CN116478393A - Polyether macromonomer, preparation method and application of polyether macromonomer in polycarboxylate water reducer - Google Patents
Polyether macromonomer, preparation method and application of polyether macromonomer in polycarboxylate water reducer Download PDFInfo
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 122
- 229920000570 polyether Polymers 0.000 title claims abstract description 122
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 239000003999 initiator Substances 0.000 claims abstract description 29
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000004321 preservation Methods 0.000 claims abstract description 5
- 230000004913 activation Effects 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 10
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical group CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 claims description 8
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 6
- JGQFVRIQXUFPAH-UHFFFAOYSA-N beta-citronellol Natural products OCCC(C)CCCC(C)=C JGQFVRIQXUFPAH-UHFFFAOYSA-N 0.000 claims description 6
- QMVPMAAFGQKVCJ-UHFFFAOYSA-N citronellol Chemical compound OCCC(C)CCC=C(C)C QMVPMAAFGQKVCJ-UHFFFAOYSA-N 0.000 claims description 6
- ZYTMANIQRDEHIO-KXUCPTDWSA-N isopulegol Chemical compound C[C@@H]1CC[C@@H](C(C)=C)[C@H](O)C1 ZYTMANIQRDEHIO-KXUCPTDWSA-N 0.000 claims description 6
- -1 ethyleneoxy group Chemical group 0.000 claims description 5
- 239000001871 (1R,2R,5S)-5-methyl-2-prop-1-en-2-ylcyclohexan-1-ol Substances 0.000 claims description 3
- GIEMHYCMBGELGY-UHFFFAOYSA-N 10-undecen-1-ol Chemical compound OCCCCCCCCCC=C GIEMHYCMBGELGY-UHFFFAOYSA-N 0.000 claims description 3
- WULAHPYSGCVQHM-UHFFFAOYSA-N 2-(2-ethenoxyethoxy)ethanol Chemical compound OCCOCCOC=C WULAHPYSGCVQHM-UHFFFAOYSA-N 0.000 claims description 3
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical group OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 claims description 3
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 claims description 3
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 claims description 3
- LOFHPLKGPULNQP-UHFFFAOYSA-N 4-methylpent-4-en-1-ol Chemical compound CC(=C)CCCO LOFHPLKGPULNQP-UHFFFAOYSA-N 0.000 claims description 3
- 235000000484 citronellol Nutrition 0.000 claims description 3
- 229940095045 isopulegol Drugs 0.000 claims description 3
- ZYTMANIQRDEHIO-UHFFFAOYSA-N neo-Isopulegol Natural products CC1CCC(C(C)=C)C(O)C1 ZYTMANIQRDEHIO-UHFFFAOYSA-N 0.000 claims description 3
- WXPWPYISTQCNDP-UHFFFAOYSA-N oct-7-en-1-ol Chemical compound OCCCCCCC=C WXPWPYISTQCNDP-UHFFFAOYSA-N 0.000 claims description 3
- LQAVWYMTUMSFBE-UHFFFAOYSA-N pent-4-en-1-ol Chemical compound OCCCC=C LQAVWYMTUMSFBE-UHFFFAOYSA-N 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical group [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 18
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- 238000000889 atomisation Methods 0.000 abstract description 4
- 238000005580 one pot reaction Methods 0.000 abstract description 4
- 230000037452 priming Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 20
- 239000002994 raw material Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 239000000543 intermediate Substances 0.000 description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 10
- 239000012071 phase Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000008030 superplasticizer Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000012653 anionic ring-opening polymerization Methods 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 2
- 239000002211 L-ascorbic acid Substances 0.000 description 2
- 235000000069 L-ascorbic acid Nutrition 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000007046 ethoxylation reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 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
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 150000003077 polyols Chemical group 0.000 description 1
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2641—Polyacrylates; Polymethacrylates
- C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Polyethers (AREA)
Abstract
The invention provides a polyether macromonomer, a preparation method and application thereof in a polycarboxylate water reducer, firstly, an initiator is added into a reaction kettle for priming, and a catalyst is added under the working condition of nitrogen protection for reaction to obtain an activated initiator; transferring the activation initiator into a reaction device, heating, starting alkylene oxide feeding, reacting, and continuously feeding alkylene oxide until the molecular weight reaches a set molecular weight to obtain a polyether intermediate; and adding a viscosity reducer, continuing to introduce alkylene oxide until the material is completely introduced, carrying out heat preservation reaction, and carrying out devolatilization under reduced pressure to obtain a polyether macromonomer finished product. The viscosity reducer is added, so that the preparation of the high molecular weight polyether by the one-pot process is realized, the viscosity in the polyether production process can be reduced, and the outlet pressure of an external circulation pump and the atomization effect of a nozzle in a reactor are reduced; and no special reaction equipment is needed, and the existing PRESS reactor can meet the requirement of producing high molecular weight polyether macromonomer.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a polyether macromonomer, a preparation method and application thereof in a polycarboxylate water reducer.
