CN107200819A - A kind of siliceous synthetic method of polycarboxylate water-reducer and products thereof - Google Patents
A kind of siliceous synthetic method of polycarboxylate water-reducer and products thereof Download PDFInfo
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- CN107200819A CN107200819A CN201710579598.8A CN201710579598A CN107200819A CN 107200819 A CN107200819 A CN 107200819A CN 201710579598 A CN201710579598 A CN 201710579598A CN 107200819 A CN107200819 A CN 107200819A
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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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/40—Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
- C04B24/42—Organo-silicon compounds
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2639—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing elements other than oxygen, nitrogen or sulfur
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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Abstract
The invention provides a kind of synthetic method of siliceous polycarboxylate water-reducer, mainly including three-step reaction：The first step, makes silicon alcohol compound occur ring-opening polymerization with oxirane, to generate intermediate A；Second step, in the presence of esterification catalyst, polymerization inhibitor, makes intermediate A occur esterification with acrylic acid or/and methacrylic acid, to generate intermediate B；3rd step, in the presence of initiator, chain-transferring agent, makes intermediate B occur free radicals copolymerization reaction with acrylic acid or/and methacrylic acid, target product is finally made.Present invention also offers a kind of siliceous polycarboxylate water-reducer prepared using above-mentioned synthetic method, it is conducive to being adsorbed in cement particle surface, higher dispersiveness is obtained simultaneously, presetting period and the final setting time of precast concrete can significantly be extended, therefore, have broad application prospects and market potential.
Description
Technical field
The invention belongs to the additive field of concrete, more particularly to a kind of synthesis side of siliceous polycarboxylate water-reducer
Method, and using polycarboxylate water-reducer siliceous made from the synthetic method.
Background technology
Polycarboxylate water-reducer is most researched and developed and applied for a patent by Japanese catalyst company earlier than 1980s, belongs to the third generation
Water reducer, its water-reducing rate and function of slump protection are substantially better than conventional wooden sulfonate water reducer (first generation water reducer) and naphthalene system diminishing
Agent (second generation water reducer), polycarboxylate water-reducer key reaction raw material is the unsaturated carboxylic acid with copolyreaction activity with having
The unsaturated chain shaped polymer of copolyreaction activity.
The unsaturated chain shaped polymer of early stage is mainly by unsaturated carboxylic acid and polyethylene glycol generation esterification preparation
Into having no " the special polyethers of polycarboxylate water-reducer " concept in early days, polyethylene glycol compound used is field of printing and dyeing auxiliary chemicals.It is early
Phase polycarboxylate water-reducer is esters water reducer, and reaction is needed by two steps, for the steady of production efficiency and performance
It is qualitative to have a significant effect, and polyethylene glycol includes 2 terminal hydroxy groups, can occur esterification with unsaturated carboxylic acid, cause shape
Into the molecular structure with 2 unsaturated double-bonds, it polymerize to form cross-linked structure in free radicals copolymerization reaction, influences the carboxylic of birdsing of the same feather flock together
Sour water reducer dispersiveness.Single dibasic acid esters property is closer to, difficult and cost is higher by physical method for separation, thus its using and
Development is by a definite limitation.
Polycarboxylate water-reducer is widely used in all kinds of concrete construction engineerings, and it is generally closed by free radicals copolymerization reaction
Into key reaction raw material includes unsaturated carboxylic acid class compound, such as acrylic acid, methacrylic acid, maleic anhydride, fumaric acid.
Polycarboxylate water-reducer needs the chain polymer molecule with copolyreaction activity, and such compound is divided into ester type compound and ether
Two kinds of class compound, wherein, ester type compound is the acrylate or metering system of polyethylene glycol or MPEG-550
Acid esters；Ether polymer molecule mainly includes isopentene group APEO (TPEG), methyl allyl polyoxyethylene ether
(HPEG), allyl polyethenoxy ether (APEG) etc., above-mentioned ether polymer is with the alcohol compound with copolyreaction activity
For reaction raw materials, in the basic conditions with the reactant such as oxirane (EO), weight average molecular weight is synthesized by ring-opening polymerization
For 800~4000 straight chain polymer molecule.
The general molecular structure of polycarboxylate water-reducer includes same in the polymer molecule with pectinate texture, its side-chain structure
When there is the anionic functional groups such as carboxyl, sulfonic group and straight chain polymer molecular structure, play steric hindrance effect, the carboxylic of birdsing of the same feather flock together
It is additional that the performance of sour water reducer is substantially better than lignosulfonic acid salt building additive, naphthalene system building additive, aliphatic category building
Agent etc..
