MULTIFUNCTIONAL SUPERPLASTICIZER FOR ULTRA-HIGH PERFORMANCE CONCRETE AND PREPARATION METHOD THEREFOR

Abstract

Providing a multi-functional group superplasticizer for an ultra-high performance concrete and a method for preparing the same. Its backbone is an alkyl chain, and its side chain are some side chains with carboxylic acid or carboxylate at terminals, some polyether side chains, and some polyol amine side chains substituted with phosphoric acid or phosphite at terminals, the polyol amine side chains substituted with phosphoric acid or phosphite at terminals is connected to the backbone through a phenyl or an alkyl group of 1-9 carbons, and a ratio of a number of the side chains with carboxylic acid or carboxylate at terminals to a total number of side chains is ≥0 and ≤0.8; and a ratio of a number of the polyether side chains to the total number of side chains is ≥0.1 and ≤0.9.

Claims

1. A multi-functional group superplasticizer for an ultra-high performance concrete, whereinin its backbone is an alkyl chain, and its side chain are some side chains with carboxylic acid or carboxylate at terminals, some polyether side chains, and some polyol amine side chains substituted with phosphoric acid or phosphite at terminals, the polyol amine side chains substituted with phosphoric acid or phosphite at terminals is connected to the backbone through a phenyl or an alkyl group of 1-9 carbons, and a ratio of a number of the side chains with carboxylic acid or carboxylate at terminals to a total number of side chains is ≥0 and ≤0.8; and a ratio of a number of the polyether side chains to the total number of side chains is ≥0.1 and ≤0.9; following two structural formulas of the polyol amine side chains substituted with phosphoric acid or phosphite are combined in any proportion: ##STR00015## ##STR00016## in the structure shown, R.sub.15 represents H or a saturated alkyl group containing 1-4 carbon atoms, in a same polymer molecule, R.sub.15 can be the same or different in the structure shown in each chain; in the structure shown, R.sub.16, R.sub.20 and R.sub.22 independently represent —PO.sub.3H.sub.2 or —PO.sub.2H.sub.2; in the structure shown, Y.sub.0, Y.sub.0’ and Y.sub.0” are product functional groups of the polyols containing hydroxyl group reacting with sufficient or insufficient amount of phosphorylation reagent, such that H of the hydroxyl is substituted with phosphoryl group, and Y.sub.0, Y.sub.0’ and Y.sub.0” are connected to the remaining structure shown in structural formula (2) through a carbon-carbon bond; an original structure of polyol containing hydroxyl may have a carboxyl group or may originally contain a phosphoryl group.

2. The multi-functional group superplasticizer for an ultra-high performance concrete according to claim 1, whereinin Y.sub.0, Y.sub.0’ and Y.sub.0” in the structure shown are alkyl polyol residues connected with carboxyl, carboxylate, phosphoryl or phosphate functional group at terminals; or alkyl polyol residues substituted in part or in whole with carboxyl, carboxylate, phosphoryl or phosphate functional groups; and carboxyl group replaces the position of H atom of C—H bond, and the phosphoryl group replaces the position of H of C—H bond or hydroxyl group; hydroxyl group of the polyol is substituted with phosphoryl to form a structure of —O—PO.sub.3H.sub.2.

3. The multi-functional group superplasticizer for an ultra-high performance concrete according to claim 1, whereinin Y.sub.0, Y.sub.0’ and Y.sub.0” in the structure shown independently represent any one or more of the structure shown in following general formula (3), in a same polymer molecule, Y.sub.0, Y.sub.0’ and Y.sub.0” in the structures shown by each chain can be the same or different respectively, wherein chirality of all carbon atoms can be arbitrary: ##STR00017## wherein R.sub.23 represents H or —PO.sub.3H.sub.2 or any one or more of functional groups shown in general Formula (4) below, R.sub.24 represents H or —CH.sub.2OPO.sub.3H.sub.2 or —COOH or —COONa or —COOK or —CH.sub.2OPO.sub.3Na.sub.2 or —CH.sub.2OPO.sub.3K.sub.2, x.sub.4 represents a positive integer between 2-6, and comprising 2 and 6; each of Y.sub.0, Y.sub.0’ and Y.sub.0” functional groups can respectively have at most one functional group as shown in general Formula (4), ##STR00018## wherein R.sub.25 and R.sub.26 independently represent H or —PO.sub.3H.sub.2, and x.sub.6 represents positive integers between 1 and 4, and comprising 1 and 4.

4. The multi-functional group superplasticizer for an ultra-high performance concrete according to claim 1, whereinin the side chain with carboxylic acid or carboxylate at terminals is any one of following structural formulas: ##STR00019## ##STR00020## ##STR00021## structural formula (5), structural formula (6), structural formula (7); wherein R.sub.18 represents H or methyl, M1.sup.+, M2.sup.+, M3.sup.+, M4.sup.+, and M5.sup.+ independently represent H.sup.+ or NH4.sup.+ or Na.sup.+ or K.sup.+, respectively, and the polyether segment is connected to the backbone by carbonyl, phenyl, —OCH.sub.2CH.sub.2—, —OCH.sub.2CH.sub.2CH.sub.2—, —CO—NH—CH.sub.2CH.sub.2 —, or —(CH.sub.2).sub.pp—, wherein pp is an integer between 1 and 6, and comprising 1 and 6.

