CN101983944B - Polycarboxylic acids water reducing agent containing low molecular weight carbon dioxide copolymer, and preparation method thereof - Google Patents
Polycarboxylic acids water reducing agent containing low molecular weight carbon dioxide copolymer, and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polycarboxylic acids water reducing agent containing low molecular weight carbon dioxide copolymer, which is a copolymerization product of unsaturated large monomer, polyethylene glycol monomethyl ether monounsaturated acid ester, cyclic monomer and other unsaturated monomer containing low molecular weight carbon dioxide copolymer, wherein the low molecular weight carbondioxide copolymer is the copolymer of the carbon dioxide and the epoxy compound. In the invention, the low molecular product generated by the copolymerization reaction of the carbon dioxide and the epoxy compound is used. According to the reasonable design of the molecular structure, the low molecular carbon dioxide copolymer is esterified for blocking to generate the unsaturated large monomer, and then the novel polycarboxylic acids water reducing agent with long/short functional branch is prepared through the copolymerization of the unsaturated large monomer and other functional monomer. The polycarboxylic acids water reducing agent for concrete has stable product quality, and the preparation method has the advantages of short process, simple technology, easily controlled reaction condition, and easy industrial production.
Description
Technical field
The present invention relates to a kind of novel green cement water reducing agent and preparation method thereof, specifically a kind of poly carboxylic acid series water reducer that contains the lower molecular weight carbon dioxide copolymer and preparation method thereof.
Technical background
In Concrete Industry now, development along with engineerings such as the skyscraper of water power, traffic, hundred multilayers, bridge spanning the sea, airport, high-speed railway, subbottom tunnels, mix high performance water reducer and reduce unit consumption of water, become the industry common recognition thereby effectively improve concrete weather resistance, high strength, high workability.The exploitation of high efficiency water reducing agent and use have become a core technology of high performance concrete.The exploitation of cement water reducing agent and use have been experienced sulfonated lignin, naphthalene system and melamine based water reducer progressively to the evolution of polycarboxylate high performance water-reducing agent.Compare with traditional water reducer, poly carboxylic acid series water reducer by long-chain branch polyoxyethylene groups and short-chain branch suede fixed layer (such as-OH ,-SH ,-COR ,-CONH
2,-CN ,-NH
2,-COO
-,-SO
3 -) the super plasticizing of formation distinctive " comb shape " structure, these hydrophilic radicals are by effects such as absorption, electrostatic repulsion, sterically hindered, moistened surfaces, provide dispersed and dispersed to cement granules and keep, greatly improved concrete flowability and flowing property hold facility.
Poly carboxylic acid series water reducer at first is the concrete admixture by Japan's exploitation and application, and has realized suitability for industrialized production in the nineties in 20th century; The research emphasis of the states such as America and Europe has also turned to polycarboxylic acid series, and a plurality of launch products are successively arranged.By contrast, the time of domestic research poly carboxylic acid series water reducer is shorter, and the production technique of product, raw-material selection and technology control etc. are all ripe not as good as external.
Open the technology of utilizing of novel carbon source take carbonic acid gas and epoxy compounds as the carbon dioxide copolymer of representative, had the industrial prospect of large-scale production.Take carbonic acid gas as raw material synthetic macromolecule amount carbon dioxide copolymer, be expected to be applied at aspects such as degradable medical packaging material, ceramic sizing agent and matrix materials.It is various urethane and the polyethers that catalyzer has prepared carbon dioxide copolymer and different molecular weight that US Patent No. P3585168, USP3900424 and USP3953383 adopt zinc alkyl(s)/active hydrogen compounds.The molecular weight that the catalyzer that Chinese patent application 00136189.9 adopts rare earth compounding/metallorganics/polyol/annular lactone to form, catalysis gained carbon dioxide copolymerization close product surpasses 100,000.Feng Chao in Chinese invention patent CN101220534A with low-molecular-weight carbon dioxide copolymer (M
n=4,000～8,000) PLLA or the poly butyric ester with high molecular prepared a kind of full-biological degradation nonwoven cloth material.Low-molecular-weight carbon dioxide copolymer is used for the synthetic of poly carboxylic acid series water reducer still not to be reported.
