CN105294952B - A kind of preparation method of polycarboxylate water-reducer - Google Patents
A kind of preparation method of polycarboxylate water-reducer Download PDFInfo
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- CN105294952B CN105294952B CN201510828087.6A CN201510828087A CN105294952B CN 105294952 B CN105294952 B CN 105294952B CN 201510828087 A CN201510828087 A CN 201510828087A CN 105294952 B CN105294952 B CN 105294952B
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 46
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 178
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- 238000003756 stirring Methods 0.000 claims abstract description 68
- 239000002994 raw material Substances 0.000 claims abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006073 displacement reaction Methods 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- -1 polyoxyethylene Polymers 0.000 claims description 23
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 18
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 18
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 18
- 239000007800 oxidant agent Substances 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 230000001590 oxidative effect Effects 0.000 claims description 15
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 14
- 229940117958 vinyl acetate Drugs 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 9
- 235000010323 ascorbic acid Nutrition 0.000 claims description 9
- 229960005070 ascorbic acid Drugs 0.000 claims description 9
- 239000011668 ascorbic acid Substances 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 7
- JPAOMENBKRZQDR-UHFFFAOYSA-N CC=CC.[Na] Chemical compound CC=CC.[Na] JPAOMENBKRZQDR-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 6
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 235000012208 gluconic acid Nutrition 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 235000019394 potassium persulphate Nutrition 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 4
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 3
- 230000000694 effects Effects 0.000 abstract description 14
- 239000012966 redox initiator Substances 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 description 33
- 150000003254 radicals Chemical class 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 14
- 239000003999 initiator Substances 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 229920000570 polyether Polymers 0.000 description 12
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical group CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 239000004721 Polyphenylene oxide Substances 0.000 description 8
- 238000007259 addition reaction Methods 0.000 description 8
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 230000000977 initiatory effect Effects 0.000 description 7
- 229920000056 polyoxyethylene ether Polymers 0.000 description 7
- 229940051841 polyoxyethylene ether Drugs 0.000 description 7
- 230000009257 reactivity Effects 0.000 description 7
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000037048 polymerization activity Effects 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000012648 alternating copolymerization Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- WCASXYBKJHWFMY-UHFFFAOYSA-N crotyl alcohol Chemical compound CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical class OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XBDUTCVQJHJTQZ-UHFFFAOYSA-L iron(2+) sulfate monohydrate Chemical compound O.[Fe+2].[O-]S([O-])(=O)=O XBDUTCVQJHJTQZ-UHFFFAOYSA-L 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000006049 ring expansion reaction Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000011895 specific detection Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GDSOZVZXVXTJMI-SNAWJCMRSA-N (e)-1-methylbut-1-ene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C(/C)=C(C(O)=O)\CCC(O)=O GDSOZVZXVXTJMI-SNAWJCMRSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical class [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000037081 physical activity Effects 0.000 description 1
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- 150000003384 small molecules Chemical class 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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Abstract
The invention discloses a kind of preparation method of polycarboxylate water-reducer, mainly comprise the following steps：The raw material of preparation is prepared as material A, material B and material C respectively；Then inserted material A as bed material in reaction vessel, be passed through the air in nitrogen displacement reaction vessel；Material B and material C are started simultaneously at and are continuously added in reaction vessel by measuring equipment again, material B added the time for 2~4 hours, material C addition addition time of the time than material B is long 15~45 minutes, material C continues stirring reaction 30 minutes to 90 minutes after all adding, and it is 5~7 to be eventually adding aqueous slkali adjustment pH value；The speed that material B and material C adds reaction vessel is adjusted, temperature in reaction vessel is maintained between 5~40 DEG C；The present invention makes the performance of polycarboxylate water-reducer be greatly improved by optimizing redox initiation system, introducing high activity minor comonomer, the charging technology for adjusting raw material etc. there is provided a kind of preparation method for the polycarboxylate water-reducer for not needing external heat source.
Description
Technical field
The invention belongs to water reducer preparation field, and in particular to a kind of preparation method of polycarboxylate water-reducer.
Background technology
In recent years, years development is passed through in China's polycarboxylate water-reducer production, and the imitation from beginning is gradually in international neck
First status, China's polycarboxylate water-reducer has reached the 35% of the market share within 2011.As people are to environment and environmental requirement
Further improve, polycarboxylate water-reducer will replace other traditional additives.But at the same time, China is in polycarboxylate water-reducer
Still the leading level in the world is lagged behind, it is necessary to put into more energy in terms of research and development.
