CN105601905A - Preparation method and application of polymer additive - Google Patents
Preparation method and application of polymer additive Download PDFInfo
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- CN105601905A CN105601905A CN201511029309.4A CN201511029309A CN105601905A CN 105601905 A CN105601905 A CN 105601905A CN 201511029309 A CN201511029309 A CN 201511029309A CN 105601905 A CN105601905 A CN 105601905A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/338—Polymers modified by chemical after-treatment with inorganic and organic compounds
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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
- C04B24/24—Macromolecular compounds
- C04B24/243—Phosphorus-containing polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/327—Polymers modified by chemical after-treatment with inorganic compounds containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G65/32—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G65/32—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
- C08G65/3324—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof cyclic
- C08G65/3326—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof cyclic aromatic
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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
- C04B2103/40—Surface-active agents, dispersants
- C04B2103/408—Dispersants
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Abstract
The invention provides a preparation method and application of a polymer additive. A new polymer additive with a phosphorous acid group is obtained and can be used as a dispersing agent of an aqueous dispersion body of a hydraulic binding agent and/or a potential hydraulic binding agent. The method includes the following steps of a, conducting polycondensation through big polyether monomers A of the specific structure, monomers B with carboxyl groups or ester groups, and aldehyde C; b, conducting phosphorous acidification on carboxyl groups or ester groups, wherein carboxyl groups or ester groups are converted into C(OH)(PO3H2)2 through phosphorous acidification.
Description
Technical field
The present invention relates to a kind of preparation method and application thereof of polymeric additive, belong to concrete admixture technologyField.
Background technology
Water reducer is a kind of surfactant in essence, mainly improves concrete flowability, controls and condenseOr firm time, raising concrete strength etc. In concrete preparation process, conventionally need to add and compare waterClose or mixing water that the needed water of hardening process is much more, but along with extra water evaporation can cause coagulationThe long-living gap of sun-dried mud brick body, thus make mechanical strength and the remarkable variation of tolerance, and therefore concrete is additionalAgent is to be mainly very important adding of water reducer.
Polycarboxylate water-reducer is a kind of high-performance water reducing agent, and from the eighties in last century, catalyst company of Japan opens firstSince sending poly carboxylic acid series water reducer, poly carboxylic acid series water reducer research has at home and abroad obtained very much progress.At present poly carboxylic acid series water reducer, key project, especially high ferro great in nearly all country, airport,In the engineering such as water conservancy and hydropower, bridge, be all widely used. At present about polycarboxylate water-reducer property modification patentReport is existing a lot, relates generally to the dispersive property that aspect is polycarboxylic acids, long-term function of slump protection and strong in early daysThe raising of degree.
Patent documentation EP0924174A1 discloses the copolymer of the different side chains of a kind of length, wherein long polyethersSide chain is used for improving polymer dispersed performance, and short side chain is used for improving function of slump protection. By adjusting two kinds of sidesThe ratio of chain makes copolymer reach different dispersion and slump hold facilities. The shortcoming of the method is polymerDispersed and slump retention can not be satisfactory, and the production of different polyether chains and collocation, bringsWorkload is large, and production process is loaded down with trivial details. Patent US5362829 has also reported changing of the different side chains of similar lengthProperty polycarboxylic acids research.
Patent documentation CN1096774A discloses and has a kind ofly subtracted for the polycarboxylic acids of controlling concrete slump lossAqua, this composition is by chain base ether, and two alkenyl ethers and maleic anhydride are monomer, use azodiisobutyronitrileFor initiator system, in toluene solvant, be polymerized. Although having stronger guarantor, the described water reducer of this invention collapsesAbility, shortcoming is that diminishing ability is slightly poor, volume need higher, not environmental protection of production technology, and adopt formerMaterial alkenyl ether is expensive.
EP1547986A1 discloses a kind of early-strength polycarboxylate additive, and the method can significantly improve mixedSolidifying native early strength. But its preparation technology is comparatively complicated, and can not solve polycarboxylate dehydragent at low temperature barThe problem of early strength slower development under part. CN101186461A discloses a kind of multiple with polycarboxylate water-reducerAdditive-the one of the raising early concrete intensity of joining is by organic alkoxy amine, water soluble sulfate and water groupBecome. Preparation technology is simple in this invention, and can not cause concrete coagulating time extend and cause after concretePhase intensity declines.
