CN111848944A - Synthesis method of vinyl polyether macromonomer - Google Patents
Synthesis method of vinyl polyether macromonomer Download PDFInfo
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- CN111848944A CN111848944A CN202010758954.4A CN202010758954A CN111848944A CN 111848944 A CN111848944 A CN 111848944A CN 202010758954 A CN202010758954 A CN 202010758954A CN 111848944 A CN111848944 A CN 111848944A
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- Prior art keywords
- polyether macromonomer
- reaction
- ether
- alkoxy
- acetylene
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 164
- 229920000570 polyether Polymers 0.000 title claims abstract description 164
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 45
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 44
- 238000001308 synthesis method Methods 0.000 title description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 152
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 55
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 claims abstract description 55
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 26
- 125000005233 alkylalcohol group Chemical group 0.000 claims abstract description 21
- 239000003112 inhibitor Substances 0.000 claims abstract description 20
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 17
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 14
- -1 alcohol potassium/sodium salt Chemical class 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 11
- 230000009471 action Effects 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 44
- 239000007788 liquid Substances 0.000 claims description 31
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 238000004321 preservation Methods 0.000 claims description 19
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 8
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 6
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 6
- 229950000688 phenothiazine Drugs 0.000 claims description 6
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 6
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 5
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 claims description 5
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 claims description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229960005323 phenoxyethanol Drugs 0.000 claims description 5
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 4
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 4
- 239000012312 sodium hydride Substances 0.000 claims description 4
- JKLOHVRPWUWEKJ-UHFFFAOYSA-N 2-(6-methylheptoxy)ethanol Chemical compound CC(C)CCCCCOCCO JKLOHVRPWUWEKJ-UHFFFAOYSA-N 0.000 claims description 3
- BDLXTDLGTWNUFM-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]ethanol Chemical compound CC(C)(C)OCCO BDLXTDLGTWNUFM-UHFFFAOYSA-N 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 3
- UPGSWASWQBLSKZ-UHFFFAOYSA-N 2-hexoxyethanol Chemical compound CCCCCCOCCO UPGSWASWQBLSKZ-UHFFFAOYSA-N 0.000 claims description 3
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 3
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 3
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000007172 homogeneous catalysis Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 239000003638 chemical reducing agent Substances 0.000 description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 14
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 13
- 238000005303 weighing Methods 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 229960000834 vinyl ether Drugs 0.000 description 7
- 239000004568 cement Substances 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229920005646 polycarboxylate Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WULAHPYSGCVQHM-UHFFFAOYSA-N 2-(2-ethenoxyethoxy)ethanol Chemical compound OCCOCCOC=C WULAHPYSGCVQHM-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-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
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- ZXHDVRATSGZISC-UHFFFAOYSA-N 1,2-bis(ethenoxy)ethane Chemical compound C=COCCOC=C ZXHDVRATSGZISC-UHFFFAOYSA-N 0.000 description 2
- 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
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001348 alkyl chlorides Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- WCASXYBKJHWFMY-UHFFFAOYSA-N crotyl alcohol Chemical compound CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000008030 superplasticizer Substances 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- SAMJGBVVQUEMGC-UHFFFAOYSA-N 1-ethenoxy-2-(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOC=C SAMJGBVVQUEMGC-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZENUHLSFOIKZKR-UHFFFAOYSA-N butane-1,4-diol;potassium Chemical compound [K].OCCCCO ZENUHLSFOIKZKR-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Chemical group 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011787 zinc oxide Substances 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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
-
- 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
- C08G65/2648—Alkali metals or compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyethers (AREA)
Abstract
The invention discloses a method for synthesizing vinyl polyether macromonomer, which comprises the preparation of alkoxy polyether macromonomer and the preparation of vinyl polyether macromonomer, wherein alkyl alcohol and alkylene oxide are used as raw materials, ring opening polymerization is carried out under the action of a catalyst and under the condition of certain temperature and pressure to obtain alkoxy polyether macromonomer, polymerization inhibitor is added into the alkoxy polyether macromonomer, acetylene is added into the alkoxy polyether macromonomer under the condition of certain temperature and pressure, and volatile components are distilled out under reduced pressure after the reaction is finished to obtain the vinyl polyether macromonomer. On one hand, the catalyst is completely converted into polyether alcohol potassium/sodium salt with higher activity; on the other hand, alkyl alcohol is changed into alkoxy polyether with larger molecular weight and better solubility through ring-opening polymerization, so that the catalyst is promoted to be completely dissolved in a reaction system, and the catalytic efficiency of homogeneous catalysis is better exerted.
Description
Technical Field
The invention relates to a method for synthesizing vinyl polyether macromonomer, in particular to a method for synthesizing vinyl polyether macromonomer, belonging to the field of concrete admixture application.
Background
Concrete is widely applied to various fields as a building material and is formed by mixing cement, gravel aggregate, water and a concrete additive, wherein the concrete additive is an essential component in the concrete, can adjust and improve the working performance of the concrete material and plays a central role in the concrete production technology. The water reducing agent is a concrete admixture with the largest concrete dosage and the most extensive application, in particular to a third-generation high-performance polycarboxylic acid water reducing agent, has high water reducing rate and good slump retaining performance, is widely applied to the concrete industry, and accounts for more than 80 percent of the market share of the water reducing agent.
