CN115819748A - Ester-terminated polyether monomer and preparation method and application thereof - Google Patents
Ester-terminated polyether monomer and preparation method and application thereof Download PDFInfo
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 52
- 229920000570 polyether Polymers 0.000 title claims abstract description 52
- 239000000178 monomer Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 27
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 11
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 18
- -1 enol ester Chemical group 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 12
- 125000002947 alkylene group Chemical group 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 150000002910 rare earth metals Chemical class 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- 229920005646 polycarboxylate Polymers 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 3
- 239000008030 superplasticizer Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims 5
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- 230000000740 bleeding effect Effects 0.000 abstract description 6
- 238000012661 block copolymerization Methods 0.000 abstract description 2
- 125000003700 epoxy group Chemical group 0.000 abstract description 2
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 238000005204 segregation Methods 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229960005070 ascorbic acid Drugs 0.000 description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 235000010323 ascorbic acid Nutrition 0.000 description 4
- 239000011668 ascorbic acid Substances 0.000 description 4
- 125000004185 ester group Chemical group 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 101150065749 Churc1 gene Proteins 0.000 description 2
- 102100038239 Protein Churchill Human genes 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000007655 standard test method Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- AEUVIXACNOXTBX-UHFFFAOYSA-N 1-sulfanylpropan-1-ol Chemical compound CCC(O)S AEUVIXACNOXTBX-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- WVYSWPBECUHBMJ-UHFFFAOYSA-N 2-methylprop-1-en-1-ol Chemical compound CC(C)=CO WVYSWPBECUHBMJ-UHFFFAOYSA-N 0.000 description 1
- PMNLUUOXGOOLSP-UHFFFAOYSA-M 2-sulfanylpropanoate Chemical compound CC(S)C([O-])=O PMNLUUOXGOOLSP-UHFFFAOYSA-M 0.000 description 1
- UFQDKRWQSFLPQY-UHFFFAOYSA-N 4,5-dihydro-1h-imidazol-3-ium;chloride Chemical compound Cl.C1CN=CN1 UFQDKRWQSFLPQY-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-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
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Landscapes
- Polyethers (AREA)
Abstract
The invention relates to an ester-terminated polyether monomer and a preparation method and application thereof. The molecular structure of the ester-group-capped polyether monomer prepared by the invention is obtained by block copolymerization of Ethylene Oxide (EO) and Propylene Oxide (PO), wherein EO is a hydrophilic group, PO is a lipophilic group, the hydrophilicity and lipophilicity are adjustable, the molecular weight is controllable, and compared with the polyether monomer of the traditional water-reducing polycarboxylic acid water reducing agent, the ester-group-capped polyether monomer is gradually hydrolyzed in concrete, so that the prepared water reducing agent has higher slump retaining performance. According to the invention, the epoxy group is introduced into the macromonomer molecule to form the hydrophobic unit in the water reducing agent molecule, so that the problems of poor concrete workability and the like caused by easy bleeding and segregation of the water reducing agent synthesized by the traditional straight-chain monomer are solved, the workability of the synthesized polycarboxylic acid water reducing agent is greatly improved, and the slump retaining performance is further improved.
Description
Technical Field
The invention relates to the technical field of concrete admixtures, in particular to an ester-terminated polyether monomer and a preparation method and application thereof.
Background
With the higher and higher technical requirements of modern concrete, high-speed rail and other heavy-duty engineering on gravels, the quantity of natural gravels capable of meeting the requirements is less and less, in order to meet the rigidity requirement of the gravels market, machine-made sand becomes the first choice of the construction market, and the machine-made sand gradually replaces natural gravels to meet the requirement of market situation development.
However, the quality of the machine-made sand is difficult to guarantee, the mud content and the stone powder content in the machine-made sand are relatively high, the additional adsorption capacity is large, and great influence is caused on the workability and the retention performance of concrete.
Disclosure of Invention
Based on the above, the ester-terminated polyether monomer with improved workability and slump retention property, and the preparation method and application thereof are needed.
In order to achieve the above purpose, the present invention provides a technical solution:
an ester-terminated polyether monomer having the formula:
wherein R is 1 ＝(CH 2 ) n N is an integer of 2 to 8;
R 2 is C 1 -C 12 A straight or branched saturated alkyl group of (a);
b is an integer of 0 to 100;
b is an integer of 0 to 100.
The invention also provides a preparation method of the ester-terminated polyether monomer, and the preparation raw materials of the ester-terminated polyether monomer comprise terminal enol ester, a catalyst and alkylene oxide.
Preferably, the terminal enol ester has the following structural formula:
wherein R is 1 ＝(CH 2 ) n And n is an integer of 2 to 8.