The main component of polycarboxylate water-reducer is polycarboxylate, and the paradigmatic structure of polycarboxylate determines polycarboxylate water-reducer
Performance, polycarboxylate water-reducer is by the free-radical polymerized synthesis of aqueous phase, its substantially course of reaction, the initiator in initiation system
Primary group of free radicals is produced, the primary group of free radicals addition that double bond containing alkenyl monomer is produced with initiator generates monomer radical, single
Body free radical generates macromolecular chain free radical with alkenyl monomer rapid polymerization chain extension, and chain reaction generates chain macromolecule after terminating
Polymer；The characteristics of reaction, is that initiation is slow, it is fast to increase, terminates suddenly.
Trigger slow, be to say that reaction that initiator produces primary group of free radicals is a step most slow in whole synthetic reaction, this makes
Obtain primosome and be tied to form the first key that can be carried out for free radicals copolymerization reaction, i.e., the primary group of free radicals that initiator is produced is reaction
The precondition of generation.At present, conventional initiation system is thermal decomposition initiation system, and thermal decomposition system is by the way of thermal decomposition
Primary group of free radicals is produced, the temperature of thermal decomposition is generally 40~100 DEG C, this thermal source for needing offer extra goes to lift thermal initiation body
The temperature of system, so that it can produce primary group of free radicals, extra thermal source improves technological requirement and the life of polycarboxylate water-reducer
Cost is produced, this limits the development of polycarboxylate water-reducer industry to a certain extent.The temperature of primary group of free radicals is produced for reduction,
Have started to substitute thermal decomposition initiation system using redox initiation system now, redox initiation system, it is generated just
The reaction activity of level free radical is relatively low, can be effectively reduced the temperature of free radicals copolymerization reaction generation.
Increase fast, refer to that the addition reaction of primary group of free radicals and alkenyl monomer and follow-up chain reaction are all very fast；Just
With dilute base monomer the speed that addition reaction generates monomer radical, the close phase of polymerization activity with alkenyl monomer occur for level free radical
Close；The polymerization activity of monomer is generally characterized with reactivity ratio, and the reactivity ratio of different monomers is up to hundred times of gaps, due to chain growth speed
Quickly, so the high monomer of reactivity ratio can preferentially polymerize, it polymerize after the low monomer of reactivity ratio or polymerization of having no chance.
Terminate suddenly, refer to the production process of polycarboxylate water-reducer, monomer is rapidly converted into macromolecular chain free radical, and reaction is held
Macromolecular chain number of free radical drastically increases in device, because macromolecular chain free radical activity is very high, two macromolecular chain freedom
Base can interact and lose activity to form stable polymer；Or macromolecular chain free radical is acted on chain-transferring agent, is lost
Activity forms stable polymer.
The paradigmatic structure of polycarboxylate determines the performance of polycarboxylate water-reducer, and the composition of the copolymer of polycarboxylate is by list
The combined influence of the factors such as body activity, free radical activity, temperature, solvent, the pH value of medium, the optimal paradigmatic structure of copolymer
It is：Alkenyl polyether polymeric monomer and alkenyl minor comonomer alternating polymerization by a certain percentage, formed by main chain of minor comonomer, alkenyl polyether it is big
Monomer is the polymer of side chain, and this is also direction that current industry is made great efforts certainly；The ideal structure of polycarboxylate is：…MGreatlyMIt is small
MIt is smallMIt is smallMGreatlyMIt is smallMIt is smallMIt is smallMGreatlyMIt is smallMIt is smallMIt is small..., M thereinGreatlyRepresent long-chain polymeric monomer, MIt is smallRepresent small molecule minor comonomer.
Current conventional production process, is disposably to be added to raw material in reaction vessel, due to existing in the feed
The larger alkenyl polyether polymeric monomer of molecular weight, also there is dilute base minor comonomer such as the relatively small acrylic acid of molecular weight, methacrylic acid,
The reactivity ratio of alkenyl polyether polymeric monomer be less than other alkenyl minor comonomers reactivity ratio, namely polymeric monomer and minor comonomer conversion ratio not
Together, then the actual composition of copolymer just has difference with monomer blends；In addition, polymeric monomer and small in the linear macromolecule that copolymerization is formed
The skewness of monomer, first generates the low polymeric monomer content of the high minor comonomer content height of polymerization activity in product, polymerization activity
Low, rear generation product is then on the contrary, this causes the paradigmatic structure and the ideal structure according to monomer ratio alternating polymerization of polycarboxylate
Difference becomes big.