Summary of the invention
The object of the present invention is to provide a kind of novel polycarboxylic acid series water reducing agent that contains the lower molecular weight carbon dioxide copolymer and preparation method thereof, make product performance stable, and preparation method's mild condition, technique are simple.
In order to reach above-mentioned purpose, solution of the present invention is:
A kind of poly carboxylic acid series water reducer that contains the lower molecular weight carbon dioxide copolymer is characterized in that this water reducer is the copolymerization product that contains lower molecular weight carbon dioxide copolymer, poly glycol monomethyl ether cholesterol acid esters, cyclic monomer and other unsaturated monomers.Wherein, described lower molecular weight carbon dioxide copolymer is the multipolymer of carbonic acid gas and epoxy compounds, its molecular formula W
1Represented by formula (a):
R＝H，CH
3，
R
1＝OH，H；
x＝0.05-0.8；
N is integer, between 1 to 20;
The lower molecular weight carbon dioxide copolymer is carbonic acid gas-ethylene oxide copolymer, carbon dioxide-epoxy propane copolymer, carbon dioxide-cyclohexene oxide copolymer, carbonic acid gas-Styrene oxide 98min. multipolymer, carbon dioxide-epoxy propane-oxyethane terpolymer, carbonic acid gas-oxyethane-cyclohexene oxide terpolymer, a kind of in carbon dioxide-epoxy propane-cyclohexene oxide terpolymer or carbon dioxide-epoxy propane-Styrene oxide 98min. terpolymer, two or three mixes;
The molecular formula W of described poly glycol monomethyl ether cholesterol acid esters
2Represented by formula (b):
M is the integer between 5-200;
Described cyclic monomer and other unsaturated monomers are the mixture of a kind of, two or more components in oxyethane, propylene oxide, cyclohexene oxide, Styrene oxide 98min., methacrylic acid, unsaturated sulfonic acid or its salt, unsaturated amides, methacrylic ester or its salt, unsaturated dicarboxylic acid salt and the acid anhydrides thereof, wherein:
(1) unsaturated sulfonic acid or its salt are the mixture of a kind of, two or three component in vinyl sulfonic acid or its salt, α-sodium olefin sulfonate, methallylsulfonic acid sodium, styrene sulfonic acid or its salt;
(2) unsaturated amides is one or both the mixture in acrylamide, the 2-Methacrylamide;
(3) methacrylic ester is the mixture of a kind of, two or more components in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate and the sodium salt of methacrylic acid;
(4) unsaturated dicarboxylic acid and acid anhydrides thereof are the mixture of a kind of, two or more components in maleic acid, fumaric acid, MALEIC ANHYDRIDE, the fumaric acid anhydride.
The number-average molecular weight of described lower molecular weight carbon dioxide copolymer is 350～2800.
The described preparation method who contains the poly carboxylic acid series water reducer of lower molecular weight carbon dioxide copolymer comprises following reactions steps:
The first step, esterification end capping: take the sulphonated polystyrene resin of acidifying as catalyzer, with lower molecular weight carbon dioxide copolymer and MALEIC ANHYDRIDE, perhaps lower molecular weight carbon dioxide copolymer and methacrylic acid, the perhaps mixture of lower molecular weight carbon dioxide copolymer and MALEIC ANHYDRIDE and methacrylic acid, at 60～90 ℃, esterification is 3～6 hours under the reduced pressure, remove solid acid, obtain the lower molecular weight carbon dioxide copolymer of MALEIC ANHYDRIDE end-blocking and the mixture of residue MALEIC ANHYDRIDE, the perhaps mixture of the lower molecular weight carbon dioxide copolymer of methacrylic acid blocked and residue methacrylic acid, perhaps the lower molecular weight carbon dioxide copolymer of methacrylic acid and MALEIC ANHYDRIDE mixture end-blocking and residue methacrylic acid and remain the mixture of MALEIC ANHYDRIDE;
Second step, copolymerization: one or both in ammonium persulphate, Sodium Persulfate, the Potassium Persulphate are as initiator, with the resulting mixture of esterification end capping in the first step, deionized water, poly glycol monomethyl ether cholesterol acid esters, cyclic monomer and other unsaturated monomers are introduced in the reactor, at 60～95 ℃ of lower copolymerizations that occur, the reaction times is 3～8 hours; After polyreaction finishes, cooling, regulating pH with alkali lye is 7～8, obtains red-brown or brown yellow transparent liquid, is the poly carboxylic acid series water reducer that the present invention contains the lower molecular weight carbon dioxide copolymer.
