CN117903427A - Preparation method of polycarboxylate superplasticizer macromonomer with high double bond retention rate - Google Patents
Preparation method of polycarboxylate superplasticizer macromonomer with high double bond retention rate Download PDFInfo
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- CN117903427A CN117903427A CN202410082976.1A CN202410082976A CN117903427A CN 117903427 A CN117903427 A CN 117903427A CN 202410082976 A CN202410082976 A CN 202410082976A CN 117903427 A CN117903427 A CN 117903427A
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- monovinyl ether
- glycol monovinyl
- ethylene glycol
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- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 36
- 230000014759 maintenance of location Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 23
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 claims abstract description 69
- -1 alkoxy lithium aluminum hydride Chemical compound 0.000 claims abstract description 45
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 30
- 239000012280 lithium aluminium hydride Substances 0.000 claims abstract description 30
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 30
- 239000002879 Lewis base Substances 0.000 claims abstract description 18
- 150000007527 lewis bases Chemical class 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 18
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 22
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000006722 reduction reaction Methods 0.000 claims description 9
- GEPJPYNDFSOARB-UHFFFAOYSA-N tris(4-fluorophenyl)phosphane Chemical compound C1=CC(F)=CC=C1P(C=1C=CC(F)=CC=1)C1=CC=C(F)C=C1 GEPJPYNDFSOARB-UHFFFAOYSA-N 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- WULAHPYSGCVQHM-UHFFFAOYSA-N 2-(2-ethenoxyethoxy)ethanol Chemical compound OCCOCCOC=C WULAHPYSGCVQHM-UHFFFAOYSA-N 0.000 claims description 4
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 claims description 3
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 32
- 229910001868 water Inorganic materials 0.000 abstract description 32
- 239000003054 catalyst Substances 0.000 abstract description 27
- 239000003638 chemical reducing agent Substances 0.000 abstract description 19
- 238000009826 distribution Methods 0.000 abstract description 12
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 6
- 229920000570 polyether Polymers 0.000 abstract description 6
- 150000007529 inorganic bases Chemical class 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 74
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- 239000000203 mixture Substances 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 239000000047 product Substances 0.000 description 12
- 239000011261 inert gas Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 229910010199 LiAl Inorganic materials 0.000 description 6
- 229910010084 LiAlH4 Inorganic materials 0.000 description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 238000005815 base catalysis Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000007046 ethoxylation reaction Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 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
- 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
- C08G65/2642—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 catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2654—Aluminium or boron; Compounds thereof
-
- 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
- C08G65/2642—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 catalyst used
- C08G65/2669—Non-metals or compounds thereof
- C08G65/2672—Nitrogen or compounds thereof
-
- 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
- C08G65/2642—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 catalyst used
- C08G65/2669—Non-metals or compounds thereof
- C08G65/2675—Phosphorus or compounds thereof
-
- 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
- C08G65/2642—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 catalyst used
- C08G65/2669—Non-metals or compounds thereof
- C08G65/2678—Sulfur or compounds thereof
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- Chemical & Material Sciences (AREA)
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
The invention belongs to the technical field of polycarboxylate water reducers, and particularly relates to a preparation method of a polycarboxylate water reducer macromonomer with high double bond retention rate. The invention provides a preparation method of a polycarboxylate superplasticizer macromonomer with high double bond retention rate, which comprises the following steps: first mixing first ethylene glycol monovinyl ether, alkoxy lithium aluminum hydride and first alkylene oxide, and performing a first polymerization reaction to obtain ethylene glycol monovinyl ether oligomer; and (3) mixing the ethylene glycol monovinyl ether oligomer, the Lewis base and the second alkylene oxide for the second time, and performing a second polymerization reaction to obtain the Gao Shuangjian-retention-rate polycarboxylate superplasticizer macromonomer. The preparation method provided by the invention adopts lithium aluminum alkoxide and Lewis base to replace the traditional inorganic base catalyst, and carries out step polymerization, so that a polyether product with high double bond retention rate, narrow molecular weight distribution and high molecular weight can be prepared, and the polyether product can be used as a polycarboxylate superplasticizer macromonomer with excellent performance.