R 2 Is C 1 -C 12 A straight-chain or branched saturated alkyl group.
Preferably, the catalyst comprises a mixture of catalyst a and catalyst B;
wherein the catalyst A comprises KOH, naOH and CH 3 At least one of ONa;
the catalyst B comprises a rare earth metal catalyst.
Preferably, the alkylene oxide includes at least one of ethylene oxide and propylene oxide.
Preferably, the step of preparing the ester-terminated polyether monomer comprises:
under the catalysis of a catalyst, the terminal enol ester and the alkylene oxide are subjected to ring-opening polymerization reaction at the temperature of 100-120 ℃ and the pressure of 0.2-0.5 MPa, and the ester-terminated polyether monomer is obtained after the reaction is finished.
The invention also provides an application of the ester-based terminated polyether monomer in preparing a raw material in a polycarboxylic acid water reducing agent.
Preferably, the preparation raw materials of the polycarboxylate superplasticizer comprise, by weight:
preferably, the preparation step of the polycarboxylic acid water reducing agent comprises the following steps:
stirring and dissolving the ester-terminated polyether monomer, the oxidant and the water to obtain a macromonomer solution;
uniformly stirring and mixing the functional monomer, the unsaturated acid and water to obtain solution A;
uniformly stirring and mixing the molecular weight regulator, the reducing agent and water to obtain a solution B;
and (3) under the condition of stirring at normal temperature, simultaneously dropwise adding the solution A and the solution B into the macromonomer solution, and after dropwise adding, adding alkali to adjust the pH of the solution to 5-7 to obtain the polycarboxylic acid water reducer.
Preferably, the unsaturated acid includes at least one of acrylic acid, methacrylic acid, and itaconic acid.
The invention has the beneficial effects that:
the molecular structure of the ester-group-capped polyether monomer prepared by the invention is obtained by block copolymerization of Ethylene Oxide (EO) and Propylene Oxide (PO), wherein EO is a hydrophilic group, PO is a lipophilic group, the hydrophilicity and lipophilicity are adjustable, the molecular weight is controllable, and compared with the polyether monomer of the traditional water-reducing polycarboxylic acid water reducing agent, the ester-group-capped polyether monomer is gradually hydrolyzed in concrete, so that the prepared water reducing agent has higher slump retaining performance.
According to the invention, the epoxy group is introduced into the macromonomer molecule to form the hydrophobic unit in the water reducer molecule, so that the problems of poor concrete workability and the like caused by easy bleeding and segregation of the water reducer synthesized by the traditional straight-chain monomer are solved, the workability of the synthesized polycarboxylic acid water reducer is greatly improved, and the slump retaining performance is further improved.
Detailed Description
The present invention will be further described with reference to specific examples for better illustrating the objects, technical solutions and advantages of the present invention.
In the examples, the test methods used were conventional methods unless otherwise specified, and the materials, reagents and the like used were commercially available without otherwise specified.
An ester-terminated polyether monomer, the structural formula of the ester-terminated polyether monomer is as follows:
wherein R is 1 ＝(CH 2 ) n N is an integer of 2 to 8;
R 2 is C 1 -C 12 A straight or branched saturated alkyl group of (a);
a is an integer of 0 to 100;
b is an integer of 0 to 100.
The invention also provides a preparation method of the ester-terminated polyether monomer, and the preparation raw materials of the ester-terminated polyether monomer comprise the terminal enol ester, the catalyst and the alkylene oxide.
The dosage of the terminal enol ester is 0.1-15% of the total mass of the raw materials for preparing the ester group terminated unsaturated polyether monomer;
in one embodiment, the terminal enol ester has the following structural formula:
wherein R is 1 ＝(CH 2 ) n ；
R 2 Is C 1 -C 12 A straight-chain or branched saturated alkyl group.
In one embodiment, the catalyst comprises a mixture of catalyst a and catalyst B;
wherein catalyst A comprises KOH, naOH and CH 3 At least one of ONa;
catalyst B comprises a rare earth metal catalyst, specifically a metal lanthanum catalyst.
The dosage of the catalyst is 0.01 to 0.2 percent of the total mass of the raw materials for preparing the ester group terminated unsaturated polyether monomer; wherein the dosage of the catalyst B is 0.002-0.01 percent of the total mass of the raw materials for preparing the ester group terminated unsaturated polyether monomer, and the catalyst B rare earth metal catalyst is added to improve the catalytic effect.
