CN116239766A - Water-soluble RAFT reagent and preparation method thereof, and polycarboxylate water reducer and preparation method thereof - Google Patents
Water-soluble RAFT reagent and preparation method thereof, and polycarboxylate water reducer and preparation method thereof Download PDFInfo
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- CN116239766A CN116239766A CN202211686666.8A CN202211686666A CN116239766A CN 116239766 A CN116239766 A CN 116239766A CN 202211686666 A CN202211686666 A CN 202211686666A CN 116239766 A CN116239766 A CN 116239766A
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- Prior art keywords
- water
- polyethylene glycol
- soluble
- glycidyl ether
- glycol glycidyl
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- 239000003153 chemical reaction reagent Substances 0.000 title claims abstract description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 30
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 81
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 81
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 67
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 239000012987 RAFT agent Substances 0.000 claims description 67
- AISZNMCRXZWVAT-UHFFFAOYSA-N 2-ethylsulfanylcarbothioylsulfanyl-2-methylpropanenitrile Chemical compound CCSC(=S)SC(C)(C)C#N AISZNMCRXZWVAT-UHFFFAOYSA-N 0.000 claims description 61
- 238000000034 method Methods 0.000 claims description 20
- 239000003999 initiator Substances 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 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 12
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000008030 superplasticizer Substances 0.000 claims description 10
- VMSIYTPWZLSMOH-UHFFFAOYSA-N 2-(dodecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCOCC1CO1 VMSIYTPWZLSMOH-UHFFFAOYSA-N 0.000 claims description 9
- HUJKKJBFQWMSPC-UHFFFAOYSA-N 4-cyano-5-ethylsulfanyl-4-methyl-2-sulfanyl-5-sulfanylidenepentanoic acid Chemical compound CCSC(=S)C(C)(C#N)CC(S)C(O)=O HUJKKJBFQWMSPC-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012989 trithiocarbonate Substances 0.000 claims description 8
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 230000000977 initiatory effect Effects 0.000 claims description 7
- KFNUBPMMXWWWGU-UHFFFAOYSA-N 2-(2-carboxypropan-2-ylsulfanylcarbothioylsulfanyl)-2-methylpropanoic acid Chemical compound OC(=O)C(C)(C)SC(=S)SC(C)(C)C(O)=O KFNUBPMMXWWWGU-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- YOQLRQUGJROXRV-UHFFFAOYSA-N benzenecarbodithioic acid;4-cyanopentanoic acid Chemical compound N#CC(C)CCC(O)=O.SC(=S)C1=CC=CC=C1 YOQLRQUGJROXRV-UHFFFAOYSA-N 0.000 claims description 6
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 6
- 150000007942 carboxylates Chemical class 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 6
- AJHQBPWPZRRSKR-UHFFFAOYSA-N 3-benzylsulfanylcarbothioylsulfonylpropanoic acid Chemical compound OC(CCS(C(SCC1=CC=CC=C1)=S)(=O)=O)=O AJHQBPWPZRRSKR-UHFFFAOYSA-N 0.000 claims description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 claims description 4
- SIDXFGMQLJSRTB-UHFFFAOYSA-N (2-butylphenyl)-diphenylphosphanium bromide Chemical compound [Br-].CCCCC1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 SIDXFGMQLJSRTB-UHFFFAOYSA-N 0.000 claims description 3
- KCFOLUKWAIAKFB-UHFFFAOYSA-N CCC(C=CC=C1)=C1P(C1=CC=CC=C1)C1=CC=CC=C1.Br Chemical compound CCC(C=CC=C1)=C1P(C1=CC=CC=C1)C1=CC=CC=C1.Br KCFOLUKWAIAKFB-UHFFFAOYSA-N 0.000 claims description 3
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 claims description 3
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 3
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 claims description 3
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 3
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 3
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 3
- LSEFCHWGJNHZNT-UHFFFAOYSA-M methyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 LSEFCHWGJNHZNT-UHFFFAOYSA-M 0.000 claims description 3
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 3
- XMQSELBBYSAURN-UHFFFAOYSA-M triphenyl(propyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCC)C1=CC=CC=C1 XMQSELBBYSAURN-UHFFFAOYSA-M 0.000 claims description 3
- 229940005605 valeric acid Drugs 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 238000007142 ring opening reaction Methods 0.000 abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 6
- 125000003700 epoxy group Chemical group 0.000 abstract description 5
- 150000003254 radicals Chemical class 0.000 abstract description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 239000004576 sand Substances 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000002002 slurry Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- -1 3-benzylthiocarbonylsulfonylpropionic acid Chemical compound 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000004568 cement Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- JGHKDVSIFPFNIJ-UHFFFAOYSA-N dodecylsulfanylmethanedithioic acid Chemical group CCCCCCCCCCCCSC(S)=S JGHKDVSIFPFNIJ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- BGPJLYIFDLICMR-UHFFFAOYSA-N 1,4,2,3-dioxadithiolan-5-one Chemical compound O=C1OSSO1 BGPJLYIFDLICMR-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001409 amidines Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011083 cement mortar Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000009189 diving Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
- C08G65/3344—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur
- C08G65/3346—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur having sulfur bound to carbon and oxygen
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/04—Acids; Metal salts or ammonium salts thereof
- C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F128/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
- C08F128/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
-
- 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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/04—End-capping
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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The application provides a water-soluble RAFT reagent and a preparation method thereof, and a polycarboxylate water reducer and a preparation method thereof. Wherein the water-soluble RAFT reagent is formed by reacting a thiocarbonate type RAFT reagent with polyethylene glycol glycidyl ether, the thiocarbonate type RAFT reagent contains carboxyl groups, and the water-soluble RAFT reagent comprises a chain segment structure shown in a formula 1 and can be prepared byThe water-soluble RAFT reagent with various structures and target molecular weights can be conveniently prepared by adjusting the molecular weight and molecular structure of the polyethylene glycol glycidyl ether and the types and the proportions of the thiocarbonate type RAFT reagent, so that the water-soluble RAFT reagent has good water solubility, adjustable molecular weight and molecular structure, and is suitable for free radical controllable polymerization and emulsion polymerization in aqueous solution, and on the other hand, the hydroxyl in the thiocarbonate type RAFT reagent and the epoxy group in the polyethylene glycol glycidyl ether perform ring-opening reaction, so that the reaction efficiency is higher, and the product purity is higher.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to a water-soluble RAFT reagent and a preparation method thereof, and a polycarboxylate water reducer and a preparation method thereof.