Background
The concrete admixture is an indispensable component in the concrete production process, can adjust and improve the working performance of concrete, and the water reducer is a main product in the concrete admixture, and is applied to the concrete in the development stages of lignin sulfonate, naphthalene sulfonate, polycarboxylic acid water reducer and the like. Compared with the sulfonate water reducer with a linear structure, the molecular structure of the polycarboxylate water reducer is comb-shaped, has the electrostatic effect of a carboxylic acid adsorption group and the steric hindrance effect of a polyether side chain, has higher water reducing rate and fluidity maintaining capability, and is the largest water reducer in China at present.
The polyether macromonomer is one of core raw materials of the polycarboxylate water reducer, more than 80% of the mass of the water reducer is the polyether macromonomer, and the mass of the polyether macromonomer has an important influence on the performance of the water reducer. The molecular structure of the polyether macromonomer comprises ester type and ether type (Liu Guanjie and the like, the application research progress of the polycarboxylate water reducer polyether macromonomer [ J ], the science of daily chemicals, 2018,41 (10), 13-16), the ester type polyether macromonomer takes unsaturated carboxylic acid and methoxy polyether as raw materials, an esterification dehydration process is generally adopted, and a preparation method and a post-treatment method are complex; the ether type polyether macromonomer uses unsaturated alcohol containing double bonds and alkylene oxide as raw materials, and the preparation method is simple and does not need special post treatment through an anionic ring-opening polymerization process. At present, the domestic ether type polyether macromonomer is the most important polyether macromonomer product in China.
The reaction equipment of the ether type polyether macromonomer mainly comprises reactor forms such as a kettle type reactor, a BUSS reactor, a PRESS reactor and the like, the PRESS reactor has large amplification factor and high production efficiency, and is most widely applied in the polyether industry, the fifth generation PRESS reactor is developed at present, the single kettle capacity reaches more than 30 tons, and the production efficiency and the capacity of the polyether macromonomer are greatly improved (Qin Yong, shallow talking about the development trend [ J ] of the ethoxylation production process in China, science of daily chemicals, 2014,37 (11), and 1-6). Along with the increase of the number average molecular weight, the viscosity of the polyether macromonomer can be obviously increased, the atomization effect of a spray head is affected, the pumping pressure of an external circulation pump is increased, and the number average molecular weight of the polyether macromonomer which can be prepared by the PRESS reactor is generally lower than 4000.
Researches show that the polycarboxylate water reducer prepared from the polyether macromonomer with the number average molecular weight larger than 4000 has good early strength effect (Zhou Dongliang and the like, the influence of the molecular structure of the polycarboxylate on the early strength performance of concrete [ J ],2022, (03): 1-5.), and Chinese patent CN103724557A also reports that high molecular weight polyether is used for synthesizing the early strength polycarboxylate water reducer. How to prepare polyether macromonomers with higher number average molecular weight becomes a problem to be solved in the industry of polycarboxylate water reducers.
