CN109111551B - Preparation method of anti-mud polycarboxylate superplasticizer based on 3000-molecular-weight polyether - Google Patents
Preparation method of anti-mud polycarboxylate superplasticizer based on 3000-molecular-weight polyether Download PDFInfo
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 44
- 229920000570 polyether Polymers 0.000 title claims abstract description 44
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 100
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000178 monomer Substances 0.000 claims abstract description 41
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 38
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 17
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 17
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 17
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 17
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 14
- 239000010452 phosphate Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 52
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 18
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 18
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 claims description 16
- -1 methacryloyloxyethyl trimellitic anhydride Chemical compound 0.000 claims description 14
- 150000003871 sulfonates Chemical class 0.000 claims description 13
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 8
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 5
- VQIDGTFLGAAJGI-UHFFFAOYSA-M sodium;prop-1-ene-1-sulfonate Chemical compound [Na+].CC=CS([O-])(=O)=O VQIDGTFLGAAJGI-UHFFFAOYSA-M 0.000 claims description 5
- AEUVIXACNOXTBX-UHFFFAOYSA-N 1-sulfanylpropan-1-ol Chemical compound CCC(O)S AEUVIXACNOXTBX-UHFFFAOYSA-N 0.000 claims description 4
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 3
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims description 3
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 abstract 1
- 239000004568 cement Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 18
- 239000004927 clay Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- 239000000203 mixture Substances 0.000 description 14
- 239000010410 layer Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 239000004567 concrete Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000013461 design Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000002156 adsorbate Substances 0.000 description 5
- 230000036571 hydration Effects 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 4
- 125000005394 methallyl group Chemical group 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000004873 anchoring Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 230000036962 time dependent Effects 0.000 description 3
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 2
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229930003268 Vitamin C Natural products 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- BYZDRRAHLZZRGC-UHFFFAOYSA-N ethyl 2-(2-methylprop-2-enoylperoxycarbonyl)benzoate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OOC(=O)C(C)=C BYZDRRAHLZZRGC-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 235000019154 vitamin C Nutrition 0.000 description 2
- 239000011718 vitamin C Substances 0.000 description 2
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 241000860832 Yoda Species 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000004574 high-performance concrete Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- QVDTXNVYSHVCGW-ONEGZZNKSA-N isopentenol Chemical compound CC(C)\C=C\O QVDTXNVYSHVCGW-ONEGZZNKSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention provides a preparation method of a mud-resistant polycarboxylate superplasticizer based on 3000 molecular weight polyether, which comprises the following steps: 1) adding a 3000-molecular-weight polyether macromonomer, a phenyl carboxylic acid functional monomer, a phosphate functional monomer and water in a certain mass ratio into a reaction kettle, and stirring and heating until the polyether macromonomer, the phenyl carboxylic acid functional monomer, the phosphate functional monomer and the water are dissolved; 2) controlling the temperature at 46-52 ℃, and starting to add a certain amount of hydrogen peroxide; 3) after 5min, beginning to dropwise add the solution B; after the solution B is dripped, the solution A is dripped within 10min, the dripping time of the solution A is a hour, the value of a is 2-4, and the dripping time of the solution B is a +0.5 hour; the solution A consists of acrylic acid, unsaturated sulfonate and water in a certain mass ratio, and the solution B consists of ascorbic acid, a chain transfer agent and water in a certain mass ratio; 4) after the dropwise addition is finished, keeping the temperature constant, curing for 1-3 hours, slowly adding a certain amount of neutralizing agent when the temperature of the reaction solution is lower than 30 ℃, and replenishing water to 1000 parts to obtain the anti-mud polycarboxylate superplasticizer based on 3000 molecular weight polyether with the mass fraction of 40%.
Description
Technical Field
The invention belongs to the technical field of building materials, relates to the field of concrete admixtures, and particularly relates to a preparation method of a mud-resistant polycarboxylate superplasticizer based on polyether with the molecular weight of 3000.