Background
In the field of polymer synthesis, reversible addition-fragmentation chain transfer polymerization (Reversible Addition-Fragmentation Chain Transfer Polymerization, RAFT) is one of the active/controllable radical polymerizations (Controlled Radical Polymerization, CRP). When RAFT polymerization is carried out, a RAFT reagent is introduced into a traditional free radical polymerization system, and the molecular chain is grown by reversible addition reaction and cleavage reaction with free radicals.
RAFT agents are important raw materials in RAFT polymerization, most of the currently common RAFT agents are oil-soluble small molecules, and RAFT agents suitable for aqueous solution polymerization are relatively few.
Disclosure of Invention
In view of the above, the embodiments of the present application provide a water-soluble RAFT agent and a preparation method thereof, a polycarboxylate water reducer and a preparation method thereof, and a water-soluble RAFT agent with a target molecular weight.
In a first aspect, embodiments of the present application provide a water-soluble RAFT agent, where the water-soluble RAFT agent is formed by reacting a thiocarbonate type RAFT agent with a polyethylene glycol glycidyl ether, the thiocarbonate type RAFT agent contains a carboxyl group, and the water-soluble RAFT agent includes a segment structure represented by formula 1
Alternatively, the thiocarbonate type RAFT agent comprises one or more of 3-benzylthiocarbonylsulfonylpropionic acid, 4-cyanovaleric acid dithiobenzoate, 2- (1-carboxy-1-methylethylsulfanylthiocarbonyl sulfanyl) -2-methylpropionic acid, 4-cyano-4- (ethylsulfanylthiocarbonyl) sulfanyl pentanoic acid, bis (carboxylate) trithiocarbonate, and 2- (dodecyltrithiocarbonate) -2-methylpropionic acid.
Optionally, the polyethylene glycol glycidyl ether comprises one or more of polyethylene glycol diglycidyl ether, methoxy polyethylene glycol glycidyl ether, polyethylene glycol glycidyl dodecyl ether and multi-arm polyethylene glycol glycidyl ether.
Optionally, the number average molecular weight of the polyethylene glycol glycidyl ether is 200Da to 20000Da.
In a second aspect, embodiments of the present application provide a method for preparing a water-soluble RAFT agent, including the steps of:
dissolving thiocarbonate type RAFT reagent containing carboxyl, polyethylene glycol glycidyl ether and a catalyst in a solvent, and reacting at the catalytic temperature of the catalyst to obtain a mixed product;
and precipitating the mixed product, and washing to obtain the water-soluble RAFT reagent.
Alternatively, the thiocarbonate type RAFT agent comprises one or more of 3-benzylthiocarbonylsulfonylpropionic acid, 4-cyanovaleric acid dithiobenzoate, 2- (1-carboxy-1-methylethylsulfanylthiocarbonyl sulfanyl) -2-methylpropionic acid, 4-cyano-4- (ethylsulfanylthiocarbonyl) sulfanyl pentanoic acid, bis (carboxylate) trithiocarbonate, and 2- (dodecyltrithiocarbonate) -2-methylpropionic acid.
Optionally, the polyethylene glycol glycidyl ether comprises one or more of polyethylene glycol diglycidyl ether, methoxy polyethylene glycol glycidyl ether, polyethylene glycol glycidyl dodecyl ether and multi-arm polyethylene glycol glycidyl ether.
Optionally, the catalyst comprises one or more of triphenylphosphine, N-dimethylaniline, tetrabutylammonium bromide, tetrapropylammonium bromide, tetraethylammonium bromide, benzyltriethylammonium bromide, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, methyltriphenylphosphine bromide, ethyltriphenylphosphine bromide, propyltriphenylphosphine bromide, butyltriphenylphosphine bromide, benzyltriethylammonium chloride, tetramethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, benzyltrimethylammonium chloride and methyltrioctylammonium chloride.
