CN100345789C - Water reducing agent for highly active concrete in copolymerization carboxylic acids - Google Patents
Water reducing agent for highly active concrete in copolymerization carboxylic acids Download PDFInfo
- Publication number
- CN100345789C CN100345789C CNB031574432A CN03157443A CN100345789C CN 100345789 C CN100345789 C CN 100345789C CN B031574432 A CNB031574432 A CN B031574432A CN 03157443 A CN03157443 A CN 03157443A CN 100345789 C CN100345789 C CN 100345789C
- Authority
- CN
- China
- Prior art keywords
- monomer
- ammonium
- expression
- hydrogen atom
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 39
- 239000004567 concrete Substances 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 38
- 238000007334 copolymerization reaction Methods 0.000 title abstract description 3
- 150000001735 carboxylic acids Chemical class 0.000 title abstract 2
- 239000000178 monomer Substances 0.000 claims abstract description 47
- -1 acrylic acid hydroxyalkyl ester Chemical class 0.000 claims abstract description 37
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 37
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 32
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 25
- 239000004568 cement Substances 0.000 claims description 24
- 229910052783 alkali metal Inorganic materials 0.000 claims description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 13
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 12
- 150000001768 cations Chemical class 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 239000004160 Ammonium persulphate Substances 0.000 claims description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 3
- 229920001577 copolymer Polymers 0.000 abstract description 2
- 239000003431 cross linking reagent Substances 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 9
- 125000005210 alkyl ammonium group Chemical group 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 4
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 2
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 2
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- BZYFSQTXMFJOEB-UHFFFAOYSA-N buta-2,3-dienoic acid Chemical compound OC(=O)C=C=C BZYFSQTXMFJOEB-UHFFFAOYSA-N 0.000 description 2
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 2
- 229940018557 citraconic acid Drugs 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 201000006747 infectious mononucleosis Diseases 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- LPQOADBMXVRBNX-UHFFFAOYSA-N ac1ldcw0 Chemical compound Cl.C1CN(C)CCN1C1=C(F)C=C2C(=O)C(C(O)=O)=CN3CCSC1=C32 LPQOADBMXVRBNX-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- ZXVOCOLRQJZVBW-UHFFFAOYSA-N azane;ethanol Chemical compound N.CCO ZXVOCOLRQJZVBW-UHFFFAOYSA-N 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 229920005684 linear copolymer Polymers 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 125000005209 triethanolammonium group Chemical class 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The present invention relates to a high-efficiency copolymerization carboxylic acid type water-reducing agent for concrete, a preparation method and the application thereof on concrete manufacture. The water-reducing agent is a copolymer polymerized by an acrylic acid or an acrylate monomer represented in a general formula (A), an acrylic acid hydroxyalkyl ester monomer represented in a general formula (B), an alkenyl sulfonic acid or an alkenyl sulphonate monomer represented in a general formula (C) and a crosslinking agent including one or a plurality of monomers represented in general formulas (D) and (E), wherein (A), (B), (C), (D) and (E) are defined in specifications.
Description
Technical field
The present invention relates to a kind of cement water reducing agent and preparation method thereof, more specifically, the present invention relates to a kind of carboxylic acid group, carboxylic acid ester groups, sulfonic co-poly carboxylic acid class cement water reducing agent and preparation method thereof of in polymeric chain, containing.The invention still further relates to the purposes of above-mentioned water reducer aspect the making concrete.
Background technology
Poly carboxylic acid series water reducer is that a class obtains by various vinyl-based body copolyreaction, has introduced the carboxylic acid group on polymer molecular chain.Sulfonic group, carboxylic acid ester groups etc. be to the water reducer of the dispersing group of cement granules, its good water solubility, stable performance, join in the concrete as water reducer after, can make concrete have high workability, low slump.