Background
The water reducing agent is used as an important component in high-performance concrete, develops very rapidly, and with the continuous expansion of scale, higher requirements are provided for the water reducing rate, slump retaining property, adaptability and the like of the water reducing agent. The problem that present high-quality grit resource reduces, the grit use amount of secondary material constantly increases, and the mud content in the grit material has the trend of constantly increasing, and more uncomfortable circumstances appear in ordinary polycarboxylate water reducing agent product in use, awaits urgently to have new design, and the product of new molecular configuration supplements. The sandstone material with high mud content, wherein the clay strong adsorbate often has a layered structure, the length of the main chain and the side chain of the common polycarboxylic acid water reducing agent is difficult to exert the effect under the condition, and the side chain with normal length can enable the whole chain segment to enter the interlayer pores of the clay, so that the steric hindrance effect cannot be exerted; the configuration of the length of the main chain and the density of the side chain of the common water reducer also enables the water reducer molecules to be easily restrained by strong adsorbates, so that the whole water reducer molecules are difficult to break loose and lose the dispersing effect.
According to the invention, the initial adsorption capacity of water reducing agent molecules on the surfaces of cement particles is improved and the adsorption probability of the water reducing agent molecules on the surfaces of the cement particles is increased by increasing the proportion of hydrophilic groups such as carboxyl, sulfonic group, phosphate group and the like and increasing the length of a main chain. The method comprises the steps of using 3000 molecular weight polyether as a raw material to obtain a longer side chain, preparing a longer main chain and a high acid-ether ratio design to solve the problem that two cement particles are too close to each other due to unobvious mutual steric hindrance effect between the molecules of a water reducing agent caused by larger side chain disturbance, and separating the two cement particles to a position where the long side chain can play a steric hindrance effect by utilizing a strong electrostatic repulsion force caused by the high carboxyl density; in the higher hydration environment of mud content, the side chain is longer lets the side chain also can not lose whole steric hindrance effect even get into between the adsorbed layer, and the side chain is longer and side chain density is less moreover, leads to even have the side chain when adsorbed between the clay layer, and the side chain that gets into between the layer can cause the screens because there is the difference in angle in getting into direction and the interlaminar direction, makes the adsorbate can't further influence whole water-reducing agent molecule. The introduction of the phenyl carboxylic acid functional monomer can enhance the steric hindrance effect, and simultaneously, the benzene ring can also be butted against the end face of the layered clay to prevent the side chain from entering the interlayer of the clay.
The patent CN107337766A discloses a high-adaptability polycarboxylate superplasticizer and a preparation method thereof, and the high-adaptability polycarboxylate superplasticizer is prepared by carrying out free radical copolymerization on a carboxylic acid monomer A, a high molecular weight polyether macromonomer B, a functional polycation macromonomer C and an unsaturated phosphate ester monomer D. The high-adaptability polycarboxylate superplasticizer is suitable for areas with high sand-aggregate mud content, and has the advantages of low mixing amount, high water reduction and high slump loss resistance; the high-adaptability polycarboxylate superplasticizer disclosed by the invention is simple in preparation process, green and environment-friendly in production process and low in cost.
The patent CN107011489A discloses a preparation method of a slump-retaining polycarboxylic acid water reducing agent with a high acid-ether ratio, and the preparation method specifically comprises a kettle bottom solution, an A1 material solution, an A2 material solution and a B material solution; s1, providing double-bond-terminated polyoxyethylene ether, a double-bond monomer, an oxidant, unsaturated ester, a chain transfer agent and a reducing agent vitamin C; s2, preparing kettle bottom liquid: mixing polyoxyethylene ether with terminal double bonds, double bond monomers, an oxidant and water to prepare a kettle bottom solution; preparation of S3 and A1 material solution: the A1 material solution is formed by mixing a double-bond monomer and water; preparation of S4 and A2 material solution: the A2 material solution is composed of unsaturated ester, double bond monomer and water; s5, preparation of material B solution: the solution of the material B consists of a reducing agent vitamin C, a chain transfer agent and water. Compared with the slump retaining polycarboxylic acid water reducing agent, the acid ether provided by the invention has the advantages that the consumption of the double-bond-terminated polyoxyethylene ether is less, the cost is reduced, the good water reducing and slump retaining performances are kept, the preparation method is simple in process, and the slump retaining polycarboxylic acid water reducing agent is suitable for industrial production.
