CN104592528B - A kind of method of low temperature lactate synthesis combed carboxylic acid polyalcohol - Google Patents
A kind of method of low temperature lactate synthesis combed carboxylic acid polyalcohol Download PDFInfo
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Abstract
The present invention relates to a kind of method of low temperature lactate synthesis combed carboxylic acid polyalcohol, under vacuum, makes monohydroxy polyethers and polyacrylic aqueous solution, and the catalyst of reactant folding 0.2 4wt% of solid gross mass, stirs, be passed through nitrogen；Under vacuum, nitrogen flow control air pressure is adjusted, and is warming up to esterification reaction temperature, add the solid acid catalyst of reactant folding 0.1 2wt% of solid gross mass, be esterified 4～8h, carboxylic acid polyalcohol of the synthesis with comb-type structure.The method that the present invention synthesizes polycarboxylate water-reducer using direct esterification between the polyacrylic acid and Polyethylene Glycol monoether macromole under high catalytic activity catalyst, the method has process is simple, products molecule structure design degree of freedom is big, product quality is stable, reaction temperature is low, energy consumption is low, the characteristics of low production cost.
Description
Technical field
The present invention relates to a kind of synthetic method for improving the polycarboxylate water-reducer of workability of concrete, more particularly, to
A kind of method of low temperature lactate synthesis combed carboxylic acid polyalcohol, belongs to technical field of concrete additives.
Background technology
The polycarboxylic acid polymer of comb-type structure is that a kind of novel concrete disperses water reducer, the ion-type polycarboxylic acids that it has
Main chain, nonionic polyether side chain so as to show the dispersibility special to cement granules, are generally acknowledge both at home and abroad new,
Environmental type third generation cement water reducing agent, represents the developing direction of concrete admixture from now on.
The characteristics of there is polycarboxylate water-reducer volume to support, little loss of slump, water-reducing rate high, cement adaptability is extensive, and
And the concrete prepared occurs without the phenomenons such as bleeding, isolation, can increase substantially cement replacement (the such as admixture such as flyash)
Consumption, improve concrete strength；Cement consumption can be saved under the conditions of equality strength, compared with other species water reducers, can be big
Width saves construction material manufacturing cost, increases economic efficiency.
The synthesis of polycarboxylate water-reducer typically adopts first lactate synthesis macromole polyethylene glycol monoacrylate polymeric monomer, so
The small molecule monomer copolymerization containing active group such as carboxylic acid, sulfonic acid, ester are carried with other again afterwards.The water reducer point of the method synthesis
Minor structure degree of freedom is big, and water reducer adjusting performance scope is wide, but will first prepare surface-active macromonomer, synthesizes high cost, economic benefit
Lowly, and the polymerization inhibitor that added in esterification process of surface-active macromonomer causes monomer purification technique very loaded down with trivial details, and diminishing
Agent performance quality also directly depends on the height of polymeric monomer esterification yield and double bond storage rate, and properties of product are difficult control, synthesize bar
Part requires strict, esterification reaction temperature height, and the degree of polymerization of product is not high, and water-reducing property is relatively low.
In order to avoid the loaded down with trivial details technique of lactate synthesis polymeric monomer, there is researcher to employ first polymerization and prepare carboxylic acid macromole master
After chain, then with the mode of monohydroxy polyethers esterification synthesizing polycarboxylate water-reducer.
Such as in patent publication No. CN 1275966A, the aqueous solution of polyacrylic acid and polyglycol ether is just existed by inventor
Eliminating water lactate synthesis polycarboxylate water-reducer under 180 celsius temperatures.But as, under enzymatic synthesis condition, the easy high temperature of Polyethylene Glycol divides
Solution, decomposes the terminal hydroxy group for producing and continues and the hydroxy-acid group condensation in polyacrylic acid backbone, can not only affect to be esterified endpoint,
Intermolecular crosslinking is easily caused simultaneously, affects properties of product.In patent No. US 6387176B1, inventor adopts polyacrylic acid
With monohydroxy polyethers as reaction raw materials, with sulphuric acid as catalyst, under nitrogen band water conservation, under 160 degrees Celsius, Jing divides greatly
Direct esterification between son has synthesized polycarboxylate water-reducer, synthesis technique is simple, it is to avoid the synthesis of unimolecule monomer and different anti-
The copolymerization between activated monomer is answered, resulting product structure controllability is good, and product quality is stable.