In the prior art, the polycarboxylate water-reducer containing element silicon has more preferable dispersiveness, can be lifted at prefabricated mixed
Water-reducing rate in solidifying soil, extension presetting period and final setting time；In the synthesis technique that prior art is provided, generally use and contain
Silane coupler (acrylic trimethoxy silane, acrylic triethoxysilane, the Ethenylbenzene of the double bond of copolyreaction can be carried out
Base trimethoxy silane, vinyl phenyl triethoxysilane etc.) or containing the silane compound (three of copolyreaction double bond can be carried out
Ethylene methacrylic base silane, trimethacrylate base silane, vinyltriethylsilane, acrylic triethyl silicane etc.)；Existing synthesis
Technique is generally by the above-mentioned organo-silicon compound for carrying out copolyreaction and straight chain polymer, unsaturated carboxylic acid compounds, insatiable hunger
Free radicals copolymerization reaction is carried out with sulfoacid compound etc., however, solubility of the organic matter containing element silicon in water in itself is smaller,
And for example, the silane coupler containing unsaturated double-bond has higher apparent activation energy, and hydrophobic grouping proportion is larger, therefore
It is smaller that silicone functionalities account for polymer molecule, it is difficult to reaches obvious effect.In addition, the organosilicon used in the prior art
Class copolymer compound reactivity is relatively low, and the unsaturated carboxylic acid class compound higher easily with reactivity ratio carries out copolyreaction, is difficult
Reacted with the straight chain polymer with copolyreaction activity, so that the polycarboxylate water-reducer molecule for causing reaction to synthesize is homogeneous
Degree is low, and retarding performance is undesirable；In addition, multiple aggregation reaction also improves the operation difficulty of reaction and not true to a certain extent
It is qualitative, it is unfavorable for large-scale industrial production and application.
The content of the invention
For a variety of technological deficiencies present in prior art, inventor designs and implements a kind of new technique for synthesizing, uses
In preparing a kind of siliceous polycarboxylate water-reducer, the synthesis technique mainly includes three-step reaction：The first step, makes silicon alcohol compound
Occurs ring-opening polymerization with oxirane, to generate intermediate A；Second step, in the presence of esterification catalyst, polymerization inhibitor,
Intermediate A is set to occur esterification with acrylic acid or/and methacrylic acid, to generate intermediate B；3rd step, in initiator, chain
In the presence of transfer agent, intermediate B is occurred free radicals copolymerization reaction with acrylic acid or/and methacrylic acid, mesh is finally made
Mark product.
Specifically, the first aspect of the present invention provide a kind of synthetic method of siliceous polycarboxylate water-reducer, including with
Lower step：
S1：Silicon alcohol compound, organic alkali catalyst, oxirane are added into pressure reacting container, 145 DEG C~
In 185 DEG C of reaction temperature and 0.17Mpa~0.32Mpa reaction vessel under pressure, ring-opening polymerization is carried out, is made
Intermediate A；
S2：Esterification catalyst, polymerization inhibitor, the intermediate A and acrylic acid or/and methyl are added into another reaction vessel
Acrylic acid, esterification is carried out under 75 DEG C~95 DEG C of reaction temperature, and intermediate B is made；Wherein, the esterification catalyst is
P-methyl benzenesulfonic acid, the polymerization inhibitor is hydroquinones or/and benzoquinone；Wherein, the effect of polymerization inhibitor is to prevent unsaturated carboxylic
The self-polymeric reaction of acid compounds (acrylic acid or/and methacrylic acid)；
S3：The intermediate B, acrylic acid or/and methacrylic acid are added into another reaction vessel, heats up and machinery is stirred
Mix, be subsequently added into initiator, chain-transferring agent, polymerisation is carried out under 55 DEG C~75 DEG C of reaction temperature, post-process, that is, be made
The siliceous polycarboxylate water-reducer.
Preferably, in the S1 of above-mentioned synthetic method, the silicon alcohol compound is selected from following any one or more：Front three
Base silanol, triethyl silanol, triphenyl silanol；The organic alkali catalyst is selected from following any one or more：Sodium methoxide, methanol
Potassium, caustic alcohol, potassium ethoxide.