The polycarboxylate superplasticizer synthesized by polyether macromonomer taking methyl allyl alcohol and 3-methyl-3-butylene-1-alcohol as initiators is sensitive to the clay and stone powder content in sandstone aggregate, and along with the reduction of natural high-quality sandstone aggregate resources and the application of industrial waste residues and machine-made sandstone in commercial concrete, the application problems of large fluctuation of water reducing performance, poor slump loss resistance and the like of the polycarboxylate superplasticizer are more and more prominent. Research and development find that the polycarboxylic acid water reducing agent prepared by using hydroxyl-containing vinyl ether such as ethylene glycol vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether and the like as an initiator has certain advantages in the aspects of mud resistance, stone powder resistance and the like.
Lei Lei et al found that the polycarboxylic acid water reducing agent synthesized by using a polyether macromonomer prepared by using 4-hydroxybutyl vinyl ether as an initiator is superior to the polycarboxylic acid water reducing agent synthesized by allyl alcohol, methyl allyl alcohol and 3-methyl-3-butene-1-ol in the dispersing ability and clay tolerance of the water reducing agent, (Lei Lei, Johann plant.
In the Wenxiang et al, 4-hydroxybutyl vinyl polyoxyethylene ether is used as a polyether macromonomer, and a low-sensitivity polycarboxylate water reducer is synthesized, has low doping amount sensitivity, low temperature sensitivity and low water consumption sensitivity, and has a good application effect in machine-made sand and low-grade concrete (in the Wenxiang et al, the research and evaluation of the low-sensitivity polycarboxylate water reducer [ J ] novel building materials, 2019,46(11):30-32+ 54).
The performance research of the polycarboxylic acid water reducing agent shows that the hydroxyl-containing vinyl ether represented by 4-hydroxybutyl vinyl ether is used as an initiator, and the polycarboxylic acid water reducing agent has certain performance advantages on a polyether macromonomer obtained by ring-opening polymerization of ethylene oxide. At present, hydroxyl-containing vinyl ether is mainly synthesized by an acetylene method, acetylene, ethylene glycol, diethylene glycol, 1, 4-butanediol and the like are used as raw materials to perform catalytic addition reaction under certain pressure and temperature conditions, and after the reaction is finished, the raw materials are rectified, separated and purified to obtain the hydroxyl-containing monovinyl ether.
Zhang Jibo et al [ research on continuous synthesis process of diethylene glycol vinyl ether [ J ], proceedings of Jilin chemical academy of Industrial science, 2012,29(3),20-23] use diethylene glycol and acetylene as raw materials, use fixed bed reactor and gas-liquid heterogeneous reaction process, synthesize diethylene glycol vinyl ether continuously, the yield is about 46%; meanwhile, the yield of the diethylene glycol divinyl ether byproduct is about 26%, and the total yield is about 72%.
Patent CN 102173982B reports a synthesis method of ethylene glycol vinyl ether and ethylene glycol divinyl ether. Acetylene and ethylene glycol are used as raw materials, firstly, ethylene glycol, potassium hydroxide and polyethylene glycol dimethyl ether are mixed to prepare a potassium alkoxide solution, then zinc oxide, triphenylphosphine and the like are added and uniformly mixed to serve as a base solution, a reaction kettle is heated to 80-200 ℃, acetylene is introduced, and after the reaction is finished, reduced pressure distillation is carried out to obtain ethylene glycol vinyl ether and ethylene glycol divinyl ether crude products.
Patent CN103394371A reports a synthesis method of 4-hydroxybutyl vinyl ether. Taking 1, 4-butanediol potassium alcoholate and 1, 4-butanediol as base solutions, controlling the reaction temperature to be 80-150 ℃, introducing acetylene for reaction, and after the reaction is finished, transferring the reaction product into a rectifying tower for rectification to obtain the 4-hydroxybutyl vinyl ether.
The acetylene process reported in the above documents and patents is currently an industrial process. Acetylene reacts with a diol monomer, but potassium hydroxide, potassium alkoxide and the like are used as a catalyst, the amount of the catalyst is generally 2 to 5 percent, the molecular weight of the diol monomer is small, and particularly for hydrophobic diol monomers, the compatibility between the catalyst and the diol monomer is not particularly good, so that the catalytic efficiency is reduced; on the other hand, the reaction product of acetylene and diol monomer is monovinyl ether and by-product divinyl ether, and further rectification, separation and purification are required. Because the boiling ranges of the hydroxyl-containing monovinyl ether and the hydroxyl-containing divinyl ether are not different greatly (generally between 5 and 10 ℃), the difference of the boiling ranges of the two components is further reduced under the condition of vacuum rectification, so that the rectification separation and purification time is long and the energy consumption is high. In addition, the research and development of gazel and the like find that the polyether macromonomer with the methyl-terminated end has high conversion rate and the prepared polycarboxylate water reducer has good water reducing rate and slump retaining performance (the preparation of the methoxy polyethylene glycol allyl-terminated polyether and the application thereof in the cement water reducer [ A ]; the national Special concrete technology and engineering application academy and the 2008 year concrete quality Special Committee annual meeting statement [ C ]: 2008 year).
