CN1935733A - Low molecular weight copolymer dispersant and its preparing method - Google Patents
Low molecular weight copolymer dispersant and its preparing method Download PDFInfo
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- CN1935733A CN1935733A CN 200610096550 CN200610096550A CN1935733A CN 1935733 A CN1935733 A CN 1935733A CN 200610096550 CN200610096550 CN 200610096550 CN 200610096550 A CN200610096550 A CN 200610096550A CN 1935733 A CN1935733 A CN 1935733A
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- 238000000034 method Methods 0.000 title claims abstract description 26
- 229920001577 copolymer Polymers 0.000 title claims abstract description 23
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 17
- 239000012429 reaction media Substances 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 10
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- 239000004159 Potassium persulphate Substances 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 8
- 235000019394 potassium persulphate Nutrition 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 239000007858 starting material Substances 0.000 claims description 7
- 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 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 150000003254 radicals Chemical class 0.000 claims description 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- -1 amine salt Chemical class 0.000 claims description 5
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical group OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 150000001261 hydroxy acids Chemical group 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 230000003335 steric effect Effects 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 abstract description 25
- 239000004568 cement Substances 0.000 abstract description 22
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 16
- 239000004567 concrete Substances 0.000 abstract description 16
- 239000000843 powder Substances 0.000 abstract description 11
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 239000004927 clay Substances 0.000 abstract description 5
- 239000004570 mortar (masonry) Substances 0.000 abstract description 5
- 239000000919 ceramic Substances 0.000 abstract 1
- 239000011440 grout Substances 0.000 abstract 1
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 239000011505 plaster Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000243 solution Substances 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 235000010216 calcium carbonate Nutrition 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 229910052602 gypsum Inorganic materials 0.000 description 7
- 239000010440 gypsum Substances 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000008399 tap water Substances 0.000 description 6
- 235000020679 tap water Nutrition 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 229920006243 acrylic copolymer Polymers 0.000 description 5
- 238000005304 joining Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 2
- CVEPFOUZABPRMK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;styrene Chemical compound CC(=C)C(O)=O.C=CC1=CC=CC=C1 CVEPFOUZABPRMK-UHFFFAOYSA-N 0.000 description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010931 ester hydrolysis Methods 0.000 description 1
- GDCRSXZBSIRSFR-UHFFFAOYSA-N ethyl prop-2-enoate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CCOC(=O)C=C GDCRSXZBSIRSFR-UHFFFAOYSA-N 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 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
- WPONNXIJPKZHGB-UHFFFAOYSA-N formaldehyde;sulfamic acid Chemical compound O=C.NS(O)(=O)=O WPONNXIJPKZHGB-UHFFFAOYSA-N 0.000 description 1
- PKJZYOFPPJHDRW-UHFFFAOYSA-N formaldehyde;sulfuric acid Chemical compound O=C.OS(O)(=O)=O PKJZYOFPPJHDRW-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920001427 mPEG Polymers 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention relates to a low molecular weight copolymer dispersant and the preparing method thereof, adopting 40%-70mol% monomer a, 30-60mol% monomer b, 0-15mol% unit c and 0-10mol% monomer d, using water as reaction medium, one-off adding in water soluble initiator and monomer mixture, controlling initial reaction temperature and using a large amount of reaction heat produced in the self-accelerating course of polymerication reaction to fast polymerize the monomer mixture and making it. And it can directly act as dispersant for cement, superfine calcium carbonate, plaster, clay, ceramics and other organic powder, especially for cement-base materials, such as concrete, mortar and grout, having excellent dispersivity and good dispersion retention.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to the preparation and the application of a kind of lower molecular weight (methyl) acrylic copolymer.Product of the present invention can directly be used as the dispersion agent of inorganic powders such as cement, calcium carbonate superfine powder, gypsum, clay and pottery, and particularly the dispersion agent as cement has excellent dispersion and disperses to keep performance.
Background technology
The dispersion of solid particulate in liquid phase is the problem that fundamental research field and industrial technology department generally run into, and almost spreads all over fields such as chemical industry, material, food, medicine, coating, printing ink, papermaking, building and metallurgy.Disperse to have become to improve the quality of products and performance, improve the essential and crucial technique means of process efficiency.At present, all adopt chemical process to realize the dispersion of ultra-fine grain at many industrial sectors, wherein, dispersion agent is vital to dispersion technology efficiently.