The described poly carboxylic acid series water reducer that contains the lower molecular weight carbon dioxide copolymer in massfraction by all or part of being polymerized in the following raw materials according:
10～150 parts of one or more of the resulting mixture of the first step esterification end capping,
30～150 parts of poly glycol monomethyl ether cholesterol acid esters,
5～35 parts of unsaturated sulfonic acid or its salt,
3～35 parts of acrylamides,
3～30 parts of methacrylic acids,
3～35 parts of methacrylic ester or its salt
5～80 parts of oxyethane, propylene oxide, cyclohexene oxide or Styrene oxide 98min.s,
5～60 parts on unsaturated dicarboxylic acid and acid anhydrides thereof,
0.05～15 part of ammonium persulphate, Sodium Persulfate or Potassium Persulphate,
260～900 parts of deionized waters.
In the described esterification end capping process, the mol ratio n of the mixture of methacrylic acid, MALEIC ANHYDRIDE or methacrylic acid and maleic acid and lower molecular weight carbon dioxide copolymer is in the scope of 5: 1≤n≤1: 1, and excessive methacrylic acid, MALEIC ANHYDRIDE or methacrylic acid need not separate with the mixture of maleic acid and be directly used in polyreaction after the esterification.
The existence form of described lower molecular weight carbon dioxide copolymer in the gained poly carboxylic acid series water reducer has following two kinds:
(1) the lower molecular weight carbon dioxide copolymer becomes a kind of long-chain branch in polymkeric substance, its general molecular formula W
3Represented by formula (c);
Or
R
1，R
2，R
3＝H，CH
3；
M
1＝H，Na，NH
4；
M
2=H, Na, NH
4, or CH
3, C
2H
5, C
4H
7
M
3＝H，CH
3，Na，NH
4；
Wherein, a, b, c, d, e, f are the molar fractions of each component, and a+b+c+d+e+f=1.0;
(2) or the lower molecular weight carbon dioxide copolymer in polymkeric substance, form cross-linking set, the general structure W of its crosslinking structure multipolymer
4(d) is expressed as by formula:
Or:
Or:
The present invention utilizes the lower molecular weight carbon dioxide copolymer, by rational Molecular Structure Design, first with lower molecular weight carbon dioxide copolymer esterification end-blocking, and then with poly glycol monomethyl ether cholesterol acid esters, cyclic monomer and other unsaturated monomer copolymerizations, prepare the novel poly carboxylic acid series water reducer with length/functional side chain of weak point, thereby realized purpose of the present invention.
Compared with prior art, advantage of the present invention:
One, provides a kind of method of utilizing greenhouse gases carbonic acid gas synthetic macromolecule fine chemical product, and can fully utilize the low molecular weight product that produces in the high molecular carbon dioxide copolymer production of resins process, cheap and have a good social benefit;
Two, remove easily and regenerate at lower molecular weight carbon dioxide copolymer esterification end capping rear catalyst, the mixture that esterification obtains can directly use in copolymerization;
In a word, the preparation method who contains the novel poly carboxylic acid series water reducer of lower molecular weight carbon dioxide copolymer provided by the invention has that flow process is short, technique is simple, reaction conditions is easily controlled, be easy to the advantages such as industrialization production.