Based on the method, the invention provides a method for directly preparing vinyl polyether macromonomer, avoids the problems of by-products and rectification and purification in the process of synthesizing hydroxyl-containing monovinyl ether, and has the advantages of obvious technical advancement, energy conservation, consumption reduction and the like.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a method for synthesizing a vinyl polyether macromonomer.
The invention achieves the aim through the following technical scheme, and the synthesis method of the vinyl polyether macromonomer comprises the following steps:
(1) preparation of alkoxy polyether macromonomer:
taking alkyl alcohol and alkylene oxide as raw materials, and performing ring opening polymerization under certain temperature and pressure conditions under the action of a catalyst to obtain an alkoxy polyether macromonomer;
(2) preparation of vinyl polyether macromonomer:
adding a polymerization inhibitor into the alkoxy polyether macromonomer in the step (1), adding acetylene into the alkoxy polyether macromonomer under certain temperature and pressure conditions, and distilling out volatile components under reduced pressure after the reaction is finished to obtain the vinyl polyether macromonomer.
Preferably, one structural formula of the alkoxy polyether macromonomer is shown as the following formula (1);
wherein R is1Is methyl, ethyl, isopropyl, butyl, n-hexyl, cyclohexyl, isooctyl and other carbon atoms1-10 alkyl groups; r2Is one of hydrogen and methyl; y is the number of ethylene oxide structural units and is an integer between 20 and 100; x is the number of structural units of propylene oxide and is an integer between 0 and 10, and the ratio of x/y is less than or equal to 0.1.
Preferably, the alkyl alcohol in step (1) includes one of alkyl alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-tert-butyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol monoisooctyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether.
Preferably, the alkylene oxide in step (1) includes one or two of ethylene oxide, propylene oxide and other alkylene oxides, and in the reaction of the alkyl alcohol and the alkylene oxide in step (1), the ethylene oxide and the propylene oxide may be block polymerization or random polymerization.
Preferably, the catalyst in step (1) comprises one of sodium hydroxide, metallic sodium, sodium hydride, sodium methoxide, potassium hydroxide, potassium methoxide or potassium tert-butoxide, and the amount of the catalyst is 10-20% of the mass of the alkyl alcohol.
Preferably, the reaction temperature in the step (1) is between 100 and 120 ℃, and the reaction pressure is less than or equal to 0.4 MPa.
Preferably, the vinyl polyether macromonomer in step (2), one of the structural formulas is represented by the following formula (2):
wherein R is1The alkyl group with the number of carbon atoms of 1-10, such as methyl, ethyl, isopropyl, butyl, n-hexyl, cyclohexyl, isooctyl and the like; r2Is one of hydrogen and methyl; y is the number of ethylene oxide structural units and is an integer between 20 and 100; x is the number of structural units of propylene oxide and is an integer between 0 and 10, and the ratio of x/y is less than or equal to 0.1.
Preferably, a polymerization inhibitor is added before the alkoxy polyether macromonomer reacts with acetylene in the step (2), the dosage of the polymerization inhibitor is 0.001-0.005% of the mass of the alkoxy polyether macromonomer, and the polymerization inhibitor comprises one of hydroquinone, p-benzoquinone, phenothiazine, p-tert-butylcatechol and the like.
Preferably, in the step (2), the alkoxy polyether macromonomer is reacted with acetylene, the molar ratio of acetylene to the alkoxy polyether macromonomer is (1.1-2.0): 1, the reaction temperature is 170-200 ℃, the reaction pressure is 0.3-0.7 MPa, nitrogen is used as a mode for increasing the pressure in the reaction kettle, and the reaction time of acetylene feeding is 10-24 h.
Preferably, the alkoxy polyether macromonomer reacts with acetylene in the step (2), after the acetylene feeding is finished, the reaction is continued for 0.5 hour under heat preservation, the temperature is reduced to 50-70 ℃, volatile components are distilled out under reduced pressure, and a brown yellow viscous liquid, namely the vinyl polyether macromonomer, is obtained.
The invention has the beneficial effects that: the invention provides a preparation method of vinyl polyether macromonomer, which is simple in preparation method, strong in structure adjustability and less in by-product.
Specifically, the vinyl polyether macromonomer reported by the invention has the following advantages:
(1) according to the invention, through the ring-opening polymerization reaction of alkyl alcohol and ethylene oxide, on one hand, all the catalyst is converted into polyether alcohol potassium salt with higher activity; on the other hand, alkyl alcohol is changed into alkoxy polyether with larger molecular weight and better solubility through ring-opening polymerization, so that the catalyst is promoted to be completely dissolved in a reaction system, and the catalytic efficiency of homogeneous catalysis is better exerted.
(2) The vinyl polyether macromonomer is prepared by reacting the alkoxy polyether macromonomer with only one hydroxyl at the tail end with acetylene, so that the problems of reaction selectivity and rectification purification of a generated divinyl ether byproduct are solved, and the monovinyl ether macromonomer can be prepared more conveniently.
(3) One end of the vinyl polyether macromonomer is a vinyl double bond, and the other end of the vinyl polyether macromonomer is an alkoxy end capping; compared with the conventional williamson etherification reaction for polyether macromonomer end capping, the method disclosed by the invention has no etherification side reaction problems of chlorinated waste salt and chlorinated hydrocarbon.