Disclose a kind of co-poly carboxylic acid class water reducer among the CN1041816C, this water reducer is to be obtained by the polyalkylene glycol mono ester monomer that contains long-chain oxyalkylene group and Acrylic Acid Monomer/unsaturated dicarboxylic acid monomer and allyl sulphonic acid monomer copolymerizable.Also disclose a kind of among the EP889096A by unsaturated carboxylic acid short chain hydroxy alkyl ester; the co-poly carboxylic acid water reducer that unsaturated carboxylic acid and unsaturated sulfonic acid copolymerization form; but no matter contain the long-chain alkylene ester or contain the short-chain alkyl ester; though can improve the slump; and has an effect that reduces slump-loss; the common problem that exists of above linear copolymer is exactly to cause processed cement composition excessive slow setting to occur; early strength does not have or is very low, so that influences form removal or construction speed.
In order to overcome above-mentioned defective, the inventor has carried out extensive studies, finds that finally by add little amount of crosslinking agent in polymerization system, making polymer chain form partial cross-linked reticulated structure can address the above problem well.Finished the present invention for this reason.
Technology contents
One object of the present invention is to provide a kind of co-poly carboxylic acid class cement water reducing agent;
Another object of the present invention is to provide the preparation method of above-mentioned water reducer;
A further object of the present invention is to provide the purposes of above-mentioned water reducer aspect the making concrete.
Below will be described in detail the present invention.
The present invention relates to a kind of co-poly carboxylic acid class cement water reducing agent, it is characterized in that comprising by the monomer of following general formula (A) expression, by the monomer of following general formula (B) expression with by the monomer of following general formula (C) expression and the multipolymer that is polymerized by one or more linking agents formed in following general formula (D) and the monomer (E) represented:
Wherein: R
1, R
2And R
3Represent hydrogen atom, C independently of one another
1-5Alkyl, preferred hydrogen atom and methyl, M
1The alkane ammonium that expression hydrogen atom, alkali metal cation, alkaline-earth metal univalent cation, ammonium, alkane ammonium or hydroxyl replace;
Wherein: R
4And R
5Represent hydrogen atom, C independently of one another
1-5Alkyl, preferred hydrogen atom and methyl, A represents C
2-4Alkylidene group, a are 1-10.
Wherein: R
6Expression hydrogen atom, C
1-5Alkyl, preferred hydrogen atom and methyl, M
2The alkane ammonium that expression hydrogen atom, alkali metal cation, alkaline-earth metal univalent cation, ammonium, alkane ammonium or hydroxyl replace;
Wherein: R
7, R
8And R
9Represent hydrogen atom or C independently of one another
1-5Alkyl, preferred hydrogen atom and methyl, M
3The alkane ammonium that expression hydrogen atom, alkali metal cation, alkaline-earth metal univalent cation, ammonium, alkane ammonium or hydroxyl replace;
Wherein: R
10, R
11, R
12And R
13Represent hydrogen atom or C independently of one another
1-5Alkyl, preferred hydrogen atom and methyl, M
4And M
5Represent the alkane ammonium that hydrogen atom, alkali metal cation, alkaline-earth metal univalent cation, ammonium, alkane ammonium or hydroxyl replace independently of each other, B and D represent C independently of one another
2-4Alkylidene group, b and c all respectively the do for oneself number of 0-25 and 25 〉=b+c 〉=2.
In following formula (A)-(E), the alkyl in the alkane ammonium can be the alkyl of straight or branched, as long as chain length does not have a negative impact to the solubility property of polymkeric substance in water, and preferred C
1-5Alkyl, more preferably C
1-3Alkyl.
In with following formula (A)-(E), alkali metal cation is meant the positively charged ion of periodic table of elements IA family element, as lithium, sodium, potassium ion etc.Alkaline earth metal cation is meant the positively charged ion of periodic table of elements IIA family element, as magnesium, calcium, barium ion etc.
Monomer by general formula (A) expression comprises unsaturated monocarboxylic and salt thereof, and the example of unsaturated monocarboxylic is vinylformic acid, methacrylic acid, Ba Dousuan, and its salt comprises the alkylammonium salt that an alkali metal salt, alkaline earth salt, ammonium salt, alkylammonium salt and hydroxyl replace.Wherein, preferably use vinylformic acid, methacrylic acid and an alkali metal salt thereof.Alkyl in the alkylammonium salt preferably comprises 1-5 carbon atom, preferred 1-3 carbon atom.The example of the alkylammonium salt that hydroxyl replaces comprises monoethanolamine, diethanolamine and trolamine.