Optionally, the solvent is one or more of dioxane, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, propylene carbonate and propylene glycol methyl ether acetate.
Optionally, the molar ratio of the thiocarbonate type RAFT reagent containing carboxyl to the polyethylene glycol glycidyl ether is 1:0.25 to 1:4.
in a third aspect, embodiments of the present application provide a polycarboxylate water reducer formed by reacting a water-soluble RAFT agent as described above, an acrylic monomer under initiation conditions of a water-soluble initiator.
Optionally, the water-soluble initiator comprises one or more of azodiisobutyl amidine hydrochloride, azodiiso Ding Mi hydrochloride, azodicyanovaleric acid, azodiisopropyl imidazoline and the like; and/or the acrylic monomer comprises one or more of acrylic acid, methacrylic acid, sodium methacrylate sulfonate and N-methyl pyrrolidone.
Optionally, the mass ratio of the water-soluble RAFT agent, the acrylic monomer and the water-soluble initiator is 1: (3-30): (0.1-0.5).
In a fourth aspect, an embodiment of the present application provides a method for preparing a polycarboxylate superplasticizer, which is characterized in that a water-soluble RAFT agent, a monomer and a water-soluble initiator as described above are dissolved in water, and react at an initiation temperature of the water-soluble initiator to obtain an aqueous solution of the polycarboxylate superplasticizer.
Compared with the prior art, the application has the following beneficial effects:
the application utilizes the thiocarbonate type RAFT reagent containing carboxyl to react with polyethylene glycol glycidyl ether, and the thiocarbonate type RAFT reagent is connected with the polyethylene glycol glycidyl ether through the ring-opening reaction of hydroxyl in the thiocarbonate type RAFT reagent and epoxy in the polyethylene glycol glycidyl ether. The polyethylene glycol glycidyl ether has good water solubility, can conveniently prepare water-soluble RAFT reagents with various structures and target molecular weights by adjusting the molecular weight and molecular structure of the polyethylene glycol glycidyl ether and the types and proportions of thiocarbonate type RAFT reagents, on one hand, the water solubility of the obtained water-soluble RAFT reagents is good, the molecular weight and molecular structure can be regulated and controlled, and the method is suitable for free radical controllable polymerization and emulsion polymerization in aqueous solution, and on the other hand, hydroxyl in the thiocarbonate type RAFT reagents and epoxy groups in the polyethylene glycol glycidyl ether are subjected to ring-opening reaction, so that the reaction efficiency is high, and the product purity is high.
Detailed Description
In order to make the application purposes, technical solutions and beneficial technical effects of the present application clearer, the present application is further described in detail below with reference to examples. It should be understood that the embodiments described in this specification are for purposes of illustration only and are not intended to limit the present application.
For simplicity, only a few numerical ranges are explicitly disclosed in this application. However, any lower limit may be combined with any upper limit to form a range not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and any upper limit may be combined with any other upper limit to form a range not explicitly recited. Furthermore, each point or individual value between the endpoints of the range is included within the range, although not explicitly recited. Thus, each point or individual value may be combined as a lower or upper limit on itself with any other point or individual value or with other lower or upper limit to form a range that is not explicitly recited.
In the description of the present application, unless otherwise indicated, "above" and "below" are intended to include the present number, and the meaning of "multiple" in "one or more" means two or more.
As mentioned above, RAFT agents are important raw materials in RAFT polymerization, but most of the RAFT agents currently in common use are oil-soluble small molecules, and RAFT agents suitable for aqueous solution polymerization are relatively few. The inventor notes that the water-soluble RAFT agent can be obtained by esterification reaction of polyethylene glycol and a RAFT agent with carboxyl, but the esterification reaction is generally low in efficiency and low in product purity.
Based on this, the inventors have conducted a great deal of experimental investigation, and have found that a water-soluble RAFT agent of various structures and target molecular weights can be conveniently prepared by reacting a thiocarbonate type RAFT agent having a carboxyl group with a polyethylene glycol type glycidyl ether, grafting the polyethylene glycol type glycidyl ether to the thiocarbonate type RAFT agent, to obtain a water-soluble RAFT agent, and by adjusting the molecular weight, molecular structure, and kind and proportion of the polyethylene glycol type glycidyl ether, and the thiocarbonate type RAFT agent.
