A kind of polycarboxylate water-reducer and preparation method thereof
Technical field
The invention belongs to building material technical field, and in particular to a kind of polycarboxylate water-reducer and preparation method thereof.
Background technology
Polycarboxylate water-reducer is as new water reducer, with volume is low, water-reducing rate is high, slump-retaining good, shrinkage factor
It is small, relative with cement and admixture adaptability preferably, enhancing effect substantially etc. a series of protrusions performance, have been widely used at present
In every engineering field.
Sand is the important composition material of concrete, although national standard and professional standard are to its clay content, clod content
Index has strict limitation, and because the Area distribution of natural resources is different, various regions Sand for Concrete has a great difference, including:River
The mixed sand of husky, Machine-made Sand and river sand and Machine-made Sand composition, the clay content of wherein Machine-made Sand is higher, and Machine-made Sand application in recent years increases
It is many, but poly carboxylic acid series water reducer is more sensitive to the clay content of aggregate, is mainly shown as increasing with sand clay content, polycarboxylic acids
The diminishing dispersibility degradation of based water reducer, protect effect of collapsing poor, the problems such as causing maturing intensity decreases.Therefore,
Polycarboxylate water-reducer is applied in Machine-made Sand, the problem of generally existing water-reducing rate is low and collapsing property of guarantor is poor, it is impossible to ensure concrete
Construction quality.
In addition in recent years, the various synthesis techniques of polycarboxylate water-reducer emerge in an endless stream, and CN 103553409A are by methallyl
The monomer such as base APEO and acrylic acid, maleic anhydride dimethyl ester, methylpropene sodium sulfonate turns in molecular weight chain oxidant, chain
Gathered in the presence of shifting agent TGA or mercaptopropionic acid, obtain a kind of polycarboxylate water-reducer.The A of CN 103723945 will contain
The polyether monomer of double bond, double bond containing carboxylic acid monomer and water-soluble micro- crosslinking function additive, in water-soluble oxidizers and chain tra nsfer
Under the participation of agent, after aqueous solution polymerization reaction, and it is 7~8 to adjust reaction system pH with alkali, obtains hydrolyzing the poly- carboxylic of spacetabs type soon
Sour water reducer, its Chain transfer agent be mercaptoethanol, 2- hydroxyls propanethiol, TGA, 2 mercaptopropionic acid, 3- mercaptopropionic acids,
The one or several kinds of mixtures in any proportion of 2- dimercaptosuccinic acids.It can be seen that the chain-transferring agent used in most of technique is mercapto
The sulfydryl class raw material such as guanidine-acetic acid, mercaptopropionic acid, such raw material taste weight, the operation to environment and industrial workman is unfavorable.
The content of the invention
It is an object of the invention to overcome prior art defect, there is provided a kind of polycarboxylate water-reducer.
Another object of the present invention is to provide the preparation method of above-mentioned polycarboxylate water-reducer.
The concrete technical scheme of the present invention is as follows:
A kind of polycarboxylate water-reducer, its raw material includes the component of following parts by weight:
The ether type monomer is that methacrylic polyoxyethylene poly-oxygen propylene aether (HPEG) and isopentene group polyoxyethylene are poly-
At least one of oxypropylene ether (TPEG);
The unsaturation monomer containing phosphine is isopropylene and phosphonic acid, 2~acrylamide~2~methyl-propyl phosphonic acids and ethylene diamine
At least one of~dimethyl phosphonic acids;
The unsaturated silicon-containing monomer is that vinyltrimethoxy silane, VTES and vinyl three are different
At least one of npropoxysilane
In a preferred embodiment of the invention, its raw material includes the component of following parts by weight:
In a preferred embodiment of the invention, the oxidant is hydrogen peroxide, potassium peroxydisulfate, sodium peroxydisulfate or mistake
Ammonium sulfate.
In a preferred embodiment of the invention, the accelerator is at least one in frerrous chloride and ferrous sulfate
Kind.
A kind of preparation method of above-mentioned polycarboxylate water-reducer, comprises the following steps:
(1) ether type monomer, unsaturated monomer containing phosphine, unsaturated silicon-containing monomer are added in reactor together with water, in
At 5-40 DEG C after stirring and dissolving, aqueous oxidizing agent solution and acrylic acid, sodium hypophosphite and accelerator mixed aqueous solution, drop are added dropwise respectively
It is 2~4 hours, constant temperature 1~2 hour after completion of dropwise addition between added-time;
(2) copolyreaction:After copolyreaction terminates, pH value is adjusted in the range of 6.0-7.0 with alkaline matter, obtains clear
Clear solution is the polycarboxylate water-reducer.
In a preferred embodiment of the invention, the step (1) is::By ether type monomer, unsaturated list containing phosphine
Body, unsaturated silicon-containing monomer are added in reactor together with water, and in after stirring and dissolving at 5-35 DEG C, oxidant water is added dropwise respectively
Solution and acrylic acid, sodium hypophosphite and accelerator mixed aqueous solution, time for adding are 2.5~4 hours, constant temperature 1 after completion of dropwise addition
~1.5 hours.