Dispersion agent also is used for preparation such as concrete, mortar and the cement slurry etc. of cement-based material in a large number.Cement dispersants is called water reducer again, in concrete, can play a part three kinds different or play three kinds of effects simultaneously: (1) improves the workability of concrete energy under the condition that does not change the concrete component; (2) under given workability condition, reduce mixing water and water cement ratio, to improve concrete strength, improve weather resistance; (3) under given workability, reduce the consumption of water and cement, with save cement reduce creep, thermal stresses that drying shrinkage and hydration heat of cement cause.
Domestic and international widely used water reducer mainly contains at present: naphthalenesulfonate formaldehyde condensation compound, condensate of melamine and formaldehyde, sulfamate formaldehyde condensation products, aliphatic hydroxyl sulphonate formaldehyde condensation products and novel carboxylic acid copolymer.Though condensation polymer type water reducers such as traditional naphthalene system, trimeric cyanamide system have good dispersiveness, but the fresh concrete flowability is big through time loss, and such water reducer has caused certain pollution because to have adopted the formaldehyde of strong stimulation nature and flavor and oleum or the vitriol oil in the production engineering be starting material to environment.
Its molecular weight was all lower when novel carboxylic acid copolymer was used as dispersion agent, being generally several thousand does not wait to hundreds thousand of, and it is higher to prepare the monomer general polymerization activity that this base polymer adopts, the molecular weight size of polymkeric substance is difficult to control, and the molecular weight size is very big to the dispersive ability influence of dispersion agent, and the molecular weight that present technique field those skilled in the art know is too big, and dispersity is bad, molecular weight is too little, disperses the confining force variation.The method of controlling polymers molecular weight size mainly contains following several at present: 1) use sulfhydryl compound to come the controlling polymers molecular weight as chain-transfer agent, EP1304314, US5911820, US6444780 use mercaptoethanol, Dodecyl Mercaptan and thiohydracrylic acid to prepare the lower molecular weight aqueous-based polymers as chain-transfer agent, but mercaptoethanol, Dodecyl Mercaptan foul smelling, contaminate environment, and the thiohydracrylic acid price is very expensive, and these materials do not play a role as the necessary component of product; 2) polymerization (US4301266) in water one isopropyl alcohol mixed solvent, this method needs the loaded down with trivial details last handling process of removing Virahol, and the part isopropyl alcohol that remains in the multipolymer not only has peculiar smell, and can influence the application performance of product; 3) use some water-soluble azo compounds to make initiator (Japanese Patent 6438403), this method need prepare specific azo-compound; 4) adopt metal-salt such as Cu
2+, Fe
2+As molecular weight regulator (US5100980, US5244988, US6335404, CN1085570), the shortcoming of this method is to contain metal ion in the multipolymer to cause environmental pollution easily.Its molecular weight distribution of multipolymer as cement dispersants (water reducer) is very big to the mobile hold facility influence of multipolymer in addition, must have suitable molecular weight distribution.EP1304314 controls by the rate of addition or the feed way of control monomer and initiator, this is the mode that generally adopts at present, but this method hold facility, US5854318, US5362324 adopts the crosslinked technological approaches of ester, the crosslinked body of this ester is bigger in the water management difficulty, produce more loaded down with trivial details, difficult quality guarantee.Under the alkaline medium for the slump mud that improves the poly carboxylic acid admixture, chain rupture takes place, molecular weight reduces, thereby has good slump hold facility, but dispersiveness is not very excellent, the production control more complicated of getting up.
In sum, the synthesis technique of at present relevant low molecular weight copolymer dispersant is unsafty, is unclean and uneconomic.
Summary of the invention
Of the present invention what will solve is exactly the problem that above-mentioned prior art exists, and provides that a kind of production technology is simple relatively, dispersing property is excellent, mobile good and cheap low molecular weight copolymer dispersant and the preparation technology thereof of performance that keep.
The applicant finds through a large amount of experimental studies, adopt water-soluble persulfate initiator of disposable adding and monomer mixture, by the control initial reaction temperature, utilize a large amount of reaction heat that produce in the polyreaction autoacceleration process to make monomer mixture generation rapid polymerization, can prepare low-molecular weight copolymer.
