Preparation method for polymer and applications thereof

Abstract

The present invention provides a method for preparing a polymer and a use of the polymer. The resulting polymer is used as a dispersant for an aqueous dispersion of a hydraulic binder and/or a latent hydraulic binder, such that water-reducing rate is improved, and suitable control of air content can be achieved, thereby improving the strength of concrete. The method for preparing a polymer includes polycondensation of a polyether macromonomer A of a specific structure, a monomer B and an aldehyde C to obtain the polymer. The monomer B is phenylsulfonic acid, p-/o-aminophenylsulfonic acid, p-/o-hydroxylbenzoic acid, p-/o-aminobenzoic acid, p-/o-hydroxylphenylsulfonic acid, or a phosphoric acid group or phosphorous acid group-containing monomer of a specific structure. A molar ratio of the polyether macromonomer A and the monomer B is 1:(0.5 to 12).

Claims

1. A method for preparing a polymer, comprising performing a polycondensation of a polyether macromonomer A, a monomer B and an aldehyde C, wherein the polyether macromonomer A has a structural formula (Ia), (Ib), (Ic), or (Id): ##STR00005## in which Z is NR.sup.3, O or O(CH.sub.2).sub.fO, L=O(CH.sub.2).sub.f or (CH.sub.2).sub.f, f is an integer from 1 to 10, Q is C2 to C24 alkylene, R.sup.2 is H or C1 to C10 alkyl, R.sup.3 is a C1 to C10 alkyl, m=8 to 112, n=8 to 112; the monomer B p-aminophenylsufonic acid, o-aminophenylsulfonic acid, p-hydroxylbenzoic acid, o-hydroxylbenzoic acid, p-aminobenzoic acid, o-aminobenzoic acid, p-hydroxylphenylsulfonic acid, o-hydroxylphenylsulfonic acid, or has a structural formula (IIa) or (IIb): ##STR00006## in which G is N(CH.sub.2PO.sub.3H.sub.2).sub.2, NHCH.sub.2PO.sub.3H.sub.2, NR.sup.6CH.sub.2PO.sub.3H.sub.2, C(OH)(PO.sub.3H.sub.2).sub.2, CH(OPO.sub.3H.sub.2)CH.sub.2OPO.sub.3H.sub.22, OPO.sub.3H.sub.2, wherein R.sup.1 is H, a C1 to C10 alkyl or SO.sub.3H, K is a C1 to C10 alkylene, X=NR.sup.8 or O, Y is OH or OR.sup.7, R.sup.7 is a C1 to C10 alkyl, R.sup.6 and R.sup.8 are independently from each other are a C1 to C10 alkyl, the aldehyde C has a structural formula (III):
R.sup.5CHO(III) in which R.sup.5 is H, COOH, or a C1 to C10 alkyl; and a molar ratio of the polyether macromonomer A and the monomer B is 1:0.5 to 1:12, wherein the polymer has a weight average molecular weight of 4000 g/mol to 150000 g/mol.

2. The method for preparing a polymer of claim 1, wherein, Z is O or O(CH.sub.2).sub.fO, f=1 to 3; L is (CH.sub.2).sub.f, f=1 to 3; Q is C2 to C4 alkylene; R.sup.1 is H or a C1 to C3 alkyl; R.sup.2 is H or a C1 to C3 alkyl; R.sup.3 is a C1 to C3 alkyl; X is NR.sup.8 or O; R.sup.8 is a C1 to C3 alkyl; Y is OH or OR.sup.7; R.sup.7 is preferably a C1 to C3 alkyl; K is a C1 to C3 alkylene; and R.sup.5 is H, COOH or a C1 to C3 alkyl.

3. The method for preparing the polymer of claim 2, wherein the monomer B has a structural formula (IIa) or (IIb) in which G is N(CH.sub.2PO.sub.3H.sub.2).sub.2, C(OH)(PO.sub.3H.sub.2).sub.2, or CH(OPO.sub.3H.sub.2)CH.sub.2OPO.sub.3H.sub.2.

4. The method for preparing the polymer of claim 1, wherein the polyether macromonomer A has a molecular weight of 1000 to 10000 g/mol.

