CN107602870A - A kind of aminated polyethers, the preparation method of its condensation polymer containing phosphorous acid and its application as cement dispersants - Google Patents
A kind of aminated polyethers, the preparation method of its condensation polymer containing phosphorous acid and its application as cement dispersants Download PDFInfo
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- CN107602870A CN107602870A CN201710975607.5A CN201710975607A CN107602870A CN 107602870 A CN107602870 A CN 107602870A CN 201710975607 A CN201710975607 A CN 201710975607A CN 107602870 A CN107602870 A CN 107602870A
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- polycondensation
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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
- C04B24/246—Phosphorus-containing polymers containing polyether side chains
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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
Abstract
The invention discloses a kind of aminated polyethers, the preparation method of its condensation polymer containing phosphorous acid and its application as cement dispersants.The aminated polyethers have the polyether segment of steric hindrance and hydrophilic and hydrophobic, and its one end is methoxy group；The other end is blocked for amine monomers, and polyether segment is connected on primary amine groups N H or secondary amine the N H of amine monomers, and random the characteristics of being grafted is presented.The polycondensation monomer formed on the phenyl ring of phenolic monomers and aldehyde monomers are grafted on using the aminated polyethers and phosphorous acid carries out polycondensation reaction, are obtained a kind of condensation polymer of phosphitylation, can be used as cement dispersants, there is preferable dispersion effect.
Description
Technical field
The invention belongs to concrete admixture preparation field, specifically a kind of aminated polyethers, it contains phosphorous acid
Condensation polymer preparation method and its application as cement dispersants.
Technical background
Water reducer is that the concrete for reducing the dosage of mixing water is additional under conditions of one kind ensures that concrete slump is constant
Agent.It is most of to belong to anion surfactant, there is peptizaiton, Neng Gougai to cement granules after adding concrete mix
The service behaviour of kind concrete.With the development of the industries such as super-long span bridges, ultra-large volume concrete and high-rise building,
The performances such as intensity and durability to concrete propose higher requirement, and water reducer is also from initial lignosulfonates diminishing
The Sulfonates water reducer such as agent, naphthalene water reducer develops into high-performance polycarboxylic acids water reducing agent of new generation.
It is the main chain of carboxylic acid adsorption group relative to the sulfonate based water reducer of linear structure, in polycarboxylate water-reducer structure
With the polyether lateral chain with certain length, not only with electrostatic repulsive force, and polyether lateral chain has certain steric hindrance
Effect.Two kinds of effect synergies, polycarboxylate water-reducer have the characteristics of water-reducing rate is high, volume is low, function of slump protection is excellent.With
The reduction of quality sand and stone aggregate, for the low-quality sandstone aggregate or Machine-made Sand that content of stone powder is high or clay content is high, tradition
Polycarboxylate water-reducer do not have good solution, mostly by improve water reducer volume, increase mix water consumption or
The methods of adding sacrifice agent, to ensure the performance of concrete.
The A of patent CN 103342500 report a kind of clay screener, by phosphate, silicate, sodium gluconate, ten
The raw materials such as sodium dialkyl sulfate carry out blending compounding and are made, the clay particle surface that can be preferentially adsorbed in sandstone aggregate, from
And ensure the effect of polycarboxylate water-reducer.
Wan Tianming etc. reports a kind of composite mud earth adsorbing (with answering for the anti-soil side effect of polycarboxylic acids water reducing agent compositional
Close soil adsorbent research [J] New Building Materials, 2014.10,34-37).With scattered diluent, retarder, ion complexation,
Surfactant and water are raw material, and composite mud earth adsorbing is made according to certain mass percent compounding, improves polycarboxylic acids
Initial flow performance and function of slump protection of the water reducer in low quality aggregate.
Existing research work shows that the adsorption capacity of phosphate radical is better than carboxylate radical, is compounded in polycarboxylate water-reducer
Small molecule phosphate, phosphate are preferentially adsorbed to clay particle surface, so as to reduce polycarboxylate water-reducer on clay particle
Absorption, ensure that using effect of the polycarboxylate water-reducer in low quality aggregate, but what this micromolecular phosphate played
Primary electron effect, the space steric effect of the compound of phosphorous acid groups how is developed, obtain increasing work in the industry
The attention of author.
The A of patent CN 105152565 report a kind of preparation method of polyphosphonic acid class water reducer, with methacrylic polyoxy
Vinethene, acrylic acid, vinyl phosphonate are raw material, are polymerize by random radical and polyphosphonic acid class water reducer is made, relative to general
Effect that logical polycarboxylate water-reducer has a more preferable diminishing and guarantor is collapsed, while there is certain deferred action.Patent CN
105713150 A utilize reversible addition-fracture transfer polymerization method, and bound phosphate groups calling sequence structure distribution is clearly embedding
On section polycarboxylic acids backbone structure, the water reducer prepared has obvious resistance to sulfates energy, and diminishing, guarantor is collapsed and cement is fitted
Answering property be improved significantly.
The A of patent CN 105713151 report one kind using phosphorous acid as adsorption group, are made using free radicals copolymerization reaction
A kind of combed water reducer using phosphite as adsorption group, the mobile performance and service behaviour for being effectively improved concrete keep energy
Power.The A of patent CN 106008853 are first by unsaturated halogenated hydrocarbons and unsaturated polyether, unsaturated carboxylic acid free radical prepolymerization, so
It is reacted with alkyl phosphate by Arbuzov afterwards to obtain the copolymerization product of phosphoric acid ester group, volume is low, water-reducing rate is high, protects
The advantages of time long and anti-mud that collapses is strong, can avoid the adverse effect that mud-containing aggregates are brought in concrete.