Embodiment
Embodiment of the present invention provides a kind of novel poly carboxylic acid series water reducer that contains the lower molecular weight carbon dioxide copolymer and preparation method thereof, this water reducer is all or part of employing ammonium persulphate initiator system by following each component, and copolymerization generates distinctive " comb shape " super plasticizing structure in water solvent.Weight fraction according to reactant composition is
The lower molecular weight carbon dioxide copolymer of MALEIC ANHYDRIDE end-blocking and the mixture that remains MALEIC ANHYDRIDE, perhaps, lower molecular weight carbon dioxide copolymer and the residue of (methyl) vinylformic acid end-blocking, (methyl) acrylic acid mixture, perhaps, lower molecular weight carbon dioxide copolymer and the residue of (methyl) vinylformic acid and MALEIC ANHYDRIDE mixture end-blocking, the mixture of (methyl) vinylformic acid and residue MALEIC ANHYDRIDE, (a) 10～150 parts
30～150 parts of poly glycol monomethyl ether cholesterol acid esters,
5～35 parts of unsaturated sulfonic acid or its salt,
3～35 parts of acrylamides,
3～30 parts in (methyl) vinylformic acid,
3～35 parts of (methyl) acrylate or its salt
5～80 parts of oxyethane, propylene oxide, cyclohexene oxide or Styrene oxide 98min.s,
5～60 parts on unsaturated dicarboxylic acid (salt) and acid anhydrides thereof,
0.05～15 part of ammonium persulphate, Sodium Persulfate or Potassium Persulphate,
260～900 parts of deionized waters.
In polymerization process, according to mass ratio each component is fed intake, and under 50～98 ℃ temperature, adopting the persulphate initiator system, the red-brown that obtains after the polymerization in aqueous phase solution or brown color homogeneous liquid are the novel poly carboxylic acid series water reducer that contains the lower molecular weight carbon dioxide copolymer.
The present invention is further illustrated below by specific embodiment:
Embodiment 1:
Be 350～2400 lower molecular weight carbon dioxide copolymer 48.7g with number-average molecular weight, MALEIC ANHYDRIDE 5g, sulfonated polystyrene 8g adds in the reactor, after stirring, heating also maintains the temperature at 80 ± 5 ℃ of lower reaction 4h, obtains the lower molecular weight carbon dioxide copolymer of MALEIC ANHYDRIDE end-blocking and the mixture of residue MALEIC ANHYDRIDE.
Then, in the reactor of being furnished with agitator, thermometer, Dropping feeder, reflux exchanger, add 540g deionized water, 20g sodium vinyl sulfonate, after being warming up to 75 ℃, in 5h, introduce the mixture, 6g propylene oxide, 125g poly glycol monomethyl ether monomethacrylates, 22g vinylformic acid, 15g butyl methacrylate of 48g lower molecular weight carbon dioxide copolymer-MALEIC ANHYDRIDE esterification end-blocking product and residue MALEIC ANHYDRIDE, 2.5% ammonium persulfate solution 80g in the aforesaid reaction vessel, temperature of reaction is controlled at 75 ± 5 ℃, and polyreaction is finished.Cool off adding sodium hydroxide neutralization in the backward polymerization system, regulate pH=7～8, obtain polycarboxylic acid series high-performance cement water reducing agent of the present invention, with this water reducer called after mx-1.
Embodiment 2:
Be 350～2400 lower molecular weight carbon dioxide copolymer 48.7g with number-average molecular weight, MALEIC ANHYDRIDE 5g, sulfonated polystyrene 8g adds in the reactor, after stirring, heating also maintains the temperature at 80 ± 5 ℃ of lower reaction 4h, obtains the lower molecular weight carbon dioxide copolymer of MALEIC ANHYDRIDE end-blocking and the mixture of residue MALEIC ANHYDRIDE.
Then, disposing agitator, thermometer, Dropping feeder, add the 536g deionized water in the reactor of reflux exchanger, the 20g sodium vinyl sulfonate, 24g poly glycol monomethyl ether monomethacrylates, after being warming up to 75 ℃, in 3h, in aforesaid reaction vessel, introduce 48g lower molecular weight carbon dioxide copolymer-MALEIC ANHYDRIDE esterification end-blocking product and the mixture that remains MALEIC ANHYDRIDE, the 6g propylene oxide, 100g poly glycol monomethyl ether monomethacrylates, 22g vinylformic acid, the 15g butyl methacrylate, the 15g acrylamide, 2.5% ammonium persulfate solution 80g, temperature of reaction is controlled at 75 ± 5 ℃, and polyreaction is finished.Add the sodium hydroxide neutralization after the cooling, regulate pH=7～8, obtain polycarboxylic acid series high-performance cement water reducing agent of the present invention, with this water reducer called after mx-2.