Water-soluble RAFT agent
In a first aspect, embodiments of the present application provide a water-soluble RAFT agent, where the water-soluble RAFT agent is formed by reacting a thiocarbonate type RAFT agent with a polyethylene glycol glycidyl ether, the thiocarbonate type RAFT agent contains a carboxyl group, and the water-soluble RAFT agent includes a segment structure represented by formula 1
According to the embodiment of the application, hydrophilic polyethylene glycol glycidyl ether reacts with thiocarbonate type RAFT reagent with carboxyl, hydroxyl in the thiocarbonate type RAFT reagent and epoxy in the polyethylene glycol glycidyl ether carry out ring opening reaction, so that the thiocarbonate type RAFT reagent is connected with the polyethylene glycol glycidyl ether, and the water-soluble RAFT reagent is synthesized. The polyethylene glycol glycidyl ether has good water solubility, the water-soluble RAFT reagent with target molecular weight of various structures can be conveniently prepared by adjusting the molecular weight and molecular structure of the polyethylene glycol glycidyl ether and the types and proportion of the thiocarbonate type RAFT reagent, on one hand, the water solubility of the obtained water-soluble RAFT reagent is good, the molecular weight and molecular structure can be regulated and controlled, and the method is suitable for free radical controllable polymerization and emulsion polymerization in aqueous solution, and on the other hand, hydroxyl in the thiocarbonate type RAFT reagent and epoxy in the polyethylene glycol glycidyl ether are subjected to ring-opening reaction, so that the reaction efficiency is high, and the product purity is high (> 90%).
In some embodiments, the thiocarbonate type RAFT agent comprises one or more of 3-benzylsulfanyl thiocarbonylsulfonyl propionic acid, 4-cyanovalerate dithiobenzoate, 2- (1-carboxy-1-methylethylsulfanylthiocarbonyl sulfanyl) -2-methylpropionic acid, 4-cyano-4- (ethylsulfanyl thiocarbonyl) sulfanyl pentanoic acid, bis (carboxylate) trithiocarbonate, and 2- (dodecyltrithiocarbonate) -2-methylpropionic acid.
According to the embodiment of the present application, the thiocarbonate type RAFT agent may be a dithiocarbonate type RAFT agent, or may be a trithiocarbonate type RAFT agent, and the thiocarbonate type RAFT agent may include one carboxyl group or may include two carboxyl groups.
In some embodiments, the polyethylene glycol glycidyl ether comprises one or more of polyethylene glycol diglycidyl ether, methoxypolyethylene glycol glycidyl ether, and polyethylene glycol glycidyl dodecyl ether, multi-arm polyethylene glycol glycidyl ether.
Compared with the straight-chain polyethylene glycol glycidyl ether, the multi-arm polyethylene glycol glycidyl ether has divergent structure and multi-branched structure, and a plurality of epoxy groups are arranged in one molecule of the multi-arm polyethylene glycol, so that the combination with the thiocarbonate type RAFT reagent and the hydrophilicity are improved. The multi-arm polyethylene glycol glycidyl ether has three arms, four arms, six arms, eight arms and the like.
According to the embodiment of the application, the water-soluble RAFT reagent with various structures and target molecular weights can be conveniently prepared by adjusting the molecular weight and molecular structure of the polyethylene glycol glycidyl ether.
Illustratively, when the thiocarbonate type RAFT agent is 2- (dodecyl trithiocarbonate group) -2-methylpropanoic acid, and the glycidyl ether is polyethylene glycol diglycidyl ether, the structure shown in the water-soluble RAFT agent 1 can be obtained, and the synthetic route of the reaction is as follows:
n in the water-soluble RAFT agent 1 is an integer of 25 to 500.
Illustratively, when the thiocarbonate type RAFT agent is 3-benzylsulfanyl thiocarbonylsulfonyl propionic acid and the polyethylene glycol glycidyl ether is methoxypolyethylene glycol glycidyl ether, the structure shown in water-soluble RAFT agent 2 can be obtained by the following synthetic route:
m in the water-soluble RAFT reagent 2 is an integer of 5 to 500.
Illustratively, when the thiocarbonate type RAFT agent is 4-cyano-4- (ethylsulfanylthiocarbonyl) sulfanyl pentanoic acid and the polyethylene glycol glycidyl ether is polyethylene glycol glycidyl dodecyl ether, the structure shown in the water-soluble RAFT agent 3 can be obtained, and the synthetic route of the reaction is as follows:
in the water-soluble RAFT reagent 3, t is an integer of 20 to 500.
In some embodiments, the number average molecular weight of the polyethylene glycol glycidyl ether is from 200 to 20000. For example, the number average molecular weight of the polyethylene glycol glycidyl ether may be 1000, 2000, 5000 or 15000, or any combination thereof.
According to the embodiment of the application, the number average molecular weight of the polyethylene glycol glycidyl ether is in the range, so that the obtained water-soluble RAFT reagent has proper molecular weight and water solubility, and is suitable for free radical controllable polymerization and emulsion polymerization in aqueous solution.
Preparation method of water-soluble RAFT reagent
In a second aspect, embodiments of the present application provide a method for preparing a water-soluble RAFT agent, including the steps of:
dissolving thiocarbonate type RAFT reagent containing carboxyl, polyethylene glycol glycidyl ether and a catalyst in a solvent, and reacting at the catalytic temperature of the catalyst to obtain a mixed product;
and precipitating the mixed product, and washing to obtain the water-soluble RAFT reagent.
In some embodiments, the catalytic temperature is 60-120 ℃ and the reaction time is 3-8 hours.
In some embodiments, after the reaction is finished, the mixed product is precipitated in a mixed solvent of petroleum ether and acetone (volume ratio is 5:1) after rotary evaporation concentration, and the solid is subjected to suction filtration, washing and drying to obtain the target product.