As mentioned above, polycarboxylate water-reducer property modification research at present obtains already compared with much progress, but polycarboxylic acidsWater reducer still has huge challenge in application aspect, as the adaptability problem of clay. Polycarboxylate water-reducerIn clay mineral, have stronger absorption trend, aggregate clay content is had to high susceptibility, this is to coagulationSoil transport, duty and intensity are all brought very large impact. Although country and professional standard are to concreteMiddle clay content, clod content's index have strict restriction, but are subject to material condition restriction, various places Sand for ConcreteAmount and kind difference, cause polycarboxylate water-reducer show in these places larger water-reducing rate and guarantor collapse poorThe opposite sex, and volume is changed to the sensitiveness embodying greatly. The method of the high clay content aggregate of reply, logical at presentNormal super volume and the composite two kinds of methods of adopting. Super mixing can make the initial serious segregation of concrete, and air content is high and tightGhost image rings products appearance and later strength. In polycarboxylate water-reducer more composite little molecules as gluconic acid sodium salt,Sucrose, citric acid, sylvite etc. improve concrete character, can not fundamentally solve polycarboxylate water-reducerAt the adaptability problem in high clay content area.
Patent documentation CN103508696A has reported anti-mud water reducer of a kind of polycarboxylic acids and preparation method thereof. WithTraditional polycarboxylate water-reducer is compared, author is by changing the component units of polyether structure, has introduced oilinessPropylene oxide units, thus part has weakened the suction-operated of the earth in concrete to water reducer molecule. ShouldPatent shortcoming is, the anti-mud DeGrain of synthesized polymer, and initial dispersion decreases.
From molecular structure, show as phosphate group substitutes by the functional group of introducing anti-clay adsorptionSome hydroxy-acid groups, the novel water reducer of developing a kind of high-adaptability should be the most effective approach.
Summary of the invention
Goal of the invention
An object of the present invention is to provide a kind of preparation method of polymeric additive, obtain a kind of new containingThe polymeric additive of phosphorous acid group, it can be used as hydraulic binding agent and/or latent hydraulicity cementing agentThe dispersant of aqueous dispersion.
Another object of the present invention is to provide the application of described polymeric additive as dispersant.
Summary of the invention
In a first aspect of the present invention, a kind of preparation method of polymeric additive is provided, comprise the following steps:
A. by the large monomer A of polyethers, carry out polycondensation reaction containing monomers B and the aldehyde C of carboxyl or ester group;
B. make described carboxyl or ester group phosphitylation;
The structural formula of the large monomer A of described polyethers as (I a) or (I b) as shown in:
Wherein, Z is NR3, O or O (CH2)fO, the integer that f is 1～10, the alkylene that Q is C2～C24Base, R2For H or C1～C10 alkyl, R3For C1～C10 alkyl, m=17～225, n=8～112, p=8～112;
The structural formula of described monomers B as (II a), (II b) or (II c) or as shown in:
Wherein, G is COOH or COOR4, wherein, R1For H, halogen atom, C1-C6 alkyl orSO3H, K is C1～C10 alkylidene, X=O, Y is OH or OR5，R4、R5Be independently of each otherC1～C10 alkyl,
The structural formula of described aldehyde C is as shown in (III):
R6CHO(III)
Wherein, R6For the alkyl of H, COOH or C1～C10,
Described phosphitylation is to make group G be converted into C (OH) (PO3H2)2。
In the present invention, described alkyl represents straight or branched alkyl, for example, C1～C10 alkyl can be methyl,Ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl,Sec-amyl, neopentyl, 1,1-dimethyl propyl, 1,2-dimethyl propyl, n-hexyl, isohesyl, Sec-Hexyl,New hexyl, 3-methyl amyl, 1,1-dimethylbutyl, 1,3-dimethylbutyl, 1-ethyl-butyl, 1-methyl isophthalic acid-Ethyl propyl, n-heptyl and isomers thereof, n-octyl and isomers thereof, n-nonyl and isomers thereof or positive decylAnd isomers.
The large monomer A of described polyethers can, by the benzene derivative that contains active H as initiator, cause epoxyalkaneQO ring-opening polymerisation obtains, and can make by oneself, also commercially available. Homemade method is known technology. Preferred alkylene oxideHydrocarbon QO is oxirane, expoxy propane, 1-epoxy butane, 2,3-epoxy butane, 2-methyl isophthalic acid, 2-epoxy thirdAt least one in alkane (epoxy iso-butane), 1-epoxy pentane. More preferably oxirane and/or expoxy propaneFor the present invention. Particularly use the mixture of pure oxirane or oxirane and expoxy propane, whereinIn described mixture, the mass percent of oxirane is at least 80%, can select in this case block structure orThe polyether chain of disordered structure. When the large monomer structure of polyethers as (I b) as shown in time, only need to adopt corresponding difunctionalityGroup's initiator. But because the large monomer A of polyethers of this structure has multiple reaction site, therefore partial monosomyBetween can produce crosslinked (because the large monomer reactivity of polyethers of this structure is lower, therefore just fraction is crosslinked,Do not affect the water-soluble and adsorption capacity of final products), this,, for improving condensation product molecular weight, promotes and protectsThe ability of collapsing has important effect.
The molecular weight of the large monomer A of described polyethers is preferably 1000～10000, and more preferably 1000～5000.Structure is as (the polyethers large monomer molecule amount preferable range of I as shown in b) and structure are as (the polyethers large list of I as shown in a)Body is identical, for example molecular weight can be 1000,1500,2000,2500,3000,3500,4000,4500 etc.
