CN112011043A - High-stability polyether and production method and application thereof - Google Patents
High-stability polyether and production method and application thereof Download PDFInfo
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- 229920000570 polyether Polymers 0.000 title claims abstract description 83
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 82
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 239000000047 product Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001879 copper Chemical class 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 33
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 11
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 claims description 10
- -1 alkenyl alcohol Chemical compound 0.000 claims description 10
- 239000012043 crude product Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 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 claims description 9
- 238000007664 blowing Methods 0.000 claims description 9
- 239000006227 byproduct Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 claims description 6
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical compound [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229940108925 copper gluconate Drugs 0.000 claims description 4
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 claims description 4
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 1
- NCWBSWFYABAWCH-UHFFFAOYSA-J copper disodium 2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate hydrate Chemical compound O.[Na+].[Na+].[Cu++].[O-]C(=O)CN(CCN(CC([O-])=O)CC([O-])=O)CC([O-])=O NCWBSWFYABAWCH-UHFFFAOYSA-J 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 abstract description 7
- 239000013067 intermediate product Substances 0.000 abstract description 3
- 238000005804 alkylation reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 20
- 239000007788 liquid Substances 0.000 description 12
- 238000003860 storage Methods 0.000 description 10
- 229920000056 polyoxyethylene ether Polymers 0.000 description 8
- 229940051841 polyoxyethylene ether Drugs 0.000 description 8
- 239000004568 cement Substances 0.000 description 7
- 239000004567 concrete Substances 0.000 description 7
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 229920005646 polycarboxylate Polymers 0.000 description 6
- 239000008030 superplasticizer Substances 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- WCASXYBKJHWFMY-UHFFFAOYSA-N crotyl alcohol Chemical compound CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- QVDTXNVYSHVCGW-ONEGZZNKSA-N isopentenol Chemical compound CC(C)\C=C\O QVDTXNVYSHVCGW-ONEGZZNKSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Images
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- 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
- C04B24/2605—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds 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
- 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
- C08G65/2696—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 characterised by the process or apparatus used
-
- 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
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- 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 high-stability polyether and a production method and application thereof. Compared with the prior art, the method of the invention adopts the addition of the copper salt before the alkylation reaction, so that the alkoxylation intermediate product is more stable, the double bond retention rate of the polyether product is higher, and the product quality can be further improved. The dispersing property of the polycarboxylic acid water reducing agent is more excellent.
Description
Technical Field
The invention belongs to the technical field of chemical building materials, relates to high-stability polyether and a production method and application thereof, and particularly relates to a preparation method of high-stability alkenyl alcohol polyoxyethylene ether and application thereof in production of a polycarboxylate superplasticizer.
Background
The polycarboxylate superplasticizer is a high-performance dispersing agent for concrete, and can obviously reduce the water consumption of the concrete, improve the strength of the concrete, improve the construction performance of the concrete and improve the compactness and the durability of the concrete; on the premise of unchanged strength, the consumption of clinker in concrete can be reduced, and the clinker firing needs to consume a large amount of electric power and fire coal and discharge a large amount of CO2、NOx、SO2And dust and other pollutants, can obviously save energy and reduce emission, and has obvious economic and social benefits.
The polycarboxylate superplasticizer is a water-soluble comb-shaped polymer obtained by aqueous solution free radical polymerization of vinyl alcohol polyoxyethylene ether and unsaturated carboxylic acid, carboxyl on a main chain is taken as an anchoring group to be adsorbed on the surface of cement particles, and side chain polyoxyethylene ether forms a steric hindrance effect, so that the cement particles are dispersed, aggregation of the cement particles is avoided, and excellent dispersing performance is achieved.