Description
Technical Field
The invention belongs to the technical field of polycarboxylate water reducers, and particularly relates to a preparation method of a polycarboxylate water reducer macromonomer with high double bond retention rate.
Background
The water reducing agent is a concrete additive which can reduce the mixing water consumption under the condition of maintaining the slump constant of the concrete, can achieve the purpose of keeping the quality and reducing the cost, and has wide application. Therefore, the water reducer which has better water reducing effect, lower dosage and simpler preparation is researched and developed, and has important significance in the field of concrete additives. At present, polycarboxylic acid water reducer is increasingly favored as a third-generation water reducer because of the advantages of molecular designability, stable structural performance, high water reducing rate, good fluidity maintaining performance and the like.
The performance of the water reducer is improved by improving the structure of the polycarboxylate water reducer macromonomer, and the water reducer is a current research hot spot. For example, chinese patent publication No. CN106279665A discloses a method for preparing ethylene glycol vinyl ether polyoxyethylene ether, which uses sodium methoxide as catalyst and produces water or alcohol as byproduct with the initiator, and still leads to broadening of molecular weight distribution of the product. Meanwhile, the preparation method adopts an ethoxylation one-step method, although the process is simplified, the control requirement on the reaction condition is higher, the double bond retention rate is easy to be reduced and the molecular weight distribution is widened due to the change of factors such as temperature, pressure, catalytic rate and the like, and the molecular weight of the polyether product prepared by the base catalysis is low, so that the product performance of the polyether macromonomer is affected.
The catalyst of the preparation method of ethylene glycol vinyl ether polyoxyethylene ether disclosed in China patent publication No. CN106317403A is optimized to sodium hydride, potassium hydride or sodium, water or methanol is not byproduct in the process, and the molecular weight distribution of the product is narrow. The ethoxylation is prepared by a one-step method, and the problems that the double bond retention rate is easy to be reduced and the molecular weight distribution is wide due to the change of factors such as temperature, pressure, catalytic rate and the like, which are required by high reaction control precision, exist.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method of a polycarboxylate superplasticizer macromonomer with high double bond retention rate, and the polycarboxylate superplasticizer macromonomer obtained by the preparation method provided by the invention has the excellent performances of high double bond retention rate and narrow molecular weight distribution.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a preparation method of a polycarboxylate superplasticizer macromonomer with high double bond retention rate, which comprises the following steps:
first mixing first ethylene glycol monovinyl ether, alkoxy lithium aluminum hydride and first alkylene oxide, and performing a first polymerization reaction to obtain ethylene glycol monovinyl ether oligomer;
and (3) mixing the ethylene glycol monovinyl ether oligomer, the Lewis base and the second alkylene oxide for the second time, and performing a second polymerization reaction to obtain the Gao Shuangjian-retention-rate polycarboxylate superplasticizer macromonomer.
Preferably, the first alkylene oxide and the second alkylene oxide are independently ethylene oxide and/or propylene oxide.
Preferably, the preparation method of the lithium aluminum alkoxide comprises the following steps:
and mixing the second diethylene glycol monovinyl ether with lithium aluminum hydride, and carrying out a reduction reaction to obtain the lithium aluminum alkoxide.
Preferably, the mass ratio of the second glycol monovinyl ether to the lithium aluminum hydride is 200-1000:1;
the temperature of the reduction reaction is 10-60 ℃ and the time is 1.5-6 h.
Preferably, the mass ratio of the first ethylene glycol monovinyl ether to the alkoxy lithium aluminum hydride is 1:1-1.5;
the mass ratio of the first ethylene glycol monovinyl ether to the first alkylene oxide is 1:9-17.
Preferably, the temperature of the first polymerization reaction is 60-90 ℃ and the time is 2-5 h.
Preferably, the lewis base comprises an organic amine, an organic phosphorus, an azacyclic carbene compound, or thiourea.
