polyreaction can be at 40～90 ℃, this monomer component comprises unsaturated alkyl glycol ethers polymerization single polymerization monomer, 50～1% (quality) toxilic acid polymerization single polymerization monomer and polymerisable other monomer of 0～49 (quality) of 50～99% (quality), and three kinds of monomer total amount quality are 100%.
5. the described center air-condition circle water scale inhibitor poly of claims 1 compound, polyreaction must be 1.5～300h in half-lives of initiators, the best be 5 to 250h and the certain temperature condition under carry out.
6. the described center air-condition circle water scale inhibitor poly of claims 1 compound, polyreaction must be carried out under 40 to 70 ℃, the temperature condition that the best is 50 to 65 ℃; Polyreaction the time to hear be 3 to 7h better, 4 to 5h the bests.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101927621A CN103420495A (en) | 2013-05-13 | 2013-05-13 | Preparation method for antisludging agent of central air-conditioning circulating water and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101927621A CN103420495A (en) | 2013-05-13 | 2013-05-13 | Preparation method for antisludging agent of central air-conditioning circulating water and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103420495A true CN103420495A (en) | 2013-12-04 |
Family
ID=49645937
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013101927621A Pending CN103420495A (en) | 2013-05-13 | 2013-05-13 | Preparation method for antisludging agent of central air-conditioning circulating water and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103420495A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9714181B2 (en) | 2014-01-03 | 2017-07-25 | Guangzhou Special Pressure Equipment Inspection And Research Institute | Terpolymerized corrosion and scale inhibitor used in circulating cooling water of central air conditioning and its preparation method |
| US9714182B2 (en) | 2014-01-03 | 2017-07-25 | Guangzhou Special Pressure Equipment Inspection And Research Institute | Phosphorus-free corrosion and scale inhibitor used in circulating cooling water of central air conditioning and its preparation method |
| CN117553385A (en) * | 2024-01-08 | 2024-02-13 | 联科信达物联网有限公司 | Monitoring terminal for central air conditioner intelligent management and control platform |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073115A (en) * | 2013-01-07 | 2013-05-01 | 辽宁工业大学 | High-temperature water scale inhibitor as well as preparation method and application thereof |
-
2013
- 2013-05-13 CN CN2013101927621A patent/CN103420495A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073115A (en) * | 2013-01-07 | 2013-05-01 | 辽宁工业大学 | High-temperature water scale inhibitor as well as preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9714181B2 (en) | 2014-01-03 | 2017-07-25 | Guangzhou Special Pressure Equipment Inspection And Research Institute | Terpolymerized corrosion and scale inhibitor used in circulating cooling water of central air conditioning and its preparation method |
| US9714182B2 (en) | 2014-01-03 | 2017-07-25 | Guangzhou Special Pressure Equipment Inspection And Research Institute | Phosphorus-free corrosion and scale inhibitor used in circulating cooling water of central air conditioning and its preparation method |
| CN117553385A (en) * | 2024-01-08 | 2024-02-13 | 联科信达物联网有限公司 | Monitoring terminal for central air conditioner intelligent management and control platform |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105713151A (en) | Application and preparation method of concrete superplasticizer with phosphorous acid group | |
| CN104031216B (en) | A kind of polyether-amide type high-efficiency water-reducing agent of poly-carboxylic acid and preparation method thereof | |
| CN101830663B (en) | Collapse protective poly-carboxylic acid water reducing agent and preparation method thereof | |
| CN102674568B (en) | Phosphate-free copolymer dirt dispersion agent and preparation method thereof | |
| CA2488415A1 (en) | Cement admixture having superior water-reducing properties and method for preparing the same | |
| CN103482897A (en) | Block poly-carboxylic acid concrete high-efficiency water reducing agent and preparation method thereof | |
| JPH0138408B2 (en) | ||
| JP2011525546A (en) | Aqueous solutions containing copolymers having polyether side chains | |
| CN104371078A (en) | Preparation method of hyperbranched type polycarboxylic acid copolymer cement dispersant | |
| CN103420495A (en) | Preparation method for antisludging agent of central air-conditioning circulating water and application thereof | |
| CN103788306A (en) | Preparation method of methylallyl polyoxyethylene ether type polycarboxylic water reducing agent | |
| CN102093520A (en) | Preparation method of hyperbranched polycarboxylic acid copolymer cement dispersant | |
| CN103788307A (en) | Preparation method of novel concrete slump retaining agent based on allyl polyoxyethylene ether | |
| CN102241800A (en) | Preparation method for polycarboxylate high-performance water reducer | |
| CN105348451A (en) | A self-anticorrosion polycarboxylate water reducing agent and a preparing method thereof | |
| CN109942754A (en) | The method that atom transfer radical polymerization prepares retardation setting type super plasticizer | |
| JPH0136486B2 (en) | ||
| JP2011072851A (en) | Scale inhibitor containing amino group-containing copolymer | |
| JP4243126B2 (en) | Method for producing (meth) acrylic acid copolymer | |
| CN103073115A (en) | High-temperature water scale inhibitor as well as preparation method and application thereof | |
| JP2004217899A5 (en) | (Meth) acrylic acid-based copolymer, production method thereof and use thereof | |
| JPS6121486B2 (en) | ||
| CN105504135A (en) | Method for preparing sodium salt derivative of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid copolymer | |
| CN106117452A (en) | A kind of slow formula shape high-performance polycarboxylic acids water reducing agent and preparation method thereof | |
| JPH0136487B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C05 | Deemed withdrawal (patent law before 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20131204 |