Chinese patent CN105001411 a reports a device for producing a high molecular weight polyether macromonomer dedicated for a polycarboxylate superplasticizer. The two-stage kettle type reactor is used as a preparation system of the polyether macromonomer, the stirring blade and the ethylene oxide feeding mode are improved in the first-stage kettle type reactor, an external circulation pipeline and an atomizer are added in the second-stage kettle type reactor, and the mass and heat transfer efficiency in the production process of the polyether macromonomer is improved through the two-stage kettle type reactor. Chinese patent CN114832759a reports a similar method for preparing high molecular weight polyether by using a two-stage kettle reactor, not only improves kettle equipment, but also adds a solvent to reduce the viscosity of the reaction system, and distills the solvent in vacuum after the ethoxylation reaction is completed to obtain high molecular weight polyether.
In conclusion, the increase of the molecular weight of the polyether macromonomer can endow the polycarboxylate water reducer with certain performance advantages in the aspects of early strength and the like, and further, the increase of the molecular weight of the polyether macromonomer is beneficial to solving the problem of hardening and blocking of polyether slices. However, for how polyether macromonomers with molecular weights greater than 4000 are produced, the mass and heat transfer and production energy consumption of existing PRESS reactors are adversely affected to some extent. Existing literature and patent reports still tend to employ multistage series-connected tank reactor processes, increasing equipment complexity and floor space, and employing solvents as viscosity-reducing additives. After the preparation of the polyether macromonomer is finished, the effective content and the subsequent polymerization effect of the polyether macromonomer are affected by the fact that the viscosity-reducing additive is not removed; the removal of the viscosity-reducing additive increases the difficulty of subsequent devolatilization.
Disclosure of Invention
The invention aims to provide a polyether macromonomer and a preparation method thereof, which realize the preparation of high molecular weight polyether by a one-pot process, can reduce the viscosity in the production process of polyether, and reduce the outlet pressure of an external circulation pump and the atomization effect of a nozzle in a reactor; and no special reaction equipment is needed, the process is simple, the production efficiency is high, and the existing PRESS reactor can meet the requirement of producing high molecular weight polyether macromonomer.
It is also an object of the present invention to provide the use of a polyether macromonomer in a polycarboxylate water reducer.
The specific technical scheme of the invention is as follows:
a method for preparing a polyether macromonomer, comprising the following steps:
1) Adding an initiator into a reaction kettle for bottoming, adding a catalyst under the working condition of nitrogen protection, and reacting to obtain an activated initiator;
2) Transferring the activation initiator into a reaction device, heating, starting alkylene oxide feeding, reacting, and continuously feeding alkylene oxide until the molecular weight reaches a set molecular weight to obtain a polyether intermediate;
3) And adding a viscosity reducer, continuing to introduce alkylene oxide until the material is completely introduced, carrying out heat preservation reaction, and carrying out devolatilization under reduced pressure to obtain a polyether macromonomer finished product.
The molecular structure of the initiator in the step 1) is shown in the following formula (1)
Wherein R is-CH 2 -CH 2 -，-CH 2 -CH 2 -O-CH 2 -CH 2 -，-CH 2 -CH 2 -CH 2 -CH 2 -，-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -，-CH 2 -CH(CH 3 )-CH 2 -one of the structures;
in step 1), the initiator is an unsaturated alcohol terminated with vinyloxy groups, preferably ethylene glycol monovinyl ether, diethylene glycol monovinyl ether or 4-hydroxybutyl vinyl ether.
In the step 1), the catalyst belongs to a strong alkaline catalyst, and considering the requirement of polyether macromonomer on purity, metal sodium is selected as the catalyst, and the catalyst dosage is 0.25-0.35% of the mass of the initiator.