Usually, the allyl alcohol polyoxyethylene ether mainly comprises methyl allyl alcohol polyoxyethylene ether, isoamylol polyoxyethylene ether, vinyl glycol ether polyoxyethylene ether and 4-hydroxybutyl vinyl ether polyoxyethylene ether, and the allyl alcohol, the isoamylol, the vinyl glycol ether and the 4-hydroxybutyl vinyl ether are respectively used as initiators and alkali is used as a catalyst to carry out alkoxylation with ethylene oxide to obtain a polyether product with the molecular weight of 1000-5000. The untreated polyether generally has a high peroxide value, and the degradation of the polyether is easily caused in the storage process of the polyether product due to high storage temperature, so that the rancidity and the deterioration of the polyether are caused, the quality of the polyether is seriously influenced, and particularly, the serious influence is caused when the environmental temperature is high in summer.
In order to improve the stability of polyether during storage, polymerization inhibitors such as 2, 6-di-tert-butyl-4-methylphenol (BHT), 2, 6-di-tert-butyl-p-ethylphenol (DBEP), p-hydroxyanisole (MEHQ) and the like are generally added during the post-treatment of polyether, such as reference 1: Tianwei, Zhou Ming, discussion of the problem of agglomeration of HPEG polyether for polycarboxylic acid water reducing agent [ J ] Shanghai chemical industry, 2014,39(08):12-15. However, the addition of the polymerization inhibitor can affect the copolymerization of the polyether and the unsaturated carboxylic acid, reduce the conversion rate of the polyether and affect the dispersing performance of the polycarboxylic acid water reducing agent.
Disclosure of Invention
The object of the present invention is to provide a polyether of high stability which has a high stability during storage.
The invention also aims to provide a production method of the high-stability polyether, which adds a small amount of copper salt in the preparation process of the polyether to improve the storage stability of the polyether.
The invention also aims to provide application of the high-stability polyether in preparation of the polycarboxylic acid water reducing agent.
The specific technical scheme of the invention is as follows:
a production method of high-stability polyether comprises the following steps:
1) catalyst preparation: under the protection of nitrogen, adding alkenyl alcohol into a reaction kettle, heating, adding copper salt, stirring for dissolving, adding an alkali catalyst, and reacting until no hydrogen is generated;
2) alkoxylation reaction: transferring the alkenyl alcohol with the prepared catalyst in the step 1) to a reactor, heating, adding ethylene oxide, carrying out alkoxylation reaction, and curing after the ethylene oxide is added to obtain a crude polyether product;
3) and (3) post-treatment: cooling the polyether crude product prepared in the step 2), vacuumizing, blowing nitrogen to remove micromolecule byproducts, and adjusting the pH value with acetic acid to obtain the polyether product.
In step 1), the alkenyl alcohol is selected from methallyl alcohol, vinyl glycol ether, prenol alcohol or 4-hydroxybutyl vinyl ether.
Those skilled in the art will be able to select different types of alkenyl alcohols depending on the type of polyether to be produced.
The person skilled in the art can, by calculation, derive the masses of the different types of alkenyl alcohols and of ethylene oxide to be used, depending on the molecular weight and mass of the polyether to be produced.
The micro positive pressure in the step 1) is 2-10 kPaG.
In the step 1), the temperature rise refers to the temperature rise to 35-50 ℃.
In the step 1), the copper salt is selected from one or more of copper sulfate, copper phosphate, copper acetate, copper citrate, copper nitrate, disodium ethylene diamine tetraacetate copper hydrate or copper gluconate. Preferably, the copper salt is selected from copper acetate, copper citrate or copper gluconate.
The dosage of the copper salt is 1-1000 ppm of the mass of the polyether.
Further, the dosage of the copper salt is preferably 5-200 ppm of the mass of the polyether.
The alkali catalyst in the step 1) is selected from metallic sodium or sodium hydride.
The dosage of the alkali catalyst is 0.05-0.15% of the mass of the polyether.
The heating in the step 2) is to heat the mixture to 110-120 ℃, and then ethylene oxide is added.