5. The multi-functional group superplasticizer for an ultra-high performance concrete according to claim 1, whereinin the multi-functional group superplasticizer is a comb polymer having a structure shown in following general formula (8), in which chirality of all carbon atoms is not limited: ##STR00022## in the structure shown, an average number of R.sub.11 segment is aa; in the structure shown, R.sub.12, R.sub.13, R.sub.14 and R.sub.19 independently represent —H or methyl, respectively; in the structure shown, Z.sub.0 represents carbonyl or phenyl or —OCH.sub.2CH.sub.2— or —OCH.sub.2CH.sub.2CH.sub.2CH.sub.2— or —CO—NH—CH.sub.2CH.sub.2 — or —(CH.sub.2).sub.pp—, wherein pp is an integer between 1 and 6, and comprising 1 and 6; in the structure shown, mm and nn represent a number of repeat units of isopropoxy and ethoxy, respectively, which can be an integer or not, a value of (mm+nn) ranges from 8 to 114, and mm/(mm+nn) is not greater than ½, the structure shown in general formula (0) does not limit a connection order of ethoxy and isopropoxy repeat units, which can be block or random; in the structure shown, X.sub.0 and X.sub.0’ independently represent saturated alkyl containing 1-9 carbon atoms or phenyl groups, respectively; R.sub.15 represents H or a saturated alkyl group containing 1-4 carbon atoms, in a same polymer molecule, R.sub.15 can be the same or different in the structure shown by each chain; in the structure shown, R.sub.16, R.sub.20 and R.sub.22 independently represent —PO.sub.3H.sub.2 or —PO.sub.2H.sub.2 or the corresponding sodium salt and potassium salt, respectively; and in the structure shown, aa, bb, cc and cc′ respectively represent an average of the corresponding chains of the polymer, and a ratio of cc to cc′ is arbitrary, the values of aa, bb, cc and cc′ should meet following conditions: (1) 0≤aa/(aa+bb+cc+cc′)≤0.8; (2) 0.1≤bb/(aa+bb+cc+cc′)≤0.9; and (3) a weight average molecular weight of the superplasticizer polymer ranges from 2000 to 100000.

6. A method for preparing the multi-functional group superplasticizer for an ultra-high performance concrete according to claim 1, comprising: copolymerizing terminal alkenylamine B, polyhydroxyaldehyde C and phosphorous-containing composition E under an environment of solvent A and the action of acid catalyst D, to obtain an intermediate, and free radical polymerizing with unsaturated carboxylic acid F and unsaturated polyether G in aqueous solution to produce the multi-functional group superplasticizer for an ultra-high performance concrete; whereinin the solvent A is any one of water, dimethyl sulfoxide, N,N-dimethyl formamide, N,N-dimethyl acetamide, N-methyl pyrrolidone, and dioxane, or a mixture thereof at any proportion; the terminal alkenylamine B is any one of a structure corresponding to following general formula (9), and corresponding hydrochloride and sulfate, or an arbitrary mixture of more than one thereof: ##STR00023## wherein R.sub.1 represents —H or methyl, X represents a saturated alkyl containing 1-9 carbon atoms or phenyl, and R.sub.2 represents H or a saturated alkyl containing 1-4 carbon atoms; the polyhydroxyaldehyde C is any one of a small molecular sugar with an aldehyde terminal group containing 3-14 carbon atoms, or an organic molecule corresponding to the structure shown in following general Formula (10), or an arbitrary mixture of more than one thereof: ##STR00024## wherein Y represents any one of the structures shown in following general Formula (11), wherein the configuration of any chiral carbon atom is not limited: ##STR00025## wherein R.sub.4 represents any one of H or —CH.sub.2OPO.sub.3H.sub.2 or —COOH or —COONa or —COOK or —CH.sub.2OPO.sub.3Na.sub.2 or —CH.sub.2OPO.sub.3K.sub.2 or following structures shown in general Formula (12); ##STR00026## x.sub.1 is a positive integer between 2 and 6, and comprising 2 and 6; x.sub.2 represents a positive integer between 1 and 4, and comprising 1 and 4; the acid catalyst D is a strong acid, comprising but not limited to any one of p-toluene sulfonic acid, hydrochloric acid, sulfuric acid, trifluoroacetic acid, methyl sulfonic acid, trifluoromethanesulfonic acid, sodium bisulfate, potassium bisulfate and ammonium bisulfate; the phosphorous-containing composition E is a mixture of component I and component J, wherein the component I is one of phosphorous acid, potassium dihydrogen phosphite, sodium dihydrogen phosphite, hypophosphorous acid, sodium hypophosphite and potassium hypophosphite, or an arbitrary mixture of more than one thereof, and component J is one of phosphoric acid, polyphosphate, pyrophosphoric acid, phosphorus penoxide and water, or a mixture of more than one thereof; the component I is reacted with aldehyde group of B and C; J is reacted with hydroxyl group of C, and amounts of I and J are determined by amount of B and content of hydroxyl group in C; the unsaturated carboxylic acid F is one of acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, fumaric anhydride, itaconic acid or corresponding sodium, potassium and ammonium salts thereof, or a mixture of more than one thereof; the unsaturated polyether G is one or a combination of more than one of the structures shown in following general Formula (13) ##STR00027## wherein R.sub.6 and R.sub.7 independently represent —H or methyl, Z represents carbonyl, phenyl, —OCH.sub.2CH.sub.2—, —OCH.sub.2CH.sub.2CH.sub.2—, —CO—NH—CH.sub.2CH.sub.2 —, or —(CH.sub.2).sub.p—, wherein p is an integer between 1 and 6, and comprising 1 and 6; and m and n represent a number of repeated units of isopropoxyl and ethoxyl, respectively, which can be an integer or not, values of (m+n) ranges from 8 to 114, and m/(m+n) is not greater than ½, the structure shown in general formula (13) does not limit a connection order of ethoxy and isopropoxy repeat units, which can be block or random.