The monomeric composition of general formula (A) expression is generally the 20-70% of total polymer weight, is preferably 30-60%, more preferably 40-50%.When being lower than 20%, it is bad that the slump keeps, when being higher than 70%, and diminishing rate variance then.
Monomer by general formula (B) expression comprises acrylic or methacrylic acid and epoxide, adducts as oxyethane, propylene oxide or butylene oxide ring formation, wherein acrylic or methacrylic acid is 1: 10 with the ratio of epoxide, preferred 1: 5, and more preferably 1: 3.Oversize when the oxyalkylene hydrocarbon chain, that is, ratio surpasses at 10 o'clock, and what will be unfavorable for carrying out later is crosslinked.
The monomeric composition of general formula (B) expression is generally the 10-60% of total polymer weight, is preferably 20-50%, more preferably 30-40%.When being lower than 10%, water-reducing effect is bad, when being higher than 60%, then prolongs time of coagulation.
Monomeric example by general formula (C) expression comprises allyl sulphonic acid, methallyl sulfonic acid and salt thereof, described salt comprises the alkylammonium salt that an alkali metal salt, alkaline earth salt, ammonium salt, alkylammonium salt and hydroxyl replace, alkyl in the alkylammonium salt preferably comprises 1-5 carbon atom, more preferably 1-3 carbon atom.The alkylammonium salt that hydroxyl replaces then can be single ethanol ammonium salt, di-alcohol ammonium salt and tri ethanol ammonium salt.Wherein preferably use an alkali metal salt.
The monomeric composition of general formula (C) expression is generally the 10-50% of total polymer weight, is preferably 20-40%, more preferably 25-30%.When being lower than 10%, the product solvability is bad, and when being higher than 50%, then water-reducing effect is poor.
In the present invention, partial cross-linked in order to realize, can in the above three kinds of monomer, add by general formula (D) or (E) and contain the linking agent that the monomer of at least two polymerizable carbon carbon unsaturated double-bonds is formed in one or more molecules of expression.
Include but not limited to monoene propyl diester or methylallyl ester or its salt of unsaturated dicarboxylic acid by the monomer of general formula (D) expression, described unsaturated dicarboxylic acid comprises maleic anhydride, toxilic acid, itaconic anhydride, methylene-succinic acid, citraconic anhydride, citraconic acid and fumaric acid, and described salt has aforesaid implication.Preferred toxilic acid monoene propyl ester or its an alkali metal salt of using.
The two unsaturated dicarboxylic monos or its salt that comprise polyoxyalkylenes ether or its mixture by the monomer of general formula (E) expression, the example of described unsaturated dicarboxylic acid such as maleic anhydride, toxilic acid, itaconic anhydride, methylene-succinic acid, citraconic anhydride, citraconic acid and fumaric acid, described salt has aforesaid implication.The preferred an alkali metal salt that uses.
The example of above-mentioned polyoxyalkylenes ether includes, but are not limited to polyoxyethylene thiazolinyl ether, polyoxytrimethylene base ether and polyoxybutylene base ether.Preferred polyoxyethylene thiazolinyl ether and polyoxytrimethylene base ether.
The number b of above-mentioned polyoxyalkylenes ether group and c are 0-25 respectively all, are preferably 0-15, sum 25 〉=b+c 〉=2, preferred 15 〉=b+c 〉=2.
Above-mentioned linking agent can use wherein a kind of separately, also can use two or more combination.
For not limiting as the monomeric composition of linking agent is special, in general, the 3-50% for total polymer weight is preferably 4-40%, more preferably 5-35%.
The molecular weight of multipolymer of the present invention is generally 5000-100000, is preferably 10000-50000, more preferably 15000-20000.When molecular weight was lower than 5000, multipolymer had relatively poor slump maintenance effect, and when molecular weight is higher than 100000, the dissemination variation of multipolymer.
The molecular weight of multipolymer can be given to regulate and control by selective polymerization initiator and consumption thereof when polymerization.
Above-mentioned multipolymer series concrete water-reducing agent of the present invention can prepare with any solvent polymeric method well known in the art, but selects with equipment from easy to operate, preferably uses aqueous phase synthesis method.
