CN102093522A - Polycarboxylic acid, use thereof and water reducer containing same - Google Patents
Polycarboxylic acid, use thereof and water reducer containing same Download PDFInfo
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- CN102093522A CN102093522A CN 201110001233 CN201110001233A CN102093522A CN 102093522 A CN102093522 A CN 102093522A CN 201110001233 CN201110001233 CN 201110001233 CN 201110001233 A CN201110001233 A CN 201110001233A CN 102093522 A CN102093522 A CN 102093522A
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- Prior art keywords
- carboxylic acid
- group
- water
- poly carboxylic
- water reducer
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 53
- 239000002253 acid Substances 0.000 title abstract 5
- 239000000178 monomer Substances 0.000 claims abstract description 31
- 229920000570 polyether Polymers 0.000 claims abstract description 22
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 19
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 15
- 125000005702 oxyalkylene group Chemical group 0.000 claims abstract description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 64
- -1 alkali metal salt Chemical class 0.000 claims description 23
- 125000006353 oxyethylene group Chemical group 0.000 claims description 13
- 238000012661 block copolymerization Methods 0.000 claims description 10
- 238000007334 copolymerization reaction Methods 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 5
- JPAOMENBKRZQDR-UHFFFAOYSA-N CC=CC.[Na] Chemical group CC=CC.[Na] JPAOMENBKRZQDR-UHFFFAOYSA-N 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 229920005604 random copolymer Polymers 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004568 cement Substances 0.000 abstract description 14
- 239000000654 additive Substances 0.000 abstract description 3
- 150000007942 carboxylates Chemical class 0.000 abstract 2
- 229920001577 copolymer Polymers 0.000 abstract 1
- 239000011372 high-strength concrete Substances 0.000 abstract 1
- 230000001788 irregular Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 229920005646 polycarboxylate Polymers 0.000 description 14
- 239000004160 Ammonium persulphate Substances 0.000 description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 7
- 235000019395 ammonium persulphate Nutrition 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000002146 bilateral effect Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 238000010926 purge Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- 229940059260 amidate Drugs 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- NPUKDXXFDDZOKR-LLVKDONJSA-N etomidate Chemical compound CCOC(=O)C1=CN=CN1[C@H](C)C1=CC=CC=C1 NPUKDXXFDDZOKR-LLVKDONJSA-N 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002081 enamines Chemical class 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- XMHDLKFMJMNOAX-UHFFFAOYSA-N 2-methyl-3-(2-methylprop-2-enoxy)prop-1-ene Chemical compound CC(=C)COCC(C)=C XMHDLKFMJMNOAX-UHFFFAOYSA-N 0.000 description 1
- MYCQSOCJLZBPAT-UHFFFAOYSA-N 2-methylprop-2-enoic acid;potassium Chemical compound [K].CC(=C)C(O)=O MYCQSOCJLZBPAT-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 235000019357 lignosulphonate Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
Images
Abstract
The invention provides polycarboxylic acid, use thereof and a water reducer containing the same, belongs to the technical field of cement additives and solves the problems of low water reduction rate and slump keeping performance of the conventional water reducer. The polycarboxylic acid is an irregular copolymer formed by polymerization of 50 to 80 weight percent of unsaturated polyether of a general formula below, 15 to 30 weight percent of unsaturated carboxylate or unsaturated carboxylate and 0 to 25 weight percent of third monomer which has unsaturated double bonds and polar groups, wherein R1 and R2 represent hydrogen atom or methyl; R3 and R5 represent oxyalkylene; R4 and R6 represent hydrogen atoms or C1 to C20 alkyl; a and c are integers between o and 3; b and d are 0 or 1; and m and n are integers between 10 to 50. The water reducer provided by the invention consists of 40 to 60 weight percent of polycarboxylic acid and the balance of water. The invention also discloses the use of the polycarboxylic acid in water reducer. The water reducer can be used high-strength concrete.