Patent CN107325236A discloses a non-clay sensitive polycarboxylate superplasticizer and a preparation method thereof, and the polycarboxylate superplasticizer is specifically prepared by taking a 4-hydroxybutyl vinyl ether macromonomer, unsaturated carboxylic acid, unsaturated sulfonate and unsaturated ester small monomer as comonomers and taking an initiator and a chain transfer agent as molecular regulators for copolymerization. The water reducer is insensitive to the mud content of the sandstone materials in the concrete, has higher water reducing capacity and smaller slump loss when being applied to the concrete with high mud content compared with the traditional polycarboxylic acid water reducer, and solves the problem of sensitivity to the sandstone raw material soil in the application of the traditional polycarboxylic acid water reducer to the concrete.
Different from the patents, the invention adopts a formula design of 3000 molecular weight polyether macromonomer, high acid-ether ratio and low chain transfer agent dosage, introduces groups with stronger adsorption capacity than carboxylic groups, such as sulfonic group, phosphoric group and the like, enhances the adsorption capacity and adsorption probability of anchoring groups to positively charged cement particles, introduces phenyl carboxylic acid functional monomers, and prevents a side chain from entering between clay layers by utilizing the fact that a benzene ring can be collided with the end face of layered clay. Finally, the obtained mud-resistant polycarboxylate superplasticizer has longer main chain length, larger proportion and density of carboxyl, sulfonic group and phosphate group, stronger electrostatic repulsion and more obvious steric hindrance effect.
Disclosure of Invention
The invention aims to solve the technical problem of providing a mud-resistant polycarboxylate superplasticizer based on 3000 molecular weight polyether and a preparation method thereof.
In order to obtain a target molecular configuration, 3000 molecular weight polyether is used as a raw material to obtain a longer side chain, in order to solve the problem that the side chain interference degree is larger due to the longer side chain, so that two cement particles are too close to each other due to unobvious mutual steric hindrance effect between the water reducing agent molecules, a longer main chain is prepared, a high-acid-ether ratio design is adopted, the carboxyl density higher than that of a common polycarboxylic acid water reducing agent is obtained, a strong electrostatic repulsion force caused by the high carboxyl density is utilized to enable long side chains between the two water reducing agent molecules to be crossed and in a cross connection state to be repelled to a long branched chain terminal collision state, and the collision state can better play the steric hindrance effect of the; in addition, the designed value of the carboxyl density of the water reducing agent molecules is 1.5-2 times of the carboxyl density of a normal water reducing agent, and strong anchoring groups of sulfonic acid groups and phosphoric acid groups are matched, so that the adsorption capacity and adsorption probability of the water reducing agent molecules on positively charged cement particles are enhanced. The phenyl carboxylic acid functional monomer is introduced to enhance steric hindrance, and a benzene ring can be butted against the end face of the layered clay to prevent a side chain from entering the interlayer of the clay.
The longer side chain can promote the main chain to be longer and promote the formation of a thicker hydration layer, so that the water reducer molecules can exert good dispersibility. In the higher hydration environment of mud content, the side chain is longer lets the side chain also can not lose whole steric hindrance effect even get into between the adsorbed layer, and the side chain is longer and side chain density is less moreover, leads to even have the side chain when adsorbed between the clay layer, and the side chain that gets into between the layer can cause the screens because there is the difference in angle in getting into direction and the interlaminar direction, makes the adsorbate can't further influence whole water-reducing agent molecule. The structure with long side chains and low side chain density can also reduce the probability that a large number of side chains are simultaneously adsorbed by clay particles in the adjacent area.