The studies above work successfully by phosphorous acid groups can polycondensation monomer by drawing with copolymerization such as carboxylic acid or polyether monomers
Enter into water reducer structure, the space that manufactured water reducer has the electronic effect of phosphate group concurrently simultaneously and polymer architecture provides
Steric effect, preferable water-reducing property, function of slump protection and clay tolerance are reached.But above-mentioned phosphorous acid groups gather
Monomer is closed, general phosphate group is joined directly together with polymerizable double bond or apart from close, has research work to show phosphate group
Itself there is certain chain transfer, also have and use phosphate as chain-transferring agent (Jiang Zhuo during the high performance water-reducer of part
Monarch etc., the preparation research [J] of ultrahigh concentration poly carboxylic acid series water reducer, New Building Materials, 2013, (3), 29-31).So by
, water reducer structure and molecular weight etc. be present and change in the water reducer copolymerization that the unsaturated monomer of phosphorous acid groups participates in
Possibility, the structure and molecular weight of water reducer can not be controlled accurately, it is necessary to be carried out in addition to the water reducers of phosphorous acid groups excellent
Change, complex steps and technology controlling and process difficulty.
The content of the invention
When the present invention is solves the unsaturated monomer for introducing phosphoric acid group, chain tra nsfer easily occurs for phosphorus-containing groups, that is, is copolymerized
Close reaction side reaction it is uncontrollable, make gained diminishing agent molecule structure and uncontrollable molecular weight the problem of, there is provided Yi Zhongxin
Synthetic route, introduce a kind of new polymerization intermediate-aminated polyethers, and phosphitylation reaction is carried out using aminated polyethers, obtain
A kind of structure and the controllable condensation polymer type product containing phosphorous acid of molecular weight are obtained, and uses it as cement dispersants.
The architectural feature of the aminated polyethers is：Polyether segment with certain space steric hindrance and hydrophilic and hydrophobic, one
Hold as methoxy group；The other end blocks for amine monomers, and polyether segment is connected to the primary amine groups N-H or secondary amine of amine monomers
On base N-H, random the characteristics of being grafted is presented.
It includes following structure：
Wherein, a represents the-CH in aminated polyethers2CH2NH- construction unit numbers, it is the integer between 1~45；B represents grafting
Polyether lateral chain ethylene oxide construction unit number, be 10~150 between integer；C represents the polyether lateral chain middle ring of grafting
The construction unit number of Ethylene Oxide, is similarly integer, can be 0, and no more than the 20% of ethylene oxide structure unit number b.
The structural formula of above-mentioned aminated polyethers intermediate only represents the one of which of heretofore described aminated polyethers intermediate
Architectural feature, primary amine groups N-H and secondary amine N-H is similar with the course of reaction reactivity of chloro polyethers in amine monomers, very
There is chloro polyethers and first reacts complete with the primary amine groups in amine monomers in difficulty, then the consecutive reaction with secondary amine N-H reactions again
Situation, the N-H of whole course of reaction chloro polyethers and amine monomers aminating reaction is random, the polyether lateral chain of grafting
It is random distribution.The structure of all heretofore described aminated polyethers intermediates only represents wherein the one of aminated polyethers intermediate
Kind tactic pattern, deliberately chosen to be better understood from and recognize the course of reaction of the present invention.
The preparation method of the aminated polyethers：Aminating reaction is carried out using amine monomers and chloro polyethers, amination is obtained and gathers
Ether.The mol ratio of the reaction of the amine monomers and chloro polyethers, amine monomers and chloro polyethers is 1：(1.00~1.10).
The amine monomers have the structure that is shown below
Belong to this kind of amine monomers has ethylenediamine, diethylenetriamine, triethylene tetramine, TEPA, five ethene six
One kind in the monomers such as amine, polyethylene polyamine, polyethyleneimine.
The chloro polyethers has following structure
The preparation method of the chloro polyethers, by monoalkoxy polyethers and chloro sulfoxide (SOCl2) reaction obtain with chlorine
For the chloro polyethers of structure.
The preparation technology of foregoing chloro polyethers is known to professional and technical personnel in the field, and bibliography is reported in the present invention
(He Weidong, synthesis and the evaluation [D] of polyether sulfonate, 2011, China University Of Petroleum Beijing).
The reaction of the amine monomers and chloro polyethers, using water as reaction medium, the dosage of water is chloro polyethers and amine
30wt%~60wt% of monomer gross mass, reaction temperature are 100~140 DEG C, and the reaction time is 8~15 hours.
The node configuration of the condensation polymer of the aminated polyethers containing phosphorous acid is in comb-type structure, with polycondensation monomer
The segment that phenyl ring condensation forms is main chain；To be grafted on the polyether segment on phenyl ring in polycondensation monomer as side chain, polyether segment by
Oxirane homopolymerization or oxirane and epoxypropane copolymerization are into and being amine monomers close to the polyether segment end of phenyl ring
The construction unit of composition, phosphorous acid adsorption group are grafted on amine monomers construction unit.Phosphorous acid adsorption group is in polyethers side
Block structure distribution is distributed as on chain, polyether lateral chain is distributed as disordered structure distribution on main chain.