7. The method according to claim 6, whereinin an initiator H used by the free radical polymerization is a heat-initiated or redox initiator, and the initiator can be added at a time or continuously and uniformly within a certain period of time, the initiator comprises initiator systems listed below: the heat initiator is any one of azo-diisobutyronitrile, azodiisoheptanitrile, azo-diisobutyamidine hydrochloride, azo-diisobutyimidazoline hydrochloride, ammonium persulfate, potassium persulfate and sodium persulfate; the redox initiator is composed of an oxidizing agent and a reducing agent, and the oxidizing agent is any one of hydrogen peroxide, ammonium persulfate, potassium persulfate and sodium persulfate; when the oxidizing agent is hydrogen peroxide, the reducing agent is one or an arbitrary combination of more than one of saturated alkyl thiol containing 2-6 carbon atoms, thioglycolic acid, ascorbic acid or mercaptopropionic acid. In addition, one or an arbitrary combination of more than one of ferrous acetate, ferrous sulfate or ammonium ferrous sulfate can be comprised or not as a catalyst, which is measured by a molar amount of Fe element, the amount of the catalyst is not greater than 10% of the molar amount of the reducing agent; when the oxidizing agent is any one of ammonium persulfate, potassium persulfate and sodium persulfate, the reducing agent is any one of following compositions: (1) one or an arbitrary combination of more than one of thioglycolic acid, ascorbic acid, rongalite or mercaptopropionic acid, in addition, one or an arbitrary combination of more than one of ferrous acetate, ferrous sulfate or ammonium ferrous sulfate can be comprised or not as a catalyst, which is measured by a molar amount of Fe element, the amount of the catalyst is not greater than 10% of the molar amount of the reducing agent; (2) one or an arbitrary combination of more than one of sodium bisulfite, sodium sulfite and sodium metabisulfite; and the amount of initiator is calculated based on following method, if the initiator is a thermal initiator, a mass of the initiator accounts for 0.2% to 4% of a total mass of terminal alkenylamine B, unsaturated carboxylic acid F and unsaturated polyether G; and if the initiator is a redox initiator, by calculating with the one which having more molar amount of oxidant and reductant, a molar amount of the initiator accounts for 0.2% to 4% of a total molar amount of terminal alkenylamine B, unsaturated carboxylic acid F and unsaturated polyether G, and a molar ratio of the oxidizing agent and the reducing agent is 0.25 to 4.

8. The method according to claim 6, whereinin a chain transfer agent K comprises: (1) an organic small molecule containing a sulfhydryl, which comprises a saturated alkyl sulfhydryl containing 2-6 carbon atoms, mercaptoethanol, mercaptoethylamine, cysteine, mercaptoacetic acid or mercaptopropionic acid; (2) sodium bisulfite, sodium sulfite and sodium metabisulfite; an amount of them is 0.1% to 15% of a total molar amount of polymerizable double bonds in a reaction system; the total molar amount of the polymerizable double bond is numerically equivalent to a total molar amount of the terminal alkenylamine B, the polyether G and the unsaturated carboxylic acid F.

9. The method according to claim 6, comprising following steps: (1) adding solvent A to a reactor, and adding terminal alkenylamine B, polyhydroxyaldehyde C, and acid catalyst D in sequence, adjusting the reactor to 70° C. to 120° C., stirring uniformly and reacting for 1 h to 12 h, adjusting the reactor to 60° C. to 120° C., adding phosphorus-containing composition E, stirring for 1 h to 12 h, and finishing reaction, and removing the solvent by vacuum to obtain an intermediate mixture; and (2) radical polymerizing whole intermediate mixture prepared in step (1) with the unsaturated carboxylic acid F and the unsaturated polyether G in aqueous solution under 0° C. to 90° C. to prepare the multi-functional group superplasticizer.

10. The method according to claim 9, whereinin an effective reactant in step (1) accounts for 50 to 90% of the total mass of the system, and the effective reactant comprises terminal alkenylamine B, polyhydroxyaldehyde C and phosphorous-containing composition E.

11. The method according to claim 9, whereinin a concentration of the effective reactant in step (2) is 30 wt% to 80 wt%, and the effective reactant is a sum of the intermediate mixture, the polyether G and the unsaturated carboxylic acid F.

Description

DESCRIPTION OF EMBODIMENTS

[0088] In order to better understand the present application, the contents of the present application are further described in combination with Examples below, but are not limited to following Examples. The units used below are all part by mass, and all compounds used are commercial products or synthetic products as reported in literatures.

[0089] A solvent A, a terminal alkenylamine B, a polyhydroxyaldehyde C, an acid catalyst D, a polyether G (except G3 and G6), an unsaturated carboxylic acid F, a initiator H and a chain transfer agent K are all commercial sources (J&K reagent, TCI reagent, Sigma-Aldrich, Huntsman and RON reagent, etc.). Some polyethers are industrial products, prepared by anionic ring-opening polymerization of ethylene oxide catalyzed by terminal alkenyl alcohol base, which is produced by Subert Company.

TABLE-US-00001 Names of compounds used in Examples B1 2-methylallyl amine B2 1-amino-10-undecene B3 allylamine hydrochloride B4 N-methyl-5-hexene-1-amine B5 N-ethyl methyl propenyl amine B6 4-aminostyrene C1 DL-glyceraldehyde C2 D-(+)-glucose C3 maltose C4 D-ribose C5 D-glucose-6-sodium phosphate C6 glucuronic acid G1 polyethylene glycol monomethyl ether methacrylate, number average molecular weight of 500, n≈10 G2 methylallyl polyethylene glycol ether, number average molecular weight of 2400, n≈53 G3 vinyl polyethylene glycol ether, number average molecular weight of 4000, n≈90 G4 acrylamide poly (ethoxy-isopropyl) monomethyl ether, number average molecular weight of 2050, m/(m+n)=0.3, and m+n≈4 G5 7-octenyl polyethylene glycol ether, number average molecular weight of 3000, n≈65 G6 acrylamide polyethylene glycol monomethyl ether, number average molecular weight of 5050, n≈113

[0090] The structures of compounds listed in Table 1 are as follows, and chirality of some compounds is not labeled:

##STR00014##

[0091] Polyethers G3 and G6 were prepared by dehydration and condensation of corresponding polyethylene glycol or substituted polyethylene glycol ether with the unsaturated carboxylic acid.