The traditional catalyst that esterification is usually used, such as sulphuric acid, p-methyl benzenesulfonic acid, benzenesulfonic acid etc., although catalytic effect
Preferably, but catalysis activity is relatively low, cause esterification reaction temperature high, the response time is long, esterification process side reaction degree is high so that big
Intermolecular esterification is very difficult.
The content of the invention
The invention aims to overcome above-mentioned of the prior art not enough and provide a kind of low temperature lactate synthesis comb
The method of type carboxylic acid polyalcohol；The present invention is divided with monohydroxy polyethers greatly using polyacrylic acid using the catalyst of high catalytic activity
Sub- esterification process, carries out esterification synthesis polycarboxylate water-reducer under low-temperature vacuum environment.By experiment, it has been found that using high
The catalyst of catalysis activity carries out the esterification of polyacrylic acid and monohydroxy polyethers under low-temperature vacuum environment, is not only esterified speed
Rate is fast, and only 4～8h can just reach～more than 95% esterification yield, while greatly having resisted side reaction, properties of product are stable, prepared
Final product be solid, directly can transport, also can dissolve after be configured to solution.
The technical scheme is that：A kind of method of low temperature lactate synthesis combed carboxylic acid polyalcohol, its concrete steps is such as
Under：
A)：In the reaction kettle of the esterification with vacuum equipment and water knockout drum, monohydroxy polyethers is added, the lower heating of stirring is molten
Melt；Polyacrylic aqueous solution is sequentially added, and accounts for the catalyst that reactant rolls over solid gross mass 0.2-4%, stirred,
Nitrogen is passed through, air in kettle is discharged；
B)：Start vacuum, adjust nitrogen flow, the water in reactant is separated in 4kPa～12kPa by air pressure in control kettle
To in water knockout drum；60～90 degrees Celsius of reaction temperature, addition is kept to account for the solid acid catalysis of solid gross mass 0.1-2% of reactant folding
Agent, 4～8h of esterification；
C)：Reaction stops insulation after terminating, and closes vacuum equipment, and nitrogen will be passed through in kettle, and (product is made a slip of the tongue by discharging for discharging
Filter screen separating catalyst, is released in special container, seals off air), solid carboxylic acid polymer is obtained after cooling, can root
According to practical situation or aqueous solution is configured to, serves as concrete additive.
It is preferred that above-mentioned esterification reaction temperature is at 60～90 DEG C；The temperature of melting is heated in step A typically at 60～80 DEG C.
Preferred steps A) described in catalyst be one kind or their mixture in sulphuric acid or p-methyl benzenesulfonic acid.Also may be used
With with the one kind in hydrochloric acid, phosphoric acid, sodium dihydrogen phosphate or boric acid or their mixture.
Preferred steps B) described in solid catalyst be SO4 2-/F2O3(SF)、SO4 2-/ZrO2Or SO (SZ)4 2-/TiO2
(ST) one or more in；Also or the composite load solid acid of one of which metal-oxide and aluminium oxide.
It is preferred that above-mentioned monohydroxy polyethers has following structure：
HO—(CH2CHR1O)m—(CH2CHR2O)n—R’
Its degree of functionality of hydroxyl is 1, R1And R2For H or CH3, R ' is C1—C5Alkyl, m and n is the integer between 16～90.
More preferably described monohydroxy polyethers be poly glycol monomethyl ether (such as：MPEG-1200, MPEG-700, MPEG-2400, MPEG-
Or poly(ethylene oxide) polypropylene oxide monobutyl base ether 1200)；Its number-average molecular weight is 700～4000.
Preferred steps A) described in polyacrylic acid solution solids content be 30～50wt%, polyacrylic number-average molecular weight
For 2000～4000.It is preferred that polyacrylic addition is 2～5 to control sour ether ratio between polyacrylic acid and monohydroxy polyethers.
The carboxylic acid polyalcohol that the present invention obtains state of aggregation and contains comb-type structure for solid；Have in improving cement or concrete stream
The purposes of dynamic and service behaviour.
Beneficial effect：
Cryogenic vacuum esterification technique used in the present invention, has the advantages that not available for traditional esterifications technique.For synthesis
Concrete admixture carboxylic acid polyalcohol provides the reliable and stable technology of preparing of properties of product, prepared polycarboxylate water-reducer
Water-reducing rate is high, and slump holding capacity is strong, while simple production process, energy-conservation, cleaning, are in particular in：
1st, different and traditional esterifications polymeric monomer synthesis technique, the present invention is using ester between PAA the and MPEG macromole being polymerized
Change, it is to avoid esterification monomer synthesis and copolyreaction, simplified production technology, stable and reliable product quality.
