CN102206314A - Polycarboxylic acid and application thereof, and cement water reducing agent containing polycarboxylic acid - Google Patents
Polycarboxylic acid and application thereof, and cement water reducing agent containing polycarboxylic acid Download PDFInfo
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- CN102206314A CN102206314A CN 201110109261 CN201110109261A CN102206314A CN 102206314 A CN102206314 A CN 102206314A CN 201110109261 CN201110109261 CN 201110109261 CN 201110109261 A CN201110109261 A CN 201110109261A CN 102206314 A CN102206314 A CN 102206314A
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- carboxylic acid
- poly carboxylic
- reducing agent
- acid
- water reducing
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000004568 cement Substances 0.000 title claims abstract description 74
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 62
- 239000002253 acid Substances 0.000 title abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 18
- 229920000570 polyether Polymers 0.000 claims abstract description 17
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 229920005604 random copolymer Polymers 0.000 claims abstract description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 88
- -1 oxypropylene group Chemical group 0.000 claims description 13
- 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
- 238000006116 polymerization reaction Methods 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
- 150000003839 salts Chemical class 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
- 125000006353 oxyethylene group Chemical group 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
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 abstract 1
- 150000007942 carboxylates Chemical class 0.000 abstract 1
- 150000001735 carboxylic acids Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 41
- 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
- 239000004567 concrete Substances 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 238000000034 method Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 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
- 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
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000002146 bilateral effect Effects 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 229940059260 amidate Drugs 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000013530 defoamer Substances 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 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
- 229920002125 Sokalan® Polymers 0.000 description 2
- 238000012661 block copolymerization Methods 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
- 230000002708 enhancing effect Effects 0.000 description 2
- 150000002148 esters Chemical class 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
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000003335 steric effect Effects 0.000 description 2
- 239000000126 substance 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
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy 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
- 239000002131 composite material Substances 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
- 230000000694 effects Effects 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
- 239000008187 granular material Substances 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
- 239000000047 product Substances 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 238000010008 shearing Methods 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
- 238000010998 test method Methods 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
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- Curing Cements, Concrete, And Artificial Stone (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a polycarboxylic acid and application thereof, and a cement water reducing agent containing the polycarboxylic acid, which belongs to the technical field of cement admixtures and can solve the problems of low water reducing rate and overhigh air-entraining property in the existing polycarboxylic acid. The polycarboxylic acid provided by the invention is a random copolymer of the following monomers: 50-80 wt% of unsaturated polyether disclosed as a general formula (I), 15-30 wt% of unsaturated carboxylic acid or unsaturated carboxylate and 0-25 wt% of third monomer with unsaturated double bond and polar group. In the general formula (I), R1 and R2 respectively and independently represent hydrogen atom or methyl group, R3 represents oxopropenyl group, R4 represents oxovinyl group, and R5 and R6 respectively and independently represent hydrogen atom or C1-C20 alkyl group; and a is a whole number ranging from 10 to 50, b and c are respectively and independently a whole number ranging from 30 to 100, and d is a whole number ranging from 0 to 50. The cement water reducing agent provided by the invention contains the polycarboxylic acid. The polycarboxylic acid provided by the invention can be used in the cement water reducing agent.
Description
Technical field
The present invention relates to the cement additive technical field, relate in particular to a kind of poly carboxylic acid, this poly carboxylic acid purposes, contain the cement water reducing agent of this poly carboxylic acid.
Background technology
Cement water reducing agent is one of most important concrete admixture, and it is mainly used under the constant condition of concrete workability and cement consumption and reduces the mixing water amount, improves intensity.The first-generation, s-generation cement water reducing agent are respectively sulfonated lignin cement water reducing agent and naphthalenesulfonate-formaldehyde condensation products cement water reducing agent, they can be adsorbed on cement particle surface, make cement particle surface charged, thereby cement granules is disperseed by electrostatic repulsion.