Preferably, the organic amine comprises triethylenediamine or triethylamine;
The organophosphorus includes triphenylphosphine or tris (4-fluorophenyl) phosphorus;
the azacyclic carbene compound comprises an azacyclic carbene;
The thiourea comprises diethyl thiourea.
Preferably, the mass ratio of the ethylene glycol monovinyl ether oligomer to the Lewis base is 20-100:1;
the mass ratio of the ethylene glycol monovinyl ether oligomer to the second alkylene oxide is 1:5.5-11.
Preferably, the temperature of the second polymerization reaction is 80-100 ℃ and the time is 4-6 h.
The invention provides a preparation method of a polycarboxylate superplasticizer macromonomer with high double bond retention rate, which comprises the following steps: first mixing first ethylene glycol monovinyl ether, alkoxy lithium aluminum hydride and first alkylene oxide, and performing a first polymerization reaction to obtain ethylene glycol monovinyl ether oligomer; and (3) mixing the ethylene glycol monovinyl ether oligomer, the Lewis base and the second alkylene oxide for the second time, and performing a second polymerization reaction to obtain the Gao Shuangjian-retention-rate polycarboxylate superplasticizer macromonomer. The invention adopts lithium aluminum alkoxide to replace the traditional inorganic base catalyst (such as potassium hydroxide and sodium hydroxide), and the synthesized ethylene glycol monovinyl ether oligomer byproduct polyethylene glycol has low content. Moreover, the double bond retention rate of the ethylene glycol monovinyl ether oligomer synthesized by the one-step method is higher than that of the ethylene glycol monovinyl ether oligomer synthesized by the base catalysis method under the condition that the unsaturated double bond is destroyed to a low degree without carrying out polymerization reaction at high temperature. In the second polymerization reaction, the Lewis base adopted by the invention contains a rich electron center, so that the Lewis base catalyst can form an intermediate with high selectivity with a reaction substrate, the requirement on the reaction temperature is low, the polymerization reaction is facilitated, double bond protection is facilitated, and the polyether product with high double bond retention rate, narrow molecular weight distribution and high molecular weight can be prepared and can be used as a polycarboxylate water reducer macromonomer with excellent performance.
Detailed Description
The invention provides a preparation method of a polycarboxylate superplasticizer macromonomer with high double bond retention rate, which comprises the following steps:
first mixing first ethylene glycol monovinyl ether, alkoxy lithium aluminum hydride and first alkylene oxide, and performing a first polymerization reaction to obtain ethylene glycol monovinyl ether oligomer;
and (3) mixing the ethylene glycol monovinyl ether oligomer, the Lewis base and the second alkylene oxide for the second time, and performing a second polymerization reaction to obtain the Gao Shuangjian-retention-rate polycarboxylate superplasticizer macromonomer.
In the present invention, all raw material components are commercially available products well known to those skilled in the art unless specified otherwise.
The invention carries out a first polymerization reaction by first mixing first ethylene glycol monovinyl ether, alkoxy aluminum lithium hydride and first alkylene oxide to obtain ethylene glycol monovinyl ether oligomer.
In the invention, the preparation method of the lithium aluminum alkoxide comprises the following steps:
and mixing the second diethylene glycol monovinyl ether with lithium aluminum hydride, and carrying out a reduction reaction to obtain the lithium aluminum alkoxide.
In the present invention, the mass ratio of the second glycol monovinyl ether to lithium aluminum hydride is preferably 200 to 1000:1, more preferably 300 to 800:1, and most preferably 400 to 600:1.
The process of the mixing is not particularly limited, and may be carried out in a manner well known to those skilled in the art.
In the present invention, the temperature of the reduction reaction is preferably 10 to 60 ℃, more preferably 25 to 50 ℃, and most preferably 30 to 50 ℃; the time is preferably 1.5 to 6 hours, more preferably 3 to 5 hours; the reduction reaction is preferably carried out under stirring; the reaction equipment of the reduction reaction is preferably an electromagnetic stirrer; the electromagnetic stirrer preferably comprises a water bath apparatus.