Preferably, in the S1 of above-mentioned synthetic method, the mol ratio of the silicon alcohol compound and oxirane is 1：15
~1：65；The quality that adds of the organic alkali catalyst is 0.1%~0.5% of reactant gross mass in S1.
Preferably, in the S1 of above-mentioned synthetic method, the duration of ring-opening polymerization is 3.5h~6.5h.
Preferably, in the S2 of above-mentioned synthetic method, the intermediate A and acrylic acid or/and mole of methacrylic acid
Than for 1：1.2~1：1.5；The quality that adds of the esterification catalyst is 0.5%~2.5% of reactant gross mass in S2；Institute
The quality that adds for stating polymerization inhibitor is 0.02%~0.25% of reactant gross mass in S2.
Preferably, in the S2 of above-mentioned synthetic method, the duration of esterification is 4.5h~8.5h.
Preferably, in above-mentioned synthetic method, the weight average molecular weight of the intermediate B is 1200~3600.
Preferably, in the S3 of above-mentioned synthetic method, the initiator is selected from following any one or more：Ammonium persulfate,
Sodium peroxydisulfate, potassium peroxydisulfate；The chain-transferring agent is selected from following any one or more：TGA, mercaptopropionic acid, propene sulfonic acid
Sodium, methylpropene sodium sulfonate.
Preferably, in the S3 of above-mentioned synthetic method, the intermediate B and acrylic acid or/and mole of methacrylic acid
Than for 1：2.5~1：5.5；The quality that adds of the initiator is 0.5%~2.5% of reactant gross mass in S3；The chain
The quality that adds of transfer agent is 0.2%~1.0% of reactant gross mass in S3.
Preferably, in the S3 of above-mentioned synthetic method, the duration of polymerisation is 3.0h~6.5h.
Preferably, in the S3 of above-mentioned synthetic method, the post processing includes：Sodium hydroxide water is added into reaction system
Solution, regulation pH value to 5.5~7.5.
It is further preferred that in above-mentioned synthetic method, the mass concentration of the sodium hydrate aqueous solution for 20%~
40%.
In addition, the second aspect of the present invention is made there is provided a kind of described synthetic method according to a first aspect of the present invention
Siliceous polycarboxylate water-reducer.
Compared with existing common polycarboxylate water-reducer (for example, commercially available common polycarboxylate water-reducer), the present invention is carried
The siliceous polycarboxylate water-reducer and its synthetic method supplied has following technical advantage：Using the functional group containing element silicon as straight chain
Polymer molecule part, it is to avoid the extra addition of generally existing can carry out the organic of copolyreaction in the prior art
The step of silicon compound, and often there is the low defect of solubility in such organo-silicon compound for carrying out copolyreaction, so that
Present invention significantly reduces the complexity of synthesis technique, the polymerization reaction monomer that introduces other species is fundamentally avoided
Operation；Also, siliceous molecular structure is conducive to the siliceous polycarboxylate water-reducer to be adsorbed in cement particle surface, obtains simultaneously
Get Geng Gao dispersiveness, can significantly extend presetting period and the final setting time of precast concrete.In summary, the present invention is carried
The synthetic method of confession and using polycarboxylate water-reducer siliceous made from the synthetic method, suitable for large-scale industrial production,
Have broad application prospects and market potential.
Embodiment
With reference to embodiment, the present invention is further elaborated, but the present invention is not limited to following embodiment party
Formula.
According to the synthetic method of the siliceous polycarboxylate water-reducer of first aspect, comprise the following steps：
S1：Silicon alcohol compound, organic alkali catalyst, oxirane are added into pressure reacting container, 145 DEG C~
In 185 DEG C of reaction temperature and 0.17Mpa~0.32Mpa reaction vessel under pressure, ring-opening polymerization is carried out, is made
Intermediate A；
S2：Esterification catalyst, polymerization inhibitor, the intermediate A and acrylic acid or/and methyl are added into another reaction vessel
Acrylic acid, esterification is carried out under 75 DEG C~95 DEG C of reaction temperature, and intermediate B is made；Wherein, the esterification catalyst is
P-methyl benzenesulfonic acid, the polymerization inhibitor is hydroquinones or/and benzoquinone；
S3：The intermediate B, acrylic acid or/and methacrylic acid are added into another reaction vessel, heats up and machinery is stirred
Mix, be subsequently added into initiator, chain-transferring agent, polymerisation is carried out under 55 DEG C~75 DEG C of reaction temperature, post-process, that is, be made
The siliceous polycarboxylate water-reducer.