It includes following structural formula：
A, b and c implication is same as above, and a represents the-CH in aminated polyethers2CH2NH- construction unit numbers, it is whole between being 1~45
Number；B represents the construction unit number of the polyether lateral chain ethylene oxide of grafting, is the integer between 10~150；C represents grafting
The construction unit number of polyether lateral chain oxypropylene, is similarly integer, can be 0, and no more than ethylene oxide structure list
The 20% of first number b.
The building-up process of the condensation polymer has following characteristics：Synthesized first with aminated polyethers with phenolic monomers with condensation
The polycondensation monomer of avtive spot, then polycondensation monomer, phosphorous acid and phenolic monomers are reacted, course of reaction includes polycondensation list
The phosphitylation of N-H and phosphorous acid is reacted in polycondensation reaction and polycondensation monomer between body, and two kinds of reactions are synchronous to be carried out.
The preparation method of the condensation polymer of the aminated polyethers containing phosphorous acid, it is following step：
(1) preparation of polycondensation monomer：Aminated polyethers and phenolic monomers are subjected to condensation reaction, obtain polycondensation monomer；
(2) under catalyst existence condition, the polycondensation monomer obtained by step (1), phosphorous acid, aldehyde monomers are subjected to polycondensation
Reaction, obtains the condensation polymer of the aminated polyethers containing phosphorous acid.
In previous reaction：Phenolic monomers：Aldehyde monomers：The mol ratio of amine monomers is 1：(1.00~1.20)：1.
The structure of polycondensation monomer is shown below described in step (1), and according to condensation reaction rule, amine monomers are grafted on
The ortho position of phenolic hydroxyl group on phenolic monomers or contraposition.
Wherein, the number of the substituent R of phenolic monomers is that 1, R represents H, OH ,-CH3、-OCH3、-CH2CH3、-OCH2CH3、-
OCH2CH2The carbon atom such as OH, isopropoxy, sec-butyl, the tert-butyl group, phenyl, nonyl, dodecyl, octadecyl number 0~
Alkyl group, alkoxy base or hydroxyalkyl group and its isomers between 20.
Phenolic monomers described in step (1) are phenol, 2- methylphenols, 3- methylphenols, 4- methylphenols, 2- sec-butyls
Phenol, 4- sec-butyl phenols, 2-TBP, 4-TBP, 4- nonyl phenols, 2- metoxyphenols, 3- methoxybenzenes
Phenol, 4- metoxyphenols, 2- thanatols, 3- thanatols, 4- thanatols, 2- isopropoxy phenols, 2- (2 hydroxyls
Base oxethyl) phenol, hydroquinones, catechol, resorcinol, 1- naphthols, beta naphthal etc..From the reaction site on aromatic ring
Number and reaction controlling convenience etc. consider, phenolic monomers of the present invention be preferably phenol, hydroquinones, catechol and
Any one in resorcinol.
The preparation reaction of polycondensation monomer described in step (1), has strict charging sequence.Phenolic monomers are first added, so
After be slowly added into aminated polyethers, be finally slowly added to aldehyde monomers.
The preparation reaction of polycondensation monomer described in step (1) needs to carry out in the basic conditions, due in aminated polyethers
Amido has stronger alkalescence in itself, and aminated polyethers are both reactant and base catalyst in itself in the present invention.
The preparation reaction of polycondensation monomer described in step (2), the dropping temperature of aldehyde monomers are added dropwise between 60~80 DEG C
Time is in 2~4h；Holding temperature after being added dropwise to complete is between 80~130 DEG C, and the insulation reaction time is in 2~6h.
Catalyst described in step (2) is highly acid homogeneous catalyst or heterogeneous catalysis；
Highly acid homogeneous catalyst is selected from concentrated hydrochloric acid, the concentrated sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoro ethyl sulfonic acid, benzene sulphur
Any one in acid, p-methyl benzenesulfonic acid, phosphoric acid.
Heterogeneous catalysis is selected from NKC-9 strong acidic ion resins, in Amberlyst-15 strong acidic ion resins
Any one.
Aldehyde monomers described in step (2) are formaldehyde, metaformaldehyde, paraformaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, benzaldehyde etc.
The compound of single aldehyde radical
Consider from cost and operation convenience etc., preferably using 37wt% formaldehyde as using in of the invention
Aldehyde monomers.
Foregoing polycondensation monomer, phosphorous acid, the mol ratio of aldehyde monomers are 1：(1.00~1.05) (a+1)：(1.00~
1.20)(a+2)。
The reaction of polycondensation monomer, phosphorous acid and aldehyde monomers described in step (2).In room-temperature water bath cooling and mechanical agitation
Under the conditions of, with polycondensation monomer bottoming, catalyst is slowly added into first, then adds phosphorous acid, last aldehyde monomers are using dropwise addition
Mode add above-mentioned reaction system.
Step is reacted described in (2), by controlling polycondensation reaction time, can control the condensation degree of polycondensation monomer, so as to
The molecular weight of polycondensation reaction thing is controlled, due to the phosphitylation reaction of amido simultaneously in polycondensation process be present, so needing
Ensure certain polycondensation reaction time.Preferably, reaction system is heated to 100 using oil bath or electric heater unit~
140 DEG C, it is 2~10 hours to be kept for the reaction time, obtains the condensation polymer type water reducer containing phosphorous acid.