[0092] (1) G3: prepared by the reaction of acrylic acid with amino-poly (ethylene oxide -propylene oxide) monomethyl ether (number average molecular weight of 2000, m/(m+n)=0.3, from Huntsman).

[0093] Acrylic acid (7.56 g, 0.105 mol) and amino poly (ethylene oxide-propylene oxide) monomethyl ether (number average molecular weight of 2000, 200 g, 0.1 mol) were dissolved in 1000 mL of dichloromethane, DMAP (0.122 g, 1 mmol) was then added thereto, and a solution of DCC (22.67 g, 0.1 mol) dissolved in dichloromethane (200 mL) was dropwise added thereto at room temperature for 4 h, then continued to stir for 6 h, filtered to remove white solid precipitate, vacuum distillated, a resulting paste solid was dissolved with dichloromethane, and then precipitated by diethyl ether, centrifugated, and then the resulting paste solid were precipitated by dichloromethane/diethyl ether twice, A final product was dried under vacuum to obtain monomer G3 with a yield of 83%.

[0094] (2) G6: prepared by the reaction of methacrylic acid with amino polyethylene glycol (O-(2-aminoethyl) polyethylene glycol, number average molecular weight of 5000, number of ethylene glycol repeat unit being about 113, from Sigma).

[0095] Methacrylic acid (0.0903 g, 0.00105 mol) and the above aminopolyethylene glycol (5 g, 0.01 mol) were dissolved in 50 mL of methylene chloride, DMAP (0.00122 g, 0.01 mmol) was added thereto, and a solution of DCC (0.2267 g, 0.01 mol) dissolved in methylene chloride (5 mL) was dropwise added thereto at room temperature for 12 h, white precipitate appeared in the system, after dropwise adding, the system continued to stir for 12 h, filtered, and distilled under reduced pressure. A resulting solid was dissolved with methylene chloride, then precipitated by diethyl ether, filtered, and then the resulting solid was precipitated by methylene chloride/diethyl ether twice. A final product was dried under vacuum to obtain polyether G6 with a yield of 77%.

[0096] Following are the specific steps of Examples (measurement of all the reactions below is based on terminal alkenylamine B, and the amount of substance converted to terminal alkenylamine B is 0.1 part by molar, and the amount of feed in following Examples is part by mass). The molecular weight of the product is tested by Shimadzu GPC (LC-20A), and a gel column is TSK-GELSW series of TOSOH Company. A differential refractive detector was used, a flowing phase was 0.1 M NaNO.sub.3 aqueous solution, and polyethylene glycol was used as a reference for molecular weight determination.

Example 1

[0097] (1) Dimethyl sulfoxide (82.48 parts) was added to a reactor, B1 (7.112 parts), C1 (22.52 parts) and concentrated sulfuric acid (20 parts, 98%) were added thereto in sequence, the reactor was regulated to 70° C., stirred uniformly for 1 h, regulated to 120° C., and phosphorous acid (20.5 parts) and polyphosphoric acid (85%P.sub.2O.sub.5 equivalent, 51.95 parts) were added thereto, and the reaction was continued to be stirred for 12h. After the reaction was stopped, the solvent was removed by vacuum to obtain an intermediate mixture.

[0098] (2) Water (60 parts), polyether G1 (400 parts) and the intermediate mixture prepared by step (1) were added to a flask, the reactor was regulated to a temperature of 70° C., stirred to mix evenly, and 0.462 parts of azo-diisobutylonitrile powder was added once, and then an aqueous solution (water, 67.98 parts) of methacrylic acid (4.3 parts) and sodium acrylate (4.7 parts) was uniformly dripped thereto for 4h. Starting from dripping of the monomer, 0.462 part of azo-diisobutylonitrilene powder was added thereto every half hour, a total of 8 batches were added. After feeding, the reaction continued for 4 h, and the temperature was regulated to room temperature to stop the reaction. A superplasticizer sample PCE-MP01 was obtained with a weight average molecular weight of 43.2 kDa.

Example 2

[0099] (1) Water (11.03 parts) was added to a reactor, B2 (16.93 parts), C2 (30.03 parts) and concentrated sulfuric acid (5 parts, 98%) were added thereto in sequence, the reactor was regulated to 100° C., stirred uniformly for 6 h, regulated to 60° C., and phosphorous acid (16.4 parts), P.sub.2O.sub.5 (47.33 parts) and anhydrous phosphoric acid (32.67 parts) were added thereto, and the reaction was continued to stir for 10 h. After the reaction was stopped, the solvent was removed by vacuum to obtain an intermediate mixture.

[0100] (2) Water (122.72 parts), polyether G2 (240 parts) and the intermediate mixture prepared in step (1) were added to a flask, the reactor was regulated to a temperature of 50° C., stirred to mix evenly, an aqueous solution of the initiator azo-diisobutyamidine hydrochloride (10.27 parts dissolved in 122.72 parts of water) was uniformly dripped thereto for 6 h. After the dripping, the reaction was continued for 12 h, the temperature was regulated to room temperature. After the reaction was stopped, a superplasticizer sample PCE-MP02 was obtained with a weight average molecular weight of 9.8 kDa.