Described monomers B is containing carboxyl or ester group, and such monomers B can be to, adjacent, m-hydroxybenzoic acid, to,Adjacent, gavaculine, to, adjacent, m-hydroxybenzoic acid Arrcostab, comprise methyl esters, ethyl ester, propyl ester, fourthEster etc., to, adjacent, m-methoxybenzoic acid, 4-hydroxy-2-methylbenzoic acid, 4-hydroxy-3-methyl benzoic acid,P-hydroxyphenylaceticacid, homoanisic acid, the fluoro-4-hydroxyl phenylacetic acid of 3-, 2-phenoxyacetic acid, 2-phenoxy groupPropionic acid, 3-phenoxy propionic acid, 3-phenoxybutyhc, 3-(4-toloxyl) propionic acid (CAS:25173-37-9),3-(4-hydroxy methyl phenyloxy) propionic acid (CAS:101366-61-4) etc.
Preferably, the mol ratio (being designated hereinafter simply as A/B) of the large monomer A of described polyethers and monomers B is1:(0.5～6.0), more preferably 1:(1.0～4.5).
Described aldehyde C can be formaldehyde, acetaldehyde, and the alkyl aldehydes such as propionic aldehyde, can also be glyoxalic acid.
Preferably, the weight average molecular weight of described polymer is 4000～150000, more preferably 8000～100000,Most preferably be 10000～40000.
Preferably,
Z is O or O (CH2)fO, f=1～3, more preferably f=1～2, most preferably Z is O;
Q is C2～C4 alkylidene, is preferably C2～C3 alkylidene, more preferably CH2CH2；
R1For H or C1～C3 alkyl, be preferably H;
R2For H or C1～C3 alkyl, more preferably H;
R6For the alkyl of H, COOH or C1～C3, more preferably H or COOH;
Y is OH or OR5，R5Be preferably C1～C3 alkyl, more preferably methyl or ethyl, most preferably beMethyl;
K is C1～C3 alkylidene;
G is COOH or COOR4，R4Be preferably C1～C3 alkyl.
Described polycondensation reaction is the polycondensation reaction between the large monomer A of polyethers and monomers B and aldehyde C, is this area skillThe reaction type that art personnel know, concrete reaction condition can be definite through testing in conjunction with the universal experience of prior art.Preferably, described polycondensation reaction, taking acid as catalyst, mainly contains the concentrated sulfuric acid, methanesulfonic acid, p-methyl benzenesulfonic acid, 2-Naphthalene sulfonic acids, phosphoric acid, oxalic acid, concentrated hydrochloric acid, the preferably concentrated sulfuric acid, consumption is 0.2～1.0 of the large monomer molar amount of polyethersDoubly. Preferred, the condition of described polycondensation reaction is: reaction temperature is 80～140 DEG C, and the reaction time is 1～8Hour, preferred, reaction temperature is 90～130 DEG C, the reaction time is 2～6 hours. Described aldehyde C is with (poly-Large monomer A+the monomers B of ether) mol ratio of (being designated hereinafter simply as C/ (A+B)) is for being preferably 1.0～2.0. ForTo reaction accurately control, can adopt GPC detect this step polymerization conversion substantially constant after, thenCarry out step b.
In step b, add chlorinating agent and phosphitylation reagent to make group G be converted into C (OH) (PO3H2)2, itsThe group G that makes middle chlorinating agent changes COCl group into, and phosphitylation reagent makes COCl group change sub-phosphorus intoAcid groups, preferred described chlorinating agent is phosphorus trichloride, thionyl chloride or phosphorus pentachloride, phosphitylation reagent isPhosphorous acid, phosphorus trichloride, three (trimethyl silane) phosphite ester or Trimethyl phosphite, more preferably described chlorineBe phosphorus trichloride for reagent, phosphitylation reagent is phosphorus trichloride or phosphorous acid; Preferably chlorinating agent and phosphorous acidChanging total consumption of reagent and the mol ratio (being designated hereinafter simply as E/B) of group G is 3.0～4.1, wherein chloro examinationThe mol ratio of agent and group G is 1.0～1.1, and the mol ratio of phosphitylation reagent and group G is 2.0～3.0,E/B more preferably 3.0～3.5, most preferably is 3.0～3.2. More preferably chlorinating agent is phosphorus trichloride, phosphorous acidChanging reagent is phosphorus trichloride or phosphorous acid. Described phosphitylation reaction is known response type, art technology peopleMember generally knows its reaction principle and reaction condition. Particularly, the condition of phosphitylation reaction is: be warming up to60-100 DEG C, reaction 1-24 hour, is more preferably warming up to 60-90 DEG C, reaction 1-24 hour, question response knotShu Hou, adds a certain amount of water, 100 DEG C of hydrolysis 1-2 hour.