2nd, compared with past esterification technique, esterification technique reaction temperature according to the present invention is lower, it is to avoid under high temperature
Impact of the side reaction to product quality, while energy consumption is lower, operation is simpler, production equipment easy care.
3rd, under the catalysis of high-efficient esterified catalyst, esterification activation energy is reduced significantly, and esterification rate faster, is produced
Operation is shorter.
4th, the high-efficient esterified catalyst for being used, it is easily separated after the completion of reaction, it is reusable, and equipment will not be made
Into corrosion, easy to use, effect on environment is very little.
5th, synthesized polycarboxylic acids solid product can direct packed and transported, reduce cost in solution transportation, and
And store convenient.
Specific embodiment
Below by way of the specific embodiment explanation present invention, but the present invention is not merely defined in these embodiments.
Flowing degree of net paste of cement is tested：Flowing degree of net paste of cement reference《Concrete admixture homogeneity test method》
(GB8077-2000) standard is detected.
Embodiment 1：
With the PAA 50wt% aqueous solutions of number-average molecular weight about 2000, MPEG-1200 is raw material, synthesis of carboxylic acid polymer
Method is as follows：
Reactor is added after the MPEG-1200 of 120.0g is melted under 70 degrees Celsius, 36.0g is added under agitation
PAA 50wt% aqueous solutions, sour ether ratio be 2.5:1, and the solid reactant gross mass 0.5wt% p-methyl benzenesulfonic acid of folding is added, it is passed through
Nitrogen.
Under nitrogen protection, start vacuum equipment, air pressure is about in 4kPa in regulation reactor.By nitrogen band water, remove
Water in reaction system, in water knockout drum, water is not further added by, or temperature of reaction system is stable after 70 degrees Celsius of half an hour, by
Constant pressure addition device adds the SF catalyst of solid gross mass 0.1wt% of reactant folding, is incubated 70 degrees Celsius, is esterified 6h.Stop insulation,
Nitrogen is passed through, and closes vacuum equipment, product seal isolation air is cooled to into room temperature.
Product acid value stabilization exists, 98.3mgKOH/g, esterification yield 98.7%.And it was found that it can serve as cement additive,
Increase the mobile performance and service behaviour of cement slurry, be shown in Table 1.It can be found which has preferably dispersion energy to cement granules
Power and holding capacity.
Embodiment 2：
With the PAA 50wt% aqueous solutions of number-average molecular weight about 4000, MPEG-700 is raw material, synthesis of carboxylic acid polymer
Method is as follows：
Reactor is added after the MPEG-700 of 70.0g is melted under 60 degrees Celsius, adds 28.8g's under agitation
PAA 50wt% aqueous solutions, sour ether compare 2:1, and the solid reactant gross mass 0.5wt% p-methyl benzenesulfonic acid of folding is added, it is passed through nitrogen.
Under nitrogen protection, start vacuum equipment, air pressure is about in 8kPa in regulation reactor.By nitrogen band water, remove
Water in reaction system, in water knockout drum, water is not further added by, or temperature of reaction system is stable after 70 degrees Celsius of half an hour, by
Constant pressure addition device adds the SF catalyst of solid gross mass 0.2wt% of reactant folding, is incubated 60 degrees Celsius, is esterified 7h.Stop insulation,
Nitrogen is passed through, and closes vacuum equipment, product seal isolation air is cooled to into room temperature.
Product acid value stabilization is in 73.3mgKOH/g, esterification yield 97.9%.And it was found that it can serve as cement additive,
Increase the mobile performance and service behaviour of cement slurry, be shown in Table 2.It can be found that in raising PAA molecular weight, and reduce polyethers side
After chain molecular weight, carboxylic acid polyalcohol has very high score cement dispersibility, and while has prolonged holding capacity.
Embodiment 3：
With the PAA 50wt% aqueous solutions of number-average molecular weight about 2000, MPEG-2400 is raw material, synthesis of carboxylic acid polymer
Method is as follows：
Reactor is added after the MPEG-2400 of 120.0g is melted under 80 degrees Celsius, 21.6g is added under agitation
PAA 50wt% aqueous solutions, sour ether compares 3:1, and the solid reactant gross mass 0.5wt% p-methyl benzenesulfonic acid of folding is added, it is passed through nitrogen
Gas.