The poly-carboxylic-acid cement water reducer is a third generation cement water reducing agent, and it also has polyether lateral chain except producing the electrostatic repulsion, thereby has as shown in Figure 1 " pectination "; This side chain can produce sterically hindered effect, thus with electrostatic repulsion synergy, so the poly-carboxylic-acid cement water reducer have than first and second in generation cement water reducing agent higher water-reducing rate is arranged.The poly-carboxylic-acid cement water reducer also has environmental protection simultaneously, objectionable impurities (alkali, chlorion, sodium sulfate etc.) content is low, advantages such as low-dosage.Because these significant advantages of poly-carboxylic-acid cement water reducer make it obtain vigorous growth in nearly decades.Emerged the patent of large quantities of relevant poly-carboxylic-acid cement water reducers; Patent US005661206A as MBT company, patent US006294015B1, US20070039515A1, the US20090234046A1 of Japan catalyst company (Nippon Shokubai), the patent US2005985989 of A Ke chemical industry (ARCO Chemical Technology) etc.These patents are mainly by selecting for use different raw materials, technology to obtain higher water-reducing rate.As obtaining macromonomer, obtain ester class poly carboxylic acid cement water reducing agent with the methacrylic acid polymerization again with poly glycol monomethyl ether and methacrylated; Or, obtain ethers poly-carboxylic-acid cement water reducer with 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; This two classes cement water reducing agent be use at present poly-carboxylic-acid cement water reducer the most widely, we are referred to as existing poly-carboxylic-acid cement water reducer.
Along with the development of technology, more and more higher to the requirement of the intensity of building structure, weather resistance etc., the application of strong concrete more and more widely.Because the water cement ratio of strong concrete is very low, viscosity is big, so be used for the higher water-reducing rate of cement water reducing agent needs of high strength coagulation, but the water-reducing rate of existing poly-carboxylic-acid cement water reducer does not reach the requirement of strong concrete, also has the excessive problem of bleed simultaneously.Use the concrete 's air-containing of existing poly-carboxylic-acid cement water reducer excessive, can obviously reduce concrete intensity, its use in strong concrete is restricted.
In order to reach the required high water reducing rate of strong concrete, (Grace) company of U.S. W. R. Grace ﹠ Co and Japanese catalyst all develop the poly-carboxylic-acid cement water reducer that new texture, but have problems such as preparation process complexity, preparation condition harshness.In patent US006352952B1, US005432212A, US005393343A, CN1196714A etc., introduced a kind of polyethers as U.S. W. R. Grace ﹠ Co (Grace), i.e. polyoxygenated enamine, the one end is with the methoxyl group end-blocking, and the other end is with the primary amine groups end-blocking; Can obtain the poly-carboxylic-acid cement water reducer by this polyethers and polyacrylic acid etc. are carried out amidate action, this poly-carboxylic-acid cement 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 poly-carboxylic-acid cement 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 poly-carboxylic-acid cement water reducer, in this reaction, carboxylate radical is except reaction generates the polymeric amide polyamines of two keys with primary amine groups, also the primary amine groups reaction at possibility while and polymeric amide polyamines two ends generates the structure that two ends all are two keys, perhaps also may generate structure with the secondary amine reaction in the chain with 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.
In order to solve the too high problem of existing poly-carboxylic-acid cement water reducer bleed, a kind of method is composite a certain amount of defoamer, but the solubleness of defoamer in the polycarboxylic acid aqueous solution is less, though can defoamer be uniformly dispersed by strong shearing action etc., but because of its less stable, still inconsistent problem can appear so place the back of for some time.In patent US6187841, then obtain to have the poly-carboxylic-acid cement water reducer of suitable bleed, thereby but this density that can reduce the poly carboxylic acid side chain again causes water-reducing rate to reduce by the ratio that reduces alkoxyl group polyoxyethylene glycol unsaturated ester and unsaturated acid.
Summary of the invention
Embodiments of the invention provide a kind of poly carboxylic acid, have high water-reducing rate and suitable bleed when it is used for cement water reducing agent.