In the step 1), the reaction is carried out at the temperature of 40-70 ℃ and the reaction pressure is normal pressure, and the reaction time is 4-6 hours; in the reaction process, nitrogen is needed to protect, on one hand, the nitrogen is utilized to timely discharge hydrogen generated by the reaction of the initiator and the sodium metal, and on the other hand, the influence of moisture and oxygen in the air on the reaction process is avoided.
In the step 1), the prepared active initiator is an initiator sodium alkoxide solution obtained after the initiator and metal sodium are completely reacted.
In step 2), the reaction device is a common PRESS reactor, comprising a third generation, a fourth generation and a fifth generation PRESS reactor, and the existing PRESS reactor is directly used for preparing the polyether macromonomer without technical modification of equipment.
In the step 2), the nitrogen of the reaction device is replaced for 3 times, then the vacuum is pumped to-0.1 MPa, the reaction device is heated, and then alkylene oxide is introduced.
In the step 2), the alkylene oxide comprises propylene oxide, ethylene oxide, and when ethylene oxide and propylene oxide are simultaneously fed into the reactor, the propylene oxide is used in an amount of 0.0-5.0% of the mass of the ethylene oxide.
In the step 2), the reaction temperature is 115+/-5 ℃ and the reaction pressure is less than or equal to 450KPa;
in step 2), the polyether intermediate has a set molecular weight of number average molecular weight, and the number average molecular weight of the polyether intermediate is set to be between 3800 and 4200.
In step 2), the anionic ring-opening polymerization of the reactive initiator with the alkylene oxide is well known to those skilled in the art and will not be described in detail herein.
In the step 3), the viscosity reducer has smaller molecular weight and can react with the alkylene oxide, and is added into the polyether intermediate in the step 2), the viscosity reducer and the alkylene oxide are synthesized into a low molecular weight polyether macromonomer through ring-opening polymerization, so that the plasticizing and viscosity reducing effects can be achieved, the viscosity of the polyether intermediate is reduced, and the external circulation pumping and nozzle atomizing effects of the PRESS reactor are improved.
The viscosity reducer in the step 3) is alcohol containing unsaturated double bonds and has free radical polymerization activity, and can be used as a polymerizable monomer for the subsequent synthesis of the polycarboxylate water reducer. Preferably, the viscosity reducer comprises one or more of unsaturated alcohols such as allyl alcohol, methallyl alcohol, 3-isopentenyl alcohol, 2-isopentenyl alcohol, 4-penten-1-ol, 4-methyl-4-penten-1-ol, isopulegol, 7-octen-1-ol, 3, 7-dimethyl-7-octenol, 3, 7-dimethyl-6-octen-1-ol, 10-undecenol and the like.
In the step 3), the dosage of the viscosity reducer is 5-15% of the mass of the initiator in the step 1).
In the step 3), the alkylene oxide is ethylene oxide, and the dosage of the alkylene oxide is 20-30% of that of the alkylene oxide in the step 2).
In step 3), the incubation reaction means: controlling the reaction temperature to be 115+/-5 ℃, controlling the reaction pressure to be less than or equal to 450KPa, and preserving the heat for reaction for 0.5h after the ethylene oxide feeding is finished.
In the step 3), the reduced pressure devolatilization is specifically as follows: devolatilizing under reduced pressure at 80 ℃ and under the working condition of minus 0.01 MPa.
The polyether macromonomer provided by the invention is prepared by adopting the method, and comprises a polyether macromonomer with high molecular weight and a polyether macromonomer with low molecular weight to form a multi-distribution polyether macromonomer with different molecular weights. The high molecular weight polyether macromonomer is a raw material for preparing the early strength water reducing agent, and the low molecular weight polyether macromonomer is a raw material for preparing the workability improving water reducing agent. The invention adopts a one-pot process to prepare the polyether macromonomer with multiple distributions, which is a raw material for synthesizing the polycarboxylate water reducer with early strength and workability improving effects.
The invention provides an application of a polyether macromonomer in a polycarboxylate water reducer, which comprises the following steps: polyether macromonomer and acrylic acid are subjected to water phase free radical polymerization reaction to prepare the polycarboxylate superplasticizer mother liquor with the solid content of 40%.