CN104262547A discloses a kind of method that prenol polyethers low temperature synthesizes polycarboxylate water-reducer, in this application
In, mode of heating dissolving prenol polyethers is employed, adjustment system temperature is 10 DEG C~45 DEG C, reacts 4~12 hours and completes,
Heating can accelerate the dissolving of prenol polyethers, but need additional heat.
CN103965413A discloses a kind of low-temperature synthetic method of high performance water reducing agent of polyocarboxy acid, by unsaturated polyoxy second
Alkene ether is dissolved in deionized water, is stirred, then by unsaturated monocarboxylic acid or part unsaturated sulfonic acid salt monomer solution
Add, then reducing agent and chain-transferring agent are sequentially added, aqueous oxidizing agent solution reaction is finally added dropwise；APEO therein is
Alkenyl polyether polymeric monomer；The low-temperature synthetic method is by the unsaturated sulphur of alkenyl polyether polymeric monomer and unsaturated monocarboxylic acid or part
The minor comonomers such as hydrochlorate disposably add reaction vessel, and the reaction in the low-temperature synthetic method is alkenyl polyether polymeric monomer and alkenyl
The copolyreaction of minor comonomer, it is this disposable because the Copolymerization activity difference of alkenyl polyether polymeric monomer and alkenyl minor comonomer is larger
Homopolymerization occurs first for the technique of the whole alkenyl minor comonomers of input, the minor comonomer that activity will be caused high, then just with polyoxyethylene
Ether polymeric monomer copolymerization, it is impossible to form the uniform long side chain distribution structure of alternating copolymerization, the product property of generation is poor, and is difficult to protect
Active poor APEO polymeric monomer is demonstrate,proved with higher conversion ratio.
In the production technology of polycarboxylate water-reducer, solution environmental has significant impact to initiator generation free radical, especially
It is that reducing agent is especially sensitive to the metal ion in reaction environment when using redox initiation system, so, how to reduce anti-
The influence for answering the metal ion in system is also a current problem.
The content of the invention
In view of the above-mentioned problems, the present invention is by optimizing redox initiation system, introducing high activity minor comonomer, adjustment raw material
Charging technology etc. there is provided a kind of preparation method for the polycarboxylate water-reducer for not needing any external heat source, using the present invention
The performance of the polycarboxylate water-reducer of preparation is greatly improved.
The present invention concrete technical scheme be：
The raw material for preparing polycarboxylate water-reducer is prepared as material A, material B and material C respectively；Then using material A as
Bed material is inserted in reaction vessel, is passed through the air in nitrogen displacement reaction vessel；Material B and material C are passed through into measuring equipment again
Start simultaneously at and be continuously added in reaction vessel, material B added the time for 2~4 hours, and the material C addition time is than material B
Addition time length 15~45 minutes, material C continues stirring reaction 30 minutes to 90 minutes after all adding, is eventually adding alkali soluble
Liquid adjustment pH value is 5~7；Adjust the speed that material B and material C add reaction vessel, make in reaction vessel temperature be maintained at 5~
Between 40 DEG C；
The preparation process of the material A is：Using 5~15 DEG C of deionized water as solvent, add organic acid and stir,
Then add alkenyl polyoxyethylene poly-oxygen propylene aether and stir, add vinylacetate and continue to stir, be made
Mass concentration is 40%-60%, and pH value≤4.5, temperature is 5~15 DEG C of material A；Material A can be directly poly- in above-mentioned preparation
Prepare, after can also being prepared in other reaction vessels, be again added to property in the reaction vessel of carboxylic acid water reducer
State in the reaction vessel for preparing polycarboxylate water-reducer；
The preparation process of the material B is：Using 5~15 DEG C of deionized water as solvent, add acrylic acid and stir equal
It is even, oxidant and stirring and dissolving are added, the material B that mass concentration is 20%~40% is made；
The preparation process of the material C is：Using 5~15 DEG C of deionized water as solvent, add chain-transferring agent and stir
Uniformly, reducing agent and stirring and dissolving are added, the material C that mass concentration is 20%~40% is made；
The oxidant is at least one of hydrogen peroxide, ammonium persulfate or potassium peroxydisulfate, oxidant and material A, material B
Mol ratio with all raw materials containing alkenyl in tri- kinds of materials of material C is 1: 20~1: 60；
The reducing agent is at least one of ascorbic acid, six ferrous sulfate hydrate ammoniums, reducing agent and material A, material B
Mol ratio with all raw materials containing alkenyl in tri- kinds of materials of material C is 1: 80~1: 400；
The chain-transferring agent is at least one of TGA, mercaptopropionic acid or methylpropene sodium sulfonate, chain-transferring agent with
The mol ratio of all sums of raw material containing alkenyl is 1: 40~1: 80 in material A, tri- kinds of materials of material B and material C.