According to embodiments of the present application, the method of preparation may be monitored according to any suitable method known in the art. For example, the product formation may be carried out by spectroscopic means such as nuclear magnetic resonance spectroscopy (NMR, for example 1 H-NMR or 13 C-NMR), infrared spectroscopy (IR), spectrophotometry (e.g., UV-Vis), mass Spectrometry (MS), or by chromatography such as High Performance Liquid Chromatography (HPLC), gas Chromatography (GC), gel Permeation Chromatography (GPC), or Thin Layer Chromatography (TLC).
The reaction condition of the preparation method is relatively mild, and the preparation process is simple and efficient.
In some embodiments, the thiocarbonate type RAFT agent comprises one or more of 3-benzylsulfanyl thiocarbonylsulfonyl propionic acid, 4-cyanovalerate dithiobenzoate, 2- (1-carboxy-1-methylethylsulfanylthiocarbonyl sulfanyl) -2-methylpropionic acid, 4-cyano-4- (ethylsulfanyl thiocarbonyl) sulfanyl pentanoic acid, bis (carboxylate) trithiocarbonate, and 2- (dodecyltrithiocarbonate) -2-methylpropionic acid.
According to the embodiment of the present application, the thiocarbonate type RAFT agent may be a dithiocarbonate type RAFT agent, or may be a trithiocarbonate type RAFT agent, and the thiocarbonate type RAFT agent may include one carboxyl group or may include two carboxyl groups.
In some embodiments, the polyethylene glycol glycidyl ether comprises one or more of polyethylene glycol diglycidyl ether, methoxypolyethylene glycol glycidyl ether, polyethylene glycol glycidyl dodecyl ether, and multi-arm polyethylene glycol glycidyl ether.
According to the embodiment of the application, the water-soluble RAFT reagent with various structures and target molecular weights can be conveniently prepared by adjusting the molecular weight and molecular structure of the polyethylene glycol glycidyl ether.
According to the embodiment of the application, the polyethylene glycol glycidyl ether has good water solubility, the water-soluble RAFT reagents with various structures and target molecular weights can be conveniently prepared by adjusting the molecular weight and molecular structure of the polyethylene glycol glycidyl ether and the types and the proportions of the thiocarbonate type RAFT reagents, the hydroxyl in the thiocarbonate type RAFT reagents and the epoxy groups in the polyethylene glycol glycidyl ether are subjected to ring-opening reaction, the reaction efficiency is high, and the purity of the product is high.
In some embodiments, the catalyst comprises one or more of triphenylphosphine, N-dimethylaniline, tetrabutylammonium bromide, tetrapropylammonium bromide, tetraethylammonium bromide, benzyltriethylammonium bromide, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, methyltriphenylphosphine bromide, ethyltriphenylphosphine bromide, propyltriphenylphosphine bromide, butyltriphenylphosphine bromide, benzyltriethylammonium chloride, tetramethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, benzyltrimethylammonium chloride, and methyltrioctylammonium chloride.
In some embodiments, the solvent is one or more of dioxane, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, propylene carbonate, propylene glycol methyl ether acetate.
In some embodiments, the molar ratio of carboxyl group-containing thiocarbonate-type RAFT agent, polyethylene glycol-type glycidyl ether is 1:0.25 to 1:4. for example, the molar ratio of the thiocarbonate-type RAFT agent containing a carboxyl group to the polyethylene glycol-type glycidyl ether may be 1:0.5, 1: 1. 1:2 or 1:3, may be any combination of the above values.
According to the embodiment of the application, the molar ratio (or mass ratio) of the thiocarbonate type RAFT reagent containing carboxyl to the glycidyl ether is in the range, so that the ring-opening reaction of the carboxyl and the epoxy group is more facilitated, and the water solubility is improved.
In some embodiments, the catalyst is used in an amount of 0.2 to 4%.
Polycarboxylate water reducer
In a third aspect, embodiments of the present application provide a polycarboxylate water reducer formed by reacting a water-soluble RAFT agent as described above, an acrylic monomer under initiation conditions of a water-soluble initiator.
According to the embodiment of the application, the polycarboxylate water reducer with controllable molecular structure can be prepared by adopting the water-soluble RAFT reagent and the conventional water-soluble acrylic monomer under the action of a water-soluble initiator. Therefore, the high-efficiency synthesis and structure regulation of the molecules of the polycarboxylate superplasticizer are realized, and the defects of wide molecular weight distribution, insufficient polyether macromonomer activity and high macromonomer residual rate existing in the synthesis of the conventional polycarboxylate superplasticizer are avoided.
In some embodiments, the water-soluble initiator comprises one or more of azobisisobutylamidine hydrochloride, azobisiso Ding Mi hydrochloride, azobiscyano valeric acid, azobisisopropylimidazoline, and the like.
In some embodiments, the acrylic monomer comprises one or more of acrylic acid, methacrylic acid, sodium methacrylate sulfonate, and N-methylpyrrolidone.