In conclusion, the polycarboxylic acid water reducing agent with high water reducing rate and good mud resistance effect is prepared by adopting multiple designs aiming at the condition of high mud content.
The technical scheme of the invention is as follows:
a preparation method of a mud-resistant polycarboxylate superplasticizer based on 3000 molecular weight polyether is disclosed, wherein the superplasticizer is mainly prepared from the following components: 3000 molecular weight polyether macromonomer, hydrogen peroxide, acrylic acid, unsaturated sulfonate, ascorbic acid, phenyl carboxylic acid functional monomer, phosphate functional monomer, chain transfer agent, neutralizer and water; the total mass is 1000 parts, the mass fraction of the prepared finished product is 40%, and the preparation method comprises the following steps:
1) adding 335-350 parts of 3000 molecular weight polyether macromonomer, 2-7 parts of phenylcarboxylic acid functional monomer, 1.5-5.5 parts of phosphate functional monomer and 180-220 parts of water into a reaction kettle, stirring and heating until the monomers are dissolved;
2) measuring the temperature in the kettle, controlling the temperature at 46-52 ℃, and adding 0.8-1.5 parts of hydrogen peroxide at one time after the temperature is stable;
3) after 5min, beginning to drip the solution B, after finishing dripping the solution B, beginning to drip the solution A within 10min, wherein the dripping time of the solution A is a hours, the value of a is 2-4, and the dripping time of the solution B is a +0.5 hour; the solution B consists of 0.35 to 0.55 part of ascorbic acid, 0.3 to 0.6 part of chain transfer agent and 80 to 100 parts of water, and the solution A consists of 33 to 40 parts of acrylic acid, 1.5 to 5 parts of unsaturated sulfonate and 50 to 70 parts of water;
4) after the dropwise addition is finished, keeping the temperature constant, curing for 1-3 hours, slowly adding 6-12 parts of neutralizing agent when the temperature of the reaction solution is lower than 30 ℃, and replenishing water to 1000 parts to obtain the anti-mud polycarboxylate superplasticizer based on 3000 molecular weight polyether with the mass fraction of 40%.
In the preparation method, the polyether macromonomer with the molecular weight of 3000 consists of one or more of allyl polyoxyethylene ether, methyl allyl polyoxyethylene ether, prenol polyoxyethylene ether and vinyl butyl ether polyoxyethylene ether with the molecular weight of 3000; preferably one or more of prenyl polyoxyethylene ether with molecular weight of 3000, methallyl polyoxyethylene ether with molecular weight of 3000 and methallyl polyoxyethylene ether with molecular weight of 3000; preferably, the prenol polyoxyethylene ether has a molecular weight of 3000.
In the preparation method, the unsaturated sulfonate is composed of one or more of sodium vinyl sulfonate, sodium propenyl sulfonate, sodium methyl propylene sulfonate, sodium styrene sulfonate and 2-acrylamide-2-methylpropanesulfonic acid; a composition of sodium propenyl sulfonate and sodium methyl propylene sulfonate in a mass ratio of 1:1 is preferred.
In the preparation method, the phenyl carboxylic acid functional monomer is composed of one or more of methacryloyloxyethyl trimellitic anhydride, methacryloyloxyethyl phthalic monoester and pyromellitic dianhydride hydroxyethyl dimethacrylate; preferably, the pyromellitic dianhydride hydroxyethyl dimethacrylate with larger molecular weight and certain steric hindrance effect is selected.
In the preparation method, the phosphate functional monomer is one or two of methacryloyloxyethyl phosphate and ethylene glycol methacrylate phosphate; a composition of methacryloyloxyethyl phosphate and ethylene glycol methacrylate phosphate in a mass ratio of 2:1 is preferred.