5. The method for preparing the polymer of claim 1, wherein a molar ratio of the polyether macromonomer A and the monomer B is 1:1.0 to 1:6.0.

6. The method for preparing the polymer of claim 1, wherein a molar ratio between the aldehyde C and a combinded molar amount of polyether macromonomer A and monomer B is 1.0 to 2.0.

7. The method for preparing the polymer of claim 1, wherein the conditions of the polycondensation are: a reaction temperature of 80 to 140 C. and a reaction time of 1 to 8 h.

8. A method of using the polymer obtained by the method of claim 1 including using the polymer as a dispersant for an aqueous dispersion of a hydraulic binder and/or a latent hydraulic binder.

9. The method of claim 8, wherein the hydraulic binder is at least one of cement, lime, gypsum, and anhydrous gypsum, and the latent hydraulic binder is pozzolana, fly ash or blast furnace slag.

10. The method for preparing the polymer of claim 1, wherein the polymer has a weight average molecular weight from 8000 g/mol to 100000 g/mol.

11. The method for reparing the polymer of claim 1, wherein the polymer has a weight average molecular weight from 10000 g/mol to 40000 g/mol.

12. The method for preparing the polymer of claim 2, wherein Z is O or O(CH.sub.2).sub.fO, f=1 to 2; Q is C2 to C3 alkylene; R.sup.1 is H; R.sup.2 is H; R.sup.3 is methyl; R.sup.8 is methyl or ethyl; R.sup.7 is methyl or ethyl; and R.sup.5 is H or COOH.

13. The method for preparing the polymer of claim 3, wherein the monomer B has a structural formula (IIa) or (IIb) in which G is N(CH.sub.2PO.sub.3H.sub.2).sub.2, or C(OH)(PO.sub.3H.sub.2).sub.2.

14. The method for preparing the polymer of claim 7, wherein the conditions of the polycondensation are: the reaction temperature of 90 to 130 C. and the reaction time of 2 to 6 h.

15. The method of using the polymer of claim 9, wherein the hydraulic binder is cement.

16. The method for preparing the polymer of claim 12, wherein Z is O; Q is CH.sub.2CH.sub.2; R.sup.8 is methyl; R.sup.7 is methyl; and R.sup.5 is H or COOH.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) The present invention will be described in detail by way of examples, and these examples are merely illustrative and should not be construed as limiting the invention thereto. All chemicals or reagents used in the examples are of analytical grade and are commercially available.

(2) In the examples of the present invention, the molecular weight of the polymer is determined by Gel Permeation Chromatography (GPC), and the molecular weight in the present invention is weight average molecular weight (Mw); the reaction conversion rate can be obtained by determination by GPC and calculation of the residual amount of the polyether macromonomer, and clearly, the conversion rate here refers to the conversion rate of the polyether macromonomer A.

(3) The GPC in the above tests is produced by Wyatt Technology Corporation, where the conditions are as follows: gel column: Shodex SB806+803 columns in series; eluant: 0.1M NaNO.sub.3 solution; mobile phase velocity: 0.8 ml/min; injection: 20 l 0.5% aqueous solution; detector: Shodex RI-71 differential refractive index detector; standard: PEG GPC calibration standards (Sigma-Aldrich, molecular weight 1010000, 478000, 263000, 118000, 44700, 18600, 6690, 1960, 628, 232).

(4) In all the application examples of the present invention, unless otherwise stated, the cement used is JIANGNAN-Onoda cement (P.O 42.5), and the stone is continuously graded broken stone having a particle size of 5 to 20 mm. The sand is shown in Table 2.0. Fluidity of cement paste is tested according to the GB/T8077-2000 standard, where using 300 g cement and 87 g water addition, the fluidity of cement paste is determined on a flat glass after stirring for 3 min. The results are shown in Table 1.0. The properties of concrete mixed with the polymer of the present invention are tested with reference to related provisions in JC473-2001Pumping Aid for Concrete.