The present invention uses and raw material is prepared as to material A, material B and material C respectively in advance；Material A is with alkenyl polyoxy second
The aqueous solution based on alkene polyethenoxy ether, material B is the aqueous solution based on the oxidant in acrylic acid and initiator, material C
It is the aqueous solution based on the reducing agent in chain-transferring agent and initiator；Previously prepared aqueous solution of raw material, during the course of the reaction
Can with rapid dispersion into system, make reacting balance, completely.
In process of production, it is to be added to material A as bed material, material B and material C simultaneously in material A, and uses
The mode being continuously added to, makes reaction more steady and complete；Because material C is based on chain-transferring agent and initiator, to make thing
Expect that the C addition time is most long, can so control redox initiation system to produce the speed of primary group of free radicals, so as to control whole
The speed of individual reaction, makes raw material of the raw material with being continuously added in bed material be reacted in the way of alternating copolymerization, so as to get reaction
Product meets design object, excellent performance.
And the currently used production method that raw material is disposably added to reaction vessel, due to radical polymerization have compared with
Strong exothermic effect, easily makes high double bond minor comonomer acrylic acid of activity etc. carry out autohemagglutination or produces gel, or even sudden and violent poly-, makes anti-
Target should be deviateed；Simultaneously because exothermic effect, whole reaction system is heated up, easily make reducing agent in advance with oxidant reaction and
Lose the effect of initiator.
The present invention adjusts the addition time, it is ensured that the stabilization of reaction is entered by control material B, material C addition speed
OK, material C addition Duration Ratio material B is slightly long, can avoid because initiator runs out of, and causes material B or material C
Middle alkenyl monomer can not initiated polymerization and reduce the conversion ratio of raw material.
Oxidant in redox initiation system of the present invention is in hydrogen peroxide, ammonium persulfate or potassium peroxydisulfate
At least one, reducing agent be at least one of ascorbic acid or six ferrous sulfate hydrate ammoniums, improve the adaptation of reducing agent
Property, free radicals copolymerization reaction is carried out at very low temperature, while control reaction maximum temperature so that reaction according to
Design object is steadily carried out, it is ensured that the performance and economy of target product.
Chain-transferring agent of the present invention is at least one in TGA, mercaptopropionic acid or methylpropene sodium sulfonate
Kind, it can be conveniently adjusted and control the molecular size range of polymerizate；Wherein, turn when using methylpropene sodium sulfonate as chain
When moving agent, it is possible to reduce have TGA, the consumption of mercaptopropionic acid of certain toxicity, the usage amount of noxious material is reduced, to carry
The feature of environmental protection of high product.
The present invention substitutes acrylic acid by using the high vinyl acetate ester moiety of reactivity, reduces free-radical polymerized anti-
The initial temperature answered.
The present invention is using pH value≤4.5 that material in organic acid, control reaction vessel is added in material A, to reduce oxygen
Change the activation energy of reduction reaction, so as to reduce the initial temperature of free radicals copolymerization reaction.Due to the alkenyl polyoxyethylene in material A
The molecular weight of polyethenoxy ether is higher, and dissolution velocity at low temperature is slower, using adding organic acid in material A, and controls
PH value≤4.5 processed, can effectively improve the dissolution velocity of alkenyl polyoxyethylene poly-oxygen propylene aether, without introducing external heat source
To improve the dissolution velocity of alkenyl polyoxyethylene poly-oxygen propylene aether.
The present invention reduces redox reaction by using organic acid and vinylacetate premixing is added in material A
Activation energy, so that the initial temperature of Raolical polymerizable is reduced, while alkenyl polyoxyethylene polyoxy third can also be improved
The conversion ratio of alkene ether.
In the production process of whole polycarboxylate water-reducer, include the difference preparation process of raw material, need not outside heat
Source, reduces production cost.
Further, the organic acid in material A is acetic acid, propionic acid, citric acid, gluconic acid, acrylic or methacrylic acid
At least one of.The addition of organic acid effectively reduces the pH value of material A, can improve alkenyl polyoxyethylene poly-oxygen propylene aether
Dissolution velocity, reduce free-radical polymerized initial temperature.
In this application, the μ s/cm of preferential electrical conductivity using deionized water≤50.Using going for the μ s/cm of electrical conductivity≤50
Ionized water is solvent, reaction environment is more conformed to the condition that initiation reaction occurs for initiator, it is to avoid the metal ion in water makes
Oxidant failure in reductant-oxidant system, so as to reduce free-radical polymerized efficiency.