In order to ensure phosphitylation reaction effect, the dosage of catalyst typically with the quality such as amine monomers.In addition, step
(2) reaction dissolvent water is no longer additionally added in, the water in reaction system is step (1) and aldehyde monomers introducing, to ensure to react
System is carried out in higher reaction density, improves reaction conversion ratio.
The condensation polymer type water reducer containing phosphorous acid, molecular weight is between 10000~100000, and it is as cement point
Powder uses.
Preferably molecular weight has preferable dispersive property between 10000~50000.
Beneficial outcomes：The preparation method of the condensation polymer of aminated polyethers of the present invention containing phosphorous acid, specifically,
Have the advantage that：
(1) solve the problems, such as the chain tra nsfer of phosphorus-containing groups in the polymerisable monomer that is run into radical polymerization process, pass through
The polycondensation reaction of phosphorous-containing monomers obtains the water reducer with certain molecular weight.This outer control is condensed the polycondensation reaction time of monomer,
The molecular weight of water reducer can be easily controlled, obtains being expected the water reducer product of molecular weight.
(2) the grafted amine groups polyethers on aromatic series phenolic monomers, the mol ratio of two kinds of monomers is controlled so that on phenolic monomers
Leave the vacant site for being available for carrying out condensation reaction.Phosphitylation reaction and the condensation of phenolic monomers for carrying out amido simultaneously are anti-
Should, obtain the condensation polymer type water reducer containing phosphorous acid.
(3) it is made by polycondensation mode, there is the molecular structure of similar comb shape.Using phosphorous acid as adsorption group, carry
Acted on for electrostatic repulsion；Using the polyethers with certain molecular weight as side chain, there is provided space steric effect.The collaboration of two kinds of effects is made
With so that water reducer has excellent diminishing, protects effect of collapsing, while phosphorous acid has certain slow setting and delay cement water
The effect of change.In addition, in terms of sulfate resistance, clay tolerance, the water reducer reported in the present invention is respectively provided with excellent application
Effect.
Specific embodiment
The present invention is described in detail below by example, and these examples are merely illustrative, do not represent the limitation present invention
The scope of application, according to disclosure herein, those skilled in the art can be within the scope of the present invention to reagent, catalyst and reaction work
Skill condition is changed.All equivalence changes made according to spirit of the invention or modification, it should all cover the present invention's
Within protection domain.
In the embodiment of the present invention, the conversion ratio of chloro polyethers in the synthetic yield and aminated polyethers synthetic reaction of chloro polyethers
It can be identified by liquid chromatogram, 120 Λ 250mm × 4.6mmid of pillar model Bioband GP120-C185 μm used are anti-phase
Post, mobile phase are first alcohol and water, and its volume ratio is 4：1, flow velocity 1ml/min.The number-average molecular weight of polymer uses Wyatt
Technology corporation gel permeation chromatographs determine.(gel column：The root chromatogram column strings of Shodex SB806+803 two
Connection；Elutriant：0.1M NaNO3Solution；Flow phase velocity：0.8ml/min；Injection：The aqueous solution of 20 μ l 0.5%；Detector：
Shodex RI-71 type differential refraction detectors；Reference material：Polyethylene glycol GPC standard specimen (Sigma-Aldrich, molecular weight
1010000,478000,263000,118000,44700,18600,6690,1960,628,232)。
In Application Example of the present invention, except special instruction, used cement is reference cement (P.O42.5), and sand is
Modulus of fineness Mx=2.6 middle sand, stone are the rubble that particle diameter is 5~20mm continuous gradings.Flowing degree of net paste of cement test ginseng
Carried out according to GB/T8077-2000 standards, amount of water 87g, flowing degree of net paste of cement is determined on plate glass after stirring 3min.
Air content, water-reducing rate test method are with reference to GB8076-2008《Concrete admixture》Relevant regulations perform.The slump and slump
Degree loss is with reference to JC473-2001《Concrete pump-feed agent》Relevant regulations perform.
Synthetic method in embodiment is divided into three parts, is the preparation of chloro polyethers first, followed by the amine of chloro polyethers
Change reaction, be finally the preparation and polycondensation reaction of polycondensation monomer.Part described in embodiment refers in particular to add for mass parts, unclassified stores
Enter amount and be scaled mass parts.
Embodiment 1
Chloro polyethers M-1 preparation.
Weigh 1000 parts of (M of methoxyl group polyethersn=1000, b=18, c=3) add reactor in, -0.08MPa~-
Under the conditions of 0.1MPa, 1h is vacuumized, removes the water in polyethers and a little volatile component.40~60 DEG C are cooled to, in N2Ceiling
Under part, SOCl is added into above-mentioned reaction system2155 parts, temperature of reaction system is controlled to be no more than 60 DEG C during dropwise addition.Drop
Add into and be followed by cooling and reflux device, temperature of reaction system is increased to 80~90 DEG C, continues 3~5h of insulation reaction, then
The acid volatile component being evaporated under reduced pressure out in reaction system, obtains pale tan product, is tested through liquid phase, chloro polyethers M-1's
Yield is 98.7%.Similarly, following chloro polyethers, the synthesis for aminated polyethers is made.
M-2：Methoxyl group polyethers (Mn=2000, b=45, c=0) 2000 parts, SOCl2155 parts, reaction temperature 80~90
DEG C, 3~5h of reaction time, yield 98.4%.
M-3：Methoxyl group polyethers (Mn=3000, b=54, c=10) 3000 parts, SOCl2180 parts, reaction temperature 80~90
DEG C, 3~5h of reaction time, yield 98.6%.