(5) The polyether macromonomers A used in the examples are numbered as follows:

(6) ##STR00003## A part of the monomers B used are numbered as follows:

(7) ##STR00004##

(8) Specific preparation of the part of the monomers B is as follows:

(9) For the phosphorous-containing monomers A, P-1, P-2, P-4, P-5, and P-6 compounds, the Mannich reaction in organic chemistry is used. For example, for P-1, 16.4 g phosphorous acid (0.2 mol) and 12 g (0.11 mol) 35 wt % hydrochloric acid (or 0.5 mol sulfuric acid) are added into 13.8 g (0.1 mol) 2-phenoxyethylamine, and placed in a 500 ml three-necked flask, and the reaction mixture is heated to 100 C. for 5 h. Then, 17.8 g (0.22 mol) of a 37% aqueous formaldehyde solution is added, and heated to reflux for 24 h. The crude reaction product is washed three times with cold methanol, and the residual methanol and water are removed by distillation under reduced pressure, to obtain 31.8 g of a product with a yield of 98%. It is to be noted that for P-2, inert gas protection is required, and for P-4, halving the amounts of phosphorous acid and the aldehyde is required.

(10) Preparation of phosphorous-containing monomer P-3: 16.6 g (0.1 mol) 3-phenoxypropionic acid is placed in a 250 ml three-necked flask, 43.94 g (0.32 mol) phosphorus trichloride is added within 30 min and heated to 75 C. for 12 h, and then 101.1 g (5.6 mol) water is added and heated to 105 C. for hydrolysis for 1 h. The reaction is cooled to room temperature. Water in the reaction is removed by distillation under reduced pressure, and then the crude reaction product is washed three times with cold methanol, and the residual methanol is removed by vacuum suction, to obtain a final targeted product with a yield of 75%. Other similar structures may be prepared following this method.

(11) Polyether macromonomers are prepared by the ethoxylation method, and the description is made here with the preparation of the polyether macromonomer M1 as an example. Hydroquinone is used as initiator, sodium hydroxide is used as catalyst, and ethylene glycol dimethyl ether is used as reaction solvent (for dissolving the initiator). 110 g ethylene glycol dimethyl ether and 3 g sodium hydroxide are added to 110 g hydroquinone, these materials are added to a reactor, and the reactor is evacuated to 0.1 MPa at room temperature. Then, the reactor is heated to 100 C., 50 g ethylene oxide is charged into the reactor, and decrease in pressure and increase in temperature in the reactor indicates beginning of the polymerization reaction. 1840 g ethylene oxide is further charged into the reactor, the reactor is maintained at a temperature of between 100 and 120 C. and a pressure of between 0.2 and 0.4 MPa during the addition, and after the addition of ethylene oxide is finished, the temperature is kept at 100 C. for about 1 h. Once the pressure of the reactor does not decrease again, the temperature and the pressure of the reactor are respectively reduced to about 90 C. and 0.1 MPa, and the solvent ethylene glycol dimethyl ether is removed by distillation under reduced pressure. Once no solvent is distilled off, a relief valve is opened to reduce the pressure in the reactor to normal pressure, the reactor is opened to discharge the material, to obtain a light brown liquid, which is determined by GPC to have a molecular weight of 1973 with a molecular weight distribution of 1.02. It is to be noted that for an initiator having a low melting point, the ethoxylation reaction may be directly performed without dissolution by adding ethylene glycol dimethyl ether.

EXAMPLE 1

(12) In this example, A/B=1:2, C/(A+B)=1.2.

(13) In a 1000 ml four-necked flask equipped with an electro-mechanical stirrer and a thermostatic heating bath, 250 g (0.25 mol) polyether M1 (Mw=1000), 87 g (0.50 mol) p-hydroxylphenylsulfonic acid, 45 g (2.5 mol) water, and 25 g (0.25 mol) sulfuric acid were added, heated and stirred to be a homogeneous one phase system. Then, 72.9 g (0.9 mol) of a 37% aqueous formaldehyde solution was dropwise added in half an hour. After the dropwise addition was completed, the reaction lasted for 5 h at 100 C. After the reaction was finished, it was cooled to room temperature, neutralized with a 30% base solution to a pH of about 10, and further reacted for 0.5 to 1 h at 110 C. to remove unreacted formaldehyde. The reaction was cooled to room temperature, and diluted with water to a solution concentration of about 30% to 40%.

EXAMPLE 2

(14) In this example, A/B=1:2, C/(A+B)=1.0.