In a preferred embodiment, in S1, the silicon alcohol compound is selected from following any one or more：Trimethyl
Silanol, triethyl silanol, triphenyl silanol；The organic alkali catalyst is selected from following any one or more：Sodium methoxide, methanol
Potassium, caustic alcohol, potassium ethoxide.
In a preferred embodiment, in S1, the mol ratio of the silicon alcohol compound and oxirane is 1：15~
1：65；The quality that adds of the organic alkali catalyst is 0.1%~0.5% of reactant gross mass in S1.
In a preferred embodiment, in S2, the intermediate A and the mol ratio of acrylic acid or/and methacrylic acid
For 1：1.2~1：1.5；The quality that adds of the esterification catalyst is 0.5%~2.5% of reactant gross mass in S2；It is described
The quality that adds of polymerization inhibitor is 0.02%~0.25% of reactant gross mass in S2.
In a preferred embodiment, the weight average molecular weight of the intermediate B is 1200~3600.
In a preferred embodiment, in S3, the initiator is selected from following any one or more：Ammonium persulfate, mistake
Sodium sulphate, potassium peroxydisulfate；The chain-transferring agent is selected from following any one or more：TGA, mercaptopropionic acid, propene sulfonic acid
Sodium, methylpropene sodium sulfonate.
In a preferred embodiment, in S3, the intermediate B and the mol ratio of acrylic acid or/and methacrylic acid
For 1：2.5~1：5.5；The quality that adds of the initiator is 0.5%~2.5% of reactant gross mass in S3；The chain turns
The quality that adds for moving agent is 0.2%~1.0% of reactant gross mass in S3.
In a preferred embodiment, in S3, the post processing includes：Sodium hydroxide is added into reaction system water-soluble
Liquid, regulation pH value to 5.5~7.5.
In a further preferred embodiment, the mass concentration of the sodium hydrate aqueous solution is 20%~40%.
According to the siliceous polycarboxylate water-reducer of second aspect, it is made as the synthetic method described in first aspect.
Synthesis step in following each embodiments is routine operation unless otherwise instructed, and reaction raw materials therein are such as without spy
Bright equal can be obtained from open commercial sources is not mentionleted alone.
Embodiment 1
The addition 1000g trimethyl silanols into pressure reacting container, 35g potassium ethoxides, 15000g oxirane (EO),
In 175 DEG C of reaction temperature and 0.22Mpa reaction vessel under pressure, ring-opening polymerization is carried out, the reaction time is 4.5h, system
Intermediate A 1 must be made.
Addition 2000g intermediate As 1,95g methacrylic acids, 35g p-methyl benzenesulfonic acid into another reaction vessel, 5g is to benzene
Diphenol, carries out esterification under 85 DEG C of reaction temperature, and the reaction time is 6.5h, and intermediate B 1 is made.
1000g intermediate Bs 1 and 150g acrylic acid are added into another reaction vessel, heats up and mechanical agitation is uniform, then
Add under 18g sodium peroxydisulfates, 8.5g TGAs, mechanical agitation and react, reaction temperature is 65 DEG C, and the reaction time is 5h, reaction
The sodium hydrate aqueous solution of mass concentration 30% is added after end, siliceous polycarboxylate water-reducer is made in regulation pH value to 6.5
P1。
Embodiment 2
The addition 1200g triethyl silanols into pressure reacting container, 30g potassium methoxides, 12000g oxirane (EO),
In 165 DEG C of reaction temperature and 0.27Mpa reaction vessel under pressure, ring-opening polymerization is carried out, the reaction time is 4h, be made
Intermediate A 2 is made.
Addition 2000g intermediate As 2,85g acrylic acid, 30g p-methyl benzenesulfonic acid into another reaction vessel, 5.5g is to benzene two
Quinone, carries out esterification under 80 DEG C of reaction temperature, and the reaction time is 6h, and intermediate B 2 is made.
1000g intermediate Bs 2 and 165g methacrylic acids are added into another reaction vessel, heats up and mechanical agitation is uniform,
It is subsequently added under 20g potassium peroxydisulfates, 9g mercaptopropionic acids, mechanical agitation and reacts, reaction temperature is 70 DEG C, and the reaction time is 4.5h,
Reaction adds the sodium hydrate aqueous solution of mass concentration 25% after terminating, siliceous polycarboxylic acids diminishing is made in regulation pH value to 6.8
Agent P2.