In the preparation process of the above-mentioned multipolymer series concrete water-reducing agent of the present invention, can earlier the monomer of general formula (A) expression, the monomer of general formula (B) expression and the monomer of general formula (C) expression be added in the polymeric kettle, again to the monomer or its mixture that wherein add general formula (D) or (E) represent, and then according to well known to a person skilled in the art the method initiated polymerization as linking agent; Perhaps, also can be in the monomer process of monomer that causes the monomer of general formula (A) expression, general formula (B) expression with initiator and general formula (C) expression or afterwards, monomer or its mixture to wherein adding the general formula (D) as linking agent or (E) representing obtain water reducer.
The initiator that uses in the aqueous phase synthesis method comprises persalt or hydrogen peroxide, and described persalt includes but not limited to Sodium Persulfate, ammonium persulphate, Potassium Persulphate etc.
The consumption of initiator depends on the molecular weight of the multipolymer of setting.The determining of this consumption well known to a person skilled in the art.
In addition, in the water reducer preparation process, also can add reaction promoter.Described auxiliary agent includes but not limited to, tensio-active agent is as anion surfactant, as alkylbenzene sulfonate, aliphatic alcohol polyethenoxy base ether sulfate etc., cats product is as quaternary ammonium salt, season phosphonium salt etc., and nonionogenic tenside, as peregal, tween, take charge of this etc.
No matter cement composition with co-poly carboxylic acid cement water reducing agent preparation of the present invention (is the dry mixture form of making cement and polymkeric substance, or the part as the wet not agglomerative cement composition composition of making at the construction field (site)), when the weight of solid water hardened cement is calculated the weight percentage of solid polymer product in based on cement composition, the content of polymeric articles is 0.3-0.9 weight %, be preferably 0.4-0.8 weight %, more preferably 0.5-0.7 weight %.
The cement composition made from co-poly carboxylic acid cement water reducing agent of the present invention has higher flowability (slump is higher), bigger water-reducing rate than the cement composition made from ordinary water-reducing agent.In addition, made cement composition all can keep their the high slump in the whole time length, so that the workman has the longer time cement composition to be made their net shape.The problem of excessive slow setting can not appear in the cement composition made from co-poly carboxylic acid cement water reducing agent of the present invention, therefore, uses this cement admixture can not incur loss through delay the construction period.
Below with reference to embodiment the present invention is described in more detail, but should be appreciated that the purpose of described embodiment only is to illustrate the present invention, and absolutely not the present invention is carried out any qualification.
Embodiment
In following examples, except as otherwise noted, all umbers are parts by weight, and percentage ratio is weight percentage.
Molecular weight described in the embodiment is to use gel permeation chromatography, is the weight-average molecular weight that reference material is measured with the polyoxyethylene glycol.
Concrete test among the embodiment is that (GB8076-1997, JC473-2000 GBJ81-85), measure water-reducing rate and slump conservation degree etc. according to national standard and building material industry standard.
Embodiment 1
In 1000 milliliters of glass reactors that have mechanical stirrer, thermometer, dropping funnel, prolong, add entry 250 weight parts, be stirred and heated to 80 ℃, drip the aqueous solution that the water of the ammonium persulphate of toxilic acid monoene propyl diester (linking agent D), 30 weight parts of methallylsulfonic acid sodium, 10 weight parts of hydroxypropyl methacrylate, 50 weight parts of methacrylic acid, 60 weight parts of blended 80 weight parts and 100 weight parts is mixed with afterwards together.The dropping time is 2 hours, and dropping temperature is 70-80 ℃, drips the back and keeps 3 hours under this temperature, to finish polyreaction, obtains copolymer 1 of the present invention thus, and its weight-average molecular weight is 21000, can be used as concrete water reducer.Its composition is listed in table 1, and concrete test the results are shown in table 2.
Embodiment 2
With with embodiment 1 identical operations process, except replacing the methacrylic acid of 80 weight parts with 68 parts by weight of acrylic.Obtain multipolymer 2 of the present invention, its weight-average molecular weight is 25000, can be used as concrete water reducer.Its composition is listed in table 1, and concrete test the results are shown in table 2.