(15) In a 1000 ml four-necked flask equipped with an electro-mechanical stirrer and a thermostatic heating bath, 500 g (0.25 mol) polyether M1 (Mw=2000), 162.5 g (0.50 mol) P-1, 45 g (2.5 mol) water, and 25 g (0.25 mol) sulfuric acid were added, and heated and stirred to be a homogeneous one phase system. Then, 60.75 g (0.75 mol) of a 37% aqueous formaldehyde solution was dropwise added in half an hour. After the dropwise addition was completed, the reaction lasted for 5 h at 100 C. After the reaction was finished, it was cooled to room temperature, neutralized with a 30% base solution to a pH of about 10, and further reacted for 0.5 to 1 h at 110 C. to remove unreacted formaldehyde. The reaction was cooled to room temperature, and diluted with water to a solution concentration of about 30% to 40%.

EXAMPLE 3

(16) In this example, A/B=1:2, C/(A+B)=1.0.

(17) In a 1000 ml four-necked flask equipped with an electro-mechanical stirrer and a thermostatic heating bath, 250 g (0.25 mol) polyether M1 (Mw=1000), 162.5 g (0.50 mol) P-1, 90 g (5.0 mol) water, and 25 g (0.25 mol) sulfuric acid were added, and heated and stirred to be a homogeneous one phase system. Then, 60.75 g (0.75 mol) of a 37% aqueous formaldehyde solution was dropwise added in half an hour. After the dropwise addition was completed, the reaction lasted for 6 h at 90 C. After the reaction was finished, it was cooled to room temperature, neutralized with a 30% base solution to a pH of about 10, and further reacted for 0.5 to 1 h at 110 C. to remove unreacted formaldehyde. The reaction was cooled to room temperature, and diluted with water to a solution concentration of about 30% to 40%.

EXAMPLE 4

(18) In this example, A/B=1:3, C/(A+B)=1.0.

(19) In a 5 L four-necked flask equipped with an electro-mechanical stirrer and a thermostatic heating bath, 250 g (0.25 mol) polyether M1 (Mw=1000), 233.7 g (0.75 mol) P-2, 90 g (5.0 mol) water, and 25 g (0.25 mol) sulfuric acid were added, and heated and stirred to be a homogeneous one phase system. Then, 81 g (1.0 mol) of a 37% aqueous formaldehyde solution was dropwise added in half an hour. After the dropwise addition was completed, the reaction lasted for 2 h at 130 C. After the reaction was finished, it was cooled to room temperature, neutralized with a 30% base solution to a pH of about 10, and further reacted for 0.5 to 1 h at 110 C. to remove unreacted formaldehyde. The reaction was cooled to room temperature, and diluted with water to a solution concentration of about 30% to 40%.

EXAMPLE 5

(20) In this example, A/B=1:2, C/(A+B)=1.0.

(21) In a 2000 ml four-necked flask equipped with an electro-mechanical stirrer and a thermostatic heating bath, 1000 g (0.25 mol) polyether M2 (Mw=4000), 156 g (0.50 mol) P-3, 90 g (5.0 mol) water, and 25 g (0.25 mol) sulfuric acid were added, and heated and stirred to be a homogeneous one phase system. Then, 60.75 g (0.75 mol) of a 37% aqueous formaldehyde solution was dropwise added in half an hour. After the dropwise addition was completed, the reaction lasted for 5 h at 100 C. After the reaction was finished, it was cooled to room temperature, neutralized with a 30% base solution to a pH of about 10, and further reacted for 0.5 to 1 h at 110 C. to remove unreacted formaldehyde. The reaction was cooled to room temperature, and diluted with water to a solution concentration of about 30% to 40%.

EXAMPLE 6

(22) In this example, A/B=1:3, C/(A+B)=2.0.

(23) In a 1000 ml four-necked flask equipped with an electro-mechanical stirrer and a thermostatic heating bath, 500 g (0.25 mol) polyether M3 (Mw=2000), 183.81 g (0.75 mol) P-4, 90 g (5.0 mol) water, and 25 g (0.25 mol) sulfuric acid were added, and heated and stirred to be a homogeneous one phase system. Then, 162 g (2.0 mol) of a 37% aqueous formaldehyde solution was dropwise added in half an hour. After the dropwise addition was completed, the reaction lasted for 5 h at 100 C. After the reaction was finished, it was cooled to room temperature, neutralized with a 30% base solution to a pH of about 10, and further reacted for 0.5 to 1 h at 110 C. to remove unreacted formaldehyde. The reaction was cooled to room temperature, and diluted with water to a solution concentration of about 30% to 40%.