The method comprises the following steps: 240.0 parts of polyether macromonomer, 240.0 parts of water are added to dilute to 50 percent of solid content, fully stirred to be completely dissolved, and H is added 2 O 2 4.0 parts of a reaction base solution; weighing 20.5 parts of acrylic acid, adding 52.0 parts of water, and naming the mixture as a dropwise adding solution A; weighing 0.35 part of L-ascorbic acid and 1.0 part of mercaptopropionic acid, adding 100.0 parts of water, fully dissolving to obtain clear solution, and naming the clear solution as dropwise adding solution B; and (3) in a water bath kettle at 20 ℃, dropwise adding the solution A and the solution B into the reaction base solution, setting the dropwise adding time of the dropwise adding solution A to be 1.0h, setting the dropwise adding time of the dropwise adding solution B to be 1.5h, and keeping the temperature for 1.0h after the dropwise adding is finished. After the reaction is finished, the polycarboxylate superplasticizer mother liquor with the theoretical solid content of 40% is obtained.
According to the invention, the polyether intermediate with the number average molecular weight of 3800-4200 is prepared by using the 6C alcohol head, other unsaturated alcohol is added into the polyether intermediate, the unsaturated alcohol and the polyether intermediate compete for ring-opening polymerization of alkylene oxide, and the unsaturated alcohol is used for synthesizing low molecular weight polyether with a certain molecular weight through ring-opening reaction, so that the polyether finished product obtained by improving the viscosity of a high molecular weight polyether system is obtained, and the polyether finished product contains the high molecular weight polyether prepared by the 6C alcohol head and the low molecular weight polyether prepared by other unsaturated alcohol, and has the effects of early strength and workability improvement.
Compared with the prior art, the invention has the following effects:
the viscosity reducer is added, so that the preparation of the high molecular weight polyether by the one-pot process is realized, the viscosity in the polyether production process can be reduced, and the outlet pressure of an external circulation pump and the atomization effect of a nozzle in a reactor are reduced; and no special reaction equipment is needed, and the existing PRESS reactor can meet the requirement of producing high molecular weight polyether macromonomer.
The viscosity of the high molecular weight polyether in the production process is reduced by the reaction viscosity reduction method for the first time, and the viscosity reducer and the alkylene oxide can also undergo an anionic ring-opening polymerization reaction to obtain the low molecular weight polyether macromonomer, so that the viscosity of the high molecular weight polyether macromonomer is reduced. In addition, the viscosity reducer is unsaturated alcohol with free radical polymerization activity, and the polyether macromonomer obtained after polymerization with alkylene oxide can be used for the subsequent synthesis of a polycarboxylate water reducer without subsequent process operation for removing plasticizers. The production method of the polyether macromonomer simplifies the production process of the high molecular weight polyether and reduces the production bottleneck and post-treatment problems of the high molecular weight polyether macromonomer. Furthermore, the polyether macromonomer has higher molecular weight, high polyether slicing efficiency and difficult slice hardening.
The invention finally prepares the multi-distribution polyether macromonomer containing different molecular weights, which contains the polyether macromonomer with high molecular weight and the polyether macromonomer with low molecular weight. After the water reducer is polymerized with acrylic acid and the like through water phase free radicals, the water reducer prepared by the high-molecular-weight polyether macromonomer has better early strength performance, and the water reducer prepared by the low-molecular-weight polyether macromonomer has better workability improving effect. Not only solves the production problem of the macromolecular polyether macromonomer, but also endows the finally prepared water reducer with early strength and workability improving effects.