Further, in material B preparation process, after deionized water is added, add before oxidant, add methyl-prop
At least one of olefin(e) acid, acrylate or methacrylate, so can further improve oxidant steady in system
It is qualitative, it is to avoid oxidant is reduced failure before the reaction.
Further, the number-average molecular weight of the alkenyl polyoxyethylene poly-oxygen propylene aether in material A is 330~3600；Material A,
Number-average molecular weight is that 330~3600 alkenyl polyoxyethylene poly-oxygen propylene aethers contain alkene with other in three kinds of materials in material B and material C
The mol ratio of based raw material sum is 1: 2.8~1: 4.8.After alternating copolymerization, alkenyl polyoxyethylene poly-oxygen propylene aether polymeric monomer is poly-
The long side chain of compound, other raw materials containing alkenyl are the main chain of polymer, and long side chain replaces with main chain, product is had optimal knot
Structure, reaches that optimal diminishing and guarantor are collapsed performance；The molal quantity of alkenyl polyoxyethylene poly-oxygen propylene aether is carried out by its number-average molecular weight
Calculate.
The number-average molecular weight of alkenyl polyoxyethylene poly-oxygen propylene aether, which is calculated, quotes JCT 2033-2010《Concrete admixture
With polyethers and its derivative》Hydroxyl value I is calculated, MNumber is equal=56100/I, MNumber is equalRepresent the number of alkenyl polyoxyethylene poly-oxygen propylene aether
Average molecular weight.
The mass ratio of vinylacetate and alkenyl polyoxyethylene poly-oxygen propylene aether is 1: 10~1: 1000 in material A, is made certainly
It can be carried out by base copolyreaction under the conditions of 5 DEG C.
In summary, the advantage of the invention is that：
Under the minimum environment temperature that can reach 5 DEG C, it is not necessary to introduce external heat source, entered by redox initiator
Row Raolical polymerizable, the progress of polymerisation is promoted using the heat discharged in course of reaction, production can be effectively reduced
The required energy, reduces production cost.
The pH value of the material A of bed material is used as by the minor comonomer, the pre-prepared aqueous solution of raw material of packet, adjustment that introduce high activity
For faintly acid, to reduce the start-up temperature of redox reaction, by the way that minor comonomer is distinguished into continuous dosing, Oxidizing and Reducing Agents
Feed respectively, control the means such as feed time, polymerisation is carried out more complete, monomer conversion is higher, control product
Structure.
By optimizing the proportion scale between each raw material, making the polycarboxylate water-reducer of synthesis has higher water-reducing rate, more
Good collapsing property of guarantor.As shown by data, the polycarboxylate water-reducer produced using the present invention can improve the glue sand water-reducing rate of cement
In the case of 50% or so, its 5 minutes paste flowing degrees still improve 50~170mm compared with comparative example, and paste flowing degree is carried within 60 minutes
High 125~200mm, and paste flowing degree kept stable in 120 minutes；Slump is held essentially constant within 60 minutes, is relatively contrasted
Example improves a lot；Divergence improves 50% or so, and keeps stable in 60 minutes.
Specific embodiment
With reference to embodiment, the invention will be further elaborated.
Embodiment 1
Prepare material A：By 300 grams of addition reaction vessels of deionized water that electrical conductivity is 10 μ s/cm, temperature is 15 DEG C, plus
Enter 6.16 grams of acetic acid and 1.28 grams of gluconic acids stir, add 288 grams of TPEG3600 and stir, be eventually adding 2.88
Gram vinylacetate, is passed through the air in nitrogen displacement reaction vessel after stirring, obtained temperature is 15 DEG C, pH value is 4.1
Material A.
Prepare material B：Acrylic acid 19.5 is added in the deionized water that 40 grams of electrical conductivity are 10 μ s/cm, temperature is 15 DEG C
Gram stir, then add 2.37 grams of 27.5% hydrogen peroxide and stir, the material B that temperature is 15 DEG C is made.
Prepare material C：0.87 gram of TGA stirring is added in 30 grams of electrical conductivity is 10 μ s/cm deionized waters equal
It is even, then add 0.84 gram of ascorbic acid and stir, the material C that temperature is 15 DEG C is made.
Material B and material C is continuously added to the reaction vessel where material A simultaneously by constant flow pump, material B adds the time
3 hours, material C added the time for 3.5 hours, and reaction temperature is up to 35 DEG C, and material C continues stirring reaction after all adding
1 hour, it was 6.0 to be eventually adding caustic-soda aqueous solution adjustment pH value.