EXAMPLE 7

(24) In this example, A/B=1:4, C/(A+B)=1.6.

(25) In a 1000 ml four-necked flask equipped with an electro-mechanical stirrer and a thermostatic heating bath, 500 g (0.25 mol) polyether M4 (Mw=2000), 325 g (1.0 mol) P-1, 90 g (5.0 mol) water, and 25 g (0.25 mol) sulfuric acid were added, and heated and stirred to be a homogeneous one phase system. Then, 162 g (2.0 mol) of a 37% aqueous formaldehyde solution was dropwise added in half an hour. After the dropwise addition was completed, the reaction lasted for 5 h at 100 C. After the reaction was finished, it was cooled to room temperature, neutralized with a 30% base solution to a pH of about 10, and further reacted for 0.5 to 1 h at 110 C. to remove unreacted formaldehyde. The reaction was cooled to room temperature, and diluted with water to a solution concentration of about 30% to 40%.

EXAMPLE 8

(26) In this example, A/B=1:2, C/(A+B)=1.0.

(27) In a 1000 ml four-necked flask equipped with an electro-mechanical stirrer and a thermostatic heating bath, 500 g (0.25 mol) polyether M4 (Mw=2000), 69 g (0.50 mol) p-hydroxylphenylbenzoic acid, 45 g (2.5 mol) water, and 25 g (0.25 mol) sulfuric acid were added, heated and stirred to be a homogeneous one phase system. Then, 111 g (0.75 mol) of a 50% aqueous glyoxylic acid solution was dropwise added in half an hour. After the dropwise addition was completed, the reaction lasted for 5 h at 100 C. After the reaction was finished, it was cooled to room temperature, neutralized with a 30% base solution to a pH of about 10, and further reacted for 0.5 to 1 h at 110 C. to remove unreacted formaldehyde. The reaction was cooled to room temperature, and diluted with water to a solution concentration of about 30% to 40%.

EXAMPLE 9

(28) In this example, A/B=1:1, C/(A+B)=1.2.

(29) In a 1000 ml four-necked flask equipped with an electro-mechanical stirrer and a thermostatic heating bath, 250 g (0.25 mol) polyether M4 (Mw=1000), 81.1 g (0.25 mol) P-1, 45 g (2.5 mol) water, and 34.2 g (0.25 mol, 70% aqueous solution) methanesulfonic acid were added, and heated and stirred to be a homogeneous one phase system. Then, 44.4 g (0.3 mol) of a 50% aqueous glyoxylic acid solution and 24.3 g (0.3 mol) of a 37% aqueous formaldehyde solution were dropwise added in half an hour. After the dropwise addition was completed, the reaction lasted for 5 h at 100 C. After the reaction was finished, it was cooled to room temperature, neutralized with a 30% base solution to a pH of about 10, and further reacted for 0.5 to 1 h at 110 C. to remove unreacted formaldehyde. The reaction was cooled to room temperature, and diluted with water to a solution concentration of about 30% to 40%.

EXAMPLE 10

(30) In this example, A/B=1:2, C/(A+B)=1.33.

(31) In a 1000 ml four-necked flask equipped with an electro-mechanical stirrer and a thermostatic heating bath, 250 g (0.25 mol) polyether M4 (Mw=1000), 162.2 g (0.5 mol) P-1, 45 g (2.5 mol) water, and 34.2 g (0.25 mol, 70% aqueous solution) methanesulfonic acid were added, and heated and stirred to be a homogeneous one phase system. Then, 81 g (1.0 mol) of a 37% aqueous formaldehyde solution was dropwise added in half an hour. After the dropwise addition was completed, the reaction lasted for 5 h at 105 C. After the reaction was finished, it was cooled to room temperature, neutralized with a 30% base solution to a pH of about 10, and further reacted for 0.5 to 1 h at 110 C. to remove unreacted formaldehyde. The reaction was cooled to room temperature, and diluted with water to a solution concentration of about 30% to 40%.