Description
Technical field
The present invention relates to the cement additive technical field, relate in particular to a kind of poly carboxylic acid and uses thereof, contain the water reducer of this poly carboxylic acid.
Background technology
Water reducer is a kind of important cement additive, and it is mainly used under the constant condition of concrete workability and cement consumption, reduces the mixing water amount, improves intensity.The first-generation, s-generation water reducer are respectively sulfonated lignin water reducer and naphthalenesulfonate-formaldehyde condensation products water reducer, and they can be adsorbed on cement particle surface, make cement particle surface charged, thereby by electrostatic repulsion cement granules are disperseed.
Polycarboxylate water-reducer is a third generation water reducer, and it has as shown in Figure 1 " pectination ", and " tooth " of " pectination " is the side chain of polyethers.Owing to have " pectination ", thus polycarboxylate water-reducer except producing the electrostatic repulsion, polyether lateral chain also can produce sterically hindered effect, with better dispersion cement granules, obtains higher water-reducing rate.Polycarboxylate water-reducer also has environmental protection simultaneously, objectionable impurities (alkali, chlorion, sodium sulfate etc.) content is low, advantages such as low-dosage.
Existing polycarboxylate water-reducer generally is divided into two big classes: use the poly carboxylic acid of the polyethers that has machine amine group, use the poly carboxylic acid of hydroxyl polyethers; Their structure, preparation method etc. are known.
For example, use the polycarboxylate water-reducer of hydroxyl polyethers that the patent US005661206A of MBT company is arranged, patent US006294015B1, US20070039515A1, the US20090234046A1 of Japan catalyst company (Nippon Shokubai), the patent US2005985989 of A Ke chemical industry (ARCOChemical Technology) etc.These patents are mainly by selecting for use different raw materials, technology to obtain higher water-reducing rate.As obtaining macromonomer, obtain polycarboxylate water-reducer with the methacrylic acid polymerization again with poly glycol monomethyl ether and methacrylated; Perhaps use other double bond containing organic acid polymerizations such as allyl ether polyethers (as polyoxyethylene glycol allyl ethers, polyoxyethylene glycol methallyl ether etc.) and vinylformic acid, obtain polycarboxylate water-reducer.
A kind of polyethers has been introduced by U.S. W. R. Grace ﹠ Co (Grace) in patent US006352952B1, US005432212A, US005393343A, CN1196714A etc., i.e. polyoxygenated enamine, and the one end is with the methoxyl group end-blocking, and the other end is with the primary amine groups end-blocking.Can obtain polycarboxylate water-reducer by this polyethers and polyacrylic acid etc. are carried out amidate action, this polycarboxylate water-reducer has very high slump retaining, and can not cause excessive slow setting.But, there is compatibility problem when polyoxygenated enamine and polyacrylic acid generation amidate action, take place in order to impel reaction, water that need venting generates in reaction process, this just must use a large amount of organic solvents; And the condition of this amidate action is also comparatively harsh, temperature of reaction height (100～225 ℃); Simultaneously, the solubleness of product poly carboxylic acid in water is lower; These have all influenced its practical application.
Japan's catalyst has been introduced a kind of polycarboxylate water-reducer in patent CN1537126A, it is polymerized by polymeric amide polyamines and unsaturated carboxylic acid with unsaturated link(age), has very high water-reducing rate, also can reduce concrete viscosity.But comprise the reaction of unsaturated polyester carboxylic acid and polymeric amide polyamines in the preparation process of this polycarboxylate water-reducer, in this reaction, carboxylate radical is except reaction generates the polymeric amide polyamines of two keys with primary amine groups, also may be simultaneously and the reaction of the primary amine groups at polymeric amide polyamines two ends, generating two ends all is the structure of two keys, perhaps with chain in secondary amine react, generation is with the structure of a plurality of pairs of keys, these structures form gel easily when next step polymerization, make the reaction failure, so its preparation is very difficult.