TPEG3600 is the prenol polyoxyethylene poly-oxygen propylene aether that number-average molecular weight is 3600, using prenol as rise
Beginning agent, using 0.1% volume sodium methoxide as catalyst, epoxyethane ring-expansion polymerization is synthesized at 130 DEG C, and the degree of polymerization is 80.
Embodiment 2
Prepare material A：By 200 grams of addition reaction vessels of deionized water that electrical conductivity is 20 μ s/cm, temperature is 10 DEG C, plus
Enter 5.76 grams of acrylic acid to stir, add 192 grams of TPEG2400 and stir, be eventually adding 0.192 gram of vinylacetate,
It is passed through the air in nitrogen displacement reaction vessel after stirring, the material A that obtained temperature is 10 DEG C, pH value is 3.9.
Prepare material B：Acrylic acid 10.9 is added in the deionized water that 40 grams of electrical conductivity are 20 μ s/cm, temperature is 10 DEG C
Gram, 4.3 grams of methacrylic acid, 2.0 grams of ethyl acrylate stir, then add 4.38 grams of ammonium persulfates stir, make
Obtain the material B that temperature is 10 DEG C.
Prepare material C：In 30 grams of electrical conductivity 0.55 gram of TGA, 0.21 gram of mercapto are added for 20 μ s/cm deionized water
Base propionic acid and 0.23 gram of methylpropene sodium sulfonate stir, and then add 0.22 gram of six ferrous sulfate hydrate ammonium and stir,
It is eventually adding 0.16 gram of ascorbic acid to stir, the material C that temperature is 10 DEG C is made.
Material B and material C is continuously added to the reaction vessel where material A simultaneously by constant flow pump, material B adds the time
3 hours, the material C addition times were 3.5 hours, and reaction temperature is up to 35 DEG C, and material C continues stirring reaction after all adding
1 hour, it was 6.0 to be eventually adding caustic-soda aqueous solution adjustment pH value.
TPEG2400 is the isoamyl alcohol polyoxyethylene ether that number-average molecular weight is 2400, using prenol as initiator, with
0.1% volume sodium methoxide is catalyst, oxirane and expoxy propane ring-opening polymerisation synthesis at 130 DEG C, and the degree of polymerization is 52.
Embodiment 3
Prepare material A：By 200 grams of addition reaction vessels of deionized water that electrical conductivity is 20 μ s/cm, temperature is 5 DEG C, add
2.96 grams of propionic acid, 3.84 grams of citric acids, 1.96 grams of gluconic acids and 0.86 gram of methacrylic acid stir, and add 192 grams
HPEG2400 stirs, and is eventually adding 1.92 grams of vinylacetates, is passed through after stirring in nitrogen displacement reaction vessel
Air, it is 5 DEG C that temperature, which is made, and pH value is 3.8 material A.
Prepare material B：20.3 grams of acrylic acid is added in the deionized water that 40 grams of electrical conductivity are 20 μ s/cm, temperature is 5 DEG C
Stir, then add 1.2 grams of 27.5% hydrogen peroxide and stir, be eventually adding 1.0 grams of ammonium persulfate and potassium peroxydisulfate 0.8
Gram stir, the material B that temperature is 5 DEG C is made.
Prepare material C：Added in 30 grams of electrical conductivity is 20 μ s/cm deionized waters 0.68 gram of mercaptopropionic acid, 0.22 gram
TGA, 0.23 gram of methylpropene sodium sulfonate stir, and then add 0.84 gram of ascorbic acid and stir, temperature is made
For 5 DEG C of material C.
Material B and material C is continuously added to the reaction vessel where material A simultaneously by constant flow pump, material B adds the time
3 hours, the material C addition times were 3.5 hours, and reaction temperature is up to 25 DEG C, and material C continues stirring reaction after all adding
1 hour, it was 6.0 to be eventually adding caustic-soda aqueous solution adjustment pH value.
HPEG2400 is the methyl allyl alcohol polyoxyethylene ether that number-average molecular weight is 2400, using methallyl alcohol as starting
Agent, using 0.1% volume sodium methoxide as catalyst, epoxyethane ring-expansion polymerization is synthesized at 130 DEG C, and the degree of polymerization is 53.
Embodiment 4
Prepare material A：By 200 grams of addition reaction vessels of deionized water that electrical conductivity is 20 μ s/cm, temperature is 10 DEG C, plus
Enter 5.76 grams of acrylic acid to stir, add 192 grams of TPEG2400 and stir, be eventually adding 1.92 grams of vinylacetates,
It is passed through the air in nitrogen displacement reaction vessel after stirring, the material A that obtained temperature is 10 DEG C, pH value is 3.7.