EXAMPLE 11

(32) In this example, A/B=1:6, C/(A+B)=1.0.

(33) In a 1000 ml four-necked flask equipped with an electro-mechanical stirrer and a thermostatic heating bath, 500 g (0.25 mol) polyether M1 (Mw=2000), 487.5 g (1.50 mol) P-1, 45 g (2.5 mol) water, and 50 g (0.5 mol) sulfuric acid were added, and heated and stirred to be a homogeneous one phase system. Then, 141.75 g (1.75 mol) of a 37% aqueous formaldehyde solution was dropwise added in half an hour. After the dropwise addition was completed, the reaction lasted for 5 h at 100 C. After the reaction was finished, it was cooled to room temperature, neutralized with a 30% base solution to a pH of about 10, and further reacted for 0.5 to 1 h at 110 C. to remove unreacted formaldehyde. The reaction was cooled to room temperature, and diluted with water to a solution concentration of about 30% to 40%.

EXAMPLE 12

(34) In this example, A/B=1:2, C/(A+B)=1.33.

(35) In a 1000 ml four-necked flask equipped with an electro-mechanical stirrer and a thermostatic heating bath, 500 g (0.25 mol) polyether M5 (Mw=2000), 169 g (0.50 mol) P-6, 45 g (2.5 mol) water, and 50 g (0.5 mol) sulfuric acid were added, and heated and stirred to be a homogeneous one phase system. Then, 81 g (1.0 mol) of a 37% aqueous formaldehyde solution was dropwise added in half an hour. After the dropwise addition was completed, the reaction lasted for 5 h at 100 C. After the reaction was finished, it was cooled to room temperature, neutralized with a 30% base solution to a pH of about 10, and further reacted for 0.5 to 1 h at 110 C. to remove unreacted formaldehyde. The reaction was cooled to room temperature, and diluted with water to a solution concentration of about 30% to 40%.

EXAMPLE 13

(36) In this example, A/B=1:2, C/(A+B)=1.33.

(37) In a 1000 ml four-necked flask equipped with an electro-mechanical stirrer and a thermostatic heating bath, 500 g (0.25 mol) polyether M5 (Mw=2000), 162.5 g (0.50 mol) P-5, 45 g (2.5 mol) water, and 25 g (0.25 mol) sulfuric acid were added, and heated and stirred to be a homogeneous one phase system. Then, 81 g (1.0 mol) of a 37% aqueous formaldehyde solution was dropwise added in half an hour. After the dropwise addition was completed, the reaction lasted for 5 h at 100 C. After the reaction was finished, it was cooled to room temperature, neutralized with a 30% base solution to a pH of about 10, and further reacted for 0.5 to 1 h at 110 C. to remove unreacted formaldehyde. The reaction was cooled to room temperature, and diluted with water to a solution concentration of about 30% to 40%.

COMPARATIVE EXAMPLE

(38) The preparation of the comparative example was made with reference to Example 5 disclosed in a Chinese invention patent CN 103183792 B.

(39) Fluidity of cement paste was tested according to the GB/T 8077-2000Methods for testing uniformity of concrete admixture, where the used cement was Onoda cement (300 g) and the water/cement ratio was 0.29. The results are shown in Table 1.0.

(40) TABLE-US-00001 TABLE 1.0 Conversion rate of polymerization and fluidity of paste Conversion No. Mw PDI rate (%) Dosage Paste (mm) Example 1 21385 1.56 94 1.1 242 Example 2 22356 1.63 93 1.0 254 Example 3 20396 1.72 92 1.0 263 Example 4 25642 1.65 89 1.0 258 Example 5 23654 1.66 90 1.0 253 Example 6 21089 1.73 95 1.0 254 Example 7 22356 1.59 93 1.0 262 Example 8 30000 1.63 90 1.1 258 Example 9 39657 1.82 91 1.0 249 Example 10 21934 1.89 87 1.0 232 Example 11 11293 1.52 81 1.1 210 Example 12 21323 1.49 88 1.0 249 Example 13 20357 1.56 89 1.0 233 Comparative 24100 1.15 92 1.2 223 Example

(41) The properties of concrete mixed with the polymer of the present invention were tested with reference to related provisions in JC473-2001Pumping Aid for Concrete, and the air content was tested with reference to related provisions in GB8076-2008Concrete Admixtures. The sand samples as shown in Table 2.0 were used in these tests. The results are shown in Tables 3.0 and 4.0.