Conventionally for polycondensation reaction system, finally also need to remove unreacted aldehyde C. Concrete, the present invention existsPhosphitylation reaction finishes rear adjusting pH value, reaction a period of time, removes unreacted aldehyde C.
In order to obtain good storage stability, conventionally also need to adjust last production concentration to being no more than40%, preferably 30%～40%, described percentage is mass percent.
According to a second aspect of the invention, also provide described polymer as hydraulic binding agent and/or potential waterThe application of the dispersant of the aqueous dispersion of rigid cementing agent. Conventionally, described hydraulic binding agent be cement, lime,At least one in gypsum, anhydrous gypsum, preferably cement, described latent hydraulicity cementing agent is volcanic ash, powderCoal ash or blast-furnace cinder. Based on described hydraulic binding agent and/or latent hydraulicity cementing agent, of the present invention poly-The volume of compound is in 0.01% weight to 10% weight, especially 0.05% weight to 5% weight.
It should be noted that, in the present invention, the large monomer A of most of polyethers and monomers B have participated in reaction, transformFor the polymer containing phosphorous acid group, conversion ratio is more than 80%. But unreacted monomer and accessory substance be without separation,Can directly apply, can not cause obvious impact to its dispersion effect.
Beneficial effect of the present invention is:
1. phosphate can be hydrolyzed rapidly under strong alkali environment as adsorption group, thereby causes water reducer diminishingAbility is lost rapidly, and the present invention's application bidentate phosphorous acid is as adsorption group, and in phosphorous acid group, P and C are formerSon is directly connected, and can avoid hydrolysis, and function of slump protection is good. As shown in the Examples, even if use clay content higherSand test, compared with carboxylic acid type water reducing agent, polymer volume of the present invention will reduce, 1 hourAfter function of slump protection promote to some extent.
2. bidentate phosphorous acid has stronger coordination ability, can be adsorbed onto faster cement particle surface, and this hasBenefit the adaptability problem that solves current water reducer and clay.
3. compared with conventional carboxylic acid water reducer, the polymeric additive of bidentate phosphorous acid class of the present invention, to coagulationThe soil intensity of 3,7,28 days has castering action to a certain degree.
4. preparation method of the present invention can carry out in same reactor, and this is conducive to improve reaction efficiency,Reaction time shorten, thus realize the production of industrial large-scale.
Detailed description of the invention
Describe the present invention in detail below by example, these examples are only illustrative, do not represent that restriction originallyThe scope of application of invention, in embodiment, to be general analysis pure for medicine used or reagent, can be by normal wayFootpath buys.
In the embodiment of the present invention,
The molecular weight of polymer adopts gel permeation chromatograph (being called for short GPC) to measure molecular weight of the present inventionBe weight average molecular weight (hereinafter to be referred as Mw);
Reaction conversion ratio, by GPC test, the large monomer surplus of calculating polyethers, can obtain, obviously, and hereinConversion ratio refers to the conversion ratio of the large monomer A of polyethers.
The described GPC of above-mentioned test is that Wyatt Technology of the U.S. produces, wherein gel column: ShodexSB806+803 two root chromatogram column series connection; Elutriant: 0.1MNaNO3Solution; Mobile phase speed:0.8ml/min; Injection: the 20 μ l0.5% aqueous solution; Detector: ShodexRI-71 type differential refraction inspectionSurvey device; Reference material: polyethylene glycol GPC standard specimen (aldrich company of Sigma of the U.S., molecular weight 1010000,478000，263000，118000，44700，18600，6690，1960，628，232)。
In Application Example of the present invention, except special instruction, the cement adopting is the south of the River-little wild water in field mud (P.O42.5), stone is that particle diameter is the rubble of 5～20mm continuous grading. Sand is as shown in table 2.0. Cement pasteFluidity test is carried out with reference to GB/T8077-2000 standard, cement 300g, and amount of water is 87g, stirs 3minAfter on plate glass, measure flowing degree of net paste of cement. Relevant with reference to JC473-2001 " concrete pump-feed agent "The concrete performance of polymer of the present invention is mixed in regulation test.
The large monomer of polyethers is prepared as ethoxylation process, this with the large monomer of polyethers to methylphenoxy polyethylene glycolThe example that is prepared as be described. Initiator 2-(4-methylphenoxy) ethanol, catalyst NaOH. Take2-(4-methylphenoxy) ethanol 152g, NaOH 3g, adds reactor by above-mentioned material, room temperatureLower reactor is evacuated to-0.1MPa. Then reactor is warming up to 100 DEG C, in reactor, passes into epoxyEthane 50g, question response still internal pressure declines, temperature rise, illustrates that polymerisation starts. Continue to reactorInside pass into oxirane 1798g, in reinforced process, maintain temperature of reaction kettle between 100～120 DEG C, pressureBetween 0.2～0.4MPa, after the reinforced end of oxirane, 100 DEG C of insulation 1h left and right, question response still is pressedTill power no longer reduces, temperature of reaction kettle is reduced to 80 DEG C of left and right, opens atmospheric valve by reacting kettle inner pressureReduce to normal pressure, open reactor discharging, obtain sundown liquid, with the large monomer of polyethers to methylphenoxyPolyethylene glycol, it is 1987 that GPC tests its molecular weight, molecular weight distribution is 1.04.