In a preferred embodiment of the invention, the alkaline matter is sodium hydroxide, calcium hydroxide, hydroxide
At least one of potassium, calcium oxide, ammoniacal liquor and triethanolamine.
The beneficial effects of the invention are as follows:
1st, some unsaturations are added in the raw material of polycarboxylate water-reducer of the invention and contains phosphine, silicon-containing monomer, so that in diminishing
Some are introduced in agent molecule chain containing phosphine, silicon-containing group, a kind of water-reducing rate height, slump retaining is prepared good, strong beneficial to concrete early stage
The polycarboxylate water-reducer of development is spent, overcomes polycarboxylate water-reducer to apply in Machine-made Sand, generally existing water-reducing rate is low and collapsing property of guarantor
Poor the problem of.
2nd, the sodium hypophosphite in the raw material of polycarboxylate water-reducer of the present invention can be with oxidant formation Redox Initiator body
System, can play a part of chain-transferring agent again, it is to avoid the use of traditional chain-transferring agent, beneficial to improving workshop environment, green
Environmental protection.
Embodiment
It is further detailed and describes below by way of embodiment technical scheme.
Embodiment 1
(1) each raw material components are weighed by following proportioning:
(2) copolyreaction:TPEG, isopropylene and phosphonic acid, vinyltrimethoxy silane are added together with 190 parts by weight water
Into reactor, in after stirring and dissolving at 5~35 DEG C, sodium persulfate aqueous solution (sodium peroxydisulfate and 30 parts by weight water) is added dropwise respectively
And mixed aqueous solution (acrylic acid, frerrous chloride, sodium hypophosphite and 30 parts by weight of acrylic acid, sodium hypophosphite and frerrous chloride
Water), time for adding is 2.5 hours, constant temperature 1.5 hours after completion of dropwise addition, and reaction products therefrom concentration is about 40%;
(3) after copolyreaction terminates, pH value is adjusted in the range of 6.0~7.0 with sodium hydroxide, settled solution is obtained i.e.
For the polycarboxylate water-reducer.
Embodiment 2
(1) each raw material components are weighed by following proportioning:
(2) copolyreaction:By TPEG, 2- acrylamide -2- methyl-propyls phosphonic acids, VTES and 190
Parts by weight water is added in reactor together, and in after stirring and dissolving at 5~35 DEG C, ammonium persulfate aqueous solution (over cure is added dropwise respectively
Sour ammonium and 30 parts by weight water) and acrylic acid, sodium hypophosphite and frerrous chloride mixed aqueous solution (acrylic acid, ferrous sulfate, secondary phosphorus
Sour sodium and 30 parts by weight water), time for adding is 3 hours, constant temperature 1 hour after completion of dropwise addition, and reaction products therefrom concentration is about
40%;
(3) after copolyreaction terminates, pH value is adjusted in the range of 6.0~7.0 with potassium hydroxide, settled solution is obtained i.e.
For the polycarboxylate water-reducer.
Embodiment 3
(1) each raw material components are weighed by following proportioning:
(2) copolyreaction:By HPEG, ethylene diamine-dimethyl phosphonic acids, vinyl silane triisopropoxide and 190 weight
Part water is added in reactor together, in after stirring and dissolving at 5~35 DEG C, be added dropwise respectively aqueous hydrogen peroxide solution (hydrogen peroxide and
30 parts by weight water) and acrylic acid, sodium hypophosphite, frerrous chloride and ferrous sulfate mixed aqueous solution (acrylic acid, frerrous chloride,
Ferrous sulfate, sodium hypophosphite and 30 parts by weight water), time for adding is 4 hours, constant temperature 1 hour after completion of dropwise addition, and reaction gained is produced
Thing concentration is about 40%;
(3) after copolyreaction terminates, pH value is adjusted in the range of 6.0~7.0 with triethanolamine, settled solution is obtained i.e.
For the polycarboxylate water-reducer.
Embodiment 4
By the polycarboxylate water-reducer obtained by embodiment 1-3 and control sample (standard type polycarboxylate water-reducer), using standard
Cement, according to GB 8076-2008《Concrete admixture》, when surveying its water-reducing rate and each age compressive strength rate of concrete, coagulation
Native match ratio is:Cement 330kg/m3, sand 740kg/m3, stone 1116kg/m3;When surveying its slump retaining, concrete mix is:
Cement 360kg/m3, sand 803kg/m3, stone 982kg/m3;Acquired results are as shown in Table 1 and Table 2.
The embodiment water-reducing rate of table 1 and concrete crushing strength compare ratio
The embodiment slump retaining of table 2 is contrasted
Result of the test illustrates that environmental type polycarboxylate water-reducer water-reducing rate of the invention is high, slump retaining is good, beneficial to coagulation
Native early strength development, may be applicable in high diminishing, early strong concrete.Synthesis technique is without heating, it is to avoid apply mercapto
Base class chain-transferring agent, beneficial to workshop environment is improved, simple production process, easy control of reaction conditions is energy-saving, green
Environmental protection.
The foregoing is only a preferred embodiment of the present invention, therefore can not limit the scope that the present invention is implemented according to this, i.e.,
The equivalent changes and modifications made according to the scope of the claims of the present invention and description, all should still belong in the range of the present invention covers.