Detailed Description
The present invention is described in detail below by way of examples, which are intended to be illustrative only and not to be construed as limiting the scope of the invention, and one skilled in the art will be able to make variations within the scope of the invention based on the disclosure herein, in reagents, catalysts and reaction process conditions. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
All chemical reagents in the invention are commercial industrial grade purity products, and the raw materials are measured in parts by mass.
The molecular weight of the alkoxy polyether macromonomer is tested by referring to a hydroxyl value method recommended in JC/T2033-2018 polyether for concrete admixture and derivatives thereof, and the effective content of the polyether macromonomer is tested by a high performance liquid test method reported in a reference document (Xiliana and the like, high performance liquid chromatography is used for measuring the mass fraction [ J ],2016,33(6) and 53-60) of polyethylene glycol in the polycarboxylic acid water reducer macromonomer).
A method for synthesizing vinyl polyether macromonomer comprises the following steps:
(1) preparation of alkoxy polyether macromonomer:
taking alkyl alcohol and alkylene oxide as raw materials, and performing ring opening polymerization under certain temperature and pressure conditions under the action of a catalyst to obtain an alkoxy polyether macromonomer;
(2) preparation of vinyl polyether macromonomer:
adding a polymerization inhibitor into the alkoxy polyether macromonomer in the step (1), adding acetylene into the alkoxy polyether macromonomer under certain temperature and pressure conditions, and distilling out volatile components under reduced pressure after the reaction is finished to obtain the vinyl polyether macromonomer.
In the reaction of the alkyl alcohol and the alkylene oxide in the step (1), on one hand, the molecular weight and the mass ratio of the alkyl alcohol are improved through ring-opening polymerization, the mass ratio of the catalyst is reduced, and the solubility of the catalyst is improved; on the other hand, the catalyst is converted into alcohol potassium salt of polyether macromonomer with higher activity by ring-opening polymerization.
In the reaction of the alkoxy polyether macromonomer and acetylene in the step (2), because the alkoxy polyether macromonomer only has one terminal hydroxyl group, only monovinyl ether and a small amount of cyclic acetal byproducts can be generated in the reaction process of the alkoxy polyether macromonomer and acetylene, and the reaction is basically free of bi-vinyl ether byproducts, so that the acetylene consumption with high economic value is saved, the separation of the monovinyl ether and the byproducts is easier to realize, and the energy-saving effect is obvious.
One structural formula of the alkoxy polyether macromonomer is shown as the following formula (1);
wherein R is1The alkyl group with the number of carbon atoms of 1-10, such as methyl, ethyl, isopropyl, butyl, n-hexyl, cyclohexyl, isooctyl and the like; r2Is one of hydrogen and methyl; y is the number of ethylene oxide structural units and is an integer between 20 and 100; x is the number of structural units of propylene oxide and is an integer between 0 and 10, and the ratio of x/y is less than or equal to 0.1.
The alkyl alcohol in the step (1) comprises one of alkyl alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-tert-butyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol monoisooctyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether.
The alkylene oxide in the step (1) comprises one or two of ethylene oxide, propylene oxide and other alkylene oxides, and in the reaction of the alkyl alcohol and the alkylene oxide in the step (1), the ethylene oxide and the propylene oxide can be block polymerization or random polymerization.
The catalyst in the step (1) comprises one of sodium hydroxide, metal sodium, sodium hydride, sodium methoxide, potassium hydroxide, potassium methoxide or potassium tert-butoxide and the like, and the dosage of the catalyst is 10-20% of the mass of the alkyl alcohol.
In the step (1), the reaction temperature is 100-120 ℃, and the reaction pressure is less than or equal to 0.4 MPa.
The vinyl polyether macromonomer in the step (2), wherein one structural formula is shown as the following formula (2):
wherein R is1The alkyl group with the number of carbon atoms of 1-10, such as methyl, ethyl, isopropyl, butyl, n-hexyl, cyclohexyl, isooctyl and the like; r2Is one of hydrogen and methyl; y is the number of ethylene oxide structural units and is an integer between 20 and 100; x is the number of structural units of propylene oxide and is an integer between 0 and 10, and the ratio of x/y is less than or equal to 0.1.
And (3) adding a polymerization inhibitor before the alkoxy polyether macromonomer reacts with acetylene in the step (2), wherein the dosage of the polymerization inhibitor is 0.001-0.005% of the mass of the alkoxy polyether macromonomer, and the polymerization inhibitor comprises one of hydroquinone, p-benzoquinone, phenothiazine, p-tert-butylcatechol and the like.
And (3) reacting the alkoxy polyether macromonomer with acetylene in the step (2), wherein the molar ratio of acetylene to the alkoxy polyether macromonomer is (1.1-2.0): 1, the reaction temperature is 170-200 ℃, the reaction pressure is 0.3-0.7 MPa, nitrogen is used as a mode for increasing the pressure in the reaction kettle, and the acetylene feeding reaction time is 10-24 h.
And (3) reacting the alkoxy polyether macromonomer with acetylene in the step (2), continuing to perform heat preservation reaction for 0.5h after the acetylene feeding is finished, cooling to 50-70 ℃, and performing reduced pressure distillation to obtain a volatile component to obtain a brown yellow viscous liquid, namely the vinyl polyether macromonomer.