In some embodiments, the molar ratio of water-soluble RAFT agent, acrylic monomer, and water-soluble initiator is 1: (3-30): (0.1-0.5).
Preparation method of polycarboxylate superplasticizer
In a fourth aspect, an embodiment of the present application provides a method for preparing a polycarboxylate superplasticizer, which is characterized in that a water-soluble RAFT agent, a monomer and a water-soluble initiator as described above are dissolved in water, and react at an initiation temperature of the water-soluble initiator to obtain an aqueous solution of the polycarboxylate superplasticizer.
In some embodiments, the initiation temperature is 40 ℃ to 80 ℃.
In some embodiments, the reaction time is from 3 hours to 6 hours.
According to the embodiment of the application, the polycarboxylic acid water reducer with controllable molecular structure can be prepared by adopting the preparation method of the polycarboxylic acid water reducer. Therefore, the high-efficiency synthesis and structure regulation of the molecules of the polycarboxylate superplasticizer are realized, and the defects of wide molecular weight distribution, insufficient polyether macromonomer activity and high macromonomer residual rate existing in the synthesis of the conventional polycarboxylate superplasticizer are avoided. For example, under the condition of the same monomer proportion, the conventional free radical polymerization method has wider molecular weight distribution, larger proportion of low molecular weight molecules, reduced adsorption capacity of cement particles to the water reducer, reduced fluidity of slurry and poorer correlation between the adsorption capacity and the fluidity.
Examples
The following examples more particularly describe the disclosure of the present application, which are intended as illustrative only, since numerous modifications and variations within the scope of the disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the examples below are by weight, and all reagents used in the examples are commercially available or were obtained synthetically according to conventional methods and can be used directly without further treatment, as well as the instruments used in the examples.
The sources of raw materials used in the following examples may be as follows:
polyethylene glycol diglycidyl ether: mn 2000Da, cat No. P863877, shanghai Meilin Biochemical technologies Co., ltd
Methoxy polyethylene glycol glycidyl ether: mn 2000Da, cat No. P850209, shanghai Meilin Biochemical technologies Co., ltd
Polyethylene glycol glycidyl dodecyl ether: mn 2000Da, cat No. P865875, shanghai Meilin Biochemical technologies Co., ltd
Example 1
The water-soluble RAFT reagent 1 is prepared by the following method:
75.6g of 2- (dodecyl trithiocarbonate group) -2-methylpropanoic acid, 200g of polyethylene glycol diglycidyl ether (Mn=2000 Da) and 3g of triphenylphosphine are dissolved in 500mL of dioxane and reacted for 4 hours at 80 ℃ to obtain a mixed product; the mixed product is concentrated to about 50mL by rotary evaporation, then is precipitated in a mixed solvent of petroleum ether and acetone (volume ratio is 5:1), and is subjected to suction filtration, washing and drying to obtain the water-soluble RAFT reagent 1.
The polycarboxylate water reducer 1 is prepared by the following steps:
27.6g of water-soluble RAFT reagent 1, 5.7g of acrylic acid and 2g of azo diisobutyl amidine hydrochloride are dissolved in 50mL of deionized water and reacted for 4 hours at 50 ℃ under the nitrogen atmosphere, so as to obtain the polycarboxylate water reducer 1.
Example 2
The water-soluble RAFT reagent 2 is prepared by the following method:
27.9g of 3-benzyl sulfanyl thiocarbonyl sulfonyl propionic acid, 200g of methoxypolyethylene glycol glycidyl ether (Mn=2000 Da) and 1.5g of triphenylphosphine are dissolved in 500mL of dimethyl sulfoxide and reacted for 5 hours at 100 ℃ to obtain a mixed product; and (3) rotationally evaporating and concentrating the mixed product, precipitating the mixed product in a mixed solvent of petroleum ether and acetone (volume ratio is 1:1), and carrying out suction filtration, washing and drying to obtain the water-soluble RAFT reagent 2.
The polycarboxylate water reducer 2 is prepared by the following steps:
22.8g of water-soluble RAFT reagent 2, 2.88g of methacrylic acid and 1.2g of azo diisobutyl amidine hydrochloride are dissolved in 50mL of deionized water and reacted for 4 hours at 50 ℃ under the nitrogen atmosphere, so as to obtain the polycarboxylate water reducer 2.
Example 3
The water-soluble RAFT reagent 3 is prepared by the following method:
26.3g of 4-cyano-4- (ethylsulfanylthiocarbonyl) sulfanyl pentanoic acid, 300g of polyethylene glycol glycidyl dodecyl ether (Mn=2000 Da) and 1.5g of triphenylphosphine are dissolved in dimethylformamide and reacted for 4 hours at 120 ℃ to obtain a mixed product; and (3) rotationally evaporating and concentrating the mixed product, precipitating the mixed product in a mixed solvent of petroleum ether and acetone (volume ratio is 5:1), and carrying out suction filtration, washing and drying to obtain the water-soluble RAFT reagent 3.