Embodiment 3:
Be 350～2400 lower molecular weight carbon dioxide copolymer 48.7g with number-average molecular weight, MALEIC ANHYDRIDE 5g, sulfonated polystyrene 8g adds in the reactor, after stirring, heating also maintains the temperature at 80 ± 5 ℃ of lower reaction 4h, obtains lower molecular weight carbon dioxide copolymer-MALEIC ANHYDRIDE esterification end-blocking product and the mixture that remains MALEIC ANHYDRIDE.
Then, in the reactor that disposes agitator, thermometer, Dropping feeder, reflux exchanger, add 616g deionized water, 2.0g ammonium persulphate, after being warming up to 75 ℃, in 5h, in aforesaid reaction vessel, introduce 24g lower molecular weight carbon dioxide copolymer-MALEIC ANHYDRIDE esterification products and the mixture, 10g sodium vinyl sulfonate, 124g poly glycol monomethyl ether monomethacrylates, the 20g vinylformic acid that remain MALEIC ANHYDRIDE, temperature of reaction is controlled at 85 ± 5 ℃, after dropwising, under this temperature, continue reaction 1h.Add the sodium hydroxide neutralization after the cooling, regulate pH=7～8, obtain polycarboxylic acid series high-performance cement water reducing agent of the present invention, with this water reducer called after mx-3.
Embodiment 4:
Be 350～2400 lower molecular weight carbon dioxide copolymer 97.4g with number-average molecular weight, MALEIC ANHYDRIDE 10g, sulfonated polystyrene 16g adds in the reactor, after stirring, heating also maintains the temperature at 80 ± 5 ℃ of lower reaction 4h, obtains lower molecular weight carbon dioxide copolymer-MALEIC ANHYDRIDE esterification products and the mixture that remains MALEIC ANHYDRIDE.
Then, in the reactor that disposes agitator, thermometer, Dropping feeder, reflux exchanger, add 783.0g deionized water, 3.0g ammonium persulphate, after being warming up to 75 ℃, in 3h, in aforesaid reaction vessel, drip by mixture, 10.5g sodium vinyl sulfonate, 182.0g poly glycol monomethyl ether monomethacrylates, the 30.0g vinylformic acid of 70g lower molecular weight carbon dioxide copolymer-MALEIC ANHYDRIDE esterification products with the residue MALEIC ANHYDRIDE, temperature of reaction is controlled at 75 ± 5 ℃, after dropwising, under this temperature, continue reaction 1h.Add the sodium hydroxide neutralization after the cooling, regulate pH=7～8, obtain polycarboxylic acid series high-performance cement water reducing agent of the present invention, with this water reducer called after mx-4.
The water reducer that obtains in above-described embodiment 1 to 4 is used for the clean slurry fluidity testing of standard cement, the serviceability of the water reducer for preparing in the embodiment of the invention is set forth.Adopt standard cement, the clean slurry degree of mobilization according to GB/T8077-2000 test cement the results are shown in Table 1.