Example 3

[0101] (1) N,N-dimethyl formamide (84.02 parts) was added to a reactor, B3 (9.356 parts), C3 (57.05 parts) and trifluoroacetic acid (11.402 parts) were added thereto in sequence, the reactor was regulated to 100° C., stirred uniformly for 6 h, regulated to 80° C., phosphorous acid (8.2 parts), potassium hypophosphite (10.4 parts), phosphorus penoxide (12.62 parts) and water (1.6 parts) were added thereto, and the reaction was continued to stir for 12 h. After the reaction was stopped, the solvent was removed by vacuum to obtain an intermediate mixture.

[0102] (2) Water (185.66 parts), polyether G3 (400 parts) and the intermediate mixture prepared in step (1) were added to a flask, the reactor was regulated to a temperature of 60° C., stirred to mix evenly. At the same time, a mixture of acrylic acid (57.6 parts) and mercaptopropionic acid (1.06 parts) and an aqueous solution of initiator (2.28 parts of ammonium persulfate dissolved in 92.83 parts of water, 4.16 parts sodium bisulfite dissolved in 92.83 parts of water) were uniformly dripped thereto for 5 h, and the reaction continued for 1h after the dripping was completed. The temperature was regulated to room temperature. After the reaction was stopped, a superplasticizer sample PCE-MP03 was obtained with a weight average molecular weight of 45.6 kDa.

Example 4

[0103] (1) N,N-dimethylacetamide (49.28 parts) was added to a reactor, B4 (11.32 parts), C4 (14.42 parts) and methylsulfonic acid (11.533 parts) were added thereto in sequence, the reactor was regulated to 70° C., stirred uniformly for 3 h, regulated to 100° C., hypophosphorous acid (6.6 parts), phosphorus penoxide (6.6 parts) and pyrophosphoric acid (28.48 parts) were added thereto, and the reaction was continued to stir for 4 h. After the reaction was stopped, the solvent was removed by vacuum to obtain an intermediate mixture.

[0104] (2) Water (300 parts), polyether G4 (307.5 parts) and the intermediate mixture prepared in step (1) were added to a flask, the reactor was regulated to a temperature of 40° C., an aqueous solution of hydrogen peroxide (30 wt%, 1.13 parts) was added thereto, stirred to mix evenly. At the same time, a mixture of methacrylic acid (21.5 parts) and mercaptoethanol (0.585 part) and an aqueous solution of ascorbic acid (0.88 part dissolved in 98.75 parts of water) were uniformly dripped thereto for 45 min, and the reaction continued for 15 min after the dripping was completed. The temperature was regulated to room temperature. After the reaction was stopped, a superplasticizer sample PCE-MP04 was obtained with a weight average molecular weight of 33.8 kDa.

Example 5

[0105] (1) Water (3.864 parts) was added to a reactor, B5 (9.917 parts), C5 (30.41 parts) and ammonium bisulfate (11.511 parts) were added thereto in sequence, the reactor was regulated to 100° C., stirred uniformly for 3 h, regulated to 90° C., phosphorous acid (8.2 parts), hypophosphorous acid (6.6 parts), phosphorus pentoxide (14.2 parts) and pyrophosphoric acid (17.8 parts) were added thereto, and the reaction was continued to be stirred for 6 h. After the reaction was stopped, the solvent was removed by vacuum to obtain an intermediate mixture.

[0106] (2) Water (300.43 parts), polyether G5 (300 parts) and the intermediate mixture prepared by step (1) were added to a flask, the reactor was regulated to a temperature of 45° C., an aqueous solution of hydrogen peroxide (30 wt%, 1.13 parts) and ferrous sulfate (0.0695 part) were added thereto, stirred to mix evenly. At the same time, a mixture of acrylic acid (3.6 parts) and ethanthiol (0.232 part) and an aqueous solution of ascorbic acid (0.44 part dissolved in 100 parts of water) were uniformly dripped to the mixture for 2 h, and the reaction continued for 1 h after the dripping was completed. The temperature was regulated to room temperature. After the reaction was stopped, a superplasticizer sample PCE-MP05 was obtained with a weight average molecular weight of 29.1 kDa.

Example 6

[0107] (1) N-methylpyrrolidone (37.24 parts) was added to a reactor, B6 (11.916 parts), C6 (43.14 parts) and sulfuric acid (5 parts, 98%) were added thereto in sequence, the reactor was regulated to 100° C., stirred uniformly for 6 h, regulated to 90° C., potassium dihydrogen phosphite (12.0 parts), phosphorous acid (16.4 parts), phosphorus penoxide (52.59 parts) and anhydrous phosphoric acid (36.3 parts) were added thereto, and the reaction was continued to stir for 6 h. After the reaction was stopped, the solvent was removed by vacuum to obtain an intermediate mixture.

[0108] (2) Water (677.41 parts), polyether G6 (505 parts) and the intermediate mixture prepared by step (1) were added to a flask, the reactor was regulated to a temperature of 35° C., stirred to mix evenly, 1.034 parts of azo-diisobutyimidazoline hydrochloride was added thereto once, the reaction continued for 12 h, the temperature was regulated to room temperature. After the reaction was stopped, a superplasticizer sample PCE-MP06 was obtained with a weight average molecular weight of 97.8 kDa.

Example 7

[0109] (1) B1 (7.112 parts), C1 (18.02 parts) and hydrochloric acid (20 parts, 36.5% of aqueous solution, water directly acting as a reaction solvent) were added thereto in sequence, the reactor was regulated to 80° C., stirred uniformly for 4 h, regulated to 100° C., phosphorous acid (32.8 parts) and pyrophosphoric acid (71.2 parts) were added thereto, and the reaction was continued to be stirred for 4 h. After the reaction was stopped, the solvent was removed by vacuum to obtain an intermediate mixture.