Embodiment 3
With with embodiment 1 identical operations process, except the hydroxyethyl methylacrylate with 55 weight parts replaces the Rocryl 410 of 60 weight parts.Obtain multipolymer 3 of the present invention, its weight-average molecular weight is 22000, can be used as concrete water reducer.Its composition is listed in table 1, and concrete test the results are shown in table 2.
Embodiment 4
With with embodiment 1 identical operations process, except the sodium allyl sulfonate with 45 weight parts replaces the methallylsulfonic acid sodium of 50 weight parts.Obtain multipolymer 4 of the present invention, its weight-average molecular weight is 20500, can be used as concrete water reducer.Its composition is listed in table 1, and concrete test the results are shown in table 2.
Comparative example 1-4
Adopt the composition of following table 1 comparative example 1-4, repeat the identical process of embodiment 1 under the situation that does not add linking agent, obtain comparative polymer, its composition is listed in table 1, and concrete test the results are shown in table 2.
The composition of table 1 multipolymer
| Example | MAA | AA | HPMAA | HEMAA | MPS | PS | D | Weight-average molecular weight |
| 1 | 80 | 60 | 50 | 10 | 21000 | |||
| 2 | 68 | 60 | 50 | 10 | 25000 | |||
| 3 | 80 | 55 | 50 | 10 | 22000 | |||
| 4 | 80 | 60 | 45 | 10 | 20500 | |||
| Comparative example | ||||||||
| 1 | 80 | 60 | 50 | 8000 | ||||
| 2 | 68 | 60 | 50 | 1000 | ||||
| 3 | 80 | 55 | 50 | 9000 | ||||
| 4 | 80 | 60 | 45 | 7500 |
Table is annotated:
MAA represent methylidene vinylformic acid MPS represent methylidene sodium allyl sulfonate
AA represent methylidene vinylformic acid PS represents sodium allyl sulfonate
HPMAA represent methylidene vinylformic acid hydroxypropyl fat D represents maleic acid list propylene ester
HEMAA represent methylidene vinylformic acid hydroxyethyl fat wherein arithemetic unit is parts by weight
Table two concrete test result
| Additive | Addition *1， ％ | The buck rate, % | The slump (cm) | Ultimate compression strength (Mpa) on the 28th | During time of coagulation/minute | ||||
| 0 minute | 30 minutes | 60 minutes | Initial set | Final set | |||||
| Example 1 | Interpolymer 1 | 0.6 | 30 | 25.1 | 25.1 | 25.0 | 63.2 | 6:30 | 8:00 |
| Example 2 | Interpolymer 2 | 0.6 | 32 | 25.5 | 25.4 | 25.3 | 63.4 | 6:40 | 8:20 |
| Example 3 | Interpolymer 3 | 0.6 | 31 | 25.4 | 25.3 | 25.2 | 63.3 | 6:42 | 8:30 |
| Example 4 | Interpolymer 4 | 0.6 | 30 | 25.0 | 25.0 | 24.8 | 63.1 | 6:20 | 8:10 |
| Comparative example 1 | / | 0.6 | 25 | 23.0 | 20.0 | 15.0 | 45.5 | 8:25 | 10:10 |
| Comparative example 2 | / | 0.6 | 26 | 23.1 | 22.0 | 17.0 | 46.5 | 8:40 | 10:20 |
| Comparative example 3 | / | 0.6 | 24 | 23.0 | 21.5 | 16.0 | 44.8 | 8:20 | 10:30 |
| Comparative example 4 | / | 0.6 | 23 | 22.8 | 21.0 | 14.3 | 42.5 | 8:15 | 10:45 |
*The dried agent weight % of 1 pair of cement
Claims (18)
1. co-poly carboxylic acid class cement water reducing agent, it is characterized in that comprising that by the monomer of following general formula (A) expression, the multipolymer that is polymerized by the monomer of following general formula (B) expression, by the monomer and the linking agent of following general formula (C) expression described linking agent is selected from by in following general formula (D) and the monomer (E) represented one or more:
Wherein: R
1, R
2And R
3Represent hydrogen atom, C independently of one another
1-5Alkyl, M
1Expression hydrogen atom, alkali metal cation, alkaline-earth metal univalent cation, ammonium, C
1-5The C that alkane ammonium or hydroxyl replace
1-5The alkane ammonium;
Wherein: R
4And R
5Represent hydrogen atom, C independently of one another
1-5Alkyl, A represents C
2-4Alkylidene group, a are 1-10.