Example 1
Weighing 100 parts of ethylene glycol monomethyl ether and 10.0 parts of catalyst sodium hydride, sequentially adding into a polyether reaction kettle, sealing the reaction kettle and replacing with nitrogen for 3 times. Starting the polyether reaction kettle, mechanically stirring, vacuumizing to-0.1 MPa, and vacuumizing for 30 min. Heating the polyether reaction kettle to 100 ℃, stopping feeding after 20 parts of ethylene oxide is fed, continuing to add 1200 parts of ethylene oxide into the reaction kettle after the ring opening polymerization of the ethylene oxide starts (the temperature of the polyether reaction kettle rises and the pressure drops), controlling the temperature in the reaction kettle to be 120 +/-5 ℃, controlling the pressure in the reaction kettle to be less than or equal to 0.4MPa, and keeping the temperature for reaction for 0.5h after the ethylene oxide is fed and received. After the heat preservation reaction of the polyether reaction kettle is finished, the volatile components are removed through reduced pressure distillation to obtain brown yellow viscous liquid, the molecular weight of polyether is 900 through a hydroxyl value method, and the purity of the polyether macromonomer is 97.2 through a high performance liquid chromatograph.
Weighing 1000 parts of alkoxy polyether macromonomer, adding 0.01 part of polymerization inhibitor hydroquinone, sealing the reaction kettle and replacing with nitrogen for 3 times. Heating the reaction kettle to 170 ℃, starting acetylene feeding, wherein the acetylene dosage is 31.7 parts, controlling the acetylene feeding time to be 10 hours, the reaction temperature to be 170 ℃, and the reaction pressure to be 0.3MPa by using nitrogen for pressure compensation. And (3) continuing to perform heat preservation reaction for 0.5h after acetylene feeding is finished, then cooling to 50-80 ℃, and distilling out volatile components under reduced pressure to obtain a brownish yellow vinyl polyether macromonomer named as VPEG-1, wherein the purity of the polyether macromonomer is 97.1% as tested by a high performance liquid chromatograph.
Example 2
Weighing 100 parts of ethylene glycol monoisopropyl ether and 20.0 parts of catalyst potassium methoxide, sequentially adding the ethylene glycol monoisopropyl ether and the catalyst potassium methoxide into a polyether reaction kettle, sealing the reaction kettle, and replacing the reaction kettle with nitrogen for 3 times. Starting the polyether reaction kettle, mechanically stirring, vacuumizing to-0.1 MPa, and vacuumizing for 30 min. Heating the polyether reaction kettle to 100 ℃, feeding 20 parts of ethylene oxide, stopping feeding, sequentially adding 2600 parts of ethylene oxide and 200 parts of propylene oxide into the reaction kettle when ring-opening polymerization of the ethylene oxide starts (the temperature of the polyether reaction kettle rises and the pressure drops), controlling the temperature in the reaction kettle to be 120 +/-5 ℃, controlling the pressure in the reaction kettle to be less than or equal to 0.4MPa, and carrying out heat preservation reaction for 0.5h after receiving the alkylene oxide feeding. After the heat preservation reaction of the polyether reaction kettle is finished, the volatile components are removed through reduced pressure distillation to obtain brown yellow viscous liquid, the molecular weight of polyether is 2957 through a hydroxyl value method, and the purity of the polyether macromonomer is 96.9 through a high performance liquid chromatograph.
Weighing 1000 parts of alkoxy polyether macromonomer, adding 0.03 part of polymerization inhibitor p-phenylenediamine, sealing the reaction kettle and replacing with nitrogen for 3 times. Heating the reaction kettle to 200 ℃, starting acetylene feeding, wherein the acetylene dosage is 13.2 parts, controlling the acetylene feeding time to be 24 hours, the reaction temperature to be 200 ℃, and the reaction pressure to be 0.7MPa by using nitrogen. And (3) continuing the heat preservation reaction for 0.5h after the acetylene feeding is finished, then cooling to 50-80 ℃, and distilling out volatile components under reduced pressure to obtain a brownish yellow vinyl polyether macromonomer named as VPEG-2, wherein the purity of the polyether macromonomer is 96.2% as tested by a high performance liquid chromatograph.
Example 3
Weighing 100 parts of ethylene glycol monophenyl ether and 18.0 parts of catalyst potassium tert-butoxide, sequentially adding the ethylene glycol monophenyl ether and the catalyst potassium tert-butoxide into a polyether reaction kettle, sealing the reaction kettle and replacing the reaction kettle with nitrogen for 3 times. Starting the polyether reaction kettle, mechanically stirring, vacuumizing to-0.1 MPa, and vacuumizing for 30 min. Heating the polyether reaction kettle to 100 ℃, feeding 20 parts of propylene oxide, stopping feeding, sequentially adding 200 parts of propylene oxide and 3000 parts of ethylene oxide into the reaction kettle when ring-opening polymerization of ethylene oxide begins (the temperature of the polyether reaction kettle rises and the pressure drops), controlling the temperature in the reaction kettle to be 120 +/-5 ℃, controlling the pressure in the reaction kettle to be less than or equal to 0.4MPa, and carrying out heat preservation reaction for 0.5h after receiving the ethylene oxide feeding. After the heat preservation reaction of the polyether reaction kettle is finished, removing volatile components through reduced pressure distillation to obtain brown yellow viscous liquid, wherein the molecular weight of polyether is 4516 through a hydroxyl value method, and the purity of the polyether macromonomer is 97.9 through a high performance liquid chromatograph.