In the preparation method, the chain transfer agent is composed of one or more of thioglycolic acid, mercaptopropionic acid, mercaptoethanol and mercaptopropanol; preference is given to a composition of thioglycolic acid and mercaptopropionic acid in a mass ratio of 1: 2.
In the preparation method, the neutralizing agent is composed of one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, sodium ethoxide, ethanolamine, diethanolamine, triethanolamine and triisopropanolamine; a composition of sodium methoxide and triisopropanolamine in a mass ratio of 1:1 is preferred.
In the preparation method, the hydrogen peroxide is 27.5% of industrial grade hydrogen peroxide in percentage by mass.
In step 3) of the above preparation method, the dropping time of the solution a is preferably 3 hours.
In step 4) of the above preparation method, the aging time is preferably 2.5 hours.
The invention has the beneficial effects that:
1. the 3000 molecular weight polyether is used as a raw material, so that a longer side chain is obtained, the longer side chain can promote a longer main chain to promote a thicker hydration layer to be formed, and the water reducer molecules can exert good dispersibility. In the higher hydration environment of mud content, the side chain is longer lets the side chain also can not lose whole steric hindrance effect even get into between the adsorbed layer, and the side chain is longer and side chain density is less moreover, leads to even have the side chain when adsorbed between the clay layer, and the side chain that gets into between the layer can cause the screens because there is the difference in angle in getting into direction and the interlaminar direction, makes the adsorbate can't further influence whole water-reducing agent molecule. The structure with long side chains and low side chain density can also reduce the probability that a large number of side chains are simultaneously adsorbed by clay particles in the adjacent area. The phenyl carboxylic acid functional monomer is introduced to enhance steric hindrance, and a benzene ring can be butted against the end face of the layered clay to prevent a side chain from entering the interlayer of the clay.
2. In order to solve the problem that the side chain interference degree is large due to the fact that the side chain is long, and the two cement particles are too close to each other due to the fact that the mutual steric hindrance effect between the water reducing agent molecules is not obvious, the long main chain and the high-acid-ether ratio design are prepared, the carboxyl density higher than that of a common polycarboxylic acid water reducing agent is obtained, and the long side chains between the two water reducing agent molecules are crossed and in a cross-linking state through strong electrostatic repulsion force due to the high carboxyl density, so that the long side chains are pushed to be in a collision state at the tail end of the long side chain, and the collision state; in addition, the designed value of the carboxyl density of the water reducing agent molecules is 1.5-2 times of the carboxyl density of a normal water reducing agent, and strong anchoring groups of sulfonic acid groups and phosphoric acid groups are matched, so that the adsorption capacity and adsorption probability of the water reducing agent molecules on positively charged cement particles are enhanced.
Detailed Description
The present invention will be described in further detail below by way of examples for the purpose of facilitating understanding and practicing the present invention by those of ordinary skill in the art, it being understood that the examples described herein are for the purpose of illustration and explanation only and are not intended to limit the present invention.
Aoke 702 is specifically isopentenol polyoxyethylene ether with a molecular weight of 3000, aoke 703 is specifically methallyl polyoxyethylene ether with a molecular weight of 3000, and linkage fluid WR6251 is specifically methallyl polyoxyethylene ether with a molecular weight of 3000.