The contriver finds that there is following problem at least in prior art: existing polycarboxylate water-reducer slump retaining is relatively poor mostly, the product preparation of better slump retaining is arranged and use again relatively more difficult.Simultaneously, development along with technology, requirement to the intensity of building structure, weather resistance etc. is more and more higher, the application of strong concrete more and more widely, because the water cement ratio of strong concrete is very low, viscosity big, workability is poor, so be used for the higher water-reducing rate of water reducer needs of high strength coagulation, but the water-reducing rate of existing polycarboxylate water-reducer does not reach the requirement of strong concrete.
Summary of the invention
Embodiments of the invention provide a kind of poly carboxylic acid, have high water-reducing rate and good slump retaining when it is used for water reducer concurrently.
For achieving the above object, embodiments of the invention adopt following technical scheme:
A kind of poly carboxylic acid, it is the random copolymers that is become by following monomer polymerization, wherein the unit of each monomer content accounts for the mass percent of whole monomer total masses for this monomer:
More than or equal to 50wt% and smaller or equal to the unsaturated polyether of 80wt% with general formula (I),
More than or equal to 15wt% and smaller or equal to the unsaturated carboxylic acid of 30wt% or the salt of unsaturated carboxylic acid;
More than or equal to 0wt% and smaller or equal to having of 25wt% the 3rd monomer unsaturated double-bond, the band polar group;
In general formula (I), R
1Represent hydrogen atom or methyl, R
2Represent hydrogen atom or methyl, each R
3Independently represent an oxyalkylene group, each R
5Independently represent an oxyalkylene group, R
4Represent hydrogen atom or C
1～C
20Alkyl, R
6Represent hydrogen atom or C
1～C
20Alkyl; A is 0～3 a integer, and c is 0～3 a integer, and b is 0 or 1, and d is 0 or 1, and m is 10～50 a integer, and n is 10～50 a integer.
Wherein, " unit of each monomer content accounts for the mass percent of whole monomer total masses for this monomer " is meant to be under the situation of 100wt% with whole monomeric total amounts, every kind of ratio (obviously, the summation of whole monomeric content should be 100wt%) that monomer is shared.
Wherein, " more than or equal to the 3rd monomer of 0wt% " expression the 3rd monomeric content can be 0wt%, promptly can not have the 3rd monomer.
Wherein, in each starting monomer, salt, the 3rd monomer with unsaturated polyether, unsaturated carboxylic acid, unsaturated carboxylic acid of general formula (I) etc. all is already present, commercially available at present raw materials.
Wherein, the molecular weight of described poly carboxylic acid is preferably between 20000～60000.
Wherein, it is known that each starting monomer carries out polymeric method (comprising catalyzer, reaction conditions, reaction times of reaction process, employing etc.) etc., and it can be the method for existing preparation poly carboxylic acid.
Because the unsaturated polyether in the raw material monomer of the poly carboxylic acid of embodiments of the invention has " bilateral chain " structure, therefore this poly carboxylic acid has as shown in Figure 2 " two pectination ", so it has stronger sterically hindered effect, thereby it has higher water-reducing rate and better slump retaining when being used for water reducer.
As a kind of preferred version of embodiments of the invention, the salt of described unsaturated carboxylic acid or unsaturated carboxylic acid is any one material in the ammonium salt of ammonium salt, toxilic acid of an alkali metal salt of vinylformic acid, methacrylic acid, maleic anhydride, acrylic acid an alkali metal salt, methacrylic acid, an alkali metal salt of toxilic acid, acrylic acid ammonium salt, methacrylic acid or the mixture of multiple material.
As a kind of preferred version of embodiments of the invention, described the 3rd monomer is methylpropene sodium sulfonate and/or acrylamide.
As a kind of preferred version of embodiments of the invention, each R
3Independently represent an oxyethylene group or an oxypropylene group, each R
5Independently represent an oxyethylene group or an oxypropylene group.