Detailed Description
The invention is described in detail below by way of examples which are illustrative only and are not meant to limit the scope of applicability of the invention, as the skilled artisan will be able to modify the reagents, catalysts and reaction process conditions within the scope of the invention in light of the disclosure herein. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
In the invention, the molecular weight of polyether refers to national standard GB/T12008.3-2009 Plastic polyether polyol part 3: the method described in the determination of the hydroxyl value is carried out by the acetic anhydride methodThe method comprises the steps of carrying out a first treatment on the surface of the The content of each peak of the polyether macromonomer is calculated by area percentage, and is measured by using a large Lianyite iChrom 5100 type high performance liquid chromatograph, and the specific parameters are as follows: mobile phase methanol/water volume ratio 4; the flow phase speed is 1ml/min; sample injection amount is 20 μl; sample concentration 0.5% (sample g/mobile phase g); detector, differential refractive detector. The molecular weight and molecular weight distribution of the polycarboxylate water reducer were determined using a Wyatt technology corporation gel permeation chromatograph. The specific parameters are as follows: mobile phase 0.1mol/L NaNO 3 An aqueous solution; the flow phase speed is 1ml/min; sample injection amount is 20 μl; sample concentration 0.5% (sample g/mobile phase g); a detector, namely a Shodex RI-71 type differential refraction detector; standard polyethylene glycol GPC standard (Sigma-Aldrich, molecular weight 1010000,478000,263000,118000,44700,18600,6690,1960,628,232).
The synthesis method in the examples is divided into two parts, firstly the preparation of polyether macromonomer and then the synthesis of polycarboxylate water reducer. In the embodiment, the parts are specifically referred to as mass parts, and the addition amounts of other materials are converted into mass parts.
1. Preparation of polyether macromonomers
For convenience of description of the following examples, the raw materials are simplified by code numbers, and details of the raw materials and the code numbers are shown in table 1.
TABLE 1 details of raw materials and code
| Type of material | Species of type | (Code) |
| Ethylene glycol monovinyl ether | Initiator | Q-1 |
| Diethylene glycol monovinyl ether | Initiator | Q-2 |
| 4-hydroxybutyl vinyl ether | Initiator | Q-3 |
| Ethylene oxide | Alkylene oxide | EO |
| Propylene oxide | Alkylene oxide | PO |
| Allyl alcohol | Viscosity reducer | JN-1 |
| Methallyl alcohol | Viscosity reducer | JN-2 |
| 3-Isopentenol | Viscosity reducer | JN-3 |
| 2-Isopentenol | Viscosity reducer | JN-4 |
| 4-methyl-4-penten-1-ol | Viscosity reducer | JN-5 |
| 4-penten-1-ol | Viscosity reducer | JN-6 |
| 7-octen-1-ol | Viscosity reducer | JN-7 |
| 3, 7-dimethyl-7-octenol | Viscosity reducer | JN-8 |
| Isopulegol | Viscosity reducer | JN-9 |
| 3, 7-dimethyl-6-octen-1-ol | Viscosity reducer | JN-10 |
| 10-undecenol | Viscosity reducer | JN-11 |
The raw material ratios for preparing the polyether macromonomer in the examples are shown in Table 2.
TABLE 2 raw materials proportioning table (unit is mass portion)
The polyether macromonomers of the examples were prepared as follows:
1) Weighing the initiator according to the proportion and the dosage of the raw materials in the table 2, priming the initiator in a reaction kettle, adding metal sodium according to the table 2 under the working condition of nitrogen protection, controlling the temperature of the feeding process between 40 ℃ and 70 ℃, controlling the reaction pressure to be normal pressure under the working condition of nitrogen protection, and controlling the reaction time to be 5.0h, thus obtaining the activated initiator.
2) The activation initiator was then transferred to the PRESS reactor, nitrogen sparged 3 times and again evacuated to-0.1 MPa, the reactor heated to 100deg.C using 0.8MPa steam, and the first stage ethylene oxide and propylene oxide feeds were started. Controlling the reaction temperature to be 115+/-5 ℃, controlling the reaction pressure to be less than or equal to 450KPa, and after the alkylene oxide feeding is finished, carrying out heat preservation reaction for 0.5h to obtain the polyether intermediate.