[0110] (2) Water (312.26 parts) and the intermediate mixture prepared in step (1) were added to a flask, the reactor was regulated to a temperature of 45° C., hydrogen peroxide (30% aqueous solution, 0.227 part) was added thereto, stirred to mix evenly, a mixture solution(dissolved in 312.26 parts of water) of polyether G1 (250 parts), acrylic acid (21.6 parts), itaconic acid (13 parts), mercaptopropionic acid (6.36 parts) and ascorbic acid (0.44 part) was continuously uniformly added thereto. A cumulative feeding time was 4 h, and the reaction continued for 1 h after the addition was completed. The temperature was regulated to room temperature. After the reaction was stopped, a superplasticizer sample PCE-MP07 was obtained with a weight average molecular weight of 5.2 kDa.

Example 8

[0111] (1) 4.58 parts of water were added to a reactor, then B1 (7.112 parts), C2 (36.03 parts) and p-toluenesulfonic acid (17.22 parts) were added thereto in sequence, the reactor was regulated to 80° C., stirred uniformly for 4 h, regulated to 100° C., potassium dihydrogen phosphite (24.0 parts), phosphorus penoxide (56.8 parts) and water (7.2 parts) were added thereto, the reaction was continued to stir for 4 h. After the reaction was stopped, the solvent was removed by vacuum to obtain an intermediate mixture.

[0112] (2) Water (317.68 parts) and the intermediate mixture prepared in step (1) were added to a flask, the reactor was regulated to a temperature of 60° C., ammonium persulfate (2.28 parts) was added thereto once, stirred to mix evenly, a mixed solution (dissolved in 1000 parts of water) of polyether G4 (1845 parts), mercaptopropionic acid (2.12 parts) and ascorbic acid (1.76 parts) was continuously and uniformly added thereto, and a cumulative feeding time was 4 h, and the reaction continued for 2 h after the addition was completed. The temperature was regulated to room temperature. After the reaction was stopped, a superplasticizer sample PCE-MP08 was obtained with a weight average molecular weight of 25.1 kDa.

Example 9

[0113] (1) 48.45 parts of N,N-dimethyl formamide were added to the reactor, and then B3 (9.356 parts), C2 (40.04 parts) and sulfuric acid (15 parts, 98%) were added thereto in sequence. The reactor was regulated to 80° C., stirred uniformly to react for 2 h. Phosphorous acid (24.6 parts) and polyphosphoric acid (115.45 parts, P.sub.2O.sub.5 equivalent amount 85%) were added thereto, and the reaction was continued to be stirred for 6 h. After the reaction was stopped, the solvent was removed by vacuum to obtain an intermediate mixture.

[0114] (2) Water (1000 parts) and polyether G2 (720 parts) were added to a flask, the reactor was regulated to a temperature of 75° C., ammonium persulfate (2.11 parts) was added thereto once, stirred to mix evenly, a mixed solution (dissolved in 382.49 parts of water) of the intermediate mixture, acrylic acid (5.76 parts), maleic anhydride (1.96 parts) and thioglycoacetic acid (0.552 part) prepared in step (1) was continuously and uniformly added thereto. A cumulative feeding time was 3 h. Within 3 h, the remaining ammonium persulfate was added in 6 batches. 2.11 parts was added to the reaction system every half hour, the reaction continued for 5 h after the addition was completed. The temperature was regulated to room temperature. After the reaction was stopped, a superplasticizer sample PCE-MP09 was obtained with a weight average molecular weight of 47.1 kDa.

Example 10

[0115] (1) 39.81 parts of N,N-dimethyl formamide were added to a reactor, and then B4 (11.32 parts), C2 (18.02 parts) and trifluoroacetic acid (6.84 parts) were added thereto in sequence. The reactor was regulated to 120° C., stirred uniformly to react for 12 h. Phosphorous acid (1.64 parts), sodium hypophosphite (7.04 parts) and polyphosphoric acid (10.39 parts, P.sub.2O.sub.5 equivalent amount 85%) were added thereto, the reaction was continued to stir for 12 h. After the reaction was stopped, the solvent was removed by vacuum to obtain an intermediate mixture.

[0116] (2) Water (57.2 parts) was added to a flask, the reactor was regulated to a temperature of 5° C., hydrogen peroxide (30% aqueous solution, 0.567 part) was added thereto once, stirred to mix evenly. A mixed solution (dissolved in 171.59 parts of water) of intermediate mixture prepared in step (1), polyether G4 (256.25 parts), rongalite (0.193 part) and mercaptoethanol (1.95 part) was continuously and uniformly added thereto. A feeding time lasted for 2 h, and the reaction continued for 1 h after the addition was completed. The temperature was regulated to room temperature. After the reaction was stopped, a superplasticizer sample PCE-MP10 was obtained with a weight average molecular weight of 11.4 kDa.

Example 11

[0117] (1) 13.82 parts of dimethyl sulfoxide was added to a reactor, then B5 (9.917 parts), C5 (33.79 parts) and ammonium bisulfate (6.91 parts) were added thereto in sequence, the reactor was regulated to 80° C., stirred uniformly to react for 4 h. The reactor was regulated to 90° C., and phosphite (8.2 parts), sodium hypophosphite (4.4 parts) and polyphosphoric acid (27.71 parts, P.sub.2O.sub.5 equivalent amount 85%) were added thereto. The reaction was continued to stir for 12 h. After the reaction was stopped, the solvent was removed by vacuum to obtain an intermediate mixture.