Embodiment 1
In the present embodiment, A/B=1:2, C/ (A+B)=1, E/B=3.2.
Be equipped with at one that motor machine stirs, in the 1000ml four-hole boiling flask of heated at constant temperature oil bath, add firstPhenoxyl polyethylene glycol M1 (Mw=1000) 250g (0.25mol), P-hydroxybenzoic acid 69.05(0.50mol), sulfuric acid 12.5g (0.125mol), heating is stirred to it for an even phase. Subsequently at 30minDrip 37% formalin 60.75g (0.75mol). After dropwising, 100 DEG C of reactions 5 hours.After reaction finishes, be cooled to room temperature (25 DEG C), in 30min, add phosphorus trichloride 219.7g (1.6mol),Be warming up to 75 DEG C of reaction 12h, add subsequently water 336g (18.6mol), be warming up to 105 DEG C of hydrolysis1h. Reaction is cooled to room temperature, is neutralized to pH to 10 left and right with 30% alkali lye, and 110 DEG C are continued to react 0.5-1Hour, remove unreacted formaldehyde. Reaction is cooled to room temperature, and being diluted with water to solution concentration is 30%-40%Left and right.
Embodiment 2
In the present embodiment, A/B=1:2, C/ (A+B)=1.33, E/B=3.2.
Be equipped with at one that motor machine stirs, in the 1000ml four-hole boiling flask of heated at constant temperature oil bath, add 3-benzeneOxygen base propoxyl group polyethylene glycol (Mw=2000) 500g (0.25mol), P-hydroxybenzoic acid 69.05 (0.50Mol), sulfuric acid 25g (0.25mol), heating is stirred to it for an even phase. Drip at 30min subsequently37% formalin 81g (1.0mol). After dropwising, 100 DEG C of reactions 5 hours. Reaction knotShu Hou, is cooled to room temperature (25 DEG C), adds phosphorus trichloride 219.7g (1.6mol) in 30min, heats upTo 75 DEG C of reaction 12h, add subsequently water 336g (18.6mol), be warming up to 105 DEG C of hydrolysis 1h.Reaction is cooled to room temperature, is neutralized to pH to 10 left and right with 30% alkali lye, and 110 DEG C to continue to react 0.5-1 littleTime, remove unreacted formaldehyde. Reaction is cooled to room temperature, and being diluted with water to solution concentration is a 30%-40% left sideRight.
Embodiment 3
In the present embodiment, A/B=1:2, C/ (A+B)=1.0, E/B=3.2.
Be equipped with at one that motor machine stirs, in the 1000ml four-hole boiling flask of heated at constant temperature oil bath, add poly-secondGlycol monophenyl ether (Mw=1000) 250g (0.25mol), 4-methoxy benzoic acid 76.0g (0.50mol),Sulfuric acid 12.5g (0.125mol), heating is stirred to it for an even phase. Drip 37% at 30min subsequentlyFormalin 60.75g (0.75mol). After dropwising, 90 DEG C of reactions 6 hours. After reaction finishes,Be cooled to room temperature (25 DEG C), in 30min, add phosphorus trichloride 219.7g (1.6mol), be warming up to 75 DEG CReaction 12h, adds water 336g (18.6mol) subsequently, is warming up to 105 DEG C of hydrolysis 1h. React coolingTo room temperature, be neutralized to pH to 10 left and right with 30% alkali lye, 110 DEG C are continued reaction 0.5-1 hour, removeUnreacted formaldehyde. Reaction is cooled to room temperature, and being diluted with water to solution concentration is 30%-40% left and right.
Embodiment 4
In the present embodiment, A/B=1:2, C/ (A+B)=1.5, E/B=3.2.
Be equipped with at one that motor machine stirs, in the 1000ml four-hole boiling flask of heated at constant temperature oil bath, add poly-secondGlycol monophenyl ether (Mw=1000) 250g (0.25mol), 3-phenoxy propionic acid 82.58g (0.50mol),Sulfuric acid 12.5g (0.125mol), heating is stirred to it for an even phase. Drip 37% at 30min subsequentlyFormalin 91.5g (1.13mol). After dropwising, 130 DEG C of reactions 2 hours. After reaction finishes,Be cooled to room temperature (25 DEG C), in 30min, add phosphorus trichloride 219.7g (1.6mol), be warming up to 75 DEG CReaction 12h, adds water 336g (18.6mol) subsequently, is warming up to 105 DEG C of hydrolysis 1h. React coolingTo room temperature, be neutralized to pH to 10 left and right with 30% alkali lye, 110 DEG C are continued reaction 0.5-1 hour, removeUnreacted formaldehyde. Reaction is cooled to room temperature, and being diluted with water to solution concentration is 30%-40% left and right.