3) And then transferring the metered viscosity reducer into a PRESS reactor, replacing nitrogen for 3 times, vacuumizing again to minus 0.1MPa, continuously starting ethylene oxide feeding in the second stage, controlling the reaction temperature to 115+/-5 ℃ and the reaction pressure to be less than or equal to 450KPa, after the ethylene oxide feeding is finished, carrying out heat preservation reaction for 0.5h, and carrying out reduced pressure devolatilization under the working conditions of 80 ℃ and minus 0.01MPa to obtain a polyether macromonomer finished product. The hydroxyl number test and hplc test data for the polyether intermediate and polyether macromonomer are shown in table 3.
TABLE 3 test data for polyether intermediates and polyether macromers
In the liquid phase peak-out percentages of the polyether intermediate and the polyether macromonomer, the last data of each group of data are the peak-out contents of byproducts, and the peak-out contents of the rest liquid phase chromatograms are the peak-out contents of the products.
2. Use of the polyether macromonomer prepared in the above examples in polycarboxylate water reducers:
the polyether macromonomer in each embodiment is taken as a raw material, and polymerized with acrylic acid to form the polycarboxylate water reducer by a water phase free radical polymerization method, and the raw material proportion and the technological parameters of the water reducer synthesis process are shown in table 4.
Table 4 raw material ratios and process parameters (in parts by mass) for the synthesis of polycarboxylate superplasticizers
The synthesis steps of the polycarboxylate water reducer are as follows: 240.0 parts of polyether macromonomers of example 1-example 6, comparative example 1 and comparative example 2 are weighed into four-port reaction bottles respectively, diluted to 50% solid content by adding 240.0 parts of water, and fully stirred until completely dissolved. Weighing 20.5 parts of acrylic acid, adding 52.0 parts of water, and naming the mixture as a dropwise adding solution A; 0.35 part of L-ascorbic acid and 1.0 part of mercaptopropionic acid are weighed, 100.0 parts of water is added for fully dissolving to clear liquid, and the mixture is named as dropwise added solution B. Weighing H 2 O 2 4.0 parts of the mixture is added into a four-mouth reaction bottle to be primed. The four-mouth reaction bottle is placed in a water bath kettle with the temperature of 20 ℃, the dripping time of the dripping solution A is set to be 1.0h, the dripping time of the dripping solution B is set to be 1.5h, and the reaction time is kept for 1.0h after the dripping is finished. After the reaction is finished, a polycarboxylate superplasticizer mother solution with a theoretical solid content of 40% is obtained, and the polycarboxylate superplasticizers prepared by the polyether macromonomers of the examples 1-6 are sequentially named as PCE-1 to PCE-6; the polycarboxylate water reducers prepared from the polyether macromonomers of comparative example 1 and comparative example 2 were named PCE-7 to PCE-8 in this order.
The carboxylic acid water reducer was tested by Gel Permeation Chromatography (GPC) according to a prescribed method, and the test results are shown in table 5. The monomer conversion, weight average molecular weight and molecular weight distribution were tested using GPC testing.
TABLE 5 GPC test of polycarboxylate water reducers
T with outflow time and expansion degree reaching 500mm by adopting slump flow barrel in concrete test 50 Time, evaluating workability of the polycarboxylate water reducer; and (3) adopting a concrete test to form a concrete test block, testing the 7d and 28d natural curing strength of the concrete test block, and evaluating the influence rule of the early strength effect and the later strength of the polycarboxylate water reducer. The specific experiment is as follows:
experiment one:
the performance of polycarboxylate water reducers prepared using the polyether macromonomers of the present invention was tested using a concrete test. The slump of concrete is tested by referring to the specification in national standard GB/T8076-2008 concrete admixture, and the concrete test block is molded by referring to the specification in national standard GB/T50081-2002 common concrete mechanical property test method Standard. The adopted cement is conch P.O 42.5.5 cement, and the fly ash is secondary ash; the sand is middle sand with fineness modulus mx=2.6, and the water content of the sand is 5%; the cobble is crushed stone with the particle size of 5-20 mm and continuous grading, and the water content of the cobble is 2%. Workability effect of the water reducer is achieved according to time T of a new concrete slump barrel and time T of 500mm of expansion degree 50 Is an evaluation criterion. The test data are shown in tables 6 and 7. C30 strength grade concrete volume weight 2317Kg/m 3 The concrete test materials were prepared as shown in table 6.