[0118] (2) Water (628.31 parts), polyether G2 (240 parts) and the intermediate mixture prepared in step (1) were added to a flask, then hydrogen peroxide (0.283 part, 30 wt%) and ferrous ammonium sulfate (0.002085 part) were added thereto, stirred to mix evenly, the reactor was regulated to a temperature of 40° C. A mixed solution of acrylic acid (0.72 parts), itaconic acid (5.2 parts) and mercaptoethanol (0.156 part) (dissolved in 78.54 parts of water) was continuously and uniformly added thereto within 2.5 h. At the same time, an aqueous solution of ascorbic acid (0.132 part of ascorbic acid dissolved in 78.54 parts of water) was continuously and uniformly added into the solution within 3 h, and the reaction continued for 1h after the addition was completed. The temperature was regulated to room temperature. After the reaction was stopped, a superplasticizer sample PCE-MP11 was obtained with a weight average molecular weight of 55.2 kDa.

Example 12

[0119] (1) 16.92 parts of N,N-dimethyl formamide were added to the reactor, and then B6 (11.916 parts), C1 (20.02 parts) and hydrochloric acid (24 parts, 36.5 wt% of aqueous solution) were added thereto in sequence. The reactor was regulated to 80° C., and stirred uniformly to react for 2 h. The reactor was regulated to 120° C. Phosphorous acid (24.6 parts) and polyphosphoric acid (27.71 parts, P.sub.2O.sub.5 equivalent amount 85%) were added thereto, and the reaction was continued to be stirred for 1 h. After the reaction was stopped, the solvent was removed by vacuum to obtain an intermediate mixture.

[0120] (2) Water (100 parts), polyether G2 (300 parts) and the intermediate mixture prepared in step (1) were added to a flask, stirred to mix evenly, the reactor was regulated to a temperature of 90° C. A mixed solution of acrylic acid (1.8 parts), ascorbic acid (0.44 part) and mercaptopropionic acid (0.159 part) (dissolved in 155.59 parts of water) was continuously and uniformly added thereto, and an aqueous sodium persulfate solution (1.19 parts of ascorbic acid dissolved in 155.59 parts of water) was continuously and uniformly added thereto. A feeding time was 1 h, and the reaction continued for 1 h after the addition was completed. The temperature was regulated to room temperature. After the reaction was stopped, a superplasticizer sample PCE-MP12 was obtained with a weight average molecular weight of 76.1 kDa.

Application Examples

[0121] The use effect of the superplasticizer described in present application is illustrated by experiments of cement net slurry with an ultra-low water-binder ratio and the ultra-high performance concretes, respectively.

[0122] Conch cement (P•O•42.5) was used for a net slurry, Jiangnanxiaoyetian cement (P•II•52.5) was used for a concrete, Aiken 97 silica fume was used for silica fume, and S95 mineral powder was used for mineral powder. All materials were kept constant temperature at the required temperature before the experiments. The comparison samples were a conventional commercial polycarboxylate superplasticizer (commercial 1 is ester type, commercial 2 is ether type, side chain length is 2400). It should be noted that all percentages expressed below are compared with commercial sample having better indicators.

Cement Net Slurry

[0123] According to GB/T8077-2000 “Concrete admixture uniformity test method”, the fluidity of cement net slurry was measured, all amount of dispersant were the percentage of pure solid relative to the mass of cement (wt%). To characterize the dispersion/dispersion retention properties of the samples with ultra-low water-binder ratios, the cement net slurry was prepared using 270 g of cement and 30 g of silica fume, in which a fixed water consumption amount is 51 g. Cement and silica fume are pre-mixed by a mixer to ensure uniform mixing.

[0124] Based on the standard slurry stirring process, the net slurry fluidity of different superplasticizers was tested, and the fluidity of cement net slurry was tested after placed for 30 min. The samples prepared in the Examples with the commercial polycarboxylate superplasticizer samples were compared to obtain following results.

TABLE-US-00002 Test results of cement net slurry (20° C.) Sample Amount fluidity of net slurry (mm) (wt%) 4 min 30 min PCE-MP01 0.6 224 232 PCE-MP02 0.6 290 280 PCE-MP03 0.6 254 248 PCE-MP04 0.6 266 258 PCE-MP05 0.6 289 281 PCE-MP06 0.6 280 270 PCE-MP07 0.6 237 242 PCE-MP08 0.6 296 302 PCE-MP09 0.6 292 286 PCE-MP10 0.6 260 251 PCE-MP11 0.6 277 265 PCE-MP12 0.6 284 277 Commercial 1 0.6 190 154 Commercial 2 0.6 170 162

[0125] It can be seen from the results in Table 2, although the dispersion ability of the superplasticizer prepared in the Examples of the present application, with high or low, is related to the structural parameters, compared with the commercial samples, their dispersion ability were much better at the condition of 0.17 of water-binder ratio. Except PCE-MP01 and PCE-MP07, the fluidity retention ability of most samples is basically equivalent to that of commercial sample 2, and much better than that of commercial sample 1.

Ultra-High Performance Concrete (UHPC) Test (Dispersion Performance Comparison, Mortar)

[0126] In order to investigate the maximum dispersion ability of different samples under different amounts, the fluidity of cement mortar under the condition of ultra-low water-binder ratio was investigated under the given matching ratio.

TABLE-US-00003 Formulation ratio of UHPC mortar (weight ratio) Cement Silica fume Ultrafine mineral powder Sand Water 0.60 0.12 0.28 0.7 0.15

[0127] The shear viscosity of the mortar with an initial fluidity of (240±5)mm was investigated. A rheological curve of the initial slurry was measured by a Rheometer (Brookfield R/S300 Rheometer) (refer to Constr. Build. Mater. 2017, 149, 359-366. The maximum shear rate is 25 s.sup.-1), and the shear viscosity of 15 s.sup.-1 is selected for comparison (this shear rate is at the same level as the rate of slurry treatment such as stirring and mixing). At the same time, V funnel time of the mortar with this fluidity was measured, and the results are shown in Table 4.