Embodiment 5
In the present embodiment, A/B=1:4, C/ (A+B)=1.0, E/B=3.0.
Be equipped with at one that motor machine stirs, in the 1000ml four-hole boiling flask of heated at constant temperature oil bath, add poly-secondGlycol monophenyl ether (Mw=1000) 250g (0.25mol), homoanisic acid 180.0g (1.0mol),Sulfuric acid 12.5g (0.125mol), heating is stirred to it for an even phase. Drip 37% at 30min subsequentlyFormalin 101.3g (1.25mol). After dropwising, 100 DEG C of reactions 5 hours. Reaction finishesAfter, be cooled to room temperature (25 DEG C), in 30min, add phosphorus trichloride 411.9g (3.0mol), be warming up to75 DEG C of reaction 12h, add water 336g (18.6mol) subsequently, are warming up to 105 DEG C of hydrolysis 1h. ReactionBe cooled to room temperature, be neutralized to pH to 10 left and right with 30% alkali lye, 110 DEG C are continued reaction 0.5-1 hour,Remove unreacted formaldehyde. Reaction is cooled to room temperature, and being diluted with water to solution concentration is 30%-40% left and right.
Embodiment 6
In the present embodiment, A/B=1:2, C/ (A+B)=1.0, E/B=3.2.
Be equipped with at one that motor machine stirs, in the 1000ml four-hole boiling flask of heated at constant temperature oil bath, add poly-secondGlycol monophenyl ether ((Mw=2000) 500g (0.25mol), ethyl-para-hydroxybenzoate 83.0g (0.50Mol), sulfuric acid 12.5g (0.125mol), heating is stirred to it for an even phase. Drip at 30min subsequently37% formalin 60.75g (0.75mol). After dropwising, 100 DEG C of reactions 5 hours. ReactionAfter end, be cooled to room temperature (25 DEG C), in 30min, add phosphorus trichloride 219.7g (1.6mol), riseTemperature, to 75 DEG C of reaction 12h, adds water 336g (18.6mol) subsequently, is warming up to 105 DEG C of hydrolysis 1h.Reaction is cooled to room temperature, is neutralized to PH to 10 left and right with 30% alkali lye, and 110 DEG C to continue to react 0.5-1 littleTime, remove unreacted formaldehyde. Reaction is cooled to room temperature, and being diluted with water to solution concentration is a 30%-40% left sideRight.
Embodiment 7
In the present embodiment, A/B=1:2, C/ (A+B)=1.6, E/B=3.2.
Be equipped with at one that motor machine stirs, in the 1000ml four-hole boiling flask of heated at constant temperature oil bath, add firstPhenoxyl polyethylene glycol (Mw=5000) 500g (0.125mol), P-hydroxybenzoic acid 34.5g (0.25Mol), sulfuric acid 6.25g (0.0625mol), heating is stirred to it for an even phase. Drip at 30min subsequentlyAdd 37% formalin 48.6g (0.6mol). After dropwising, 100 DEG C of reactions 5 hours. InsteadAfter should finishing, be cooled to room temperature (25 DEG C), in 30min, add phosphorus trichloride 110g (0.8mol),Be warming up to 60 DEG C of reaction 12h, add subsequently water 168g (9.3mol), be warming up to 105 DEG C of hydrolysis 1h.Reaction is cooled to room temperature, is neutralized to pH to 10 left and right with 30% alkali lye, and 110 DEG C to continue to react 0.5-1 littleTime, remove unreacted formaldehyde. Reaction is cooled to room temperature, and being diluted with water to solution concentration is a 30%-40% left sideRight.
Embodiment 8
In the present embodiment, A/B=1:2, C/ (A+B)=1.6, E/B=3.2.
Be equipped with at one that motor machine stirs, in the 1000ml four-hole boiling flask of heated at constant temperature oil bath, add poly-secondGlycol monophenyl ether (Mw=1000) 250g (0.25mol), P-hydroxybenzoic acid 69.05g (0.50mol),Sulfuric acid 6.25g (0.0625mol), heating is stirred to it for an even phase. Slowly drip 50% subsequently simultaneouslyGlyoxalic acid solution 44.4g (0.3mol) and 37% formalin 24.3g (0.3mol). DripAfter adding, 100 DEG C of reactions 5 hours. After reaction finishes, be cooled to room temperature (25 DEG C), at 30minInside add phosphorus trichloride 219.7g (1.6mol), be warming up to 110 DEG C of reaction 1h, add subsequently water 336g (18.6Mol), be warming up to 105 DEG C of hydrolysis 1h. Reaction is cooled to room temperature, is neutralized to pH with 30% alkali lyeTo 10 left and right, 110 DEG C are continued reaction 0.5-1 hour, remove unreacted aldehyde. Reaction is cooled to room temperature, usesIt is 30%-40% left and right that water is diluted to solution concentration.