M-4：Methoxyl group polyethers (Mn=4000, b=84, c=5) 4000 parts, SOCl2192 parts, reaction temperature 80~90
DEG C, 3~5h of reaction time, yield 98.1%.
M-5：Methoxyl group polyethers (Mn=5000, b=93, c=15) 5000 parts, SOCl2215 parts, reaction temperature 80~90
DEG C, 3~5h of reaction time, yield 98.7%.
M-6：Methoxyl group polyethers (Mn=6000, b=136, c=0) 6000 parts, SOCl2225 parts, reaction temperature 80~90
DEG C, 3~5h of reaction time, yield 98.9%.
M-7：Methoxyl group polyethers (Mn=7000, b=148, c=8) 7000 parts, SOCl2238 parts, reaction temperature 80~90
DEG C, 3~5h of reaction time, yield 98.8%.
Embodiment 2
Aminated polyethers N-1 preparation
1952 parts of bottoming of polyethyleneimine (a=45) are weighed, are warming up to 60~80 DEG C.Weigh 1019 parts of M-1 and add water
891 parts of dilutions, are then gradually added into reaction system.After the completion of charging, 100 DEG C are warming up to, continues to react 15h, obtains claret
Liquid.Tested through liquid phase, chloro polyethers M-1 conversion ratios are close to 100%.
Similarly, following aminated polyethers, the preparation for polycondensation monomer is made.
N-2：877 parts of polyethyleneimine (a=20), 2221 parts of chloro polyethers M-2,1239 parts of aqueous solvent, reaction temperature
120 DEG C, reaction time 10h, product is claret liquid, is tested through liquid phase, and chloro polyethers M-2 conversion ratio is close to 100%.
N-3：275 parts of polyethylene polyamine (a=6), 3019 parts of chloro polyethers M-3,1647 parts of aqueous solvent, reaction temperature 140
DEG C, reaction time 8h, product is claret liquid, is tested through liquid phase, and chloro polyethers M-3 conversion ratio is close to 100%.
N-4：146 parts of triethylene tetramine (a=3), 4220 parts of chloro polyethers M-4,2499 parts of aqueous solvent, reaction temperature 110
DEG C, reaction time 13h, product is brown color liquid, is tested through liquid phase, and chloro polyethers M-4 conversion ratio is close to 100%.
N-5：60 parts of ethylenediamine (a=3), 5019 parts of chloro polyethers M-5,1524 parts of aqueous solvent, 130 DEG C of reaction temperature, instead
11h between seasonable, product is brown color liquid, is tested through liquid phase, and chloro polyethers M-5 conversion ratio is close to 100%.
N-6：447 parts of polyethyleneimine (a=10), 6019 parts of chloro polyethers M-6,2910 parts of aqueous solvent, reaction temperature
120 DEG C, reaction time 13h, product is claret liquid, is tested through liquid phase, and chloro polyethers M-6 conversion ratio is close to 100%.
N-7：189 parts of TEPA (a=4), 7019 parts of chloro polyethers M-6,3964 parts of aqueous solvent, reaction temperature 110
DEG C, reaction time 15h, product is brown color liquid, is tested through liquid phase, and chloro polyethers M-7 conversion ratio is close to 100%.
Embodiment 3
94 parts of bottoming of phenol are weighed, N-1 is gradually added into reaction system, 60~80 DEG C are warming up to after stirring.Weigh
81 parts of 37wt% formaldehyde, it is added dropwise completely in 2~4h, then heats to 85 DEG C, insulation reaction 6h.
After reaction terminates, room temperature cycles water cooling is opened, 50~60 DEG C is cooled to, weighs 1952 parts of catalyst concentrated hydrochloric acid,
Above-mentioned reaction system is gradually added into, 3772 parts of phosphorous acid is then added, is eventually adding 3811 parts of 37wt% formaldehyde.By reaction temperature
100 DEG C are risen to, continues to react 10h, obtains rufous liquid, tested through GPC, molecular weight 44497, PDI=3.52.
Embodiment 4
110 parts of bottoming of hydroquinones are weighed, N-2 is gradually added into reaction system, 60~80 DEG C are warming up to after stirring.
89 parts of 37wt% formaldehyde is weighed, is added dropwise completely in 2~4h, then heats to 95 DEG C, insulation reaction 5h.
After reaction terminates, room temperature cycles water cooling is opened, 50~60 DEG C is cooled to, weighs 877 parts of the catalyst concentrated sulfuric acid, by
Above-mentioned reaction system is gradually added, 1808 parts of phosphorous acid is then added, is eventually adding 1962 parts of 37wt% formaldehyde.By reaction temperature liter
To 110 DEG C, continue to react 8h, obtain rufous liquid, tested through GPC, molecular weight 24830, PDI=3.19.
Embodiment 5
110 parts of bottoming of catechol are weighed, N-3 is gradually added into reaction system, 60~80 DEG C are warming up to after stirring.
97 parts of 37wt% formaldehyde is weighed, is added dropwise completely in 2~4h, then heats to 105 DEG C, insulation reaction 4h.
After reaction terminates, room temperature cycles water cooling is opened, 50~60 DEG C is cooled to, weighs catalyst p-methyl benzenesulfonic acid
275 parts, above-mentioned reaction system is gradually added into, 585 parts of phosphorous acid is then added, is eventually adding 778 parts of 37wt% formaldehyde.Will reaction
Temperature rises to 120 DEG C, continues to react 6h, obtains rufous liquid, tested through GPC, molecular weight 31514, PDI=2.79.