The polycarboxylate water reducer 3 is prepared by the following steps:
32.6g of water-soluble RAFT reagent 3, 2.2g of sodium methacrylate and 0.8g of azodicarbonyl valeric acid are dissolved in 50mL of deionized water, and reacted for 5 hours at 60 ℃ under the nitrogen atmosphere, so as to obtain the polycarboxylate water reducer 3.
Comparative example 1
The water-soluble RAFT reagent is prepared according to the following method:
75.6g of 2- (dodecyl trithiocarbonate group) -2-methylpropanoic acid, 200g of polyethylene glycol (Mn=2000 Da) and 1.8g of methylsulfonic acid are dissolved in 300mL of toluene, and the mixture is condensed and refluxed at 110 ℃ for 8 hours, and water generated in the system is discharged through a water separator in time. After the reaction is finished, the mixed product is subjected to rotary evaporation concentration and then is precipitated in a mixed solvent of petroleum ether and acetone (volume ratio is 5:1), and the water-soluble RAFT reagent comparative 1 is obtained after suction filtration, washing and drying.
Comparative example 2
The difference between the preparation method of the water-soluble RAFT agent and the preparation method of the water-soluble RAFT agent in the example 1 is that: the polyethylene glycol diglycidyl ether was replaced with an equimolar amount of ethylene glycol diglycidyl ether.
Performance testing
The method for testing the fluidity of the clean slurry and the water-reducing rate of the cement mortar is referred to GB/T8077-2012 method for testing the homogeneity of concrete admixture
The method for testing the fluidity of the net slurry comprises the following steps:
the glass plate was placed in a horizontal position and the glass plate, truncated cone circular mold, stirrer and stirrer pan were rubbed with a wet cloth so that the surface was wet without water. The truncated cone circular mould was placed in the centre of the glass plate and covered with wet cloth for use.
Weighing 300g of cement, pouring into a stirring pot. The recommended dosage of the admixture and 87g or 105g of water were added and immediately stirred (slow 120s, stop 15s, fast 120 s).
The mixed clean slurry is rapidly injected into a truncated cone circular mould, the truncated cone circular mould is scraped by a scraper, the truncated cone circular mould is lifted up in the vertical direction, a stopwatch is started for timing, any clean cement slurry flows on a glass plate until the maximum diameter of the flowing part in the two directions perpendicular to each other is measured by a ruler, and the average value is taken as the fluidity of the clean cement slurry.
The cement mortar water reduction rate testing method comprises the following steps:
firstly, the stirrer is in a waiting working state, and then the operation is carried out according to the following procedures: adding water into the pot, adding 450g of cement, placing the pot on a fixed frame, lifting to a fixed position, immediately starting the machine, stirring at a low speed for 30s, uniformly adding sand at the same time of starting at a second 30s, and turning the machine to a high speed for 30s again. Stopping stirring for 90s, scraping the blade and the mortar sand on the wall of the pot into the pot by a spatula in the first 15s, and continuing stirring for 60s at high speed, wherein the stirring time error of each stage is within +/-1 s. When the glue sand is mixed, the glass table surface of the diving table, the inner walls of the tamping rod, the truncated cone circular die and the die sleeve are wiped by wet cloth, and the tamping rod, the truncated cone circular die and the die sleeve are placed in the center of the glass table surface and covered with the wet cloth for standby.
The mixed rubber sand is quickly put into the mould twice, firstly put into two thirds of the truncated cone circular mould, respectively drawn 5 times in two directions perpendicular to each other by a spatula, uniformly rammed 15 times from the edge to the center by a rammer, then put into the second layer of rubber sand, put to be about 20mm higher than the truncated cone circular mould, drawn 10 times by the spatula, and also rammed 10 times by the rammer, and the truncated cone circular mould is pressed by hand without moving when the rubber sand is put into the mould and rammed.
After the stamping, the die sleeve is taken down, the mortar higher than the truncated cone circular die is scraped off by a spatula and smoothed, then the truncated cone circular die is lifted vertically upwards and placed on a table, and the jump table is started immediately, so that the jump table continuously jumps 25 times at a frequency of once per second.
And measuring the flowing diameter of the bottom of the rubber sand by using a caliper after the jump is finished, and taking the average value of the two diameters which are mutually perpendicular as the flowing degree of the rubber sand when the water consumption is expressed in mm.
The above steps are repeated until the fluidity reaches (180.+ -.5) mm. And when the mobility of the gum sand is (180+/-5) mm, the water consumption is the water consumption M0 of the reference mobility of the gum sand.
Adding water and the additive into a pot, uniformly stirring, and measuring the water consumption M1 when the fluidity of the glue sand reaches (180+/-5) mm after the additive is added according to the steps. Water reduction rate of sand ((%) = (M0-M1)/m0×100)
Test results
The test results are shown in Table 1.