In the step 2), the molar weight of the added ethylene oxide is 20-120 times of that of the vinyl alcohol.
In the step 2), ethylene oxide is added for reaction, and because the reaction container is sealed and the reaction releases heat, the reaction temperature and pressure can be controlled by adjusting the speed of adding ethylene oxide, so that the reaction temperature is controlled to be 120-150 ℃, and the reaction pressure is controlled to be 0.1-0.5 MPaG.
The curing in the step 2) means that the reaction is continued for 0.5 to 1 hour under the condition of heat preservation.
The temperature reduction in the step 3) means that the temperature is reduced to 80-90 ℃.
The pH value in the step 3) is 6-9.
The high-stability polyether provided by the invention is prepared by the method.
The invention provides an application of high-stability polyether in preparation of a polycarboxylic acid water reducing agent. When the prepared high-stability polyether and unsaturated carboxylic acid are used for aqueous solution free radical polymerization, particularly when a redox initiation system is adopted, the existence of copper salt does not prevent copolymerization, and the copper salt is used as a catalyst for accelerating polymerization, so that the conversion rate of the polyether can be improved, and the obtained polycarboxylic acid water reducing agent has better dispersion performance.
The specific application method comprises the following steps:
the prepared high-stability polyether and acrylic acid are synthesized into the polycarboxylic acid water reducing agent at normal temperature by using hydrogen peroxide as an oxidant and sodium formaldehyde sulfoxylate as a reducing agent.
Compared with the prior art, the method adopts the method that the copper salt is added before the alkylation reaction, the copper salt can effectively prevent the alkene alcohol from polymerizing, and can be used as a stabilizer of the alkene alcohol, so that the stability of the alkoxylation intermediate product and the polyether product in the reaction process is improved, the alkoxylation intermediate product is more stable, the double bond retention rate of the polyether product is higher, and the product quality can be further improved. The dispersing property of the polycarboxylic acid water reducing agent is more excellent.
Drawings
FIG. 1 is a GPC comparison chart of the products of example 1 and comparative example 1; 1-comparative example 1 (no copper salt added) and 2-example 1 (copper acetate added).
Detailed Description
The present invention will be further illustrated with reference to the following examples.
Example 1
A production method of high-stability polyether comprises the following steps:
1) catalyst preparation: under the protection of nitrogen, adding 1000kg of methallyl alcohol into a reaction kettle under the pressure of 5kPaG, heating to 40 ℃, adding 0.33kg of copper acetate, stirring to dissolve, adding 33kg of metallic sodium, and reacting until no hydrogen is generated;
2) alkoxylation reaction: transferring the methallyl alcohol with the prepared catalyst in the step 1) to a gas-liquid contact reactor, heating to 110 ℃, adding ethylene oxide, carrying out alkoxylation, controlling the reaction temperature to be 130 ℃, the pressure to be 0.4MPaG and keeping the temperature and curing for 0.5h after 32340kg of ethylene oxide is added by adjusting the speed of adding ethylene oxide, thus obtaining a crude polyether product;
3) and (3) post-treatment: transferring the polyether crude product to a post-treatment kettle, cooling to 85 ℃, vacuumizing, blowing nitrogen to remove micromolecular byproducts, and adjusting the pH to 6-7 with acetic acid to obtain 33369kg of polyether product.
Example 2
A production method of high-stability polyether comprises the following steps:
1) catalyst preparation: under the protection of nitrogen, 1000kg of methallyl alcohol is added, the pressure is 4kPaG, the temperature is raised to 45 ℃, 0.83kg of copper acetate is added, after stirring and dissolving, 33kg of metal sodium is added, and the reaction is carried out until no hydrogen is generated;
2) alkoxylation reaction: transferring the methallyl alcohol with the prepared catalyst in the step 1) to a gas-liquid contact reactor, heating to 112 ℃, adding ethylene oxide, carrying out alkoxylation, controlling the reaction temperature to be 132 ℃ and the pressure to be 0.45MPaG by adjusting the speed of adding the ethylene oxide, and carrying out heat preservation curing for 0.5h after 32327kg of ethylene oxide is added to obtain a crude polyether product;
3) and (3) post-treatment: transferring the polyether crude product to a post-treatment kettle, cooling to 85 ℃, vacuumizing, blowing nitrogen to remove micromolecular byproducts, and adjusting the pH value to 6-7 with acetic acid to obtain 33356kg of polyether product.