Embodiment 6
94 parts of bottoming of phenol are weighed, N-4 is gradually added into reaction system, 60~80 DEG C are warming up to after stirring.Weigh
89 parts of 37wt% formaldehyde, it is added dropwise completely in 2~4h, then heats to 115 DEG C, insulation reaction 3h.
After reaction terminates, room temperature cycles water cooling is opened, 50~60 DEG C is cooled to, weighs catalyst trifluoro ethyl sulfonic acid 146
Part, above-mentioned reaction system is gradually added into, 338 parts of phosphorous acid is then added, is eventually adding 466 parts of 37wt% formaldehyde.Will reaction temperature
Degree rises to 130 DEG C, continues to react 4h, obtains rufous liquid, tested through GPC, molecular weight 27745, PDI=2.87.
Embodiment 7
94 parts of bottoming of phenol are weighed, N-5 is gradually added into reaction system, 60~80 DEG C are warming up to after stirring.Weigh
89 parts of 37wt% formaldehyde, it is added dropwise completely in 2~4h, then heats to 125 DEG C, insulation reaction 2h.
After reaction terminates, room temperature cycles water cooling is opened, 50~60 DEG C is cooled to, weighs catalyst trifluoromethanesulfonic acid 60
Part, above-mentioned reaction system is gradually added into, 171 parts of phosphorous acid is then added, is eventually adding 292 parts of 37wt% formaldehyde.Will reaction temperature
Degree rises to 140 DEG C, continues to react 2h, obtains rufous liquid, tested through GPC, molecular weight 21376, PDI=2.72.
Embodiment 8
94 parts of bottoming of phenol are weighed, N-6 is gradually added into reaction system, 60~80 DEG C are warming up to after stirring.Weigh
81 parts of 37wt% formaldehyde, it is added dropwise completely in 2~4h, then heats to 130 DEG C, insulation reaction 3h.
After reaction terminates, room temperature cycles water cooling is opened, 50~60 DEG C is cooled to, weighs catalyst n KC-9 highly acid trees
447 parts of fat, is gradually added into above-mentioned reaction system, then adds 938 parts of phosphorous acid, is eventually adding 1070 parts of 37wt% formaldehyde.Will
Reaction temperature rises to 110 DEG C, continues to react 5h, obtains rufous liquid, tested through GPC, molecular weight 37930, PDI=
3.49。
Embodiment 9
94 parts of bottoming of phenol are weighed, N-7 is gradually added into reaction system, 60~80 DEG C are warming up to after stirring.Weigh
97 parts of 37wt% formaldehyde, it is added dropwise completely in 2~4h, then heats to 110 DEG C, insulation reaction 4h.
After reaction terminates, room temperature cycles water cooling is opened, 50~60 DEG C is cooled to, weighs 189 parts of the catalyst concentrated sulfuric acid, by
Above-mentioned reaction system is gradually added, 418 parts of phosphorous acid is then added, is eventually adding 584 parts of 37wt% formaldehyde.Reaction temperature is risen to
130 DEG C, continue to react 4h, obtain rufous liquid, tested through GPC, molecular weight 38790, PDI=3.91.
Comparative example 1
110 parts of bottoming of resorcinol are weighed, N-2 is gradually added into reaction system, 60~80 DEG C are warming up to after stirring.
243 parts of 37wt% formaldehyde is weighed, is added dropwise completely in 2~4h, then heats to 150 DEG C, insulation reaction 1h.
After reaction terminates, room temperature cycles water cooling is opened, 50~60 DEG C is cooled to, weighs 200 parts of catalyst concentrated hydrochloric acid, by
Above-mentioned reaction system is gradually added, 3444 parts of phosphorous acid is then added, is eventually adding 5351 parts of 37wt% formaldehyde.By reaction temperature liter
To 150 DEG C, continue to react 10h, obtain rufous liquid, tested through GPC, molecular weight 91784, PDI=6.57.
Comparative example 2
94 parts of bottoming of phenol are weighed, N-6 is gradually added into reaction system, 60~80 DEG C are warming up to after stirring.Weigh
89 parts of 37wt% formaldehyde, it is added dropwise completely in 2~4h, then heats to 90 DEG C, insulation reaction 10h.
After reaction terminates, room temperature cycles water cooling is opened, 50~60 DEG C is cooled to, it is strong to weigh catalyst amberlyst-15
447 parts of acidic resins, are gradually added into above-mentioned reaction system, then add 902 parts of phosphorous acid, are eventually adding 37wt% formaldehyde 389
Part.Reaction temperature is risen to 90 DEG C, continues to react 20h, obtains rufous liquid, tested through GPC, molecular weight 9145, PDI=
7.24。
Application Example：
In Application Example, except special instruction, used cement is reference cement (P.O42.5), and sand is fineness mould
Number Mx=2.6 middle sand, stone is the rubble that particle diameter is 5~20mm continuous gradings.
Application Example 1
Flowing degree of net paste of cement test is carried out with reference to GB/T8077-2000 standards, and using reference cement 300g, amount of water is
87g, flowing degree of net paste of cement is determined on plate glass after stirring 3min.Experimental result is shown in Table 1.