Embodiment 9
In the present embodiment, A/B=1:2, C/ (A+B)=1.5, E/B=3.2.
Be equipped with at one that motor machine stirs, in the 1000ml four-hole boiling flask of heated at constant temperature oil bath, add structureThe large monomer M 2 of polyethers (Mw=1000) 250g that formula is as follows, 3-phenoxy propionic acid 82.58g (0.50Mol), sulfuric acid 12.5g (0.125mol), heating is stirred to it for an even phase. Drip at 30min subsequently37% formalin 91.5g (1.13mol). After dropwising, 100 DEG C of reactions 5 hours. ReactionAfter end, be cooled to room temperature (25 DEG C), in 30min, add phosphorus trichloride 219.7g (1.6mol), riseTemperature, to 75 DEG C of reaction 12h, adds water 336g (18.6mol) subsequently, is warming up to 105 DEG C of hydrolysis 1h.Reaction is cooled to room temperature, is neutralized to pH to 10 left and right with 30% alkali lye, and 110 DEG C to continue to react 0.5-1 littleTime, remove unreacted formaldehyde. Reaction is cooled to room temperature, and being diluted with water to solution concentration is a 30%-40% left sideRight.
Embodiment 10
In the present embodiment, A/B=1:1, C/ (A+B)=2.0, E/B=3.2.
Be equipped with at one that motor machine stirs, in the 1000ml four-hole boiling flask of heated at constant temperature oil bath, add poly-secondGlycol monophenyl ether (Mw=2000) 500g (0.25mol), P-hydroxybenzoic acid 34.53g (0.25mol),Sulfuric acid 25g (0.25mol), heating is stirred to it for an even phase. Drip subsequently 37% first at 30minAldehyde aqueous solution 81g (1.0mol). After dropwising, 100 DEG C of reactions 5 hours. After reaction finishes, fallTemperature, to room temperature (25 DEG C), adds phosphorus trichloride 109.9g (0.8mol) in 30min, is warming up to 75 DEG CReaction 12h, adds water 336g (18.6mol) subsequently, is warming up to 105 DEG C of hydrolysis 1h. React coolingTo room temperature, be neutralized to pH to 10 left and right with 30% alkali lye, 110 DEG C are continued reaction 0.5-1 hour, removeUnreacted formaldehyde. Reaction is cooled to room temperature, and being diluted with water to solution concentration is 30%-40% left and right.
Comparative example
The preparation of comparative example 1 is carried out with reference to the method for the disclosed embodiment 4 of patent documentation CN103508696B.
The preparation of comparative example 2 is carried out with reference to the disclosed embodiment 5 of patent documentation CN103183792B.
Table 1.0 polymerisation conversion and only starch fluidity
| Numbering | Mw | PDI | Conversion ratio (%) | Volume | Clean slurry result |
| Embodiment 1 | 17799 | 1.52 | 91 | (1.2‰) | 251( |
| Embodiment 2 | 22356 | 1.57 | 88 | (1.2‰) | 254 |
| Embodiment 3 | 16690 | 1.60 | 91 | (1.2‰) | 263 |
| Embodiment 4 | 16067 | 1.43 | 87 | (1.2‰) | 258 |
| Embodiment 5 | 11894 | 1.67 | 90 | (1.2‰) | 253 |
| Embodiment 6 | 21089 | 1.72 | 89 | (1.2‰) | 254 |
| Embodiment 7 | 31570 | 1.89 | 92 | (1.2‰) | 235 |
| Embodiment 8 | 21100 | 1.96 | 91 | (1.2‰) | 246 |
| Embodiment 9 | 38253 | 1.86 | 87 | (1.2‰) | 235 |
| Embodiment 10 | 21067 | 1.53 | 89 | (1.2‰) | 247 |
Flowing degree of net paste of cement is undertaken by GB/T8077-2000 " concrete admixture is even to property experimental technique "Test, wherein cement used is little wild water in field mud (300g), the ratio of mud is 0.29.
With reference to JC473-2001 " concrete pump-feed agent " relevant regulations, polymer of the present invention is mixed in testConcrete performance, test adopts sand sample shown in table 2.0. Result is as shown in table 3.0.
Table 2.0 sand sample sample message
| Sand sample numbering | The place of production | Modulus of fineness | Containing mud (%) |
| Sand sample 1 | Hunan-Dongting Lake sand | 2.9 | 2.3 |
| Sand sample 2 | Mingguang City | 2.6 | 3.7 |
Comparative example 1 is disclosed described anti-earth type water reducer sample in patent documentation, and comparative example 2 is patent literary compositionDisclosed conventional type water reducer sample in offering. Can be found out by table 3.0, in the higher sand of clay content, normalFormalism water reducer comparative sample 2 volumes are higher, and initial flow is less, although anti-chamotte mould comparative example 1 initial flowProperty increases to some extent compared with conventional type, but by contrast, embodiment of the present invention water-reducing rate is high, earth is had well suitableYing Xing, and 1 as a child slump-loss was obviously little compared with comparative example.