Weighing 1000 parts of alkoxy polyether macromonomer, adding 0.05 part of polymerization inhibitor phenothiazine, sealing the reaction kettle and replacing with nitrogen for 3 times. Heating the reaction kettle to 190 ℃, starting acetylene feeding, wherein the acetylene dosage is 11.5 parts, controlling the acetylene feeding time to be 17 hours, the reaction temperature to be 190 ℃, and the reaction pressure to be 0.5MPa by using nitrogen. And (3) continuing to perform heat preservation reaction for 0.5h after acetylene feeding is finished, then cooling to 50-80 ℃, and distilling out volatile components under reduced pressure to obtain a brownish yellow vinyl polyether macromonomer named as VPEG-3, wherein the purity of the polyether macromonomer is 97.0% as tested by a high performance liquid chromatograph.
Example 4
100 parts of diethylene glycol monomethyl ether and 15.0 parts of catalyst metal sodium are weighed, added into a polyether reaction kettle in sequence, and the reaction kettle is sealed and replaced by nitrogen for 3 times. Starting the polyether reaction kettle, mechanically stirring, vacuumizing to-0.1 MPa, and vacuumizing for 30 min. Heating the polyether reaction kettle to 100 ℃, feeding 20 parts of ethylene oxide, stopping feeding, adding 1750 parts of ethylene oxide and 250 parts of propylene oxide into the reaction kettle when the ring opening polymerization of the ethylene oxide starts (the temperature of the polyether reaction kettle rises and the pressure drops), controlling the temperature in the reaction kettle to be 120 +/-5 ℃, controlling the pressure in the reaction kettle to be less than or equal to 0.4MPa, and carrying out heat preservation reaction for 0.5h after receiving the ethylene oxide feed. After the heat preservation reaction of the polyether reaction kettle is finished, the volatile components are removed through reduced pressure distillation to obtain brown yellow viscous liquid, the molecular weight of polyether is 2458 through a hydroxyl value method, and the purity of the polyether macromonomer is 99.2 through a high performance liquid chromatograph.
Weighing 1000 parts of alkoxy polyether macromonomer, adding 0.03 part of polymerization inhibitor hydroquinone, sealing the reaction kettle and replacing with nitrogen for 3 times. Heating the reaction kettle to 180 ℃, starting acetylene feeding, wherein the acetylene dosage is 12.7 parts, controlling the acetylene feeding time to be 15h, the reaction temperature to be 180 ℃, and the reaction pressure to be 0.6MPa by using nitrogen for pressure compensation. And (3) continuing the heat preservation reaction for 0.5h after the acetylene feeding is finished, then cooling to 50-80 ℃, and distilling out volatile components under reduced pressure to obtain a brownish yellow vinyl polyether macromonomer named as VPEG-4, wherein the purity of the polyether macromonomer is 98.8% as tested by a high performance liquid chromatograph.
Example 5
100 parts of diethylene glycol monobutyl ether and 13.0 parts of catalyst potassium hydroxide are weighed and sequentially added into a polyether reaction kettle, and the reaction kettle is sealed and replaced by nitrogen for 3 times. Starting the polyether reaction kettle, mechanically stirring, vacuumizing to-0.1 MPa, and vacuumizing for 30 min. Heating the polyether reaction kettle to 100 ℃, stopping feeding the ethylene oxide after 20 parts of the ethylene oxide is fed, continuing to add 1900 parts of ethylene oxide into the reaction kettle after the ring-opening polymerization of the ethylene oxide starts (the temperature of the polyether reaction kettle rises and the pressure drops), controlling the temperature in the reaction kettle to be 120 +/-5 ℃, controlling the pressure in the reaction kettle to be less than or equal to 0.4MPa, and keeping the temperature of the ethylene oxide for reaction for 0.5h after the ethylene oxide is fed and received. After the heat preservation reaction of the polyether reaction kettle is finished, the volatile components are removed through reduced pressure distillation to obtain brown yellow viscous liquid, the molecular weight of polyether is 3028 through a hydroxyl value method, and the purity of the polyether macromonomer is 98.7% through a high performance liquid chromatograph test.
Weighing 1000 parts of alkoxy polyether macromonomer, adding 0.02 part of polymerization inhibitor phenothiazine, sealing the reaction kettle and replacing with nitrogen for 3 times. Heating the reaction kettle to 185 ℃, starting acetylene feeding, wherein the acetylene dosage is 12.9 parts, controlling the acetylene feeding time to be 15h, the reaction temperature to be 185 ℃, and the reaction pressure to be 0.5MPa by using nitrogen for pressure compensation. And (3) continuing the heat preservation reaction for 0.5h after the acetylene feeding is finished, then cooling to 50-80 ℃, and distilling out volatile components under reduced pressure to obtain a brownish yellow vinyl polyether macromonomer named as VPEG-5, wherein the purity of the polyether macromonomer is 98.1% as tested by a high performance liquid chromatograph.