For achieving the above object, embodiments of the invention adopt following technical scheme:
A kind of poly carboxylic acid is the random copolymers that following monomer polymerization becomes, 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 unsaturated carboxylic acid or the salt unsaturated carboxylic acid of 30wt%;
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 the general formula (I), R
1Represent hydrogen atom or methyl, R
2Represent hydrogen atom or methyl, R
3Represent oxypropylene group, R
4Represent oxyethylene group, R
5Represent hydrogen atom or C
1～C
20Alkyl, R
6Represent hydrogen atom or C
1～C
20Alkyl; A is 10～50 integer, and b is 30～100 integer, and c is 30～100 integer, and d is 0～50 integer.
Wherein, it is technique 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 monomer polyethers that uses in the poly carboxylic acid of the embodiment of the invention has two side chains, so have as shown in Figure 2 " two pectination ", it can produce stronger space steric effect on the one hand thus, and higher water-reducing rate is arranged; On the other hand, wherein the side chain that is formed by ethylene oxide group and the block copolymerization of propylene oxide group also can make and press down the enhancing of bubble ability, thereby solves the excessive problem of poly-carboxylic-acid cement water reducer bleed from molecular structure.By changing the ratio of ethylene oxide group and propylene oxide group in this side chain, also can adjust the bleed of poly-carboxylic-acid cement 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, a is 20～40 integer, and b is 50～80 integer, and c is 50～80 integer, and d is 10～40 integer.
As a kind of preferred version of embodiments of the invention, also satisfy:
3≤b/a≤10。
As a kind of preferred version of embodiments of the invention, the weight-average molecular weight of described poly carboxylic acid is between 30000 to 80000.
As a kind of preferred version of embodiments of the invention, the weight-average molecular weight of described poly carboxylic acid is between 45000 to 65000.
Embodiments of the invention also provide a kind of cement water reducing agent, and it has high water-reducing rate and suitable bleed concurrently.
For achieving the above object, embodiments of the invention adopt following technical scheme:
A kind of cement water reducing agent, 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 cement water reducing agent of embodiments of the invention, so it has the suitable bleed of high water-reducing rate.
As a kind of preferred version of embodiments of the invention, described cement water reducing agent 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 cement water reducing agent have high water-reducing rate and and suitable bleed 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 cement water reducing agent.
Because embodiments of the invention are used for cement water reducing agent with above-mentioned poly carboxylic acid, so it can make cement water reducing agent with high water-reducing rate and suitable bleed.
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 cement water reducing agent;
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, is the random copolymers that following monomer polymerization becomes, 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 unsaturated carboxylic acid or the salt unsaturated carboxylic acid of 30wt%;
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 the general formula (I), R
1Represent hydrogen atom or methyl, R
2Represent hydrogen atom or methyl, R
3Represent oxypropylene group, R
4Represent oxyethylene group, R
5Represent hydrogen atom or C
1～C
20Alkyl, R
6Represent hydrogen atom or C
1～C
20Alkyl; A is 10～50 integer, and b is 30～100 integer, and c is 30～100 integer, and d is 0～50 integer.
Wherein, it is technique 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.
And the weight-average molecular weight of the poly carboxylic acid that finally obtains is preferably between 30000 to 80000, more preferably between 45000 to 65000.
Because the monomer polyethers that uses in the poly carboxylic acid of the embodiment of the invention has two side chains, so have as shown in Figure 2 " two pectination ", it can produce stronger space steric effect on the one hand thus, and higher water-reducing rate is arranged; On the other hand, wherein the side chain that is formed by ethylene oxide group and the block copolymerization of propylene oxide group also can make and press down the enhancing of bubble ability, thereby solves the excessive problem of poly-carboxylic-acid cement water reducer bleed from molecular structure.By changing the ratio of ethylene oxide group and propylene oxide group in this side chain, also can adjust the bleed of poly-carboxylic-acid cement 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
5Represent hydrogen atom, R
6Represent C
1Alkyl; A is 20, and b is 60, and c is 80, and d is 50, and wherein b/a is 3;
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 (accounting for whole monomeric 79wt%), 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
5Represent C
1Alkyl, R
6Represent hydrogen atom; A is 10, and b is 100, and c is 50, and d is 0, and wherein b/a is 10;
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)
1, R
2All represent hydrogen atom, R
5Represent C
10Alkyl, R
6Represent C
20Alkyl; A is 50, and b is 30, and c is 100, and d is 10;
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)
1, R
2Equal represent methylidene, R
5Represent C
20Alkyl, R
6Represent C
10Alkyl; A is 16, and b, c are 80, and d is 40, and wherein b/a is 5;
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
5Represent C
8Alkyl, R
6Represent C
12Alkyl; A is 40, and b is 50, c is 30, and d is 30;
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 cement water reducing agent 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 cement water reducing agent, 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 C50.