According to above-mentioned research, the present invention 1 is prepared from monomer a+b+c+d=100mol% by 40%～70mol% monomer a, 30～60mol% monomer b, 0～15mol%c unit, 0～10mol% monomer d by the water-based free radical copolymerization process; Wherein,
Monomer a represents with general formula (I):
R in the formula
1Be hydrogen atom or methyl, R
2Expression hydrogen atom, monovalence atoms metal, divalent metal atom, ammonium or organic amino group.
Monomer b represents with general formula (II):
R in the formula
1Same general formula (I), R
3Be expressed as-(CH
2)
xOH, the positive integer of x=2～10;
Monomer c represents with general formula (III):
R in the formula
1Same general formula (I), R1 is represented as sulfonic acid group-SO
3H-, or-C
6H
1-SO
3H, or-CO-NH-C (CH
3)
2-CH
2-SO
3H;
Monomer d represents with general formula (IV):
R in the formula
1Same general formula (I), R
5Be expressed as C
1～C
4Alkyl, AO is the oxyalkylene group of 2～4 carbon atoms or the mixture of two or more this oxyalkylene groups, if AO is the mixture of two or more this oxyalkylene groups, can add these groups with block or random form so, n is the average addition mole number of oxyalkylene group, is 2～40.
Within the scope of the present invention, monomer a (general formula I) is selected from vinylformic acid, methacrylic acid or its monovalent metal salt, divalent metal salt, ammonium salt or organic amine salt, and these monomers use separately or use with the form of mixtures of two or more composition.Its hydroxy-acid group provides adsorption site and electric repulsion in multipolymer.
Monomer b (general formula I I) is acrylic acid hydroxy alkyl ester or hydroxyalkyl methacrylate, comprises Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate or Rocryl 410, and wherein Propylene glycol monoacrylate is optimum.
(general formula III is monomer or its monovalent metal salt, divalent metal salt or the ammonium salt of band sulfonic acid group to monomer c.Object lesson as monomer c has vinyl sulfonic acid, 2-acrylamido-2-methyl propane sulfonic acid (AMPS), styrene sulfonic acid.
Monomer d (general formula I V) is alkoxy polyether acrylate or alkoxy polyether methacrylic ester, wherein the oxyalkylene that is suitable for as AO comprises oxyethane, propylene oxide, butylene oxide ring and composition thereof, they can be linearity or branched polymers, homopolymer or multipolymer, random or segmented copolymer, diblock or segmented copolymer, this alkoxy polyether acrylate or alkoxy polyether methacrylic ester are copolymerized in the main chain, and certain space steric effect mainly is provided.
The present invention adopts the water-based free radical copolymerization process to be prepared.Raolical polymerizable itself is unimportant comparatively speaking, but has described those deficiencies of background technology and defective at system each lower molecular weight (methyl) acrylic copolymer dispersion agent.
Researchist of the present invention works out the method for being prepared as follows through unremitting effort:
With water is reaction medium, adopt water-soluble persulfate initiator of disposable adding and monomer mixture, and by the control initial reaction temperature, utilize a large amount of reaction heat that produce in the polyreaction autoacceleration process to make monomer mixture generation rapid polymerization, directly prepare a kind of lower molecular weight (methyl) acrylic copolymer dispersion agent that has good distribution and disperse to keep performance.
The applicant is surprised to find, the multipolymer that the above-mentioned mode of utilizing this rapid polymerization of a large amount of reaction heat that produces in the autoacceleration process prepares is during as cement, mortar and concrete dispersion agent, not only have excellent dispersion properties, and have excellent dispersion maintenance performance.
The water soluble starter that is suitable for the inventive method is conventional free radical water soluble starter or its mixture, comprises water-soluble ammonium persulphate, Potassium Persulphate, Sodium Persulfate and hydrogen peroxide.Join whole initiators in the reaction mixture account for add 0.5～10% (mol) of total monomer mole number.Present technique field those skilled in the art know that generally the actual add-on of initiator has certain relation with the initiator type that is adopted in the polyreaction.