Under nitrogen protection, start vacuum equipment, air pressure is about in 6kPa in regulation reactor.By nitrogen band water, remove
Water in reaction system, in water knockout drum, water is not further added by, or temperature of reaction system is stable after 70 degrees Celsius of half an hour, by
Constant pressure addition device adds the SF catalyst of solid gross mass 0.1wt% of reactant folding, is incubated 80 degrees Celsius, is esterified 5h.Stop insulation,
Nitrogen is passed through, and closes vacuum equipment, product seal isolation air is cooled to into room temperature.
Product acid value stabilization is in 108.3mgKOH/g, esterification yield 99.2%.And it was found that it can serve as cement additive,
Increase the mobile performance and service behaviour of cement slurry, be shown in Table 3.It can be found that increase polyether lateral chain molecular weight can be greatly improved
Dispersibility of the carboxylic acid polyalcohol to cement, but holding capacity is declined slightly.
Embodiment 4：
With the PAA 50wt% aqueous solutions of number-average molecular weight about 2000, MPEG-1200 is raw material, synthesis of carboxylic acid polymer
Method is as follows：
Reactor is added after the MPEG-1200 of 120g is melted under 70 degrees Celsius, adds 43.2g's under agitation
PAA 50wt% aqueous solutions, sour ether compare 3:1, and the solid reactant gross mass 0.5wt% p-methyl benzenesulfonic acid of folding is added, it is passed through nitrogen.
Under nitrogen protection, start vacuum equipment, air pressure is about in 4kPa in regulation reactor.By nitrogen band water, remove
Water in reaction system, in water knockout drum, water is not further added by, or temperature of reaction system is stable after 70 degrees Celsius of half an hour, by
Constant pressure addition device adds the SZ catalyst of solid gross mass 0.1wt% of reactant folding, is incubated 70 degrees Celsius, is esterified 6h.Stop insulation,
Nitrogen is passed through, and closes vacuum equipment, product seal isolation air is cooled to into room temperature.
Product acid value stabilization is in 128.3mgKOH/g, esterification yield 98.7%.And it was found that it can serve as cement additive,
Increase the mobile performance and service behaviour of cement slurry, be shown in Table 4.It can be found which has preferably dispersion energy to cement granules
Power and holding capacity.
Embodiment 5：
With the PAA 50wt% aqueous solutions of number-average molecular weight about 2000, MPEG-1200 is raw material, synthesis of carboxylic acid polymer
Method is as follows：
Reactor is added after the MPEG-1200 of 120g is melted under 70 degrees Celsius, adds 43.2g's under agitation
PAA 50wt% aqueous solutions, sour ether compare 3:1, and the solid reactant gross mass 0.5wt% p-methyl benzenesulfonic acid of folding is added, it is passed through nitrogen.
Under nitrogen protection, start vacuum equipment, air pressure is about in 4kPa in regulation reactor.By nitrogen band water, remove
Water in reaction system, in water knockout drum, water is not further added by, or temperature of reaction system is stable after 70 degrees Celsius of half an hour, by
Constant pressure addition device adds the ST catalyst of solid gross mass 0.1wt% of reactant folding, is incubated 70 degrees Celsius, is esterified 6h.Stop insulation,
Nitrogen is passed through, and closes vacuum equipment, product seal isolation air is cooled to into room temperature.
Product acid value stabilization is in 122.3mgKOH/g, esterification yield 99.7%.And it was found that it can serve as cement additive,
Increase the mobile performance and service behaviour of cement slurry, be shown in Table 5.It can be found which has preferably dispersion energy to cement granules
Power and holding capacity.
Embodiment 6
With the PAA 50wt% aqueous solutions of number-average molecular weight about 2000, MPEG-1200 is raw material, synthesis of carboxylic acid polymer
Method is as follows：
Reactor is added after the MPEG-1200 of 120g is melted under 70 degrees Celsius, adds 43.2g's under agitation
PAA 50wt% aqueous solutions, sour ether compare 3:1, and the solid reactant gross mass 0.5wt% sulphuric acid of folding is added, it is passed through nitrogen.
Under nitrogen protection, start vacuum equipment, air pressure is about in 4kPa in regulation reactor.By nitrogen band water, remove
Water in reaction system, in water knockout drum, water is not further added by, or temperature of reaction system is stable after 70 degrees Celsius of half an hour, by
Constant pressure addition device adds the SF catalyst of 0.1wt%, is incubated 70 degrees Celsius, is esterified 6h.Stop insulation, be passed through nitrogen, and close
Product seal isolation air is cooled to room temperature by vacuum equipment.