Example 1
An anti-mud polycarboxylate superplasticizer based on 3000 molecular weight polyether is mainly prepared from the following components: 3000 molecular weight polyether macromonomer, hydrogen peroxide, acrylic acid, unsaturated sulfonate, ascorbic acid, phenyl carboxylic acid functional monomer, phosphate functional monomer, chain transfer agent, neutralizer and water; the total mass is 1000 parts, the mass fraction of the prepared finished product is 40%, and the preparation method comprises the following steps:
1) adding 335 parts of oxk 702, 5 parts of methacryloyloxyethyl phthalate monoester, 5.5 parts of ethylene glycol methacrylate phosphate and 220 parts of water into a reaction kettle, stirring and heating until the materials are dissolved;
2) measuring the temperature in the kettle, controlling the temperature at 46 ℃, and adding 0.8 part of 27.5% industrial grade hydrogen peroxide at one time after the temperature is stable;
3) after 5min, beginning to drip the solution B, and after finishing dripping the solution B, beginning to drip the solution A within 10 min; the dropping time of the solution A is 2 hours, and the dropping time of the solution B is 2.5 hours; the solution B consists of 0.35 part of ascorbic acid, 0.6 part of a composition of thioglycolic acid and mercaptopropionic acid in a mass ratio of 1:2 and 80 parts of water, and the solution A consists of 40 parts of acrylic acid, 1.5 parts of sodium propenyl sulfonate and 70 parts of water;
4) after the dropwise addition is finished, keeping the temperature constant, curing for 1 hour, slowly adding 12 parts of sodium carbonate when the temperature of the reaction solution is lower than 30 ℃, and replenishing water to 1000 parts to obtain the anti-mud polycarboxylate superplasticizer based on 3000 molecular weight polyether with the mass fraction of 40%.
Example 2
An anti-mud polycarboxylate superplasticizer based on 3000 molecular weight polyether is mainly prepared from the following components: 3000 molecular weight polyether macromonomer, hydrogen peroxide, acrylic acid, unsaturated sulfonate, ascorbic acid, phenyl carboxylic acid functional monomer, phosphate functional monomer, chain transfer agent, neutralizer and water; the total mass is 1000 parts, the mass fraction of the prepared finished product is 40%, and the preparation method comprises the following steps:
1) adding 342 parts of oxk 703, 2 parts of maleic anhydride hydroxyethyl dimethacrylate, 5.3 parts of methacryloyloxyethyl phosphate and 210 parts of water into a reaction kettle, stirring and heating until the materials are dissolved;
2) measuring the temperature in the kettle, controlling the temperature at 47 ℃, and adding 0.9 part of 27.5% industrial grade hydrogen peroxide in percentage by mass at one time after the temperature is stable;
3) after 5min, beginning to drip the solution B, and after finishing dripping the solution B, beginning to drip the solution A within 10 min; the dropping time of the solution A is 2.5 hours, and the dropping time of the solution B is 3 hours; solution B consists of 0.5 part of ascorbic acid, 0.35 part of thioglycolic acid and 95 parts of water, and solution A consists of 39 parts of acrylic acid, 4 parts of sodium vinylsulfonate and 66 parts of water;
4) after the dropwise addition is finished, keeping the temperature constant, curing for 1.5 hours, slowly adding 7 parts of ethanolamine when the temperature of the reaction solution is lower than 30 ℃, and replenishing water to 1000 parts to obtain the anti-mud polycarboxylate superplasticizer based on polyether with molecular weight of 3000 with the mass fraction of 40%.