In preparation process, monomer mixed solution and initiator solution directly add in the reactor, do not need to drip, and the polymerization reaction monomer weight concentration is controlled at 15～40%.The polymerization initial reaction temperature is relevant with the decomposition of initiator temperature that is adopted, and generally is controlled under 40～70 ℃ and carries out, and initial temperature is too low, and monomer polymerization is slow, and the reaction heat that its polyreaction produces does not reach the quick response purpose.Initial temperature is too high, and decomposition of initiator is too fast, and rapidly response carries out, and reaction heat is snap-out release also, and the danger towards still can take place.Polymerization reaction time is controlled at 2～3h.
After polyreaction finishes, also can cross in Cheng Qian or the polymerization process in polymerization certainly, by with alkali reaction the pH value of finished product being adjusted to 5.5～7.0, the package stability with the maintenance multipolymer prevents ester hydrolysis under strongly-acid or strong basicity environment.
Adopting the low-molecular weight copolymer of method for preparing is low molecular weight propylene acid copolymer or Sipacril 2739OF, and this multipolymer can directly be used as the dispersion agent of inorganic powders such as cement, calcium carbonate superfine powder, gypsum, clay and pottery., particularly as the dispersion agent of cement-based material such as concrete, mortar and cement slurry, not only have excellent dispersion, and have good dispersion maintenance performance.
The present invention compared with prior art has following advantage:
1, adopts common free radical water soluble starter or its mixture, do not adopt any chain-transfer agent and dropping program, can directly prepare a kind of low molecular weight copolymer dispersant that has good distribution and disperse to keep performance by single step reaction, raw material is cheap and easy to get, equipment is not had particular requirement, and operation is simple;
When 2, carrying out polyreaction, needn't lead to nitrogen and remove oxygen in the polymerization system, and directly adopt tap water as reaction medium;
3, initiator system is nontoxic, pollution-free;
4, do not need numerous and diverse dropping process, disposable initiator and monomer solution are joined in the reactor, can control the molecular weight of multipolymer easily;
5, the present invention is as a kind of aqueous solution, can directly be used as the dispersion agent of inorganic powders such as cement, calcium carbonate superfine powder, gypsum, clay and pottery, particularly as the dispersion agent of cement-based material such as concrete, mortar and cement slurry, under the volume of very low (0.2-0.3%), not only have excellent dispersion during as inorganic powders such as cement, calcium carbonate superfine powder, gypsum, clay and potteries, and have good dispersion and keep performance.
Embodiment
Following examples more detailed description the process of prepared according to the methods of the invention polymerisate, and these embodiment provide in the mode of explanation, but these embodiment never limit the scope of the invention.
Production example 1
Thermometer is being housed, in the 1L glass reactor of agitator and reflux exchanger, add the 400g tap water successively, 90g (1.046mol) methacrylic acid, 110g (0.846mol) Propylene glycol monoacrylate, 35g (0.875mol) sodium hydroxide, stir into uniform monomer solution, and be warming up to 60 ℃, then with 100 parts of disposable joining in the reactor of the aqueous solution of containing 4.5g (0.0167mol) Potassium Persulphate, observing reactor temperature after 20 minutes rises, the solution retrogradation, the stirring resistance strengthens, final temp is elevated to 97 ℃ naturally, and under this temperature, be incubated 2h, add 20 parts of aqueous solution that contain 1.0g (0.0037mol) Potassium Persulphate, and continue insulation 1h, obtain pH value 6.5, solid content is 29.2% thick liquid, and under 25 ℃, polymer viscosity is 225mpa.s (P-1).
Production example 2
Thermometer is being housed, in the 1L glass reactor of agitator and reflux exchanger, add the 400g tap water successively, 80g (1.111mol) vinylformic acid, 100g (0.767mol) hydroxyethyl methylacrylate, 20g (0.0965mol) 2-acrylamido-2-methyl propane sulfonic acid, 36g (0.90mol) sodium hydroxide, stir into uniform monomer solution, and be warming up to 50 ℃, then with 100 parts of disposable joining in the reactor of the aqueous solution of containing 18g (0.0789mol) ammonium persulfate, observing reactor temperature after 10 minutes rises, the solution retrogradation, the stirring resistance strengthens, final temp is elevated to 95 ℃ naturally, and under this temperature, be incubated 2h, add 20 parts of aqueous solution that contain 6.0g (0.026mol) ammonium persulfate, and continuation insulation 1h, obtain pH value 6.2, solid content is 30.1% thick liquid, and under 25 ℃, polymer viscosity is 185mpa.s (P-2).