Example 3
A production method of high-stability polyether comprises the following steps:
1) catalyst preparation: under the protection of nitrogen, 1000kg of methallyl alcohol is added, the pressure is 5kPaG, the temperature is raised to 42 ℃, 0.83kg of copper citrate is added, after stirring and dissolving, 33kg of metal sodium is added, and the reaction is carried out until no hydrogen is generated;
2) alkoxylation reaction: transferring the methallyl alcohol with the prepared catalyst in the step 1) to a gas-liquid contact reactor, heating to 115 ℃, adding ethylene oxide, carrying out alkoxylation, controlling the reaction temperature to be 135 ℃, the pressure to be 0.38MPaG and keeping the temperature and curing for 0.5h after 32315kg of ethylene oxide is added by adjusting the speed of adding ethylene oxide, thus obtaining a crude polyether product;
3) and (3) post-treatment: transferring the polyether crude product to a post-treatment kettle, cooling to 85 ℃, vacuumizing, blowing nitrogen to remove micromolecular byproducts, and adjusting the pH value to 6-7 with acetic acid to obtain 33344kg of polyether product.
Example 4
A production method of high-stability polyether comprises the following steps:
1) catalyst preparation: under the protection of nitrogen, 1000kg of methallyl alcohol is added, the pressure is 2kPaG, the temperature is raised to 40 ℃, 0.83kg of copper gluconate is added, after stirring and dissolving, 33kg of metal sodium is added, and the reaction is carried out until no hydrogen is generated;
2) alkoxylation reaction: transferring the methallyl alcohol with the prepared catalyst in the step 1) to a gas-liquid contact reactor, heating to 113 ℃, adding ethylene oxide, carrying out alkoxylation reaction, controlling the reaction temperature to be 135 ℃ and the pressure to be 0.38MPaG by adjusting the speed of adding the ethylene oxide, and curing for 0.5h after 32322kg of ethylene oxide is added to obtain a crude polyether product;
3) and (3) post-treatment: transferring the polyether crude product to a post-treatment kettle, cooling to 85 ℃, vacuumizing, blowing nitrogen to remove micromolecular byproducts, and adjusting the pH value to 6-7 with acetic acid to obtain 33351kg of polyether product.
Example 5
A production method of high-stability polyether comprises the following steps:
1) catalyst preparation: under the protection of nitrogen, adding 1220kg of vinyl glycol ether, heating to 45 ℃ under the pressure of 3kPaG, adding 0.83kg of copper acetate, stirring to dissolve, adding 33kg of metal sodium, and reacting until no hydrogen is generated;
2) alkoxylation reaction: transferring the vinyl glycol ether prepared by the catalyst in the step 1) to a gas-liquid contact reactor, heating to 115 ℃, adding ethylene oxide, carrying out alkoxylation, controlling the reaction temperature to be 135 ℃ and the pressure to be 0.38MPaG by adjusting the speed of adding the ethylene oxide, and carrying out heat preservation curing for 0.5h after 32053kg of ethylene oxide is added to obtain a crude polyether product;
3) and (3) post-treatment: transferring the polyether crude product to a post-treatment kettle, cooling to 85 ℃, vacuumizing, blowing nitrogen to remove micromolecular byproducts, and adjusting the pH value to 8-9 with acetic acid to obtain 33302kg of polyether product.