As a kind of preferred version of embodiments of the invention, (R
3)
mThe group that representative is made up of with random copolymerization mode or block copolymerization mode at least two kinds of oxyalkylene groups, (R
5)
nThe group that representative is made up of with random copolymerization mode or block copolymerization mode at least two kinds of oxyalkylene groups.
As a kind of preferred version of embodiments of the invention, (R
3)
mThe group that representative is made up of with random copolymerization mode or block copolymerization mode oxyethylene group and oxypropylene group, (R
5)
nThe group that representative is made up of with random copolymerization mode or block copolymerization mode oxyethylene group and oxypropylene group.
As a kind of preferred version of embodiments of the invention, m is 20～40 a integer, and n is 20～40 a integer.
Embodiments of the invention also provide a kind of water reducer, and it has high water-reducing rate and good slump retaining concurrently.
For achieving the above object, embodiments of the invention adopt following technical scheme:
A kind of water reducer, it is by forming more than or equal to 40wt% and smaller or equal to the above-mentioned poly carboxylic acid of 60wt% and the water of surplus.
Wherein, " water of surplus " is meant that the summation of the content of the content of water and above-mentioned poly carboxylic acid should be 100wt%.
Owing to have above-mentioned poly carboxylic acid in the water reducer of embodiments of the invention, so it has high water-reducing rate and good slump retaining.
As a kind of preferred version of embodiments of the invention, described water reducer is made up of the above-mentioned poly carboxylic acid of 50wt% and the water of surplus.
Embodiments of the invention also provide a kind of purposes of above-mentioned poly carboxylic acid, and it can make water reducer have high water-reducing rate and good slump retaining concurrently.
For achieving the above object, embodiments of the invention adopt following technical scheme:
Above-mentioned poly carboxylic acid is used for the purposes of water reducer.
Because embodiments of the invention are used for water reducer with above-mentioned poly carboxylic acid, so it can make water reducer with high water-reducing rate and good slump retaining.
Description of drawings
In order to be illustrated more clearly in the embodiment of the invention or technical scheme of the prior art, to do to introduce simply to the accompanying drawing of required use in embodiment or the description of the Prior Art below, apparently, accompanying drawing in describing below only is some embodiments of the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is the synoptic diagram of the spatial configuration of molecules of the existing poly carboxylic acid that is used for water reducer;
Fig. 2 is the synoptic diagram of spatial configuration of molecules of the poly carboxylic acid of the embodiment of the invention.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the invention, the technical scheme of the embodiment of the invention is clearly and completely described, obviously, described embodiment only is a part of embodiment of the present invention, rather than whole embodiment.Based on the embodiment among the present invention, all other embodiment that those of ordinary skills are obtained under the prerequisite of not making creative work belong to the scope of protection of the invention.
The embodiment of the invention provides a kind of poly carboxylic acid, and it is the random copolymers that is become by following monomer polymerization, and wherein the unit of each monomer content accounts for the mass percent of whole monomer total masses for this monomer:
More than or equal to 50wt% and smaller or equal to the unsaturated polyether of 80wt% with general formula (I),
More than or equal to 15wt% and smaller or equal to the unsaturated carboxylic acid of 30wt% or the salt of unsaturated carboxylic acid;
More than or equal to 0wt% and smaller or equal to having of 25wt% the 3rd monomer unsaturated double-bond, the band polar group;
In general formula (I), R
1Represent hydrogen atom or methyl, R
2Represent hydrogen atom or methyl, each R
3Independently represent an oxyalkylene group, each R
5Independently represent an oxyalkylene group, R
4Represent hydrogen atom or C
1～C
20Alkyl, R
6Represent hydrogen atom or C
1～C
20Alkyl; A is 0～3 a integer, and c is 0～3 a integer, and b is 0 or 1, and d is 0 or 1, and m is 10～50 a integer, and n is 10～50 a integer.