Production example 3
Thermometer is being housed, in the 1L glass reactor of agitator and reflux exchanger, add the 500g tap water successively, 80g (0.93mol) methacrylic acid, 90g (0.692mol) Propylene glycol monoacrylate, 10g (0.093mol) vinyl sulfonic acid, 32g (0.80mol) sodium hydroxide, 54g (0.0874mol) methoxy polyethylene glycol methacrylate-styrene polymer (general formula I V, n=12) stir into uniform monomer solution, and be warming up to 55 ℃, then with 100 parts of disposable joining in the reactor of the aqueous solution of containing 8g (0.0336mol) Sodium Persulfate, observing reactor temperature after 20 minutes rises, the solution retrogradation, the stirring resistance strengthens, final temp is elevated to 98 ℃ naturally, and under this temperature, be incubated 2h, add 20 parts of aqueous solution that contain 2.0g (0.0084mol) Sodium Persulfate, and continue insulation 1h, and obtaining pH value 6.7, solid content is 28.3% thick liquid, under 25 ℃, polymer viscosity is 238mpa.s (P-3).
Production example 4
Thermometer is being housed, in the 1L glass reactor of agitator and reflux exchanger, add the 500g tap water successively, 60g (0.697mol) methacrylic acid, 105g (0.808mol) Propylene glycol monoacrylate, 20g (0.50mol) sodium hydroxide, 7g (0.034mol) Sodium styrene sulfonate, 80g (0.074mol) methoxy poly (ethylene glycol) acrylate (general formula I V, n=23) stir into uniform monomer solution, and be warming up to 60 ℃, then with 150 parts of disposable joining in the reactor of the aqueous solution of containing 5g (0.0185mol) Potassium Persulphate, observing reactor temperature after 18 minutes rises, the solution retrogradation, the stirring resistance strengthens, final temp is elevated to 96 ℃ naturally, and under this temperature, be incubated 2h, add 20 parts of aqueous solution that contain 1.5g (0.0056mol) Potassium Persulphate, and continuation insulation 1h, obtain pH value 5.9, solid content is 27.3% thick liquid, and under 25 ℃, polymer viscosity is 215mpa.s (P-4).
Production example 5
Thermometer is being housed, in the 2L glass reactor of agitator and reflux exchanger, add the 600g tap water successively, 80g (0.93mol) methacrylic acid, 100g (0.862mol) Hydroxyethyl acrylate, 32g (0.80mol) sodium hydroxide, 150g (0.0966mol) methoxy polyethylene glycol methacrylate-styrene polymer (general formula I V, n=33) stir into uniform monomer solution, and be warming up to 55 ℃, then with 200 parts of disposable joining in the reactor of the aqueous solution of containing 12.0g (0.05mol) Sodium Persulfate, observing reactor temperature after 15 minutes rises, the solution retrogradation, the stirring resistance strengthens, final temp is elevated to 98 ℃ naturally, and under this temperature, be incubated 2h, add 20 parts of aqueous solution that contain 3.0g (0.0126mol) Sodium Persulfate, and continue insulation 1h, and obtaining pH value 6.9, solid content is 28.8% thick liquid, under 25 ℃, polymer viscosity is 242mpa.s (P-5).
Comparative example 1
Monomer is the same with production example 1 with the initiator proportioning, and just monomer and the initiator solution mode taking to drip is carried out.
Thermometer is being housed, agitator, in the glass reactor of dropping funnel and reflux exchanger, add the 200ml deionized water, use the nitrogen purging reaction vessel while stirring, and be warming up to 95 ℃, then with 90g (1.046mol) methacrylic acid, 110g (0.846mol) Propylene glycol monoacrylate, water 200g, 35g (0.875mol) sodium hydroxide stirs into uniform monomer solution, it is added dropwise to reactor, the dropping time is 2h, and while 100 parts of aqueous solution that contain 4.5g (0.0167mol) Potassium Persulphate, about 150min of dropping time, dropwise back insulation reaction 3h, in reaction flask, add 20 parts of aqueous solution that contain 1.0g (0.0037mol) Potassium Persulphate again, and continue insulation 2h, obtain pH value 6.6, solid content is 29.3% thick liquid, and under 25 ℃, polymer viscosity is 185mpa.s (CP-1)
The performance of table 1 copolymer solution
| Example | The multipolymer numbering | Solid content (%) | pH | Multipolymer viscosity mpa.s (25 ℃ of 100rpm Brookfield) |
| 1 | P-1 | 29.2 | 6.5 | 225 |
| 2 | P-2 | 30.1 | 6.2 | 185 |
| 3 | P-3 | 28.3 | 6.7 | 238 |
| 4 | P-4 | 27.3 | 5.9 | 215 |
| 5 | P-5 | 28.8 | 6..9 | 242 |
| Comparative example | CP-1 | 29.3 | 6.6 | 185 |
Application Example
The volume of multipolymer is all with effective solid part metering in the application examples.