Product acid value stabilization exists, 130.3mgKOH/g, esterification yield 96.7%.And it was found that it to can serve as cement additional
Agent, increases the mobile performance and service behaviour of cement slurry, is shown in Table 6.It can be found which has to cement granules preferably dividing
Scattered ability and holding capacity.
Embodiment 7：
With the PAA 30wt% aqueous solutions of number-average molecular weight about 2000, poly(ethylene oxide) polypropylene oxide monobutyl base ether 2000
For raw material, the method for synthesis of carboxylic acid polymer is as follows：
Reactor is added after the poly(ethylene oxide) polypropylene oxide monobutyl base ether 2000 of 200g is melted under 75 degrees Celsius,
The PAA 30wt% aqueous solutions of 60g, sour ether is added to compare 2.5 under agitation:1, and add solid reactant gross mass 4wt% of folding
P-methyl benzenesulfonic acid, is passed through nitrogen.
Under nitrogen protection, start vacuum equipment, air pressure is about in 4kPa in regulation reactor.By nitrogen band water, remove
Water in reaction system, in water knockout drum, water is not further added by, or temperature of reaction system is stable after 70 degrees Celsius of half an hour, by
Constant pressure addition device adds the SF catalyst of solid reactant gross mass 0.2wt% of folding, is incubated 70 degrees Celsius, is esterified 6h.Stop insulation,
Nitrogen is passed through, and closes vacuum equipment, product seal isolation air is cooled to into room temperature.
Product acid value stabilization exists, 100.5mgKOH/g, esterification yield 94.1%.And it was found that it to can serve as cement additional
Agent, increases the mobile performance and service behaviour of cement slurry, is shown in Table 7.It can be found which has to cement granules preferably dividing
Scattered ability and holding capacity.
Embodiment 8：
With the PAA 30wt% aqueous solutions of number-average molecular weight about 2000, MPEG-1200 is raw material, synthesis of carboxylic acid polymer
Method is as follows：
Reactor is added after the poly(ethylene oxide) polypropylene oxide monobutyl base ether 2000 of 120g is melted under 75 degrees Celsius,
The PAA 30wt% aqueous solutions of 120g, sour ether is added to compare 5 under agitation:1, and add solid reactant gross mass 4wt% of folding
P-methyl benzenesulfonic acid, is passed through nitrogen.
Under nitrogen protection, start vacuum equipment, air pressure is about in 4kPa in regulation reactor.By nitrogen band water, remove
Water in reaction system, in water knockout drum, water is not further added by, or temperature of reaction system is stable after 70 degrees Celsius of half an hour, by
Constant pressure addition device adds the SF catalyst of solid reactant gross mass 0.2wt% of folding, is incubated 70 degrees Celsius, is esterified 6h.Stop insulation,
Nitrogen is passed through, and closes vacuum equipment, product seal isolation air is cooled to into room temperature.
Product acid value stabilization exists, 180.5mgKOH/g, esterification yield 94.1%.And it was found that it to can serve as cement additional
Agent, increases the mobile performance and service behaviour of cement slurry, is shown in Table 8.It can be found which has to cement granules preferably dividing
Scattered ability and holding capacity.
Embodiment 9 (comparative example)
With the PAA 50wt% aqueous solutions of number-average molecular weight about 2000, MPEG-2400 is raw material, synthesis of carboxylic acid polymer
Method is as follows：
Reactor is added after the MPEG-2400 of 120g is melted under 80 degrees Celsius, adds 43.2g's under agitation
PAA 50wt% aqueous solutions, and add the solid reactant gross mass 2wt% concentrated sulphuric acid of folding as catalyst, it is passed through nitrogen protection.Will
Reactor is warming up to 160 degrees Celsius, reacts 8h.Now product acid number be 77.3mgKOH/g, esterification yield 117.8%.Stop heating
And lower the temperature, when temperature is reduced to 100 degrees Celsius, 212.4g water is added, now temperature is 84 degrees Celsius, under nitrogen protection,
Continue cooling down to room temperature, obtain carboxylic acid polyalcohol aqueous solution.Resulting carboxylic acid polyalcohol can serve as cement additive,
Its performance is shown in Table 9.It is found that due to the strong oxidizing property of sulphuric acid, causing serious side reaction, polyether lateral chain to decompose at high temperature
Seriously, cause product acid number well below theoretical value as the terminal hydroxy group that fracture is produced participates in esterification, significantly impact product
Performance, simultaneously because catalyst activity is low, esterification time is long, and product synthesis cost performance is low.