Because the unsaturated polyether in the raw material monomer of the poly carboxylic acid of embodiments of the invention has " bilateral chain " structure, therefore this poly carboxylic acid has as shown in Figure 2 " two pectination ", so it has stronger sterically hindered effect, thereby it has higher water-reducing rate and better slump retaining when being used for water reducer.
Embodiment one
In the glass reaction equipment of thermometer, agitator, constant pressure funnel, nitrogen conduit and reflux exchanger is housed, add the unsaturated polyether of the band bilateral chain with above-mentioned general formula (I) of 140 mass parts (accounting for whole monomeric 70wt%), the Thiovanic acid of 2 mass parts and the water of 70 mass parts; R in the general formula (I)
1, R
2All represent hydrogen atom, R
3, R
5All represent oxyethylene group, R
4Represent hydrogen atom, R
6Represent C
1Alkyl; A is 0, and c is 3, and b is 0, and d is 1, and m, n are 13;
Stir on one side, on one side with nitrogen purging conversion unit inside, after temperature rises to 70 ℃, drip the solution of the water of the vinylformic acid (accounting for whole monomeric 30wt%) of 60 mass parts and 100 mass parts evenly in conversion unit, the dropping time is 3 hours; Simultaneously, at the uniform velocity drip the solution of the water of the ammonium persulphate of 4 mass parts and 50 mass parts in conversion unit, the dropping time is 4 hours;
After ammonium persulfate aqueous solution dropwises, be incubated 1 hour, the massfraction that adds 50 mass parts is 32% sodium hydroxide solution, it is 6～7 that system is neutralized to the pH value, the poly carboxylic acid called after SP1 that obtains.
Embodiment two
In the glass reaction equipment of thermometer, agitator, constant pressure funnel, nitrogen conduit and reflux exchanger is housed, add the unsaturated polyether of the band bilateral chain with above-mentioned general formula (I) of 120 mass parts (79 account for whole monomeric wt%), the Thiovanic acid of 1.9 mass parts and the water of 66.7 mass parts; R in the general formula (I)
1, R
2Equal represent methylidene, R
3, R
5All represent oxypropylene group, R
4Represent C
20Alkyl, R
6Represent C
18Alkyl; A is 3, and c is 0, and b is 1, and d is 0, and m is 48, n is 50;
Stir on one side, on one side with nitrogen purging conversion unit inside, after temperature rises to 70 ℃, drip the solution of the water of the sodium methacrylate (accounting for whole monomeric 21wt%) of 32 mass parts and 80 mass parts evenly in conversion unit, the dropping time is 3 hours; Simultaneously, at the uniform velocity drip the solution of the water of the ammonium persulphate of 3.8 mass parts and 47.6 mass parts in conversion unit, the dropping time is 4 hours;
After ammonium persulfate aqueous solution dropwises, be incubated 1 hour; The massfraction that adds 40 mass parts is 32% sodium hydroxide solution, and it is 6～7 that system is neutralized to the pH value, the poly carboxylic acid called after SP2 that obtains.