In the present invention, the chemical reaction equation of the reduction reaction is:
LiAlH4+ROH→LiAl(OR)H3+H2
LiAlH4+2ROH→LiAl(OR)2H2+2H2
LiAlH4+3ROH→LiAl(OR)3H+3H2
in the preparation method of the alkoxy lithium aluminum hydride, the lithium aluminum hydride contains four active hydrogen atoms, is easy to react with ethylene glycol monovinyl ether, and has the advantages of simple and safe production process, low reaction temperature and low production cost. Meanwhile, the ethylene glycol monovinyl ether is reacted with no water or other byproducts, and no post-treatment is needed.
In the present invention, the mass ratio of the first ethylene glycol monovinyl ether to the lithium aluminum alkoxide hydride is preferably 1:1 to 1.5, more preferably 1:1 to 1.3.
In the present invention, the first alkylene oxide is preferably ethylene oxide and/or propylene oxide; when the first alkylene oxide is ethylene oxide and propylene oxide, the mass ratio of the ethylene oxide to the propylene oxide is preferably 8 to 14:1 to 3, more preferably 8 to 11:1 to 2.
In the present invention, the mass ratio of the first ethylene glycol monovinyl ether to the first alkylene oxide is preferably 1:9 to 17, more preferably 1:12 to 17, and most preferably 1:15 to 17.
In the present invention, the first mixing is preferably to add the first ethylene glycol monovinyl ether and the lithium aluminum alkoxide hydride first, and then to add the first alkylene oxide; the first alkylene oxide is preferably added dropwise; the dropping speed is not particularly limited in the present invention, and the dropping speed well known to those skilled in the art is used to keep the pressure of the reaction system at 0.35MPa or less.
In the present invention, the temperature of the first polymerization reaction is 60 to 90 ℃, more preferably 70 to 90 ℃; the time is 2 to 5 hours, more preferably 3 to 4 hours; the first polymerization reaction is preferably carried out in an inert gas atmosphere; the inert gas in the inert gas environment is preferably nitrogen; the inert gas environment is preferably provided by replacing air with inert gas three times; the reaction equipment for the first polymerization reaction is preferably a pressure reactor.
In the present invention, the chemical reaction equation of the first polymerization reaction is:
LiAlH4+ROH→LiAl(OR)H3+H2
LiAlH4+2ROH→LiAl(OR)2H2+2H2
LiAlH4+3ROH→LiAl(OR)3H+3H2
After the ethylene glycol monovinyl ether oligomer is obtained, the ethylene glycol monovinyl ether oligomer, lewis base and second alkylene oxide are mixed for the second time, and a second polymerization reaction is carried out, so that the Gao Shuangjian retention rate polycarboxylate superplasticizer macromonomer is obtained.
In the present invention, the lewis base preferably includes an organic amine, an organic phosphorus, an azacyclic carbene compound, or thiourea, more preferably an organic amine, an organic phosphorus, or thiourea, and most preferably an organic amine or an organic phosphorus; the organic amine preferably comprises triethylenediamine or triethylamine, more preferably triethylamine; the organophosphorus preferably includes triphenylphosphine or tris (4-fluorophenyl) phosphorus, more preferably tris (4-fluorophenyl) phosphorus; the azacyclic carbene compound preferably comprises an azacyclic carbene; the thiourea preferably comprises diethyl thiourea.
In the present invention, the mass ratio of the ethylene glycol monovinyl ether oligomer to the lewis base is preferably 20 to 100:1, more preferably 30 to 60:1;
In the present invention, the second alkylene oxide is ethylene oxide and/or propylene oxide; when the second alkylene oxide is ethylene oxide and propylene oxide, the mass ratio of the ethylene oxide to the propylene oxide is preferably 5 to 10:0.5 to 1, more preferably 7 to 10:0.5 to 1.
In the present invention, the mass ratio of the ethylene glycol monovinyl ether oligomer to the second alkylene oxide is preferably 1:5.5 to 11, more preferably 1:7 to 10.