Example 6
A production method of high-stability polyether comprises the following steps:
1) catalyst preparation: under the protection of nitrogen, adding 1190kg of isopentenol under the pressure of 5kPaG, heating to 50 ℃, adding 0.83kg of copper acetate, stirring to dissolve, adding 33kg of metal sodium, and reacting until no hydrogen is generated;
2) alkoxylation reaction: transferring the prenol prepared in the step 1) into a gas-liquid contact reactor, heating to 112 ℃, adding ethylene oxide, carrying out alkoxylation, controlling the reaction temperature to be 130 ℃ and the pressure to be 0.33MPaG by adjusting the speed of adding the ethylene oxide, and curing for 0.5h after 32019kg of ethylene oxide is added to obtain a polyether crude product;
3) and (3) post-treatment: transferring the polyether crude product to a post-treatment kettle, cooling to 85 ℃, vacuumizing, blowing nitrogen to remove micromolecular byproducts, and adjusting the pH value to 6-7 with acetic acid to obtain 33238kg of polyether product.
Example 7
A production method of high-stability polyether comprises the following steps:
1) catalyst preparation: under the protection of nitrogen, 1610kg of 4-hydroxybutyl vinyl ether is added, the pressure is 2kPaG, the temperature is raised to 40 ℃, 0.83kg of copper acetate is added, after stirring and dissolving, 33kg of metal sodium is added, and the reaction is carried out until no hydrogen is generated;
2) alkoxylation reaction: transferring the 4-hydroxybutyl vinyl ether prepared in the step 1) into a gas-liquid contact reactor, heating to 115 ℃, adding ethylene oxide, carrying out alkoxylation, controlling the reaction temperature to be 140 ℃ and the pressure to be 0.45MPaG by adjusting the speed of adding the ethylene oxide, and curing for 0.5h after 31700kg of ethylene oxide is added to obtain a crude polyether product;
3) and (3) post-treatment: transferring the polyether crude product to a post-treatment kettle, cooling to 85 ℃, vacuumizing, blowing nitrogen to remove micromolecular byproducts, and adjusting the pH value to 8-9 with acetic acid to obtain 33339kg of polyether product.
Comparative example 1
Reference is made to example 1 with the difference that no copper acetate is added.
Comparative example 2
Reference is made to example 5 with the difference that no copper acetate is added.
Comparative example 3
Reference is made to example 6, with the difference that no copper acetate is added.
Comparative example 4
Reference is made to example 7, with the difference that no copper acetate is added.
Comparative example 5
Referring to example 2, copper acetate was replaced with p-hydroxyanisole.
The technical indexes such as hydroxyl value, moisture, pH, double bond retention rate and the like of the polyether produced in the examples and the comparative examples are detected by referring to JC/T2033-.
The polyether prepared in each example and comparative example is synthesized into the polycarboxylic acid water reducing agent according to the following process:
1) adding 360g of polyether and 240g of water into a four-neck flask with a stirrer and a thermometer, and stirring until the polyether is completely dissolved;
2) preparation of A, B liquid: uniformly stirring 40g of acrylic acid, 2g of mercaptopropionic acid and 60g of water to prepare a solution A; 0.5g of sodium formaldehyde sulfoxylate and 60g of water are stirred uniformly to prepare liquid B;
3) adding 2g of hydrogen peroxide into a four-neck flask, beginning to dropwise add A, B liquid, dropwise adding A liquid for 3 hours, dropwise adding B liquid for 3.5 hours, and curing for 1 hour to obtain the polycarboxylic acid water reducer.
The obtained polycarboxylate superplasticizer is prepared into a 10% solid content water solution, P.O 42.5.5R cement is adopted according to a method for testing the fluidity of cement neat paste in GB/T8077-2000 concrete admixture homogeneity test method, the mixing amount of the polycarboxylate superplasticizer solution is 1.2% of the mass of the cement, the fluidity of the cement neat paste is tested, the dispersing performance of the polycarboxylate superplasticizer is evaluated, and the detection results are shown in Table 1.