The experiment of the clean slurry of table 1 degree of mobilization
| Water reducer of cement concrete | The solid volume, % | Clean slurry is mobile, mm |
| mx-1 | 0.21 | 280 |
| mx-2 | 0.18 | 285 |
| mx-3 | 0.13 | 308 |
| mx-4 | 0.16 | 310 |
Claims (6)
1. poly carboxylic acid series water reducer that contains the lower molecular weight carbon dioxide copolymer, it is characterized in that, this water reducer is the copolymerization product that contains lower molecular weight carbon dioxide copolymer, poly glycol monomethyl ether cholesterol acid esters, cyclic monomer and other unsaturated monomers, wherein, described lower molecular weight carbon dioxide copolymer is the multipolymer of carbonic acid gas and epoxy compounds, its molecular formula W
1Represented by formula (a):
R＝H，CH
3，
R
1＝OH，H；
x＝0.05-0.8；
N is integer, between 1 to 20;
The lower molecular weight carbon dioxide copolymer is carbonic acid gas-ethylene oxide copolymer, carbon dioxide-epoxy propane copolymer, carbon dioxide-cyclohexene oxide copolymer, carbonic acid gas-Styrene oxide 98min. multipolymer, carbon dioxide-epoxy propane-oxyethane terpolymer, carbonic acid gas-oxyethane-cyclohexene oxide terpolymer, a kind of in carbon dioxide-epoxy propane-cyclohexene oxide terpolymer or carbon dioxide-epoxy propane-Styrene oxide 98min. terpolymer, two or three mixes;
The molecular formula W of described poly glycol monomethyl ether cholesterol acid esters
2Represented by formula (b):
M is the integer between 5-200;
Described cyclic monomer and other unsaturated monomers are the mixture of a kind of, two or more components in oxyethane, propylene oxide, cyclohexene oxide, Styrene oxide 98min., methacrylic acid, unsaturated sulfonic acid or its salt, unsaturated amides, methacrylic ester or its salt, unsaturated dicarboxylic acid and the acid anhydrides thereof, wherein:
(1) unsaturated sulfonic acid or its salt are the mixture of a kind of, two or three component in vinyl sulfonic acid or its salt, α-sodium olefin sulfonate, (methyl) sodium allyl sulfonate, styrene sulfonic acid or its salt;
(2) unsaturated amides is one or both the mixture in acrylamide, the 2-Methacrylamide;
(3) methacrylic ester is the mixture of a kind of, two or more components in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate and the sodium salt of methacrylic acid;
(4) unsaturated dicarboxylic acid and acid anhydrides thereof are the mixture of a kind of, two or more components in maleic acid, fumaric acid, MALEIC ANHYDRIDE, the fumaric acid anhydride.
2. a kind of poly carboxylic acid series water reducer that contains the lower molecular weight carbon dioxide copolymer as claimed in claim 1 is characterized in that, the number-average molecular weight of described lower molecular weight carbon dioxide copolymer is 350～2800.
3. the preparation method who contains the poly carboxylic acid series water reducer of lower molecular weight carbon dioxide copolymer as claimed in claim 1 is characterized in that comprising following reactions steps:
The first step, esterification end capping: take the sulphonated polystyrene resin of acidifying as catalyzer, with lower molecular weight carbon dioxide copolymer and MALEIC ANHYDRIDE, perhaps lower molecular weight carbon dioxide copolymer and methacrylic acid, the perhaps mixture of lower molecular weight carbon dioxide copolymer and MALEIC ANHYDRIDE and methacrylic acid, at 60～120 ℃, esterification is 3～6 hours under the reduced pressure, remove solid acid, obtain the lower molecular weight carbon dioxide copolymer of MALEIC ANHYDRIDE end-blocking and the mixture of residue MALEIC ANHYDRIDE, the perhaps mixture of the lower molecular weight carbon dioxide copolymer of methacrylic acid blocked and residue methacrylic acid, perhaps the lower molecular weight carbon dioxide copolymer of methacrylic acid and MALEIC ANHYDRIDE mixture end-blocking and residue methacrylic acid and remain the mixture of MALEIC ANHYDRIDE;
Second step, copolymerization: one or both in ammonium persulphate, Sodium Persulfate, the Potassium Persulphate are as initiator, with the resulting mixture of esterification end capping in the first step, deionized water, poly glycol monomethyl ether cholesterol acid esters, cyclic monomer and other unsaturated monomers are introduced in the reactor, at 60～95 ℃ of lower copolymerizations that occur, the reaction times is 3～8 hours; After polyreaction finishes, cooling, regulating pH with alkali lye is 7～8, obtains red-brown or brown yellow transparent liquid, is the poly carboxylic acid series water reducer that contains the lower molecular weight carbon dioxide copolymer.