Table 1. is with the PAA and MPEG-1200 of number-average molecular weight about 2000 as Material synthesis carboxylic acid polyalcohol properties of product
Table 2. is with the PAA and MPEG-700 of number-average molecular weight about 4000 as Material synthesis carboxylic acid polyalcohol properties of product
Table 3. is with the PAA and MPEG-2400 of number-average molecular weight about 2000 as Material synthesis carboxylic acid polyalcohol properties of product
Table 4. is with the PAA and MPEG-1200 of number-average molecular weight about 2000 as Material synthesis carboxylic acid polyalcohol properties of product
Table 5. is with the PAA and MPEG-1200 of number-average molecular weight about 2000 as Material synthesis carboxylic acid polyalcohol properties of product
Table 6. is with the PAA and MPEG-1200 of number-average molecular weight about 2000 as Material synthesis carboxylic acid polyalcohol properties of product
Table 7. is with the PAA of number-average molecular weight about 2000 and poly(ethylene oxide) polypropylene oxide monobutyl base ether 2000 as raw material pair
Ratio properties of product
Table 8. is with the PAA and MPEG-1200 of number-average molecular weight about 2000 as Material synthesis carboxylic acid polyalcohol properties of product
Table 9. is with the PAA and MPEG-2400 of number-average molecular weight about 2000 as Material synthesis carboxylic acid polyalcohol properties of product
Claims (6)
1. a kind of method of low temperature lactate synthesis combed carboxylic acid polyalcohol, which comprises the following steps that：
A)：In the reaction kettle of the esterification with vacuum equipment and water knockout drum, monohydroxy polyethers, the lower heating melting of stirring are added；Again
Polyacrylic aqueous solution is sequentially added, and accounts for the catalyst that reactant rolls over solid gross mass 0.2-4%, stirred, be passed through
Nitrogen, air in kettle is discharged；Wherein polyacrylic number-average molecular weight is 2000～4000；
B)：Start vacuum, adjust nitrogen flow, the water in reactant is separated to point in 4kPa～12kPa by air pressure in control kettle
In hydrophone；60～90 degrees Celsius of reaction temperature, addition is kept to account for the solid acid catalyst of solid gross mass 0.1-2% of reactant folding,
4～8h of esterification；
C)：Reaction stops insulation after terminating, and closes vacuum equipment, nitrogen will be passed through in kettle, discharges, solid carboxylic is obtained after cooling
Acid polymer.
2. method according to claim 1, it is characterised in that step A) described in catalyst be sulphuric acid or to toluene sulphur
One kind or their mixture in acid.
3. method according to claim 1, it is characterised in that step B) described in solid acid catalyst be SO4 2-/F2O3、
SO4 2-/ZrO2Or SO4 2-/TiO2In one or more.
4. method according to claim 1, it is characterised in that described monohydroxy polyethers has following structure：
HO—(CH2CHR1O)m—(CH2CHR2O)n—R’
Its degree of functionality of hydroxyl is 1, R1And R2For H or CH3, R ' is C1—C5Alkyl, m and n is the integer between 16～90.
5. method according to claim 1, it is characterised in that described monohydroxy polyethers is poly glycol monomethyl ether or poly-
Oxirane polypropylene oxide monobutyl base ether；Its number-average molecular weight is 700～4000.
6. method according to claim 1, it is characterised in that polyacrylic addition is control polyacrylic acid and single hydroxyl
Between base polyethers, sour ether ratio is 2～5.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6387176B1 (en) * | 1999-06-15 | 2002-05-14 | Sika Ag, Vorm. Kaspar Winkler & Co. | Multipurpose cement dispersing polymers for high flow and high strength concrete |
| CN101445569A (en) * | 2007-11-28 | 2009-06-03 | 罗门哈斯公司 | Method for making polymers |
| CN103450415A (en) * | 2013-08-28 | 2013-12-18 | 江苏博特新材料有限公司 | Multifunctional concrete additive and preparation method thereof |
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2014
- 2014-11-19 CN CN201410666044.8A patent/CN104592528B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6387176B1 (en) * | 1999-06-15 | 2002-05-14 | Sika Ag, Vorm. Kaspar Winkler & Co. | Multipurpose cement dispersing polymers for high flow and high strength concrete |
| CN101445569A (en) * | 2007-11-28 | 2009-06-03 | 罗门哈斯公司 | Method for making polymers |
| CN103450415A (en) * | 2013-08-28 | 2013-12-18 | 江苏博特新材料有限公司 | Multifunctional concrete additive and preparation method thereof |
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