Wherein: R
6Expression hydrogen atom, C
1-5Alkyl, M
2Expression hydrogen atom, alkali metal cation, alkaline-earth metal univalent cation, ammonium, C
1-5The C that alkane ammonium or hydroxyl replace
1-5The alkane ammonium;
Wherein: R
7, R
8And R
9Represent hydrogen atom or C independently of one another
1-5Alkyl, M
3Expression hydrogen atom, alkali metal cation, alkaline-earth metal univalent cation, ammonium, C
1-5The C that alkane ammonium or hydroxyl replace
1-5The alkane ammonium;
Wherein: R
10, R
11, R
12And R
13Can be identical or different, represent hydrogen atom or C independently of one another
1-5Alkyl, M
4And M
5Represent hydrogen atom, alkali metal cation, alkaline-earth metal univalent cation, ammonium, C independently of each other
1-5The C that alkane ammonium or hydroxyl replace
1-5The alkane ammonium, B and D represent C independently of one another
2-4Alkylidene group, b and c all respectively the do for oneself number of 0-25 and 25 〉=b+c 〉=2.
2. according to the water reducer of claim 1, it is characterized in that with following formula (A), (B), (C), (D) or the one or more C (E)
1-5Alkyl is a methyl.
3. according to the water reducer of claim 1, it is characterized in that linking agent is the 3-50% of monomer weight summation.
4. according to the water reducer of claim 1, it is characterized in that the monomer by general formula (A) expression accounts for the 20-70% of monomer weight summation.
5. according to the water reducer of claim 1, it is characterized in that the monomer by general formula (B) expression accounts for the 10-60% of monomer weight summation.
6. according to the water reducer of claim 1, it is characterized in that the monomer by general formula (C) expression accounts for the 10-50% of monomer weight summation.
7. according to the water reducer of claim 1, the molecular weight that it is characterized in that multipolymer is 5 000-100000.
8. the preparation method of the described co-poly carboxylic acid cement water reducing agent of claim 1, it is characterized in that by the monomer of general formula as described below (A) expression, by the monomer of following general formula (B) expression with by the monomer polymerization of following general formula (C) expression in or afterwards, in polymerization system, add by one or more linking agents formed in following general formula (D) and the monomer (E) represented and obtain water reducer to carry out polymerization, wherein:
Wherein: R
1, R
2And R
3Represent hydrogen atom, C independently of one another
1-5Alkyl, M
1Expression hydrogen atom, alkali metal cation, alkaline-earth metal univalent cation, ammonium, C
1-5The C that alkane ammonium or hydroxyl replace
1-5The alkane ammonium;
Wherein: R
4And R
5Represent hydrogen atom, C independently of one another
1-5Alkyl, A represents C
2-4Alkylidene group, a are 1-10.
Wherein: R
6Expression hydrogen atom, C
1-5Alkyl, M
2Expression hydrogen atom, alkali metal cation, alkaline-earth metal univalent cation, ammonium, C
1-5The C that alkane ammonium or hydroxyl replace
1-5The alkane ammonium;
Wherein: R
7, R
8And R
9Represent hydrogen atom or C independently of one another
1-5Alkyl, M
3Expression hydrogen atom, alkali metal cation, alkaline-earth metal univalent cation, ammonium, C
1-5The C that alkane ammonium or hydroxyl replace
1-5The alkane ammonium;
Wherein: R
10, R
11, R
12And R
13Can be identical or different, represent hydrogen atom or C independently of one another
1-5Alkyl, M
4And M
5Represent hydrogen atom, alkali metal cation, alkaline-earth metal univalent cation, ammonium, C independently of each other
1-5The C that alkane ammonium or hydroxyl replace
1-5The alkane ammonium, B and D represent C independently of one another
2-4Alkylidene group, b and c all respectively the do for oneself number of 0-25 and 25 〉=b+c 〉=2.