In one embodiment, the alkylene oxide comprises at least one of ethylene oxide and propylene oxide. The dosage of the alkylene oxide is 85-99% of the total mass of the raw materials for preparing the ester group terminated unsaturated polyether monomer.
Specifically, the preparation steps of the ester-terminated polyether monomer comprise:
under the catalysis of a catalyst, the terminal enol ester and the alkylene oxide are subjected to ring-opening polymerization reaction at the temperature of 100-120 ℃ and the pressure of 0.2-0.5 MPa, and the ester-group-terminated polyether monomer is obtained after the reaction is finished.
The invention also provides application of the ester-based terminated polyether monomer in preparing a raw material in a polycarboxylic acid water reducing agent.
In one embodiment, the polycarboxylic acid water reducing agent is prepared from the following raw materials in parts by weight:
in one embodiment, the preparation of the polycarboxylic acid water reducer comprises the following steps:
s100, stirring and dissolving the ester-terminated polyether monomer, the oxidant and water to obtain a macromonomer solution.
S200, stirring and uniformly mixing the functional monomer, the unsaturated acid and water to obtain solution A.
S300, uniformly stirring the molecular weight regulator, the reducing agent and water to obtain a solution B.
S400, under the condition of stirring at normal temperature, simultaneously dropwise adding the solution A and the solution B into the macromonomer solution, and after dropwise adding, adding alkali to adjust the pH of the solution to 5-7, thus obtaining the polycarboxylic acid water reducer.
R 1 ＝(CH 2 ) n N is an integer of 2 to 8;
R 2 is C 1 -C 12 A straight or branched saturated alkyl group of (a);
a is an integer of 0 to 100;
b is an integer of 0 to 100.
Specifically, the unsaturated acid includes at least one of acrylic acid, methacrylic acid, and itaconic acid;
the structural formula of the functional monomer is as follows:
wherein R is H or CH 3 X is CH 2 Or CH 2 CH 2 。
The reducing agent is at least one of L-ascorbic acid, azodiisopropyl imidazoline hydrochloride, azodicyclohexyl formonitrile, sodium bisulfite, sodium metabisulfite, sodium formaldehyde sulfoxylate, ferrous sulfate heptahydrate and ferrous ammonium sulfate;
the oxidant comprises at least one of hydrogen peroxide, ammonium persulfate, potassium persulfate and sodium persulfate;
the molecular weight regulator comprises at least one of mercaptopropionic acid, mercaptoethanol, sodium hypophosphite, mercaptopropanol, mercaptopropionate, and p-phenol.
Example 1
Preparation of ester-terminated polyether macromonomer
Adding 36.1g of terminal enol ester, 1.1g of KOH and 0.03g of rare earth metal lanthanum catalyst into a reaction kettle, controlling the pre-reaction temperature to be 30-40 ℃, and pre-reacting for 0.8 hour; after the pre-reaction is finished, heating and raising the temperature, keeping the temperature at 90 ℃, vacuumizing, replacing with nitrogen, raising the temperature to 100 ℃, introducing 442g of ethylene oxide, controlling the reaction temperature at 105 ℃ and the pressure at 0.35MPa, reacting until the pressure is not reduced, continuously introducing 277g of propylene oxide, controlling the reaction temperature at 105 ℃ and the pressure at 0.35MPa, and reacting until the pressure is not reduced. After the reaction is finished, the temperature is reduced to 60 ℃, and the final product (the ester-terminated polyether monomer) is obtained after discharging.
Wherein the structural formula of the terminal enol ester is as follows: CH (CH) 2 ＝CH-OCH 2 CH 2 -OOC-CH 2 CH 3
The molecular weight of the prepared ester-terminated polyether macromonomer is 3000, and the structural formula is as follows:
CH 2 ＝CH-O-CH 2 CH 2 -O-(CH 2 CH 2 O) a -(CHCH 3 CH 2 O) b -OC-CH 2 CH 3 。
preparation of polycarboxylic acid water reducing agent
S100, adding 200 parts by weight of the prepared ester-group-terminated polyether macromonomer, 1.5 parts by weight of hydrogen peroxide as an oxidant, 5 parts by weight of ethylene glycol monoethyl polyoxyethylene ether and 180 parts by weight of deionized water into a reactor, and stirring and dissolving to obtain a macromonomer solution;
s200, stirring and uniformly mixing 17 parts by weight of acrylic acid and 20 parts by weight of deionized water to obtain solution A;
s300, stirring and uniformly mixing 1.0 part by weight of mercaptopropionic acid serving as a molecular weight regulator, 0.5 part by weight of ascorbic acid serving as a reducing agent and 20 parts by weight of deionized water to obtain solution B;
s400, under the condition of stirring at normal temperature, simultaneously dropwise adding the solution A and the solution B into the macromonomer solution, and after dropwise adding, adding alkali to neutralize the pH value of the solution to 7, thus obtaining the polycarboxylic acid water reducer.