Comparative example 1
100 parts of diethylene glycol monovinyl ether and 0.15 part of catalyst sodium methoxide are weighed and sequentially added into a polyether reaction kettle, and the reaction kettle is sealed and replaced by nitrogen for 3 times. Starting the polyether reaction kettle, mechanically stirring, vacuumizing to-0.1 MPa, and vacuumizing for 30 min. Heating the polyether reaction kettle to 100 ℃, stopping feeding after 20 parts of ethylene oxide is fed, continuing to add 2300 parts of ethylene oxide into the reaction kettle when ring-opening polymerization of the ethylene oxide starts (the temperature of the polyether reaction kettle rises and the pressure drops), controlling the temperature in the reaction kettle to be 120 +/-5 ℃, controlling the pressure in the reaction kettle to be less than or equal to 0.4MPa, and keeping the temperature of the ethylene oxide for reaction for 0.5h after the ethylene oxide is fed and received. After the heat preservation reaction of the polyether reaction kettle is finished, the volatile components are removed through reduced pressure distillation to obtain brown yellow viscous liquid, the molecular weight of polyether is 3056 through a hydroxyl value method, and the purity of the polyether macromonomer is 95.4% through a high performance liquid chromatograph.
Weighing 1000 parts of polyether macromonomer, adding 21.2 parts of potassium hydroxide and 0.03 part of polymerization inhibitor hydroquinone, heating to 110 ℃, and distilling under reduced pressure for 4 hours. And then cooling to 80-90 ℃, continuously feeding 25.4 parts of chloroethane into the reaction kettle, keeping the reaction temperature between 100-110 ℃, and supplementing pressure to 0.4MPa with nitrogen for 15 h. And (3) distilling the volatile components under reduced pressure to obtain a brown turbid viscous liquid, and filtering the liquid while the liquid is hot by using a reduced-pressure suction filtration device to separate the polyether macromonomer with the methyl terminated end and sodium chloride salt. The content of the polyether macromonomer with the methyl terminated end is 80 percent and the rest 20 percent is the polyether macromonomer without terminated end through the test of a high performance liquid chromatograph.
Comparative example 2
100 parts of diethylene glycol monomethyl ether and 0.2 part of catalyst potassium methoxide are weighed and sequentially added into a polyether reaction kettle, and the reaction kettle is sealed and replaced by nitrogen for 3 times. Starting the polyether reaction kettle, mechanically stirring, vacuumizing to-0.1 MPa, and vacuumizing for 30 min. Heating the polyether reaction kettle to 100 ℃, stopping feeding the ethylene oxide after 20 parts of the ethylene oxide is fed, continuing to add 2500 parts of ethylene oxide into the reaction kettle after the ring-opening polymerization of the ethylene oxide starts (the temperature of the polyether reaction kettle rises and the pressure drops), controlling the temperature in the reaction kettle to be 120 +/-5 ℃, controlling the pressure in the reaction kettle to be less than or equal to 0.4MPa, and keeping the temperature of the ethylene oxide for reaction for 0.5h after the ethylene oxide is fed and received. After the heat preservation reaction of the polyether reaction kettle is finished, the volatile components are removed through reduced pressure distillation to obtain brown yellow viscous liquid, the molecular weight of polyether is 2992 through a hydroxyl value method, and the purity of the polyether macromonomer is 98.7% through a high performance liquid chromatograph.
Weighing 1000 parts of polyether macromonomer, adding 28.1 parts of potassium hydroxide and 0.02 part of polymerization inhibitor phenothiazine, heating to 110 ℃, and distilling under reduced pressure for 4 hours. And then cooling to 80-90 ℃, continuously feeding 31.3 parts of chloroethylene into the reaction kettle, supplementing pressure to 0.6MPa by using nitrogen at the reaction temperature of 100-110 ℃, reacting for 20h, then distilling out volatile components under reduced pressure to obtain brown turbid viscous liquid, filtering while hot by using a reduced-pressure suction filtration device, and separating out the polyether macromonomer and sodium chloride salt with the vinyl-terminated tail end. The content of the vinyl terminated polyether macromonomer is 82% and the remaining 18% is the non-terminated polyether macromonomer, as measured by a high performance liquid chromatograph.
The application example is as follows:
in the application embodiment of the invention, the vinyl polyether macromonomer and the acrylic acid are used as synthesis raw materials to synthesize the polycarboxylic acid water reducer, and the synthesis process comprises the following steps: weighing 300 parts of vinyl polyether macromonomer, and adding water to dilute to 50% of solid content; then adding 1.5 parts of hydrogen peroxide (30%), stirring to obtain a clear and transparent solution, and then cooling the chilled water to 10-13 ℃. Weighing 35 parts of acrylic acid, adding 35 parts of water, and naming as dropwise adding solution A; 0.6 part of L-ascorbic acid, 2.0 parts of mercaptopropionic acid and 100 parts of water are weighed and named as solution B. Setting the dropping time of the solution A to be 1 hour, setting the dropping time of the solution B to be 1.2 hours, controlling the temperature in the reaction kettle to be less than or equal to 20 ℃ in the dropping process, and continuing the heat preservation reaction for 2 hours after the dropping is finished. And (4) neutralizing by using 32% liquid alkali to pH 7 to obtain a viscous polycarboxylic acid water reducing agent finished product.