Embodiment three
In the glass reaction equipment of thermometer, agitator, constant pressure funnel, nitrogen conduit and reflux exchanger is housed, add the unsaturated polyether of the band bilateral chain with above-mentioned general formula (I) of 100 mass parts (accounting for whole monomeric 50wt%), the Thiovanic acid of 1.60 mass parts and the water of 61.4 mass parts; R in the general formula (I)
1Represent methylidene, R
2Represent hydrogen atom, (R
3)
m, (R
5)
nAll represent the group of forming in the random copolymerization mode by oxyethylene group and oxypropylene group, R
4Represent C
1Alkyl, R
6Represent hydrogen atom; A is 2, and c is 1, and b, d are 1, and m, n are 20;
Stir on one side, on one side with nitrogen purging conversion unit inside, after temperature rises to 70 ℃, drip the solution of being made up of the water of the maleic anhydride of 50 mass parts (accounting for whole monomeric 25wt%), the methylpropene sodium sulfonate of 50 mass parts (accounting for whole monomeric 25wt%) and 100 mass parts evenly in conversion unit, the dropping time is 3 hours; Simultaneously, at the uniform velocity drip the solution of the water of the ammonium persulphate of 3.6 mass parts and 45.0 mass parts in conversion unit, the dropping time is 4 hours;
After ammonium persulfate aqueous solution dropwises, be incubated 1 hour.The massfraction that adds 60 mass parts is 32% sodium hydroxide solution, and it is 6～7 that system is neutralized to the pH value, the poly carboxylic acid called after SP3 that obtains.
Embodiment four
In the glass reaction equipment of thermometer, agitator, constant pressure funnel, nitrogen conduit and reflux exchanger is housed, add the unsaturated polyether of the band bilateral chain with above-mentioned general formula (I) of 120 mass parts (accounting for whole monomeric 68.5wt%), the Thiovanic acid of 3.5 mass parts and the water of 122.8 mass parts; R in the general formula (I)
1Represent methylidene, R
2Represent hydrogen atom, (R
3)
m, (R
5)
nAll represent the group of forming in the block copolymerization mode by oxyethylene group and oxypropylene group, R
4, R
6All represent C
10Alkyl; A is 1, and c is 2, and b, d are 0, and m, n are 40;
Stir on one side, on one side with nitrogen purging conversion unit inside, after temperature rises to 70 ℃, drip the solution of the water composition of the acrylamide (accounting for whole monomeric 8.5wt%) of toxilic acid ammonium (accounting for whole monomeric 23wt%), 15 mass parts of 40 mass parts and 100 mass parts evenly in conversion unit, the dropping time is 3 hours; Simultaneously, at the uniform velocity drip the solution of the water of the ammonium persulphate of 2.2 mass parts and 25 mass parts in conversion unit, the dropping time is 4 hours;
After ammonium persulfate aqueous solution dropwises, be incubated 1 hour.The massfraction that adds 50 mass parts is 32% sodium hydroxide solution, and it is 6～7 that system is neutralized to the pH value, the poly carboxylic acid called after SP4 that obtains.
Embodiment five
In the glass reaction equipment of thermometer, agitator, constant pressure funnel, nitrogen conduit and reflux exchanger is housed, add the unsaturated polyether of the band bilateral chain with above-mentioned general formula (I) of 70 mass parts (accounting for whole monomeric 70wt%), the Thiovanic acid of 1.7 mass parts and the water of 70 mass parts; R in the general formula (I)
1, R
2Equal represent methylidene, (R
3)
mGroup, (R that representative is made up of in the block copolymerization mode oxyethylene group and oxypropylene group
5)
nThe group that representative is made up of in trackless copolymerization mode oxyethylene group and oxypropylene group, R
4, R
6All represent C
13Alkyl; A, c are 2, and b, d are 1, and m, n are 26;
Stir on one side, on one side with nitrogen purging conversion unit inside, after temperature rises to 80 ℃, drip the solution of the water composition of the acrylamide (accounting for whole monomeric 15wt%) of methacrylic acid potassium (accounting for whole monomeric 15wt%), 15 mass parts of 15 mass parts and 100 mass parts evenly in conversion unit, the dropping time is 3 hours; Simultaneously, at the uniform velocity drip the solution of the water of the ammonium persulphate of 3.4 mass parts and 50 mass parts in conversion unit, the dropping time is 4 hours;
After ammonium persulfate aqueous solution dropwises, be incubated 1 hour; The massfraction that adds 50 mass parts is 32% sodium hydroxide solution, and it is 6～7 that system is neutralized to the pH value, the poly carboxylic acid called after SP5 that obtains.