Example 2
Preparation of ester terminated polyether macromonomer
Adding 56.3g of terminal enol ester, 1.3g of NaOH and 0.03g of rare earth metal lanthanum catalyst into a reaction kettle, controlling the pre-reaction temperature to be 30-40 ℃, and pre-reacting for 0.8 hour; after the pre-reaction is finished, heating and raising the temperature, keeping the temperature at 90 ℃, vacuumizing, replacing with nitrogen, raising the temperature to 100 ℃, introducing 576g of ethylene oxide, controlling the reaction temperature at 105 ℃ and the pressure at 0.35MPa, reacting until the pressure is not reduced, continuously introducing 152g of propylene oxide, controlling the reaction temperature at 105 ℃ and the pressure at 0.35MPa, and reacting until the pressure is not reduced. After the reaction is finished, the temperature is reduced to 60 ℃, and the final product (the ester-terminated polyether macromonomer) is obtained after discharging.
Wherein the structural formula of the terminal enol ester is as follows: CH (CH) 2 ＝CH-OCH 2 CH 2 CH 2 CH 2 -OOC-CH 2 CH 3 。
The molecular weight of the prepared ester-terminated polyether macromonomer is 2400, and the structural formula is as follows:
CH 2 ＝CH-O-CH 2 CH 2 CH 2 CH 2 -O-(CH 2 CH 2 O) a -(CHCH 3 CH 2 O) b -OC-CH 2 CH 3 。
preparation of polycarboxylic acid water reducing agent
S100, adding 200 parts by weight of the prepared ester-terminated polyether macromonomer, 2.5 parts by weight of hydrogen peroxide as an oxidant, 8 parts by weight of glycidyl methacrylate and 180 parts by weight of deionized water into a reactor, and stirring and dissolving to obtain a macromonomer solution;
s200, uniformly stirring and mixing 12 parts by weight of acrylic acid and 20 parts by weight of deionized water to obtain solution A;
s300, stirring and uniformly mixing 1.5 parts by weight of mercaptoethanol serving as a molecular weight regulator, 0.5 part by weight of ascorbic acid serving as a reducing agent and 20 parts by weight of deionized water to obtain solution B;
s400, under the condition of stirring at normal temperature, simultaneously dropwise adding the solution A and the solution B into the macromonomer solution, and after dropwise adding, adding alkali to neutralize the pH value of the solution to 7, thus obtaining the polycarboxylic acid water reducer.
Comparative example 1
S100, adding 200 parts by weight of ethylene glycol monoethyl polyoxyethylene ether macromonomer (with the molecular weight of 3000), 1.5 parts by weight of oxidant hydrogen peroxide, 5 parts by weight of ethylene glycol monoethyl polyoxyethylene ether and 180 parts by weight of deionized water into a reactor, and stirring and dissolving to obtain a macromonomer solution;
s200, stirring and uniformly mixing 17 parts by weight of acrylic acid and 20 parts by weight of deionized water to obtain solution A;
s300, stirring and uniformly mixing 1.0 part by weight of mercaptopropionic acid serving as a molecular weight regulator, 0.5 part by weight of ascorbic acid serving as a reducing agent and 20 parts by weight of deionized water to obtain solution B;
s400, under the condition of stirring at normal temperature, simultaneously dropwise adding the solution A and the solution B into the macromonomer solution, and after dropwise adding, adding alkali to neutralize the pH value of the solution to 7, thus obtaining the polycarboxylic acid water reducer.
Comparative example 2
S100, adding 200 parts by weight of the ester-terminated polyether macromonomer prepared in the embodiment 1, 1.5 parts by weight of oxidant hydrogen peroxide and 180 parts by weight of deionized water into a reactor, and stirring and dissolving to obtain a macromonomer solution;
s200, stirring and uniformly mixing 17 parts by weight of acrylic acid and 20 parts by weight of deionized water to obtain solution A;
s300, stirring and uniformly mixing 1.0 part by weight of mercaptopropionic acid serving as a molecular weight regulator, 0.5 part by weight of ascorbic acid serving as a reducing agent and 20 parts by weight of deionized water to obtain solution B;
s400, under the condition of stirring at normal temperature, simultaneously dropwise adding the solution A and the solution B into the macromonomer solution, and after dropwise adding, adding alkali to neutralize the pH value of the solution to 7, thus obtaining the polycarboxylic acid water reducer.