In the application example of the invention, the adopted cement is ordinary portland cement (P.O42.5) except for special description, the fluidity test of the cement paste is carried out according to the GB/T8077-2000 standard, the water addition amount is 87g, the fluidity of the cement paste is measured on plate glass, and the test data is shown in Table 1.
TABLE 1 Cement paste fluidity test
As can be seen from the data in Table 1, the polycarboxylic acid water reducer synthesized by using the vinyl polyether macromonomer as the raw material is better in water reducing performance and slump retaining performance than the water reducer synthesized by using the conventional chloroalkane or chloroalkene terminated vinyl polyether macromonomer in the comparative example. In addition, the effect of chloroalkane or chloroalkene is also inferior to the preparation method of the vinyl polyether macromonomer of the present invention in terms of the capping effect of the polyether macromonomer.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A method for synthesizing vinyl polyether macromonomer is characterized by comprising the following steps:
(1) preparation of alkoxy polyether macromonomer:
taking alkyl alcohol and alkylene oxide as raw materials, and performing ring opening polymerization under certain temperature and pressure conditions under the action of a catalyst to obtain an alkoxy polyether macromonomer;
(2) preparation of vinyl polyether macromonomer:
adding a polymerization inhibitor into the alkoxy polyether macromonomer in the step (1), adding acetylene into the alkoxy polyether macromonomer under certain temperature and pressure conditions, and distilling out volatile components under reduced pressure of-0.1 MPa after the reaction is finished to obtain the vinyl polyether macromonomer.
2. The method of claim 1, wherein one of the alkoxy polyether macromonomer has the formula (1);
wherein R is1The alkyl group with the number of carbon atoms of 1-10, such as methyl, ethyl, isopropyl, butyl, n-hexyl, cyclohexyl, isooctyl and the like; r2Is one of hydrogen and methyl; y is the number of ethylene oxide structural units and is an integer between 20 and 100; x is the number of structural units of propylene oxide and is an integer between 0 and 10, and the ratio of x/y is less than or equal to 0.1.
3. The method of claim 1, wherein the alkyl alcohol in step (1) comprises one of the alkyl alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-tert-butyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol monoisooctyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether.
4. The method of claim 1, wherein the alkylene oxide in step (1) comprises one or two of ethylene oxide and propylene oxide, and the reaction of the alkyl alcohol with the alkylene oxide in step (1) can be block polymerization or random polymerization.
5. The method of claim 1, wherein the catalyst in step (1) comprises one of sodium hydroxide, sodium metal, sodium hydride, sodium methoxide, potassium hydroxide, potassium methoxide, or potassium tert-butoxide, and the amount of the catalyst is 10-20% of the mass of the alkyl alcohol.
6. The method for synthesizing vinyl polyether macromonomer according to claim 1, wherein in step (1), the reaction temperature is 100-120 ℃ and the reaction pressure is less than or equal to 0.4 MPa.
7. The method of claim 2, wherein in the step (2), one of the vinyl polyether macromonomers has a structural formula shown in the following formula (2):
wherein R is1The alkyl group with the number of carbon atoms of 1-10, such as methyl, ethyl, isopropyl, butyl, n-hexyl, cyclohexyl, isooctyl and the like; r2Is one of hydrogen and methyl; y is the number of ethylene oxide structural units and is an integer between 20 and 100; x is the number of structural units of propylene oxide and is an integer between 0 and 10, and the ratio of x/y is less than or equal to 0.1.
8. The method for synthesizing vinyl polyether macromonomer according to claim 2, wherein a polymerization inhibitor is added before the alkoxy polyether macromonomer reacts with acetylene in step (2), the amount of the polymerization inhibitor is 0.001-0.005% of the mass of the alkoxy polyether macromonomer, and the polymerization inhibitor comprises one of hydroquinone, p-benzoquinone, phenothiazine, p-tert-butylcatechol, and the like.
9. The method for synthesizing vinyl polyether macromonomer according to claim 2, wherein in the step (2), the alkoxy polyether macromonomer is reacted with acetylene, the molar ratio of acetylene to the alkoxy polyether macromonomer is (1.1-2.0): 1, the reaction temperature is 170-200 ℃, the reaction pressure is 0.3-0.7 MPa, nitrogen is used as a way of increasing the pressure in the reaction kettle, and the reaction time of acetylene feeding is 10-24 h.
10. The method for synthesizing the vinyl polyether macromonomer according to claim 2, wherein the alkoxy polyether macromonomer reacts with acetylene in the step (2), the reaction is continued for 0.5h under heat preservation after the acetylene feeding is finished, the temperature is reduced to 50-70 ℃, volatile components are distilled out under reduced pressure, and brown yellow viscous liquid, namely the vinyl polyether macromonomer, is obtained.
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| CN113185687A (en) * | 2021-06-02 | 2021-07-30 | 江苏金木土新材料有限公司 | Preparation method of clay-resistant concrete admixture |
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| CN113185687A (en) * | 2021-06-02 | 2021-07-30 | 江苏金木土新材料有限公司 | Preparation method of clay-resistant concrete admixture |
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