Application Example 1 is as concrete high efficiency water reducing agent
Cement: the peaceful sheep 425R.P.II of the gold that cement mill, the south of the River produces; Sand: fineness modulus M
x=2.6 medium sand; Stone: basalt, particle diameter are the rubble of 5～20mm continuous grading.The fresh concrete slump and slump-loss are carried out with reference to JC473-2001 " concrete pump-feed agent " relevant regulations, water consumption is fixed (W/C=0.43), is that 21 ± 1cm is as the criterion by adjusting the multipolymer volume with the control slump, after testing slump-loss, test block is according to the moulding of GB8076-97 " concrete admixture " regulation, and measure 3d and 28d concrete crushing strength, test result sees Table 2.
Table 2
| The multipolymer numbering | Volume/% | Fresh concrete slump-loss/cm | Ultimate compression strength/MPa | ||||
| 0min | 30min | 60min | 90min | 3d | 28d | ||
| P-1 | 0.23 | 19.5 | 20.8 | 20.5 | 19.5 | 31.2 | 59.7 |
| P-2 | 0.22 | 21.2 | 20.5 | 20.0 | 18.5 | 32.3 | 61.8 |
| P-3 | 0.21 | 20.5 | 21.0 | 20.2 | 19.8 | 29.8 | 60.3 |
| P-4 | 0.21 | 22.0 | 21.5 | 21.5 | 20.7 | 33.7 | 64.3 |
| P-5 | 0.19 | 21.8 | 21.5 | 20.5 | 19.8 | 33.5 | 63.7 |
| CP-1 | 0.21 | 21.5 | 17.8 | 15.5 | 13.5 | 29.5 | 60.2 |
Find out when lower molecular weight of the present invention (methyl) acrylic copolymer is used as cement water reducing agent, not only to have good dispersing property from table 2 test-results, and have excellent slump maintenance performance.By contrast, Comparative Examples CP-1 has adopted dropping monomer and initiator technology, though the good dispersing property of its polymerization, it is unsafty disperseing to keep performance.
Application Example 2 calcium carbonate powders disperse
Adopt CaCO3, Omya Fine Chemical Co., Ltd, purity 〉=98.5%, median size 1.70 μ m, viscosity adopts Brookfield concentric cylinder viscometer R/S-CC to measure.Adopt the viscosity that preparation method's synthetic lower molecular weight of the present invention (methyl) acrylic copolymer can significantly reduced calcium carbonate superfine powder, disperse rheological property thereby improve it.
Table 3
| The multipolymer numbering | Volume/% | Suspensoid weight concentration/% | Viscosity mpa.s | |
| 20rpm | 100rpm | |||
| P-1 | 0.3 | 70.0 | 135 | 250 |
| P-2 | 0.3 | 70.0 | 105 | 220 |
| P-3 | 0.3 | 70.0 | 102 | 180 |
| P-4 | 0.3 | 70.0 | 95 | 170 |
| P-5 | 0.3 | 70.0 | 80 | 150 |
| Do not add any polymkeric substance | 65.0 | 25500 | 10800 | |
The dispersion of Application Example 3 gypsum.
Measure according to JC/T517-93 " brushing gypsum ".Adopt preparation method's synthetic multipolymer of the present invention can significantly improve the dispersing property of gypsum, thereby improve its ultimate compression strength and folding strength.