In the present invention, the second mixing is preferably to add the ethylene glycol monovinyl ether oligomer and the lewis base first, followed by adding the second alkylene oxide; the second alkylene oxide is added dropwise; the dropping speed is not particularly limited in the present invention, and the dropping speed well known to those skilled in the art is used to keep the pressure of the reaction system at 0.35MPa or less.
In the present invention, the temperature of the second polymerization reaction is 80 to 100 ℃, more preferably 90 to 100 ℃; the time is 4 to 6 hours, more preferably 5 to 6 hours; the second polymerization reaction is preferably carried out in an inert gas atmosphere; the inert gas in the inert gas environment is preferably nitrogen; the inert gas environment is preferably provided by replacing air with inert gas three times; the reaction equipment for the second polymerization reaction is preferably a pressure reactor.
The invention adopts lithium aluminum alkoxide to replace the traditional inorganic base catalyst (such as potassium hydroxide and sodium hydroxide), and the synthesized ethylene glycol monovinyl ether oligomer byproduct polyethylene glycol has low content. Moreover, the double bond retention rate of the ethylene glycol monovinyl ether oligomer synthesized by the one-step method is higher than that of the ethylene glycol monovinyl ether oligomer synthesized by the base catalysis method under the condition that the unsaturated double bond is destroyed to a low degree without carrying out polymerization reaction at high temperature. In the second polymerization reaction, the Lewis base adopted by the invention contains a rich electron center, so that the Lewis base catalyst can form an intermediate with high selectivity with a reaction substrate, the requirement on the reaction temperature is low, the polymerization reaction is facilitated, double bond protection is facilitated, and the polyether product with high double bond retention rate, narrow molecular weight distribution and high molecular weight can be prepared and can be used as a polycarboxylate water reducer macromonomer with excellent performance.
In order to further illustrate the present invention, the following examples are provided to illustrate the preparation of the high double bond retention polycarboxylate superplasticizer macromer according to the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
50G of ethylene glycol monovinyl ether is added into a 100mL round-bottom single-neck flask, the mixture is placed on an electromagnetic stirrer with water bath, 0.075g of lithium aluminum hydride is added, the reaction temperature is 30 ℃, the reaction is carried out for 3 hours, and the lithium aluminum alkoxide catalyst is prepared for standby after the reaction is completed.
50G of ethylene glycol monovinyl ether and 60g of the catalyst are added into a 2.5L pressure reaction kettle, the air in the kettle is replaced by nitrogen for 3 times, and when the temperature of the kettle is raised to 60-65 ℃, a mixture of 600g of ethylene oxide and 150g of propylene oxide is dropwise added, the pressure in the reaction kettle is kept to be less than or equal to 0.35MPa, and the reaction is continued for 3 hours after the dropwise addition is completed, so as to obtain the ethylene glycol monovinyl ether oligomer.
50G of ethylene glycol monovinyl ether oligomer and 0.975g of tris (4-fluorophenyl) phosphorus catalyst are added into a 2.5L pressure reaction kettle, the air in the kettle is replaced by nitrogen for 3 times, a mixture of 250g of ethylene oxide and 25g of propylene oxide is dropwise added into the kettle after the temperature of the reaction kettle is raised to 95-100 ℃, the pressure in the reaction kettle is kept to be less than or equal to 0.35MPa, and the reaction is continued for 4.5 hours after the dropwise addition is finished, so that the polycarboxylate superplasticizer macromonomer with high double bond retention rate is obtained.
Example 2
50G of ethylene glycol monovinyl ether is added into a 100mL round-bottom single-neck flask, the mixture is placed on an electromagnetic stirrer with a water bath, 0.15g of lithium aluminum hydride is added, the reaction temperature is 25 ℃, the reaction is carried out for 3 hours, and the alkoxy lithium aluminum hydride catalyst is prepared for standby after the reaction is completed.