9. method according to Claim 8 is characterized in that with following formula (A), (B), (C), (D) or the one or more C (E)
1-5Alkyl is a methyl.
10. method according to Claim 8, the consumption that it is characterized in that linking agent is the 3-50% of total monomer weight.
11. method according to Claim 8 is characterized in that the monomer consumption by general formula (A) expression is the 20-70% of monomer total amount.
12. method according to Claim 8 is characterized in that the monomer consumption by general formula (B) expression is the 10-60% of total monomer weight.
13. method according to Claim 8 is characterized in that the monomer consumption by general formula (C) expression is the 10-50% of total monomer weight.
14. method according to Claim 8 is characterized in that being aggregated under the existence of polymerization starter and carries out.
15., it is characterized in that polymerization starter is persalt or hydrogen peroxide according to the method for claim 14.
16., it is characterized in that the persalt polymerization starter is ammonium persulphate, Sodium Persulfate or Potassium Persulphate according to the method for claim 15.
17., it is characterized in that the consumption of initiator is selected to make that the molecular weight of multipolymer is 5 000-100 000 according to the method for one of claim 14-16.
18. the purposes of the water reducer of one of claim 1-7 aspect the making concrete.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031574432A CN100345789C (en) | 2003-09-22 | 2003-09-22 | Water reducing agent for highly active concrete in copolymerization carboxylic acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031574432A CN100345789C (en) | 2003-09-22 | 2003-09-22 | Water reducing agent for highly active concrete in copolymerization carboxylic acids |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1600736A CN1600736A (en) | 2005-03-30 |
| CN100345789C true CN100345789C (en) | 2007-10-31 |
Family
ID=34660306
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031574432A Expired - Fee Related CN100345789C (en) | 2003-09-22 | 2003-09-22 | Water reducing agent for highly active concrete in copolymerization carboxylic acids |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100345789C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101516801B (en) * | 2006-09-13 | 2012-07-18 | 东邦化学工业株式会社 | Cement dispersant |
| CN102674741B (en) * | 2012-05-30 | 2013-07-31 | 合肥工业大学 | Polycarboxylic water reducer and synthesis method thereof |
| CN105503012B (en) * | 2015-12-16 | 2017-12-05 | 广东复特新型材料科技有限公司 | It is a kind of to be used to produce the composition for being sustained anti-mud poly carboxylic acid series water reducer |
| CN107936190B (en) * | 2017-11-24 | 2020-03-10 | 湖北工业大学 | Four-drop method for preparing high water-reducing slump-retaining polycarboxylate superplasticizer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4897119A (en) * | 1988-01-11 | 1990-01-30 | Geochemical Corporation | Aqueous dispersion of ground slag |
| US6214965B1 (en) * | 1998-10-23 | 2001-04-10 | Nissan Chemical Industries, Ltd. | Process for preparing an aqueous solution of sulfanilic acid modified melamine-formaldehyde resin and a cement composition |
-
2003
- 2003-09-22 CN CNB031574432A patent/CN100345789C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4897119A (en) * | 1988-01-11 | 1990-01-30 | Geochemical Corporation | Aqueous dispersion of ground slag |
| US6214965B1 (en) * | 1998-10-23 | 2001-04-10 | Nissan Chemical Industries, Ltd. | Process for preparing an aqueous solution of sulfanilic acid modified melamine-formaldehyde resin and a cement composition |
Non-Patent Citations (4)
| Title |
|---|
| 新型羧酸类共聚型高效减水剂 李永德，化学建材，第3期 1997 * |
| 新型羧酸高效减水剂的合成 石尉云，化学工程师，第2期 2003 * |
| 聚羧酸系高性能减水剂的合成与性能 李崇智，化学建材，第8期 2002 * |
| 聚羧酸高效减水剂的研究 郑国峰，化学建材，第6期 2002 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1600736A (en) | 2005-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1041816C (en) | Admixture for concrete | |
| CN100577591C (en) | Design and preparation of coagulation time controllable high performance polycarboxylic acid water reducing agent | |