(42) TABLE-US-00002 TABLE 2.0 Data of sand samples Fineness Mud Sand sample No. Origin modulus content (%) Sand sample 1 Hunan-Dongting 2.9 2.3 Lake sand Sand sample 2 Mingguang 2.6 3.7

(43) TABLE-US-00003 TABLE 3.0 Testing results of concrete Dosage Slump Sand (solid (mm) Strength (MPa) sample Admixture content %) Initial 1 h 3 d 7 d 28 d Sand Example 1 0.15 227 203 19.8 31.8 40.1 sample 1 Example 2 0.14 224 200 20.5 33.1 40.5 Example 3 0.14 218 203 20.3 30.8 40.7 Example 4 0.15 223 207 21.7 32.1 40.9 Example 5 0.14 221 206 21.2 30.9 40.3 Example 6 0.16 228 203 21.0 30.7 40.8 Example 7 0.14 236 219 21.5 31.5 41.5 Example 8 0.16 227 205 21.8 31.9 41.6 Example 9 0.14 231 210 22.9 32.0 42.5 Example 10 0.15 223 200 21.3 30.3 41.2 Example 11 0.16 212 195 20.3 29.3 40.2 Example 12 0.15 237 215 21.9 31.7 41.5 Example 13 0.15 229 207 22.8 32.9 40.6 Comparative 0.17 225 170 18.3 27.7 37.6 Example Sand Example 1 0.16 223 202 21.8 31.2 39.7 sample 2 Example 2 0.16 221 198 20.6 30.9 38.9 Example 3 0.16 218 195 21.0 31.7 39.6 Example 4 0.16 224 201 20.4 30.8 38.3 Example 5 0.16 217 198 21.1 31.9 39.3 Example 6 0.16 224 203 21.6 31.5 39.7 Example 7 0.16 225 199 20.9 30.5 40.7 Example 8 0.18 231 171 21.3 31.6 40.3 Example 9 0.16 229 208 20.5 29.5 39.2 Example 10 0.17 221 203 22.3 31.0 40.5 Example 11 0.18 223 193 20.3 29.3 38.2 Example 12 0.16 229 209 21.7 30.9 40.6 Example 13 0.16 237 215 22.8 31.7 42.5 Comparative 0.19 223 157 18.4 27.3 35.5 Example

(44) It can be known from Table 3.0 that, compared to the comparative sample, in sand having a higher mud content, both the water-reducing and slump-retaining properties of phosphoric acid water-reducing agents as reported in the present invention are substantially improved. In particular, the dosages of the bidentate phosphoric acid products are low (examples 2-5, 7, 9-10, 12-13), while the water-reducing properties of the samples of water-reducing agents synthesized from sulfonic group-containing monomers and monodentate phosphoric acid monomers are slightly reduced compared to the bidentate samples, but are still better than the comparative sample, and the slump-retaining properties thereof are significantly improved (examples 1 and 6). In contrast, the carboxylic monomer (e.g., p-hydroxylphenylbenzoic acid in example 8) exhibits non-adaptability for concrete having a higher mud content and has an inferior effect compared to others. In addition, compared to the standard sample, all the samples synthesized from bis-polyether have controlled air-entraining ability, and the strength is increased at 3d, 7d and 28d.

(45) TABLE-US-00004 TABLE 4.0 Air content Admixture Air content Example 1 3.5 Example 2 3.0 Example 3 3.1 Example 4 3.3 Example 5 3.0 Example 6 2.9 Example 7 3.2 Example 8 3.3 Example 9 3.0 Example 10 3.1 Example 11 2.9 Example 12 3.0 Example 13 3.0 Comparative example 6.1

(46) It can be known from Table 4.0 that, under the same testing conditions of concrete, the air contents of the examples are decreased compared to the comparative example, indicating that the new polymer developed in the present invention has suitable air-entraining ability, which is very helpful for later strength improvement of concrete.