Obviously, the 3rd monomer in the various embodiments described above is except methylpropene sodium sulfonate, acrylamide, and also can be other anyly has the 3rd monomer unsaturated double-bond, the band polar group, as is crotonamide etc.The method for preparing poly carboxylic acid in the various embodiments described above is a technique known, and wherein each equipment of Cai Yonging, raw material etc. also all are known.
The comparative example one
In the glass reaction equipment of thermometer, agitator, constant pressure funnel, nitrogen conduit and reflux exchanger is housed, add the allyl polyether (have only a side chain, the ethylene oxide radix is 26) of 120 mass parts, the Thiovanic acid of 3.5 mass parts and the water of 122.8 mass parts;
Stir on one side, on one side with nitrogen purging conversion unit inside, after temperature rises to 70 ℃, drip the solution of the water of the methacrylic of 40 mass parts and 100 mass parts evenly in conversion unit, the dropping time is 3 hours; Simultaneously, at the uniform velocity drip the solution of the water of the ammonium persulphate of 2 mass parts and 25 mass parts in conversion unit, the dropping time is 4 hours;
After ammonium persulfate aqueous solution dropwises, be incubated 1 hour; The massfraction that adds 50 mass parts is 32% sodium hydroxide solution, and it is 6～7 that system is neutralized to the pH value, the poly carboxylic acid called after SP6 that obtains.
The comparative example two
In the glass reaction equipment of thermometer, agitator, constant pressure funnel, nitrogen conduit and reflux exchanger is housed, add the allyl polyether (have only a side chain, the ethylene oxide radix is 13) of 240 mass parts, the Thiovanic acid of 6.1 mass parts and the water of 214 mass parts;
Stir on one side, on one side with nitrogen purging conversion unit inside, after temperature rises to 70 ℃, drip the solution of the water of the methacrylic of 40 mass parts and 100 mass parts evenly in conversion unit, the dropping time is 3 hours; Simultaneously, at the uniform velocity drip the solution of the water of the ammonium persulphate of 3.5 mass parts and 43.8 mass parts in conversion unit, the dropping time is 4 hours;
After ammonium persulfate aqueous solution dropwises, be incubated 1 hour.The massfraction that adds 50 mass parts is 32% sodium hydroxide solution, and it is 6～7 that system is neutralized to the pH value, the poly carboxylic acid called after SP7 that obtains.
Table 1 is the concrete performance table that records when making water reducer with different samples, and wherein the slump and slump-loss are measured with reference to JC473-2001 " concrete pump-feed agent ".Test is carried out according to GB/T50081-2002 " normal concrete mechanical test method "; Wherein to contain admittedly be 20% to water reducer, volume is 1% of a cement quality, and cement is reference cement P.I 42.5, water: cement: adulterant: stone: husky ratio (mass ratio) is 160: 400: 100: 1000: 800, water cement ratio (mass ratio) is 0.32, and concrete design strength is C 50.
Table 1, testing concrete performance table when making water reducer with various kinds
As seen from the table, (in the sample of SP1～SP5), its water-reducing rate, slump retaining etc. all are significantly improved than the sample that uses existing polycarboxylate water-reducer on the whole to use poly carboxylic acid of the present invention.
The embodiment of the invention provides a kind of water reducer, and it is by forming more than or equal to 40wt% and smaller or equal to the above-mentioned poly carboxylic acid of 60wt% and the water of surplus.
Preferably, above-mentioned water reducer is made up of the above-mentioned poly carboxylic acid of 50wt% and the water of surplus.
Owing to have above-mentioned poly carboxylic acid in the water reducer of embodiments of the invention, so it has high water-reducing rate and good slump retaining.
The embodiment of the invention provides a kind of above-mentioned poly carboxylic acid to be used for the purposes of water reducer.
Because embodiments of the invention are used for water reducer with above-mentioned poly carboxylic acid, so it can make water reducer with high water-reducing rate and good slump retaining.