4. the preparation method who contains the poly carboxylic acid series water reducer of lower molecular weight carbon dioxide copolymer as claimed in claim 3 is characterized in that, the water reducer of cement concrete of described second step is comprised of all or part of of following listed raw material in massfraction:
10～150 parts of one or more of the resulting mixture of the first step esterification end capping,
30～150 parts of poly glycol monomethyl ether cholesterol acid esters,
5～35 parts of unsaturated sulfonic acid or its salt,
3～35 parts of acrylamides,
3～30 parts of methacrylic acids,
3～35 parts of methacrylic ester or its salt
5～80 parts of oxyethane, propylene oxide, cyclohexene oxide or Styrene oxide 98min.s,
5～60 parts on unsaturated dicarboxylic acid and acid anhydrides thereof,
0.05～15 part of ammonium persulphate, Sodium Persulfate or Potassium Persulphate,
260～900 parts of deionized waters.
5. the preparation method who contains the poly carboxylic acid series water reducer of lower molecular weight carbon dioxide copolymer as claimed in claim 3, it is characterized in that: in the described esterification end capping process, the mol ratio n of the mixture of methacrylic acid, MALEIC ANHYDRIDE or methacrylic acid and maleic acid and lower molecular weight carbon dioxide copolymer is in the scope of 5: 1≤n≤1: 1, and excessive methacrylic acid, MALEIC ANHYDRIDE or methacrylic acid need not separate with the mixture of maleic acid and be directly used in polyreaction after the esterification.
6. the preparation method who contains the poly carboxylic acid series water reducer of lower molecular weight carbon dioxide copolymer as claimed in claim 5, it is characterized in that: the existence form of described lower molecular weight carbon dioxide copolymer in polymkeric substance has following two kinds:
(1) the lower molecular weight carbon dioxide copolymer becomes a kind of long-chain branch in polymkeric substance, its general molecular formula W
3Represented by formula (c):
R
1，R
2，R
3＝H，CH
3；
M
1＝H，Na，NH
4；
M
2=H, Na, NH
4, or CH
3, C
2H
5, C
4H
7
M
3＝H，CH
3，Na，NH
4；
Wherein, a, b, c, d, e, f are the molar fractions of each component, and a+b+c+d+e+f=1.0;
(2) or the lower molecular weight carbon dioxide copolymer in polymkeric substance, form cross-linking set, the general structure W of its crosslinking structure multipolymer
4(d) is expressed as by formula:
Or:
Or:
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| CN103304799B (en) * | 2013-04-12 | 2015-12-02 | 华侨大学 | A kind of RAFT reaction reagent based on lower molecular weight carbon dioxide copolymer and preparation method thereof |
| CN103304798B (en) * | 2013-04-12 | 2015-12-02 | 华侨大学 | A kind of ATRP reagent based on lower molecular weight carbon dioxide copolymer and preparation method thereof |
| CN103897167B (en) * | 2014-03-21 | 2016-02-24 | 华侨大学 | Lower molecular weight carbonic acid gas-epoxide co-polymer containing epoxy group(ing) and preparation method thereof |
| CN103964727B (en) * | 2014-04-30 | 2016-03-16 | 广西金洪混凝土有限公司 | A kind of cement water reducing agent |
| CN104193215B (en) * | 2014-09-02 | 2017-01-11 | 武汉理工大学 | Ternary block macromonomer graft copolymerization high-property polycarboxylic acid water-reducing agent and preparation method thereof |
| CN106046272B (en) * | 2016-07-18 | 2018-07-17 | 江苏中铁奥莱特新材料股份有限公司 | The method for preparing polycarboxylate water-reducer using carbon dioxide |
| CN107828027B (en) * | 2017-11-17 | 2020-12-29 | 江苏苏博特新材料股份有限公司 | Concrete workability regulator with water reducing function and preparation method thereof |
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| CN1600735A (en) * | 2003-09-22 | 2005-03-30 | 北京绿色前缘技术创新中心有限公司 | High performance cement dispersing agent in copolymerization carboxylic acids with side chain of poly alkylene glycol ether |
| CN101244907A (en) * | 2007-02-13 | 2008-08-20 | 上海申立建材有限公司 | Polycarboxylic acids series concrete high efficiency water reducing agent and synthesizing process |
| CN101698693A (en) * | 2009-10-22 | 2010-04-28 | 丹凤县永鑫电子材料有限责任公司 | High performance polycarboxylic acid type concrete water reducing agent and preparation method thereof |
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