TABLE-US-00004 Test results of UHPC mortar (20° C., the control is not tested) Sample mortar fluidity (mm) under different amounts (wt%) V funnel time 15 s.sup.-1 shear viscosity 0.4 0.5 0.6 0.7 0.8 0.9 (s) (Pa.Math.s) PCE-MP01 239 262 266 264 265 27 21.5 PCE-MP02 243 277 306 308 306 305 26.7 21.0 PCE-MP03 244 266 283 288 286 27.3 22.1 PCE-MP04 245 271 279 280 279 24.8 19.9 PCE-MP05 242 271 300 320 325 322 26 19.4 PCE-MP06 238 262 277 295 293 290 29.6 22.9 PCE-MP07 242 265 270 268 266 24.3 18.5 PCE-MP08 237 274 305 317 322 320 24.2 20.0 PCE-MP09 245 279 310 319 319 317 28.1 20.7 PCE-MP10 245 270 278 277 275 23.9 17.5 PCE-MP11 235 262 278 292 290 292 27.7 22.2 PCE-MP12 238 264 282 300 301 299 27.9 22.4 Commercial 1 221 242 239 235 230 34.5 28.2 Commercial 2 200 230 237 232 228 41 30.5

[0128] It can be seen from the results in Table 4 that under the condition of the tested matching ratios, all the samples showed a trend of increasing the mortar fluidity first and then no longer increasing with the increase of the amount, while the fluidity of some samples decreased slightly with the increase of the amount, because the viscosity is increased, the flow rate slowed down, and the fluidity was slightly smaller during the measurement time. The maximum fluidity shown in the table is regarded as the limit water reduction of the sample, that is, the maximum dispersion degree can be achieved regardless of the sample amounts.

[0129] The maximum dispersion ability of all samples in the table is much greater than that of the commercial samples, which indicates the super dispersion ability of the samples prepared by Examples of the present application. In addition, even if comparing the amounts when the mortar fluidity reaches 240 mm, the required amount of the samples of Examples of the present application is 0.1 wt% to 0.2 wt% lower than that of the commercial sample (corresponding to a percentage reduction of 16% to 42%).

[0130] The shear viscosity (15 s.sup.-1) and V funnel time of the mortar at the fluidity of (240±5) mm were compared, the sample PCE-MP01-12 prepared in Example of the present application can reduce the shear viscosity by 17% to 42% and the V funnel time by 14% to 40%, which fully illustrates the viscosity reducing characteristics of the sample.

[0131] (3) Ultra-high performance concrete (UHPC) test (concrete, including fiber)

[0132] To investigate performance of the superplasticizer prepared in the present application applied in UHPC by changing the matching ratio, the concrete matching ratio is as follows.

TABLE-US-00005 UHPC ratio (weight ratio, fiber being volume fraction) Cement Silica fume Superfine mineral powder Fly ash Sand Fiber/V% Water 0.70 0.13 0.05 0.12 0.9 2 0.148

[0133] Xiaoyetian cement (P II 52.5), the sand is a coventional river sand, the fiber is steel fiber with an L/D ratio of 30 and a length of 50 mm, and the amount (unit: mass percentage, wt%) of superplasticizer PCE-MP01-12, commercial 1 and commercial 2 is calculated by the converting solid amount based on the cementing material, in the test, the slump ((20±1) cm) and expansion degree ((45±2) cm) of UHPC were controlled to be equivalent by adjusting the amount of superplasticizer. The defoaming agent used was a conventional PXP-I concrete defoaming agent sold by Jiangsu Sobute New Material Co., LTD. The gass content of UHPC in each group was basically the same by the defoaming agent. If the concrete fluidity is difficult to reach the above indexes, the fluidity of the superplasticizer at the amount of 1.0 wt% is uniformly investigated, and the fluidity of the concrete under exit from machine is investigated. At this yield, the dispersion ability of the sample has reached the limit, and the concrete fluidity is difficult to be enhanced by increasing the superplasticizer.

[0134] The cement, the silica fume, the fly ash and the sand were added to a mixer while stirring for 2 min, then the fiber was added and stirred for 3 min to exit from the machine. The slump and expansion degree of UHPC were tested respectively and recorded as “initial/exit from machine” and the amount of superplasticizer used. The results were as follows.

TABLE-US-00006 UHPC characterization (20° C.) Sample Amount (wt%) Gas content Slump/expansion degree(cm) compressive strength after 28 d (%) exit from machine (MPa) PCE-MP01 1.00 1.9 18.5/40.0 160.8 PCE-MP02 0.65 1.7 20.2/44.0 159.7 PCE-MP03 0.78 1.9 19.8/45.5 158.0 PCE-MP04 0.80 2.1 20.3/45.0 161.4 PCE-MP05 0.59 2.0 21.0/47.0 162.3 PCE-MP06 0.75 2.1 20.4/45.0 163.0 PCE-MP07 0.92 1.9 19.7/43.5 161.2 PCE-MP08 0.62 1.7 20.0/44.0 158.8 PCE-MP09 0.62 2.0 20.4/46.5 160.2 PCE-MP10 0.85 1.8 19.5/43.0 160.4 PCE-MP11 0.75 1.9 20.7/44.0 163.3 PCE-MP12 0.72 2.1 20.5/44.0 159.2 Commercial 1 1.00 2.2 15.0/- 150.4 Commercial 2 1.00 2.0 13.4/- 151.2 * “-” indicates only slump without expansion degree

[0135] It can be seen that the commercial superplasticizer can no longer meet the fluidity requirements of concrete with such a low water-binder ratio, while the superplasticizer samples prepared by the Examples can give good fluidity to concrete with a water-binder ratio of 0.148. Comparing the compressive strength of concrete after 28 days, the dispersion property of the commercial superplasticizer is not good, and the strength is slightly lower than that of the sample prepared by the Examples, which may be caused by the slightly poor uniformity of the slurry and aggregate.