| CN110305262A (en) | A kind of C30 concrete both sexes Early-strength polycarboxylate superplasticizer mother liquor | |
| CN106496445A (en) | A kind of hydrophobic minor comonomer modification viscosity reduction type polycarboxylate water-reducer masterbatch | |
| WO2021103473A1 (en) | Shrinkage-reducing polycarboxylic acid water reducing agent and preparation method thereof | |
| CN101066851A (en) | Concrete slump maintaining agent of polycarboxylate | |
| CN104628961A (en) | Method for preparing polycarboxylate superplasticizer by carrying out graft copolymerization on acrylic ester polymer and fatty acid vinyl ester | |
| CN104797697A (en) | Thickened aqueous detergent liquid | |
| CN101041571A (en) | Air entrained collapse-preventing type polycarboxylate concrete high efficiency water reducing agent and preparation method thereof | |
| CN103482897A (en) | Block poly-carboxylic acid concrete high-efficiency water reducing agent and preparation method thereof | |
| CN101817657A (en) | Polycarboxylic acid slump retaining agent | |
| CN100345789C (en) | Water reducing agent for highly active concrete in copolymerization carboxylic acids | |
| CN102093520A (en) | Preparation method of hyperbranched polycarboxylic acid copolymer cement dispersant | |
| CN108218284B (en) | Concrete water reducing agent composition | |
| CN1197775A (en) | Aqueous slurry of by-produced gypsum and process the production thereof | |
| CN1600735A (en) | High performance cement dispersing agent in copolymerization carboxylic acids with side chain of poly alkylene glycol ether | |
| CN100381387C (en) | Amphoteric carboxylic acid comb grafted copolymer as concrete super-plasticizing agent | |
| CS249989B1 (en) | Hydrophilic thre-dimensional polymer and method of its production | |
| JP2004210589A (en) | Cement dispersant and concrete composition containing the dispersant | |
| CN102206314B (en) | Polycarboxylic acid and application thereof, and cement water reducing agent containing polycarboxylic acid | |
| CN110643003A (en) | Preparation method of retarding type ester polycarboxylate superplasticizer | |
| JP2785849B2 (en) | Manufacturing method of cement molded board | |
| CN1667009A (en) | Carboxylic acids graft copolymer concrete strengthening agent | |
| CN114195953B (en) | Low-sensitivity high-water-retention polycarboxylate superplasticizer and preparation method thereof | |
| CN106496443B (en) | A kind of polycarboxylate water-reducer masterbatch of sulfonic acid phosphate double-strand transferance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| ASS | Succession or assignment of patent right |
Owner name: BEIJING GAIYA ENVIRONMENT TECHNOLOGY CO., LTD. Free format text: FORMER OWNER: LUSEQIANYUAN TECH INNOVATION CENTER CO., LTD., BEIJING Effective date: 20050617 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20050617 Address after: Room 1702, North Pacific Science and technology development center, 52 Haidian Road, Beijing, Haidian District Applicant after: Beijing Gaia Environmental Technology Co., Ltd. Address before: No. 47, Yongan Road, Changping District science and Technology Park, Beijing Applicant before: Luseqianyuan Tech Innovation Center Co., Ltd., Beijing |
|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Beijing Gaiya Techn Center Co., Ltd. Assignor: Beijing Gaia Environmental Technology Co., Ltd. Contract record no.: 2010990000537 Denomination of invention: High performance cement dispersing agent in copolymerization carboxylic acids with side chain of poly alkylene glycol ether Granted publication date: 20071031 License type: Exclusive License Open date: 20050330 Record date: 20100723 |
|
| DD01 | Delivery of document by public notice |
Addressee: Beijing Gaia Environmental Technology Co., Ltd. Document name: Notification to Pay the Fees |
|
| DD01 | Delivery of document by public notice | ||
| DD01 | Delivery of document by public notice |
Addressee: BEIJING GAIA ENVIRONMENTAL TECHNOLOGY Co.,Ltd. Document name: Notification of Termination of Patent Right |
|
| DD01 | Delivery of document by public notice | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20071031 Termination date: 20190922 |