Prepare material B：14.5 grams of acrylic acid is added in 40 grams of μ s/cm of electrical conductivity 20, temperature is 10 DEG C of deionized waters
Stir, then add 4.38 grams of ammonium persulfates and stir, be eventually adding 1.17 grams of methylpropene sodium sulfonates and stir,
The material B that temperature is 10 DEG C is made.
Prepare material C：0.25 gram of TGA stirring is added in 30 grams of electrical conductivity is 20 μ s/cm deionized waters equal
It is even, then add 0.22 gram of six ferrous sulfate hydrate ammonium and stir, be eventually adding 0.16 gram of ascorbic acid and stir, be made
Temperature is 10 DEG C of material C.
Material B and material C is continuously added to the reaction vessel where material A simultaneously by constant flow pump, material B adds the time
3 hours, the material C addition times were 3.5 hours, and reaction temperature is up to 25 DEG C, and material C continues stirring reaction after all adding
1 hour, it was 6.0 to be eventually adding caustic-soda aqueous solution adjustment pH value.
TPEG2400 is the isoamyl alcohol polyoxyethylene ether that number-average molecular weight is 2400, using prenol as initiator, with
0.1% volume sodium methoxide is catalyst, oxirane and expoxy propane ring-opening polymerisation synthesis at 130 DEG C, and the degree of polymerization is 52.
Embodiment 5
Prepare material A：By 40 grams of addition reaction vessels of deionized water that electrical conductivity is 50 μ s/cm, temperature is 5 DEG C, add
5.76 grams of acrylic acid stir, and add 56 grams of TPEG330 and stir, and are eventually adding 0.056 gram of vinylacetate, stirring
It is passed through the air in nitrogen displacement reaction vessel after uniform, the material A that obtained temperature is 9 DEG C, pH value is 4.3.
Prepare material B：15 grams of acrylic acid is added in the deionized water that 40 grams of electrical conductivity are 50 μ s/cm, temperature is 5 DEG C to stir
Mix uniform, then add 1.7 grams of 27.5% hydrogen peroxide and stir, the material B that temperature is 5 DEG C is made.
Prepare material C：0.25 gram of TGA is added in 30 grams of electrical conductivity for 50 μ s/cm deionized water to stir,
Then add 0.2 gram of ascorbic acid to stir, the material C that temperature is 5 DEG C is made.
Material B and material C is continuously added to the reaction vessel where material A simultaneously by constant flow pump, material B adds the time
3 hours, the material C addition times were 3.5 hours, and reaction temperature is up to 24 DEG C, and material C continues stirring reaction after all adding
1 hour, it was 6.0 to be eventually adding caustic-soda aqueous solution adjustment pH value.
TPEG330 is the isoamyl alcohol polyoxyethylene ether that number-average molecular weight is 2400, using prenol as initiator, with
0.1% volume sodium methoxide is catalyst, oxirane and expoxy propane ring-opening polymerisation synthesis at 130 DEG C, and the degree of polymerization is 5.5.
Comparative example 1
By 260 grams, 192 grams HPEG2400 of deionized water, 27.6 grams and 27.5% pair of the acrylic acid that electrical conductivity is 20 μ s/cm
2.37 grams of addition reaction vessel C1 of oxygen water, are passed through air in nitrogen displacement reaction vessel C1 after stirring；In reaction vessel D1
It is middle to add 0.84 gram of 40 grams of deionized water, 1.02 grams of mercaptopropionic acid and the ascorbic acid that electrical conductivity is 20 μ s/cm, stir and match somebody with somebody
Mixed liquor is made, is then continuously added to mixed liquor in reaction vessel C1 by constant flow pump, and continues stirring, the addition time is
3.5 hours, continue stirring reaction after adding 1 hour, it is 6.0 to be eventually adding caustic-soda aqueous solution adjustment pH value.