50G of ethylene glycol monovinyl ether and 55g of the catalyst are added into a 2.5L pressure reaction kettle, the air in the kettle is replaced by nitrogen for 3 times, and when the temperature of the kettle is raised to 80-85 ℃, a mixture of 555g of ethylene oxide and 132g of propylene oxide is dropwise added, the pressure in the reaction kettle is kept to be less than or equal to 0.35MPa, and the reaction is continued for 2 hours after the dropwise addition is completed, so as to obtain the ethylene glycol monovinyl ether oligomer.
50G of ethylene glycol monovinyl ether oligomer and 1.1g of tris (4-fluorophenyl) phosphorus catalyst are added into a 2.5L pressure reaction kettle, the air in the kettle is replaced by nitrogen for 3 times, a mixture of 360g of ethylene oxide and 30g of propylene oxide is dropwise added into the kettle when the temperature of the reaction kettle is raised to 95-100 ℃, the pressure in the reaction kettle is kept to be less than or equal to 0.35MPa, and the reaction is continued for 4 hours after the dropwise addition is finished, so that the polycarboxylate water reducer macromonomer with high double bond retention rate is obtained.
Example 3
50G of ethylene glycol monovinyl ether is added into a 100mL round-bottom single-neck flask, the mixture is placed on an electromagnetic stirrer with a water bath, 0.1g of lithium aluminum hydride is added, the reaction temperature is 40 ℃, the reaction time is 1.5 hours, and the lithium aluminum alkoxide catalyst is prepared for standby after the reaction is completed.
50G of ethylene glycol monovinyl ether and 65g of the catalyst are added into a 2.5L pressure reaction kettle, the air in the kettle is replaced by nitrogen for 3 times, and when the temperature of the kettle is raised to 70-75 ℃, a mixture of 650g of ethylene oxide and 125g of propylene oxide is dropwise added, the pressure in the reaction kettle is kept to be less than or equal to 0.35MPa, and the reaction is continued for 3 hours after the dropwise addition is completed, so as to obtain the ethylene glycol monovinyl ether oligomer.
50G of ethylene glycol monovinyl ether oligomer and 1.08g of tris (4-fluorophenyl) phosphorus catalyst are added into a 2.5L pressure reaction kettle, the air in the kettle is replaced by nitrogen for 3 times, and after the temperature of the reaction kettle is raised to 90-95 ℃, 332g of mixture of ethylene oxide and 35g of propylene oxide is dropwise added into the kettle, the pressure in the reaction kettle is kept to be less than or equal to 0.35MPa, and the reaction is continued for 5 hours after the dropwise addition is finished, so that the polycarboxylate superplasticizer macromonomer with high double bond retention rate is obtained.
Example 4
50G of ethylene glycol monovinyl ether is added into a 100mL round-bottom single-neck flask, the mixture is placed on an electromagnetic stirrer with water bath, 0.05g of lithium aluminum hydride is added, the reaction temperature is 50 ℃, the reaction is carried out for 2 hours, and the alkoxy lithium aluminum hydride catalyst is prepared for standby after the reaction is completed.
50G of ethylene glycol monovinyl ether and 50g of the catalyst are added into a 2.5L pressure reaction kettle, the air in the kettle is replaced by nitrogen for 3 times, and when the temperature of the kettle is raised to 85-90 ℃, a mixture of 700g of ethylene oxide and 150g of propylene oxide is dropwise added, the pressure in the reaction kettle is kept to be less than or equal to 0.35MPa, and the reaction is continued for 3.5 hours after the dropwise addition is completed, so as to obtain the ethylene glycol monovinyl ether oligomer.
50G of ethylene glycol monovinyl ether oligomer and 1.32g of tris (4-fluorophenyl) phosphorus catalyst are added into a 2.5L pressure reaction kettle, the air in the kettle is replaced by nitrogen for 3 times, a mixture of 450g of ethylene oxide and 30g of propylene oxide is dropwise added into the kettle after the temperature of the reaction kettle is raised to 90-95 ℃, the pressure in the reaction kettle is kept to be less than or equal to 0.35MPa, and the reaction is continued for 5 hours after the dropwise addition is finished, so that the polycarboxylate water reducer macromonomer with high double bond retention rate is obtained.