Table 4
| The multipolymer numbering | Volume/% | Water-reducing rate/% | Wet tenacity (MPa) | Dry strength (MPa) | ||
| Folding strength | Ultimate compression strength | Folding strength | Ultimate compression strength | |||
| P-1 | 0.2 | 21.5 | 1.72 | 4.85 | 1.82 | 5.12 |
| P-2 | 0.2 | 23.2 | 1.78 | 5.05 | 1.85 | 5.36 |
| P-3 | 0.2 | 23.8 | 1.83 | 5.16 | 1.89 | 5.55 |
| P-4 | 0.2 | 23.5 | 1.82 | 5.15 | 1.91 | 5.65 |
| P-5 | 0.2 | 25.5 | 1.87 | 5.27 | 1.98 | 5.84 |
Claims (10)
1, a kind of low molecular weight copolymer dispersant, it is characterized in that being prepared from monomer a+b+c+d=100mol% by the water-based free radical copolymerization process by 40%～70mol% monomer a, 30～60mol% monomer b, 0～15mol%c unit, 0～10mol% monomer d; Wherein,
Monomer a represents with general formula (I):
R in the formula
1Be hydrogen atom or methyl, R
2Expression hydrogen atom, monovalence atoms metal, divalent metal atom, ammonium or organic amino group.
Monomer b represents with general formula (II):
R in the formula
1Same general formula (I), R
3Be expressed as-(CH
2), OH, the positive integer of x=2～10;
Monomer c represents with general formula (III):
R in the formula
1Same general formula (I), R
1Be represented as sulfonic acid group-SO
3H-, or-C
6H
1-SO
3H, or-CO-NH-C (CH
3)
2CH
2-SO
3H;
Monomer d represents with general formula (IV):
R in the formula
1Same general formula (I), R
5Be expressed as C
1～C
4Alkyl, AO is the oxyalkylene group of 2～4 carbon atoms or the mixture of two or more this oxyalkylene groups, if AO is the mixture of two or more this oxyalkylene groups, can add these groups with block or random form so, n is the average addition mole number of oxyalkylene group, is 2～40.
2, low molecular weight copolymer dispersant according to claim 1, it is characterized in that monomer a is selected from vinylformic acid, methacrylic acid or its monovalent metal salt, divalent metal salt, ammonium salt or organic amine salt, these monomers use separately or use with the form of mixtures of two or more composition, and its hydroxy-acid group provides adsorption site and electric repulsion in multipolymer.
3, low molecular weight copolymer dispersant according to claim 1 is characterized in that monomer b is acrylic acid hydroxy alkyl ester or hydroxyalkyl methacrylate, comprises Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate or Rocryl 410.
4, as low molecular weight copolymer dispersant as described in the claim 3, it is characterized in that selecting for use Propylene glycol monoacrylate is optimum as monomer b.
5, low molecular weight copolymer dispersant according to claim 1 is characterized in that monomer or its monovalent metal salt, divalent metal salt or the ammonium salt of monomer c for the band sulfonic acid group.
6, low molecular weight copolymer dispersant according to claim 1, it is characterized in that monomer d is alkoxy polyether acrylate or alkoxy polyether methacrylic ester, wherein the oxyalkylene that is suitable for as AO comprises oxyethane, propylene oxide, butylene oxide ring and composition thereof, they can be linearity or branched polymers, homopolymer or multipolymer, random or segmented copolymer, diblock or segmented copolymer, this alkoxy polyether acrylate or alkoxy polyether methacrylic ester are copolymerized in the main chain, and certain space steric effect mainly is provided.
7, the preparation method of any described low molecular weight copolymer dispersant of claim 1 to 6, it is characterized in that with water being reaction medium, adopt disposable adding water soluble starter and monomer mixture, and by control initial reaction temperature, utilize a large amount of reaction heat that produce in the polyreaction autoacceleration process to make monomer mixture generation rapid polymerization and one the step make.
8, preparation method as claimed in claim 7, it is characterized in that described water soluble starter is conventional free radical water soluble starter or its mixture, comprise water-soluble ammonium persulphate, Potassium Persulphate, Sodium Persulfate and hydrogen peroxide, join whole initiators in the reaction mixture account for add 0.5～10% of total monomer mole number.
9, preparation method as claimed in claim 7, the monomer mixture total concentration by weight is controlled at 15～40% when it is characterized in that polyreaction, and the polymerization initial reaction temperature is controlled under 40～70 ℃, and polymerization reaction time is controlled at 2～3h.
10, preparation method as claimed in claim 7, its feature preferably is adjusted to 5.5～7.0 in the pH of final finished value.
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