HPEG2400 is the methyl allyl alcohol polyoxyethylene ether that number-average molecular weight is 2400, using methallyl alcohol as starting
Agent, using 0.1% volume sodium methoxide as catalyst, oxirane, expoxy propane ring-opening polymerisation are synthesized at 130 DEG C, and the degree of polymerization is
53。
Comparative example 2
Be 500 μ s/cm 5 DEG C of running water, 240 grams, 26.06 grams acrylic acid by electrical conductivity, 192 grams of HPEG2400,1.92 grams
Vinylacetate adds reaction vessel C2, and air in nitrogen displacement reaction vessel C2 is passed through after stirring；In reaction vessel D2
The middle electrical conductivity that adds is 500 μ s/cm 40 grams of 5 DEG C of running water, 2.37 grams of 27.5% hydrogen peroxide, 1.02 grams of mercaptopropionic acid and anti-bad
0.84 gram of hematic acid, which stirs, is made the aqueous solution, is then continuously added to the aqueous solution in reaction vessel C2 by constant flow pump, and hold
Continuous stirring, it is 3.5 hours to add the time, continues stirring reaction after adding 1 hour, is eventually adding caustic-soda aqueous solution adjustment pH value and is
6.0。
HPEG2400 is the methyl allyl alcohol polyoxyethylene ether that number-average molecular weight is 2400, using methallyl alcohol as starting
Agent, using 0.1% volume sodium methoxide as catalyst, oxirane, expoxy propane ring-opening polymerisation are synthesized at 130 DEG C, and the degree of polymerization is
53。
Implementation result
According to GB/T8077-2000《Methods for testing uniformity of concrete admixture》, detection prepare product net slurry flowing
Degree, specific detection data are shown in Table 1.
The paste flowing degree and glue sand water-reducing rate (the solid volume 0.2% of water reducer folding) of the quasi- cement of the benchmark of table 1
According to GB/T8076-2008《Concrete admixture》, detection prepares the concrete performance of the preparation of product；Water reducer
The solid volume of folding is 0.2%, and the initial slump for making concrete is 200 ± 20mm, and specific detection data are shown in Table 2.
The concrete test result of table 2
Claims (3)
1. a kind of preparation method of polycarboxylate water-reducer, it is characterised in that：
The raw material for preparing polycarboxylate water-reducer is prepared as material A, material B and material C respectively；Then it regard material A as bed material
Insert in reaction vessel, be passed through the air in nitrogen displacement reaction vessel；Again by material B and material C by measuring equipment simultaneously
Start and be continuously added in reaction vessel, the material B addition time is 2~4 hours, material C adds adding than material B time
Angle of incidence length 15~45 minutes, material C continues stirring reaction 30 minutes to 90 minutes after all adding, and is eventually adding aqueous slkali tune
Whole pH value is 5~7；The speed that material B and material C adds reaction vessel is adjusted, temperature in reaction vessel is maintained at 5~40 DEG C
Between；
The preparation process of the material A is：Using 5~15 DEG C of deionized water as solvent, add organic acid and stir,
Then add alkenyl polyoxyethylene poly-oxygen propylene aether and stir, add vinylacetate and continue to stir,
Mass concentration is made for 40%-60%, pH value≤4.5, temperature is 5~15 DEG C of material A；
Organic acid in the material A is acetic acid, in propionic acid, citric acid, gluconic acid, acrylic or methacrylic acid at least
It is a kind of；
The number-average molecular weight of alkenyl polyoxyethylene poly-oxygen propylene aether in the material A is 330~3600；
Number-average molecular weight is 330~3600 alkenyl polyoxyethylene polyoxy third in the material A, tri- kinds of materials of material B and material C
The mol ratio of alkene ether and other sums of raw material containing alkenyl is 1：2.8~1：4.8；
The mass ratio of vinylacetate and alkenyl polyoxyethylene poly-oxygen propylene aether is 1 in the material A:10~1:1000；
The preparation process of the material B is：Using 5~15 DEG C of deionized water as solvent, add acrylic acid and stir, then
Oxidant and stirring and dissolving are added, the material B that mass concentration is 20%~40% is made；
The preparation process of the material C is：Using 5~15 DEG C of deionized water as solvent, add chain-transferring agent and stir,
Reducing agent and stirring and dissolving are added, the material C that mass concentration is 20%~40% is made；
The oxidant is at least one of hydrogen peroxide, ammonium persulfate or potassium peroxydisulfate, oxidant and material A, material B and thing
The mol ratio for expecting all raw materials containing alkenyl in tri- kinds of materials of C is 1:20~1:60；
The reducing agent is at least one of ascorbic acid, six ferrous sulfate hydrate ammoniums, reducing agent and material A, material B and thing
The mol ratio for expecting all raw materials containing alkenyl in tri- kinds of materials of C is 1:80~1:400；
The chain-transferring agent is at least one of TGA, mercaptopropionic acid or methylpropene sodium sulfonate, chain-transferring agent and material
The mol ratio of all sums of raw material containing alkenyl is 1 in A, material B and tri- kinds of materials of material C:40~1:80.
2. preparation method according to claim 1, it is characterised in that the μ s/cm of the electrical conductivity of deionized water≤50.
3. preparation method according to claim 1, it is characterised in that in material B preparation process, adding deionized water
Afterwards, add before oxidant, add at least one of methacrylic acid, acrylate or methacrylate.
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