Example 5
50G of ethylene glycol monovinyl ether is added into a 100mL round-bottom single-neck flask, the mixture is placed on an electromagnetic stirrer with water bath, 0.125g of lithium aluminum hydride is added, the reaction temperature is 35 ℃, the reaction is carried out for 4 hours, and the alkoxy lithium aluminum hydride catalyst is prepared for standby after the reaction is completed.
50G of ethylene glycol monovinyl ether and 60g of the catalyst are added into a 2.5L pressure reaction kettle, the air in the kettle is replaced by nitrogen for 3 times, and after the kettle temperature rises to 75-80 ℃, 680g of a mixture of ethylene oxide and 140g of propylene oxide is dropwise added, the pressure in the reaction kettle is kept to be less than or equal to 0.35MPa, and the reaction is continued for 3 hours after the dropwise addition is finished, so as to obtain the ethylene glycol monovinyl ether oligomer.
50G of ethylene glycol monovinyl ether oligomer and 1.45g of tris (4-fluorophenyl) phosphorus catalyst are added into a 2.5L pressure reaction kettle, the air in the kettle is replaced by nitrogen for 3 times, 480g of mixture of ethylene oxide and 50g of propylene oxide is dropwise added into the kettle after the temperature of the reaction kettle is raised to 90-95 ℃, the pressure in the reaction kettle is kept to be less than or equal to 0.35MPa, and the reaction is continued for 5.5 hours after the dropwise addition is finished, so that the high double bond retention rate polycarboxylate water reducer macromonomer is obtained.
Comparative example 1
50G of ethylene glycol monovinyl ether and 3.5g of potassium hydroxide catalyst are added into a 2.5L pressure reaction kettle, the air in the kettle is replaced by nitrogen for 3 times, after the temperature of the kettle is raised to 110-115 ℃, the kettle is dehydrated for 60min under the environment with the vacuum degree of more than or equal to 0.097MPa, a mixture of 485g of ethylene oxide and 600g of propylene oxide is dropwise added into the reaction kettle after the dehydration is finished, and the reaction is continued for 8 hours after the dropwise addition is finished, so that the polycarboxylate water reducer macromonomer is obtained.
Comparative example 2
50G of ethylene glycol monovinyl ether and 2.0g of metal sodium catalyst are added into a 2.5L pressure reaction kettle, after the air in the kettle is replaced by nitrogen for 3 times, the metal sodium reacts with raw materials, after the metal sodium completely disappears, the air in the kettle is replaced by nitrogen for 3 times, then the temperature is raised, after the kettle temperature is raised to 110-115 ℃, 485g of mixture of ethylene oxide and 600g of propylene oxide is dropwise added, and after the dropwise addition is finished, the reaction is continued for 8 hours, so that the polycarboxylate water reducer macromonomer is obtained.
Comparative example 3
50G of ethylene glycol monovinyl ether is added into a 100mL round-bottom single-neck flask, the mixture is placed on an electromagnetic stirrer with water bath, 2.15g of lithium aluminum hydride is added, the reaction temperature is 20 ℃, the reaction is carried out for 3 hours, and the alkoxy lithium aluminum hydride catalyst is prepared for standby after the reaction is completed.
50G of ethylene glycol monovinyl ether and 2.3g of sodium hydride catalyst are added into a 2.5L pressure reaction kettle, the air in the kettle is replaced by nitrogen for 3 times, 200g of ethylene oxide is introduced after the kettle temperature is raised to 80-85 ℃, and the reaction is continued for 0.5 hour after 3.5 hours. Then adding 3g of sodium hydride, stirring and heating to 100-120 ℃, introducing 400g of ethylene oxide, introducing for 8 hours, and continuing the reaction for 0.5 hour. And (3) maintaining 120 ℃, introducing 60g of propylene oxide, after the completion of 1 hour, continuing to react for 0.5 hour, and cooling to 80-90 ℃ to obtain the polycarboxylate superplasticizer macromonomer.