The above; only be the specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, anyly is familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of described claim.
Claims (10)
1. a poly carboxylic acid is characterized in that, described poly carboxylic acid is the random copolymers that is become by following monomer polymerization, and wherein the unit of each monomer content accounts for the mass percent of whole monomer total masses for this monomer:
More than or equal to 50wt% and smaller or equal to the unsaturated polyether of 80wt% with general formula (I),
More than or equal to 15wt% and smaller or equal to the unsaturated carboxylic acid of 30wt% or the salt of unsaturated carboxylic acid;
More than or equal to 0wt% and smaller or equal to having of 25wt% the 3rd monomer unsaturated double-bond, the band polar group;
In general formula (I), R
1Represent hydrogen atom or methyl, R
2Represent hydrogen atom or methyl, each R
3Independently represent an oxyalkylene group, each R
5Independently represent an oxyalkylene group, R
4Represent hydrogen atom or C
1～C
20Alkyl, R
6Represent hydrogen atom or C
1～C
20Alkyl; A is 0～3 a integer, and c is 0～3 a integer, and b is 0 or 1, and d is 0 or 1, and m is 10～50 a integer, and n is 10～50 a integer.
2. poly carboxylic acid according to claim 1, it is characterized in that the salt of described unsaturated carboxylic acid or unsaturated carboxylic acid is any one material in the ammonium salt of ammonium salt, toxilic acid of an alkali metal salt of vinylformic acid, methacrylic acid, maleic anhydride, acrylic acid an alkali metal salt, methacrylic acid, an alkali metal salt of toxilic acid, acrylic acid ammonium salt, methacrylic acid or the mixture of multiple material.
3. poly carboxylic acid according to claim 1 is characterized in that, described the 3rd monomer is methylpropene sodium sulfonate and/or acrylamide.
4. poly carboxylic acid according to claim 1 is characterized in that, each R
3Independently represent an oxyethylene group or an oxypropylene group, each R
5Independently represent an oxyethylene group or an oxypropylene group.
5. poly carboxylic acid according to claim 1 is characterized in that (R
3)
mThe group that representative is made up of with random copolymerization mode or block copolymerization mode at least two kinds of oxyalkylene groups, (R
5)
nThe group that representative is made up of with random copolymerization mode or block copolymerization mode at least two kinds of oxyalkylene groups.
6. poly carboxylic acid according to claim 1 is characterized in that (R
3)
mThe group that representative is made up of with random copolymerization mode or block copolymerization mode oxyethylene group and oxypropylene group, (R
5)
nThe group that representative is made up of with random copolymerization mode or block copolymerization mode oxyethylene group and oxypropylene group.
7. poly carboxylic acid according to claim 1 is characterized in that, m is 20～40 a integer, and n is 20～40 a integer.
8. a water reducer is characterized in that, by forming more than or equal to 40wt% and smaller or equal to the water of any described poly carboxylic acid and surplus in the aforesaid right requirement 1 to 7 of 60wt%.
9. water reducer according to claim 8 is characterized in that, described water reducer is made up of the water of any described poly carboxylic acid and surplus in the aforesaid right requirement 1 to 7 of 50wt%.
10. aforesaid right requires any described poly carboxylic acid in 1 to 7 to be used for the purposes of water reducer.
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| CN103011666A (en) * | 2012-11-30 | 2013-04-03 | 太原理工大学 | Polycarboxylate-type cement water-reducing agent and preparation method thereof |
| CN108976363A (en) * | 2018-08-25 | 2018-12-11 | 太和县鑫泰高科新型建筑材料有限公司 | A kind of high water reducing rate high-performance water reducing agent |
| CN110498891A (en) * | 2019-08-22 | 2019-11-26 | 华南理工大学 | A kind of y-type structure polymeric monomer and the Y type side chain polycarboxylate water-reducer based on it |
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