Comparative example 3
The S13 polycarboxylic acid mother liquor produced by Fujian Co., ltd, a Kejie new material group, is obtained by copolymerizing isobutylene alcohol polyoxyethylene ether and acrylic acid in an oxidation-reduction system. The mother liquor is colorless transparent liquid in appearance, the solid content is 50%, and the molecular structural formula of the mother liquor is as follows:
the Fujian P.O42.5 ordinary portland cement is adopted, and the concrete mixing proportion is as follows: cement 360kg/m 3 880kg/m of sand 3 970kg/m of stones 3 170kg/m of water 3 For each example and comparative example, the test was conducted by diluting the solution with water to 10% solids.
The test method is shown in the table 1 according to GB/T8076-2008 concrete admixture, GB/T50080-2016 Standard test method for common concrete mixture Performance, and GB/T50081-2019 Standard test method for physical and mechanical Properties of concrete.
Table 1 results of performance testing
As can be seen from Table 1, the polycarboxylic acids prepared in examples 1 and 2 have high water reducing rate, good slump retaining property, fast initial flow rate of concrete, good workability and no bleeding.
Compared with the conventional polycarboxylic acid water-reducing polyether monomer (ethylene glycol monovinyl polyoxyethylene ether) adopted in the comparative example 1, the water-reducing rate of the comparative example 1 is reduced compared with that of the examples 1 and 2, the wrapping property is general, and no hydrophobic group is introduced, so that bleeding is caused.
In comparative example 2, the functional monomer ethylene glycol monoethyl ether is not added, the concrete state is obviously poor, the exposed stones are obvious, and the bleeding is more.
And in the comparative example 3, the HPEG polyether monomer is adopted to prepare the polycarboxylate superplasticizer, the initial dispersing performance is lowest, the loss is fast, and the water bleeding is easy.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications, equivalents and applications made by the present invention in the technical field of the present invention are included in the scope of the present invention.
Claims (10)
1. An ester-terminated polyether monomer, wherein the structural formula of the ester-terminated polyether monomer is as follows:
wherein R is 1 ＝(CH 2 ) n N is an integer of 2 to 8;
R 2 is C 1 -C 12 Is saturated with straight or branched chainsAn alkyl group;
a is an integer of 0 to 100;
b is an integer of 0 to 100.
2. A method for preparing the ester-terminated polyether monomer according to claim 1, wherein the raw materials for preparing the ester-terminated polyether monomer comprise a terminal enol ester, a catalyst and alkylene oxide.
3. The method of claim 2, wherein the terminal enol ester has the following structural formula:
wherein R is 1 ＝(CH 2 ) n N is an integer of 2 to 8;
R 2 is C 1 -C 12 A straight-chain or branched saturated alkyl group.
4. The method of claim 2, wherein the catalyst comprises a mixture of catalyst a and catalyst B;
wherein the catalyst A comprises KOH, naOH and CH 3 At least one of ONa;
the catalyst B comprises a rare earth metal catalyst.
5. The method of claim 2, wherein the alkylene oxide comprises at least one of ethylene oxide and propylene oxide.
6. The method of claim 2, wherein the step of preparing the ester-terminated polyether monomer comprises:
under the catalysis of a catalyst, the terminal enol ester and the alkylene oxide are subjected to ring-opening polymerization reaction at the temperature of 100-120 ℃ and the pressure of 0.2-0.5 MPa, and the ester-terminated polyether monomer is obtained after the reaction is finished.
7. Use of an ester-terminated polyether monomer according to any one of claims 1 to 6 as a starting material for the preparation of a water reducing polycarboxylate.
8. The application of the ester-based terminated polyether monomer according to claim 7, wherein the polycarboxylate water reducer is prepared from the following raw materials in parts by weight:
9. the application of the ester-based terminated polyether monomer according to claim 8, wherein the preparation step of the polycarboxylate superplasticizer comprises the following steps:
stirring and dissolving the ester-terminated polyether monomer, the oxidant and the water to obtain a macromonomer solution;
uniformly stirring and mixing the functional monomer, the unsaturated acid and water to obtain solution A;
uniformly stirring the molecular weight regulator, the reducing agent and water to obtain solution B;
and (3) under the condition of stirring at normal temperature, simultaneously dropwise adding the solution A and the solution B into the macromonomer solution, and after dropwise adding, adding alkali to adjust the pH of the solution to 5-7 to obtain the polycarboxylic acid water reducer.
10. The use of an ester-terminated polyether monomer according to claim 8, wherein the unsaturated acid comprises at least one of acrylic acid, methacrylic acid, and itaconic acid.
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