The flowing degree of net paste of cement test result of table 1
The result explanation of table 1, the condensation polymer type water reducer of the present invention containing phosphorous acid not only have preferable to cement
Dispersibility, and collapsed ability with preferably guarantor.But the especially big either molecular weight of molecule is especially small or phosphitylation
The diminishing and guarantor that effect difference or the too wide comparative example 1 and 2 of molecular weight distribution are starched only effect of collapsing are poor.
Application Example 2
Air content, water-reducing rate test method are with reference to GB8076-2008《Concrete admixture》Relevant regulations perform.And
With reference to JC473-2001《Concrete pump-feed agent》Correlation technique determine water reducer fresh concrete of the present invention the slump and
60min, 120min through when the slump change, water reducer volume is fixed as the 0.35% of cement consumption, and experimental result is shown in Table 2.
The concrete 's air-containing of table 2, water-reducing rate and slump test result
As shown in Table 2, not only water-reducing property is good, protects for the condensation polymer type water reducer of the present invention containing phosphorous acid
Collapse excellent performance, and has certain retarding performance and good bleed performance.But molecule is especially big or molecular weight is special
The diminishing of the too wide concrete test of comparative example 1 and 2 of not small either phosphitylation effect difference or molecular weight distribution and guarantor
Effect of collapsing is poor.
Application Example 3
In order to evaluate the condensation polymer type water reducer of the invention containing phosphorous acid to the sensitiveness of clay, test containing clay
Sand configuration mortar fluidity.Wherein the divergence test of mortar is with reference to GB/T17671-1999《Cement mortar flows
The assay method of degree》Tested, wherein cement on the basis of cement used, cement mortar rate 1：3；The quality of clay substitution sand
0.5%；The ratio of mud is 0.44.Determine water reducer fresh mortar of the present invention fluidity and 60min, 120min through when flow
The change of degree.Experimental result is shown in Table 3.
The Mortar'S Flowability test result of table 3
As shown in Table 3, the condensation polymer type water reducer of the present invention containing phosphorous acid is for the clay in sand
Clay tolerance it is preferable.But the especially big either molecular weight of molecule is especially small or phosphitylation effect is poor or molecular weight divides
The diminishing of the too wide mortar test of comparative example 1 and 2 of cloth and guarantor effect of collapsing are poor.
Claims (18)
1. a kind of aminated polyethers, it is characterised in that its architectural feature is：Polyether segment with steric hindrance and hydrophilic and hydrophobic,
Its one end is methoxy group；The other end be amine monomers end-blocking, polyether segment be connected to amine monomers primary amine groups N-H or
On secondary amine N-H, random the characteristics of being grafted is presented；One of its structural formula is as follows：
Wherein, a represents the-CH in aminated polyethers2CH2NH- construction unit numbers, it is the integer between 1~45；B represents the poly- of grafting
The construction unit number of ether side chain ethylene oxide, it is the integer between 10~150；C represents epoxy third in the polyether lateral chain being grafted
The construction unit number of alkane, is similarly integer, can be 0, and no more than the 20% of ethylene oxide structure unit number b.
2. the preparation method of aminated polyethers described in claim 1, it is characterised in that carry out amine using amine monomers and chloro polyethers
Change reaction, obtain the aminated polyethers；The mol ratio of the amine monomers and chloro polyethers is 1：(1.00~1.10)；
The amine monomers have the structure that is shown below：
The chloro polyethers has following structure：
3. according to the method for claim 2, it is characterised in that the amine monomers are ethylenediamine, diethylenetriamine, three second
Alkene tetramine, TEPA, pentaethylene hexamine, polyethylene polyamine, any one in polyethyleneimine.
4. according to the method for claim 2, it is characterised in that the preparation method of the chloro polyethers, gathered by monoalkoxy
Ether and chloro sulfoxide (SOCl2) reaction obtain the chloro polyethers with chloro structure.
5. according to claim 2, the method described in any one in 3, or 4, it is characterised in that the amine monomers and chloro
The reaction of polyethers, using water as reaction medium, the dosage of water is chloro polyethers and 30wt%~60wt% of amine monomers gross mass,
Reaction temperature is 100~140 DEG C, and the reaction time is 8~15 hours.
6. the condensation polymer of the aminated polyethers containing phosphorous acid of aminated polyethers described in claim 1, it is characterised in that its structure
Configuration is in comb-type structure, and the segment that the condensation between the phenyl ring in polycondensation monomer forms is main chain；To be grafted in polycondensation monomer
Polyether segment on phenyl ring is side chain, and polyether segment is by oxirane homopolymerization or oxirane and epoxypropane copolymerization
Into, and be the construction unit that amine monomers are formed close to the polyether segment end of phenyl ring, phosphorous acid adsorption group is grafted on amine
On monomeric building blocks；Phosphorous acid adsorption group is distributed as block structure distribution in polyether lateral chain, and polyether lateral chain is in main chain
On be distributed as disordered structure distribution.
One of its structural formula is as follows：
A, b and c implication is same as above, and a represents the-CH in aminated polyethers2CH2NH- construction unit numbers, it is the integer between 1~45；b
The construction unit number of the polyether lateral chain ethylene oxide of grafting is represented, is the integer between 10~150；C represents the polyethers of grafting
The construction unit number of side chain oxypropylene, is similarly integer, can be 0, and no more than ethylene oxide structure unit number b
20%.