Test case
The polycarboxylate superplasticizer macromonomer products prepared in examples 1 to 5 and comparative examples 1 to 3 were each examined, and the examination results are shown in Table 1.
Table 1 Performance index of the polycarboxylate superplasticizer macromers obtained in examples 1 to 5 and comparative examples 1 to 3
As can be seen from Table 1, compared with the product prepared by conventional base catalysis, the product of the ethylene glycol monovinyl ether polycarboxylate superplasticizer macromonomer prepared by the invention has the advantages that the molecular weight is higher than 2000, the molecular weight distribution is narrower, and the double bond retention rate is higher by about 4%. In addition, in comparative example 2, sodium metal is used as a catalyst, the melting point of the sodium metal is low, the sodium metal is inflammable, the danger coefficient is high, and the process has a large limitation. Comparative example 3 has the advantages of high double bond retention rate, narrow molecular weight distribution and high molecular weight, although the molecular weight distribution and double bond retention rate are equivalent to those of the process, the molecular weight of the obtained product can reach 3000 with the invention, and therefore, the ethylene glycol monovinyl ether polycarboxylate water reducer macromer product prepared by the invention has the advantages of high double bond retention rate, narrow molecular weight distribution and high molecular weight.
Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, it should be understood that other embodiments may be devised in accordance with the present embodiments without departing from the spirit and scope of the invention.
Claims (10)
1. The preparation method of the polycarboxylate superplasticizer macromonomer with high double bond retention rate is characterized by comprising the following steps of:
first mixing first ethylene glycol monovinyl ether, alkoxy lithium aluminum hydride and first alkylene oxide, and performing a first polymerization reaction to obtain ethylene glycol monovinyl ether oligomer;
and (3) mixing the ethylene glycol monovinyl ether oligomer, the Lewis base and the second alkylene oxide for the second time, and performing a second polymerization reaction to obtain the Gao Shuangjian-retention-rate polycarboxylate superplasticizer macromonomer.
2. The method of claim 1, wherein the first alkylene oxide and the second alkylene oxide are independently ethylene oxide and/or propylene oxide.
3. The preparation method according to claim 1, wherein the preparation method of the lithium aluminum alkoxide hydride comprises the steps of:
and mixing the second diethylene glycol monovinyl ether with lithium aluminum hydride, and carrying out a reduction reaction to obtain the lithium aluminum alkoxide.
4. The preparation method according to claim 3, wherein the mass ratio of the second diethylene glycol monovinyl ether to the lithium aluminum hydride is 200-1000:1;
the temperature of the reduction reaction is 10-60 ℃ and the time is 1.5-6 h.
5. The preparation method according to claim 1, wherein the mass ratio of the first ethylene glycol monovinyl ether to the lithium aluminum alkoxide hydride is 1:1-1.5;
the mass ratio of the first ethylene glycol monovinyl ether to the first alkylene oxide is 1:9-17.
6. The process according to claim 1 or 5, wherein the first polymerization reaction is carried out at a temperature of 60 to 90 ℃ for a time of 2 to 5 hours.
7. The method of claim 1, wherein the lewis base comprises an organic amine, an organic phosphorus, an azacyclic carbene compound, or thiourea.
8. The method of claim 7, wherein the organic amine comprises triethylenediamine or triethylamine;
The organophosphorus includes triphenylphosphine or tris (4-fluorophenyl) phosphorus;
the azacyclic carbene compound comprises an azacyclic carbene;
The thiourea comprises diethyl thiourea.
9. The preparation method according to claim 1, wherein the mass ratio of the ethylene glycol monovinyl ether oligomer to the lewis base is 20-100:1;
the mass ratio of the ethylene glycol monovinyl ether oligomer to the second alkylene oxide is 1:5.5-11.
10. The process according to claim 1 or 9, wherein the second polymerization reaction is carried out at a temperature of 80 to 100 ℃ for a time of 4 to 6 hours.
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