Embodiment 3
The addition 3000g trimethyl silanols into pressure reacting container, 85g caustic alcohols, 20000g oxirane (EO),
In 160 DEG C of reaction temperature and 0.30Mpa reaction vessel under pressure, ring-opening polymerization is carried out, the reaction time is 5.5h, system
Intermediate A 3 must be made.
Addition 2800g intermediate As 3,105g acrylic acid, 45g p-methyl benzenesulfonic acid into another reaction vessel, 5.5g is to benzene two
Phenol, carries out esterification under 82 DEG C of reaction temperature, and the reaction time is 5.5h, and intermediate B 3 is made.
1500g intermediate Bs 3 and 150g methacrylic acids are added into another reaction vessel, heats up and mechanical agitation is uniform,
It is subsequently added under 25g ammonium persulfates, 9g sodium allylsulfonates, mechanical agitation and reacts, reaction temperature is 61 DEG C, and the reaction time is 6h,
Reaction adds the sodium hydrate aqueous solution of mass concentration 35% after terminating, siliceous polycarboxylic acids diminishing is made in regulation pH value to 7.0
Agent P3.
Embodiment 4
The addition 1000g trimethyl silanols into pressure reacting container, 45g sodium methoxides, 25000g oxirane (EO),
In 170 DEG C of reaction temperature and 0.25Mpa reaction vessel under pressure, ring-opening polymerization is carried out, the reaction time is 5.5h, system
Intermediate A 4 must be made.
Addition 3000g intermediate As 4,45g methacrylic acids, 40g acrylic acid into another reaction vessel, 40g is to toluene sulphur
Acid, 2g hydroquinones and 3g benzoquinones, carry out esterification under 75 DEG C of reaction temperature, and the reaction time is 8.5h, are made
Intermediate B 4.
1100g intermediate Bs 4 and 100g acrylic acid, 60g methacrylic acids are added into another reaction vessel, is heated up and machine
Tool stirs, and is subsequently added into 10g sodium peroxydisulfates, 10g potassium peroxydisulfates, 5g sodium allylsulfonates, 5g methylpropene sodium sulfonates, machinery
Stirring is lower to react, and reaction temperature is 75 DEG C, and the reaction time is 4.5h, and reaction adds the sodium hydroxide of mass concentration 30% after terminating
Siliceous polycarboxylate water-reducer P4 is made in the aqueous solution, regulation pH value to 6.8.
Embodiment 5
The addition 1200g triethyl silanols into pressure reacting container, 32g caustic alcohols, 15000g oxirane (EO),
In 175 DEG C of reaction temperature and 0.23Mpa reaction vessel under pressure, ring-opening polymerization is carried out, the reaction time is 4.5h, system
Intermediate A 5 must be made.
The addition 1000g triethyl silanols into another pressure reacting container, 35g potassium ethoxides, 15000g oxirane (EO),
In 165 DEG C of reaction temperature and 0.26Mpa reaction vessel under pressure, ring-opening polymerization is carried out, the reaction time is 5.5h,
Obtained intermediate A 6.
1200g intermediate As 5,1000g intermediate As 6,105g methacrylic acids, 40g pairs are added into another reaction vessel
Toluenesulfonic acid, 5.5g hydroquinones carries out esterification under 80 DEG C of reaction temperature, and the reaction time is 6.5h, is made middle
Body B5.
1000g intermediate Bs 5 and 175g methacrylic acids are added into another reaction vessel, heats up and mechanical agitation is uniform,
It is subsequently added under 20g potassium peroxydisulfates, 4g TGAs, 4.5g mercaptopropionic acids, mechanical agitation and reacts, reaction temperature is 60 DEG C, instead
It is 4.5h between seasonable, reaction adds the sodium hydrate aqueous solution of mass concentration 25% after terminating, regulation pH value is made and contained to 7.5
The polycarboxylate water-reducer P5 of silicon.