TABLE 1 results of Performance test for examples 1-3 and comparative examples 1-2
As can be seen from the table, in the embodiment 1-3 of the application, the water-soluble RAFT reagent obtained by the reaction of the thiocarbonate RAFT reagent and the polyethylene glycol glycidyl ether has higher conversion rate and higher product purity compared with the water-soluble RAFT reagent obtained by the esterification reaction in the comparative example 1; meanwhile, the molecular weight of the water-soluble RAFT reagent prepared by the method is in a proper range, and the water-reducing agent obtained when the water-soluble RAFT reagent is used for preparing the water-reducing agent has narrower molecular weight distribution, better properties such as the fluidity of clean slurry and the water-reducing rate.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention, which is defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A water-soluble RAFT reagent is characterized in that the water-soluble RAFT reagent is formed by reacting a thiocarbonate type RAFT reagent with polyethylene glycol glycidyl ether, the thiocarbonate type RAFT reagent contains carboxyl groups, and the water-soluble RAFT reagent comprises a chain segment structure shown in a formula 1
2. The water-soluble RAFT agent of claim 1, wherein the thiocarbonate type RAFT agent comprises one or more of 3-benzylsulfanyl thiocarbonylsulfonyl propionic acid, 4-cyanovalerate dithiobenzoate, 2- (1-carboxy-1-methylethylsulfanylthiocarbonyl sulfanyl) -2-methylpropionic acid, 4-cyano-4- (ethylsulfanyl thiocarbonyl) sulfanyl pentanoic acid, bis (carboxylate) trithiocarbonate, and 2- (dodecyl trithiocarbonate) -2-methylpropionic acid; and/or the number of the groups of groups,
the polyethylene glycol glycidyl ether comprises one or more of polyethylene glycol diglycidyl ether, methoxy polyethylene glycol glycidyl ether, polyethylene glycol glycidyl dodecyl ether and multi-arm polyethylene glycol glycidyl ether.
3. The water-soluble RAFT agent according to claim 1 or 2, wherein the polyethylene glycol glycidyl ether has a number average molecular weight of 200Da to 20000Da.
4. The preparation method of the water-soluble RAFT reagent is characterized by comprising the following steps of:
dissolving thiocarbonate type RAFT reagent containing carboxyl, polyethylene glycol glycidyl ether and a catalyst in a solvent, and reacting at the catalytic temperature of the catalyst to obtain a mixed product;
and precipitating the mixed product, and washing to obtain the water-soluble RAFT reagent.
5. The method for preparing a water-soluble RAFT agent according to claim 4, wherein the thiocarbonate type RAFT agent comprises one or more of 3-benzylsulfanyl thiocarbonylsulfonyl propionic acid, 4-cyanovalerate dithiobenzoate, 2- (1-carboxy-1-methylethylsulfanylthiocarbonyl sulfanyl) -2-methylpropionic acid, 4-cyano-4- (ethylsulfanyl thiocarbonyl) sulfanyl pentanoic acid, bis (carboxylate) trithiocarbonate, and 2- (dodecyltrithiocarbonate) -2-methylpropionic acid; and/or the number of the groups of groups,
the polyethylene glycol glycidyl ether comprises one or more of polyethylene glycol diglycidyl ether, methoxy polyethylene glycol glycidyl ether, polyethylene glycol glycidyl dodecyl ether and multi-arm polyethylene glycol glycidyl ether; and/or the number of the groups of groups,
the catalyst comprises one or more of triphenylphosphine, N-dimethylaniline, tetrabutylammonium bromide, tetrapropylammonium bromide, tetraethylammonium bromide, benzyl triethylammonium bromide, dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, methyl triphenylphosphine bromide, ethyl triphenylphosphine bromide, propyl triphenylphosphine bromide, butyl triphenylphosphine bromide, benzyl triethyl ammonium chloride, tetramethyl ammonium chloride, dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, benzyl trimethyl ammonium chloride and methyl trioctyl ammonium chloride; and/or the number of the groups of groups,
the solvent is one or more of dioxane, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, propylene carbonate and propylene glycol methyl ether acetate.
6. The method for producing a water-soluble RAFT agent according to claim 4 or 5, wherein the molar ratio of the carboxyl group-containing thiocarbonate type RAFT agent to the polyethylene glycol glycidyl ether is 1:0.25 to 1:4.
7. a polycarboxylate water reducer, characterized in that the polycarboxylate water reducer is formed by reacting the water-soluble RAFT agent as claimed in any one of claims 1 to 3 and an acrylic monomer under the initiation condition of a water-soluble initiator.
8. The polycarboxylate water reducer according to claim 7, wherein the water-soluble initiator comprises one or more of azobisisobutylamidine hydrochloride, azobisiso Ding Mi hydrochloride, azobiscyano valeric acid, azobisisopropylimidazoline and the like; and/or the number of the groups of groups,
the acrylic monomer comprises one or more of acrylic acid, methacrylic acid, sodium methacrylate sulfonate and N-methyl pyrrolidone.
9. The polycarboxylate superplasticizer as recited in claim 8, wherein the mass ratio of the water-soluble RAFT agent, the acrylic monomer and the water-soluble initiator is 1: (3-30): (0.1-0.5).
10. A method for preparing a polycarboxylate water reducer, which is characterized in that the water-soluble RAFT agent, the monomer and the water-soluble initiator according to any one of claims 1-3 are dissolved in water and react at the initiation temperature of the water-soluble initiator to obtain an aqueous solution of the polycarboxylate water reducer.
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