Table 3.0 concrete test result
Claims (10)
1. a preparation method for polymeric additive, is characterized in that, comprises the following steps:
A. by the large monomer A of polyethers, carry out polycondensation reaction containing monomers B and the aldehyde C of carboxyl or ester group;
B. make described carboxyl or ester group phosphitylation;
The structural formula of the large monomer A of described polyethers as (I a) or (I b) as shown in:
Wherein, Z is NR3, O or O (CH2)fO, the integer that f is 1～10, the alkylene that Q is C2～C24Base, R2For H or C1～C10 alkyl, R3For C1～C10 alkyl, m=17～225, n=8～112, p=8～112;
The structural formula of described monomers B as (II a), (II b) or (II c) or as shown in:
Wherein, G is COOH or COOR4, wherein, R1For H, halogen atom, C1-C6 alkyl orSO3H, K is C1～C10 alkylidene, X=O, Y is OH or OR5，R4、R5Be independently of each otherC1～C10 alkyl,
The structural formula of described aldehyde C is as shown in (III):
R6CHO(III)
Wherein, R6For the alkyl of H, COOH or C1～C10,
Described phosphitylation is to make group G be converted into C (OH) (PO3H2)2。
2. the preparation method of polymeric additive as claimed in claim 1, is characterized in that, described polymerWeight average molecular weight be 4000～150000, be preferably 8000～100000, more preferably 10000～40000.
3. the preparation method of polymeric additive as claimed in claim 1, is characterized in that,
Z is O or O (CH2)fO, f=1～3, more preferably f=1～2, most preferably Z is O;
Q is C2～C4 alkylidene, is preferably C2～C3 alkylidene, more preferably CH2CH2；
R1For H or C1～C3 alkyl, be preferably H;
R2For H or C1～C3 alkyl, more preferably H;
R6For the alkyl of H, COOH or C1～C3;
Y is OH or OR5，R5Be preferably C1～C3 alkyl, more preferably methyl or ethyl, most preferably beMethyl;
K is C1～C3 alkylidene;
G is COOH or COOR4，R4Be preferably C1～C3 alkyl.
4. the preparation method of polymeric additive as claimed in claim 3, is characterized in that, described polyethers is largeThe structural formula of monomer A as (I b) as shown in.
5. the preparation method of polymeric additive as claimed in claim 1, is characterized in that, described polyethers is largeThe mol ratio of monomer A and monomers B is 1:(0.5～6.0), be preferably 1:(1.0～4.5).
6. the preparation method of polymeric additive as claimed in claim 1, is characterized in that, described aldehyde CWith the mol ratio of (the large monomer A+monomers B of polyethers) be 1.0～2.0.
7. the preparation method of polymeric additive as claimed in claim 1, is characterized in that, in step b, addsEntering chlorinating agent and phosphitylation reagent makes group G be converted into C (OH) (PO3H2)2, wherein chlorinating agent makes baseThe G of group changes COCl group into, and phosphitylation reagent makes COCl group change phosphorous acid group into, preferably instituteStating chlorinating agent is phosphorus trichloride, thionyl chloride or phosphorus pentachloride, and phosphitylation reagent is phosphorous acid, tri-chlorinationPhosphorus, three (trimethyl silane) phosphite ester or Trimethyl phosphite, more preferably described chlorinating agent is tri-chlorinationPhosphorus, phosphitylation reagent is phosphorus trichloride or phosphorous acid; The 1.0-1.1 that preferably consumption of chlorinating agent is group GTimes equivalent, the 2.0-3.0 that the consumption of phosphitylation reagent is group G times equivalent.
8. the preparation method of polymeric additive as claimed in claim 1, is characterized in that, described polyethers is largeThe molecular weight of monomer A is 1000～10000, is preferably 1000～5000.
9. the preparation method of polymeric additive as claimed in claim 1, is characterized in that, described polycondensation is anti-The condition of answering is: reaction temperature is 80～140 DEG C, and the reaction time is 1～8 hour, preferred, reaction temperatureBe 90～130 DEG C, the reaction time is 2～6 hours.
In claim 1～9 any one preparation method resulting polymers additive as hydraulic binding agent and/ or the application of the dispersant of the aqueous dispersion of latent hydraulicity cementing agent.
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| CN108129625A (en) * | 2017-12-20 | 2018-06-08 | 江苏苏博特新材料股份有限公司 | A kind of phosphonic acid base water-reducing agent, preparation method and its application |
| WO2018120385A1 (en) * | 2016-12-30 | 2018-07-05 | 江苏苏博特新材料股份有限公司 | Phosphonato block polymer, preparation method therefor and application thereof |
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| CN108129625B (en) * | 2017-12-20 | 2020-06-26 | 江苏苏博特新材料股份有限公司 | Phosphonic acid-based water reducing agent, and preparation method and application thereof |
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