Table 1 technical index test results
The GPC comparative spectra of the products of example 1 and comparative example 1, with peak time on the abscissa and peak height percentage on the ordinate, show that the product is more stable with less impurities than without the copper salt.
Compared with comparative examples 1-4, the retention rate of double bonds of the initial (1d) of examples 1-7 is obviously higher than that of the comparative examples, and the net slurry fluidity is better than that of the comparative examples; the retention rate of double bonds after storage (90d) of examples 1-7 is much higher than that of the comparative example, and the net slurry fluidity is much better than that of the comparative example. The polyether prepared by the method can obviously improve the storage stability of the polyether.
Compared with the comparative example 5, the double bond retention rate of the initial (1d) of the examples 1-7 is slightly better than that of the comparative example, and the net slurry fluidity is better than that of the comparative example; the retention rate of double bonds after storage (90d) of examples 1-7 is slightly higher than that of the comparative example, and the net slurry fluidity is better than that of the comparative example. The polyether prepared by the method disclosed by the invention can ensure the storage stability of the polyether, and the synthesized polycarboxylic acid water reducing agent has more excellent dispersing performance.
In conclusion, the polyether prepared by the method has better storage stability, and the synthesized polycarboxylic acid water reducing agent has more excellent dispersing performance.
The above detailed description of the preparation and use of polyethers with reference to the examples is illustrative and not restrictive, and several examples are set forth within the scope hereof, and thus variations and modifications may be made without departing from the general inventive concept within the scope hereof.
Claims (10)
1. A production method of high-stability polyether is characterized by comprising the following steps:
1) catalyst preparation: under the protection of nitrogen, adding alkenyl alcohol into a reaction kettle, heating, adding copper salt, stirring for dissolving, adding an alkali catalyst, and reacting until no hydrogen is generated;
2) alkoxylation reaction: transferring the alkenyl alcohol with the prepared catalyst in the step 1) to a reactor, heating, adding ethylene oxide, carrying out alkoxylation reaction, and curing after the ethylene oxide is added to obtain a crude polyether product;
3) and (3) post-treatment: cooling the polyether crude product prepared in the step 2), vacuumizing, blowing nitrogen to remove micromolecule byproducts, and adjusting the pH value with acetic acid to obtain the polyether product.
2. The production method according to claim 1, wherein in step 1), the copper salt is selected from any one or more of copper sulfate, copper phosphate, copper acetate, copper citrate, copper nitrate, disodium copper ethylenediaminetetraacetate hydrate, or copper gluconate.
3. The production method according to claim 1 or 2, wherein the copper salt is used in an amount of 1 to 1000ppm based on the mass of the polyether.
4. The production method according to claim 1, wherein in step 1), the alkenyl alcohol is selected from the group consisting of methallyl alcohol, vinyl glycol ether, prenol alcohol and 4-hydroxybutyl vinyl ether.
5. The production method according to claim 1, wherein the base catalyst in step 1) is selected from metallic sodium or sodium hydride.
6. The production method according to claim 1, wherein the temperature rise in the step 2) is a temperature rise to 110 to 120 ℃.
7. The production process according to claim 1, wherein the molar amount of the ethylene oxide added in the step 2) is 20 to 120 times the molar amount of the alkenyl alcohol.
8. The production process according to claim 1, wherein in the step 2), the reaction temperature and pressure are controlled by adjusting the rate of feeding ethylene oxide so that the reaction temperature is controlled to 120 to 150 ℃ and the reaction pressure is controlled to 0.1 to 0.5 MPaG.
9. A high stability polyether produced by the method for producing a high stability polyether according to any one of claims 1 to 8.
10. Use of the high stability polyether produced by the method of any one of claims 1 to 8 for the preparation of a polycarboxylic acid water reducing agent.
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