Inventor also measured were above-mentioned siliceous polycarboxylate water-reducer P1, P3 and commercially available common polycarboxylate water-reducer phase
Close performance；Specifically, it is the ordinary portland cement of Shanghai conch 42.5 to test cement used, with reference to GB/8076-2008 test water-reducing rates and
Cement paste through when divergence, extension diameter units be millimeter (mm), wherein, cement paste through when divergence be used for characterize poly- carboxylic
The slow setting function of slump protection of sour water reducer；Specifically, shown in the following Tables 1 and 2 of experimental result：
The water-reducing rate test result of table 1
| 15 DEG C of water-reducing rates (%) | 30 DEG C of water-reducing rates (%) | |
| Common polycarboxylate water-reducer | 23.5 | 22.1 |
| Polycarboxylate water-reducer P1 | 26.2 | 24.6 |
| Polycarboxylate water-reducer P3 | 25.7 | 24.2 |
The cement paste of table 2 through when divergence test result
| Initially | 30min | 60min | 90min | 120min | 180min | |
| Common polycarboxylate water-reducer | 285 | 276 | 265 | 240 | 215 | —— |
| Polycarboxylate water-reducer P1 | 315 | 308 | 301 | 285 | 268 | 237 |
| Polycarboxylate water-reducer P3 | 305 | 298 | 290 | 281 | 263 | 225 |
The specific embodiment of the present invention is described in detail above, but it is intended only as example, and the present invention is not limited
It is formed on particular embodiments described above.To those skilled in the art, it is any to the equivalent modifications that carry out of the present invention and
Substitute also all among scope of the invention.Therefore, the impartial conversion made without departing from the spirit and scope of the invention and
Modification, all should be contained within the scope of the invention.
Claims (10)
1. a kind of synthetic method of siliceous polycarboxylate water-reducer, comprises the following steps：
S1：Silicon alcohol compound, organic alkali catalyst, oxirane are added into pressure reacting container, at 145 DEG C~185 DEG C
Reaction temperature and 0.17Mpa~0.32Mpa reaction vessel under pressure, carry out ring-opening polymerization, be made in the middle of
Body A；
S2：Esterification catalyst, polymerization inhibitor, the intermediate A and acrylic acid or/and metering system are added into another reaction vessel
Acid, esterification is carried out under 75 DEG C~95 DEG C of reaction temperature, and intermediate B is made；Wherein, the esterification catalyst is to first
Benzene sulfonic acid, the polymerization inhibitor is hydroquinones or/and benzoquinone；
S3：The intermediate B, acrylic acid or/and methacrylic acid are added into another reaction vessel, is heated up and mechanical agitation,
Initiator, chain-transferring agent are subsequently added into, polymerisation is carried out under 55 DEG C~75 DEG C of reaction temperature, is post-processed, that is, institute is made
State siliceous polycarboxylate water-reducer.
2. synthetic method according to claim 1, it is characterised in that in S1, the silicon alcohol compound is selected from following
It is any one or more：Trimethyl silanol, triethyl silanol, triphenyl silanol；The organic alkali catalyst is selected from following any
Or it is a variety of：Sodium methoxide, potassium methoxide, caustic alcohol, potassium ethoxide.
3. synthetic method according to claim 1, it is characterised in that in S1, the silicon alcohol compound and epoxy second
The mol ratio of alkane is 1：15~1：65；The organic alkali catalyst add quality for reactant gross mass in S1 0.1%~
0.5%.
4. synthetic method according to claim 1, it is characterised in that in S2, the intermediate A and acrylic acid or/and
The mol ratio of methacrylic acid is 1：1.2~1：1.5；The quality that adds of the esterification catalyst is reactant gross mass in S2
0.5%~2.5%；The quality that adds of the polymerization inhibitor is 0.02%~0.25% of reactant gross mass in S2.
5. synthetic method according to claim 1, it is characterised in that the weight average molecular weight of the intermediate B is 1200~
3600。
6. synthetic method according to claim 1, it is characterised in that in S3, the initiator is selected from following any
Or it is a variety of：Ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate；The chain-transferring agent is selected from following any one or more：TGA,
Mercaptopropionic acid, sodium allylsulfonate, methylpropene sodium sulfonate.
7. synthetic method according to claim 1, it is characterised in that in S3, the intermediate B and acrylic acid or/and
The mol ratio of methacrylic acid is 1：2.5~1：5.5；The quality that adds of the initiator is reactant gross mass in S3
0.5%~2.5%；The quality that adds of the chain-transferring agent is 0.2%~1.0% of reactant gross mass in S3.
8. synthetic method according to claim 1, it is characterised in that in S3, the post processing includes：To reaction system
Middle addition sodium hydrate aqueous solution, regulation pH value to 5.5~7.5.
9. synthetic method according to claim 8, it is characterised in that the mass concentration of the sodium hydrate aqueous solution is
20%~40%.
10. siliceous polycarboxylate water-reducer made from a kind of synthetic method according to any of the above-described claim.
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