Table 1, testing concrete performance table when making cement water reducing agent with various kinds
From table 1 as seen, use poly carboxylic acid of the present invention (in the sample of SP1～SP5), its water-reducing rate all has the sample (SP6, SP7) of poly-carboxylic-acid cement water reducer now or does not use the sample (blank) of cement water reducing agent to be significantly improved than use on the whole, and air content has also had tangible reduction.
The embodiment of the invention provides a kind of cement water reducing agent, 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 cement water reducing agent 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 cement water reducing agent of embodiments of the invention, so it has high water-reducing rate and suitable bleed.
The embodiment of the invention provides a kind of above-mentioned poly carboxylic acid to be used for the purposes of cement water reducing agent.
Because embodiments of the invention are used for cement water reducing agent with above-mentioned poly carboxylic acid, so it can make cement water reducing agent with high water-reducing rate and suitable bleed.
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 unsaturated carboxylic acid or the salt unsaturated carboxylic acid of 30wt%;
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 the general formula (I), R
1Represent hydrogen atom or methyl, R
2Represent hydrogen atom or methyl, R
3Represent oxypropylene group, R
4Represent oxyethylene group, R
5Represent hydrogen atom or C
1～C
20Alkyl, R
6Represent hydrogen atom or C
1～C
20Alkyl; A is 10～50 integer, and b is 30～100 integer, and c is 30～100 integer, and d is 0～50 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,
A is 20～40 integer, and b is 50～80 integer, and c is 50～80 integer, and d is 10～40 integer.
5. poly carboxylic acid according to claim 1 is characterized in that, also satisfies:
3≤b/a≤10。
6. poly carboxylic acid according to claim 1 is characterized in that,
The weight-average molecular weight of described poly carboxylic acid is between 30000 to 80000.
7. poly carboxylic acid according to claim 1 is characterized in that,
The weight-average molecular weight of described poly carboxylic acid is between 45000 to 65000.
8. a cement water reducing agent is characterized in that, described cement water reducing agent is 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. cement water reducing agent according to claim 8 is characterized in that, described cement water reducing agent 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 cement water reducing agent.
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| CN108003301A (en) * | 2017-11-14 | 2018-05-08 | 佳化化学（茂名）有限公司 | A kind of preparation method of viscosity reduction type polycarboxylate water-reducer |
| CN108084358A (en) * | 2017-11-14 | 2018-05-29 | 佳化化学（茂名）有限公司 | A kind of preparation method of collapse-preventing type polycarboxylate water-reducer |
| CN108084357A (en) * | 2017-11-14 | 2018-05-29 | 佳化化学（茂名）有限公司 | A kind of preparation method of liquid polycarboxylate water-reducer |
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| CN102093522A (en) * | 2011-01-05 | 2011-06-15 | 武汉格瑞林建材科技股份有限公司 | Polycarboxylic acid, use thereof and water reducer containing same |
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| CN101225148A (en) * | 2007-12-21 | 2008-07-23 | 北京工业大学 | Method for synthesizing allyl polyether-type high-performance water reducing agent |
| CN101913793A (en) * | 2010-08-19 | 2010-12-15 | 上海三瑞高分子材料有限公司 | Polyocarboxylic acid high-performance water reducer |
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| CN108084358A (en) * | 2017-11-14 | 2018-05-29 | 佳化化学（茂名）有限公司 | A kind of preparation method of collapse-preventing type polycarboxylate water-reducer |
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