7. the preparation method of the condensation polymer of the aminated polyethers containing phosphorous acid of the aminated polyethers described in claim 1, it is special
Sign is, the polycondensation monomer with condensation avtive spot is synthesized with phenolic monomers first with aminated polyethers, then by polycondensation list
Body, phosphorous acid and phenolic monomers are reacted, in polycondensation reaction and polycondensation monomer of the course of reaction between polycondensation monomer N-H with
The phosphitylation reaction of phosphorous acid, two kinds of reactions are synchronous to be carried out.
8. method according to claim 7, it is characterised in that be specially following step：
(1) preparation of polycondensation monomer：Aminated polyethers and phenolic monomers are subjected to condensation reaction, obtain polycondensation monomer；
(2) it is under catalyst existence condition, the polycondensation monomer obtained by step (1), phosphorous acid, aldehyde monomers progress polycondensation is anti-
Should, obtain the condensation polymer of the aminated polyethers containing phosphorous acid；
In previous reaction：Phenolic monomers：Aldehyde monomers：The mol ratio of amine monomers is 1：(1.00~1.20)：1；
Foregoing polycondensation monomer, phosphorous acid, the mol ratio of aldehyde monomers are 1：(1.00~1.05) (a+1)：(1.00~1.20) (a+
2)。
The structure of polycondensation monomer is shown below described in step (1), and according to condensation reaction rule, amine monomers are grafted on phenols
The ortho position of phenolic hydroxyl group on monomer or contraposition；
Wherein, the number of the substituent R of phenolic monomers is that 1, R represents alkyl group of the carbon atom number between 0~20, alcoxyl
Base group or hydroxyalkyl group and its isomers；
Phenolic monomers described in step (1) are phenol, 2- methylphenols, 3- methylphenols, 4- methylphenols, 2- sec-butylbenzenes
Phenol, 4- sec-butyl phenols, 2-TBP, 4-TBP, 4- nonyl phenols, 2- metoxyphenols, 3- metoxyphenols,
4- metoxyphenols, 2- thanatols, 3- thanatols, 4- thanatols, 2- isopropoxy phenols, 2- (2 hydroxyl second
Epoxide) phenol, hydroquinones, catechol, resorcinol, 1- naphthols, any one in beta naphthal；
Catalyst described in step (2) is highly acid homogeneous catalyst or heterogeneous catalysis；
Highly acid homogeneous catalyst is selected from the concentrated hydrochloric acid, concentrated sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoro ethyl sulfonic acid, benzene sulfonic acid, right
Any one in toluenesulfonic acid, phosphoric acid；
Heterogeneous catalysis is selected from NKC-9 strong acidic ion resins, appointing in Amberlyst-15 strong acidic ion resins
Meaning is a kind of；
Aldehyde monomers described in step (2) are single aldehyde such as formaldehyde, metaformaldehyde, paraformaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, benzaldehyde
The compound of base.
9. method according to claim 8, it is characterised in that the phenolic monomers be phenol, hydroquinones, catechol and
Any one in resorcinol.
10. according to the method described in any one of claim 8 or 9, it is characterised in that polycondensation monomer described in step (1)
Reaction is prepared, phenolic monomers is first added, then adds aminated polyethers, be eventually adding aldehyde monomers.
11. according to the method described in any one of claim 8 or 9, it is characterised in that polycondensation monomer described in step (1)
Prepare reaction to carry out in the basic conditions, aminated polyethers are both reactant and base catalyst in itself.
12. according to the method described in any one of claim 8 or 9, it is characterised in that polycondensation monomer described in step (2)
Reaction is prepared, the dropping temperature of aldehyde monomers is between 60~80 DEG C, and time for adding is in 2~4h；Insulation temperature after being added dropwise to complete
Degree is between 80~130 DEG C, and the insulation reaction time is in 2~6h.
13. according to the method described in any one of claim 8 or 9, it is characterised in that polycondensation monomer, Asia described in step (2)
The reaction of phosphoric acid and aldehyde monomers；Under room-temperature water bath cooling and mechanical agitation, with polycondensation monomer bottoming, it is firstly added and urges
Agent, then phosphorous acid, last aldehyde monomers add above-mentioned reaction system by the way of being added dropwise.
14. according to the method described in any one of claim 8 or 9, it is characterised in that step is reacted described in (2), passes through control
Polycondensation reaction time processed, the condensation degree of polycondensation monomer is controlled, so as to control the molecular weight of polycondensation reaction thing, due in polycondensation reaction
During the phosphitylation reaction of amido simultaneously be present, reaction system is heated to 100 using oil bath or electric heater unit~
140 DEG C, it is 2~10 hours to be kept for the reaction time, obtains the condensation polymer of the aminated polyethers containing phosphorous acid.
15. according to the method described in any one of claim 8 or 9, it is characterised in that the dosage of catalyst and amine monomers etc.
Quality；In addition, no longer additionally adding reaction dissolvent water in step (2), the water in reaction system draws for step (1) and aldehyde monomers
Enter, to ensure that reaction system is carried out in higher reaction density, improve reaction conversion ratio.
16. according to the method for claim 14, it is characterised in that the condensation polymer containing phosphorous acid, its molecular weight
Between 10000~100000.
17. the application of the condensation polymer of the aminated polyethers containing phosphorous acid of aminated polyethers described in claim 1, its feature exist
In it is as cement dispersants application.
18. application according to claim 17, it is characterised in that the condensation polymer of the aminated polyethers containing phosphorous acid
Molecular weight between 10000~50000.
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