Table 6 concrete raw material proportioning table
And (3) molding concrete test blocks with the thickness of 100 multiplied by 100mm, curing the concrete test blocks under the curing conditions of 20+/-2 ℃ and curing the concrete test blocks in a standard curing box with the relative humidity of more than or equal to 95 percent. The concrete test data are shown in table 7.
Table 7 concrete test of the admixture
As can be seen from the data in the table, the polycarboxylate water reducer prepared by the polyether macromonomer prepared by the method has larger slump and better concrete wrapping performance under the condition of similar expansion degree. The time of the slump barrel from PCE-1 to PCE-6 and the time of the T50 when the expansion degree reaches 50mm are shorter, so that better concrete workability is achieved. Under the natural curing working condition, the water reducer synthesized by the polyether macromonomer prepared by the method has better early strength effect, the 7d natural curing strength is improved by 3-5MPa compared with the comparative examples PCE-7 and PCE-8, and the 28d natural curing strength is improved by 2-6MPa compared with the comparative examples PCE-7 and PCE-8, so that the water reducer has better early strength effect and later strength. In conclusion, the polyether macromonomer prepared by the method has better performance advantages in terms of workability, early strength and the like.
Claims (10)
1. A method for preparing a polyether macromonomer, comprising the steps of:
1) Adding an initiator into a reaction kettle for bottoming, adding a catalyst under the working condition of nitrogen protection, and reacting to obtain an activated initiator;
2) Transferring the activation initiator into a reaction device, heating, starting alkylene oxide feeding, reacting, and continuously feeding alkylene oxide until the molecular weight reaches a set molecular weight to obtain a polyether intermediate;
3) And adding a viscosity reducer, continuing to introduce alkylene oxide until the material is completely introduced, carrying out heat preservation reaction, and carrying out devolatilization under reduced pressure to obtain a polyether macromonomer finished product.
2. The process of claim 1, wherein in step 1), the initiator is an unsaturated alcohol having a terminal ethyleneoxy group.
3. The preparation method according to claim 1 or 2, wherein the initiator is ethylene glycol monovinyl ether, diethylene glycol monovinyl ether or 4-hydroxybutyl vinyl ether.
4. The preparation method according to claim 1, wherein the catalyst is used in an amount of 0.25 to 0.35% by mass of the initiator.
5. The method according to claim 1 or 4, wherein in step 1), the catalyst is sodium metal.
6. The process according to claim 1 or 2, wherein in step 2), the reaction temperature is 115.+ -. 5 ℃ and the reaction pressure is not more than 450Kpa.
7. The preparation method according to claim 1 or 2, wherein in the step 3), the viscosity reducer comprises one or more of allyl alcohol, methallyl alcohol, 3-isopentenyl alcohol, 2-isopentenyl alcohol, 4-penten-1-ol, 4-methyl-4-penten-1-ol, isopulegol, 7-octen-1-ol, 3, 7-dimethyl-7-octenol, 3, 7-dimethyl-6-octen-1-ol, 10-undecenol and other unsaturated alcohols.
8. The preparation method according to claim 1 or 2, wherein in step 3), the viscosity reducer is used in an amount of 5% -15% by mass of the initiator in step 1).
9. A polyether macromonomer obtainable by the process of any one of claims 1 to 8.
10. Use of a polyether macromonomer prepared by the preparation method of any one of claims 1 to 8 in a polycarboxylate water reducer.
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