Example 3
An anti-mud polycarboxylate superplasticizer based on 3000 molecular weight polyether is mainly prepared from the following components: 3000 molecular weight polyether macromonomer, hydrogen peroxide, acrylic acid, unsaturated sulfonate, ascorbic acid, phenyl carboxylic acid functional monomer, phosphate functional monomer, chain transfer agent, neutralizer and water; the total mass is 1000 parts, the mass fraction of the prepared finished product is 40%, and the preparation method comprises the following steps:
1) adding 340 parts of yoda WR6251, 6 parts of methacryloxyethyl trimellitic anhydride, 4 parts of a composition of methacryloxyethyl phosphate and ethylene glycol methacrylate phosphate in a mass ratio of 2:1 and 200 parts of water into a reaction kettle, stirring and heating until the components are dissolved;
2) measuring the temperature in the kettle, controlling the temperature at 48 ℃, and adding 1 part of 27.5 mass percent of industrial grade hydrogen peroxide at one time after the temperature is stable;
3) after 5min, beginning to drip the solution B, and after finishing dripping the solution B, beginning to drip the solution A within 10 min; the dropping time of the solution A is 3 hours, and the dropping time of the solution B is 3.5 hours; solution B consists of 0.34 part of ascorbic acid, 0.4 part of mercaptoethanol and 86 parts of water, and solution A consists of 37 parts of acrylic acid, 3.8 parts of 2-acrylamide-2-methylpropanesulfonic acid and 58 parts of water;
4) after the dropwise addition, keeping the temperature constant, curing for 1.8 hours, slowly adding 9 parts of potassium hydroxide when the temperature of the reaction solution is lower than 30 ℃, and replenishing water to 1000 parts to obtain the anti-mud polycarboxylate superplasticizer based on 3000 molecular weight polyether with the mass fraction of 40%.
Example 4
An anti-mud polycarboxylate superplasticizer based on 3000 molecular weight polyether is mainly prepared from the following components: 3000 molecular weight polyether macromonomer, hydrogen peroxide, acrylic acid, unsaturated sulfonate, ascorbic acid, phenyl carboxylic acid functional monomer, phosphate functional monomer, chain transfer agent, neutralizer and water; the total mass is 1000 parts, the mass fraction of the prepared finished product is 40%, and the preparation method comprises the following steps:
1) adding 343 parts of oxk 703, 5.5 parts of a composition of methacryloyloxyethyl phthalate monoester and pyromellitic dianhydride hydroxyethyl dimethacrylate in a mass ratio of 1:1, 2 parts of a composition of methacryloyloxyethyl phosphate and ethylene glycol methacrylate phosphate in a mass ratio of 1:1 and 190 parts of water into a reaction kettle, stirring and heating until the materials are dissolved;
2) measuring the temperature in the kettle, controlling the temperature at 50 ℃, and adding 1.1 parts of 27.5% industrial grade hydrogen peroxide at one time after the temperature is stable;
3) after 5min, beginning to drip the solution B, and after finishing dripping the solution B, beginning to drip the solution A within 10 min; the dropping time of the solution A is 3.5 hours, and the dropping time of the solution B is 4 hours; solution B consists of 0.45 part of ascorbic acid, 0.45 part of mercaptopropanol and 98 parts of water, and solution A consists of 36 parts of acrylic acid, 2 parts of sodium styrene sulfonate and 56 parts of water;
4) after the dropwise addition is finished, keeping the temperature constant, curing for 2 hours, slowly adding 11 parts of ethanolamine when the temperature of the reaction solution is lower than 30 ℃, and replenishing water to 1000 parts to obtain the anti-mud polycarboxylate superplasticizer based on 3000 molecular weight polyether with the mass fraction of 40%.
Example 5
An anti-mud polycarboxylate superplasticizer based on 3000 molecular weight polyether is mainly prepared from the following components: 3000 molecular weight polyether macromonomer, hydrogen peroxide, acrylic acid, unsaturated sulfonate, ascorbic acid, phenyl carboxylic acid functional monomer, phosphate functional monomer, chain transfer agent, neutralizer and water; the total mass is 1000 parts, the mass fraction of the prepared finished product is 40%, and the preparation method comprises the following steps:
1) adding 350 parts of Bihong WR6251, 4 parts of a composition of 2:1 parts by mass of methacryloyloxyethyl trimellitic anhydride and pyromellitic dianhydride hydroxyethyl dimethacrylate, 3 parts of a composition of 1:2 parts by mass of methacryloyloxyethyl phosphate and ethylene glycol methacrylate phosphate and 185 parts of water into a reaction kettle, stirring and heating until the materials are dissolved;
2) measuring the temperature in the kettle, controlling the temperature at 50 ℃, and adding 1.3 parts of 27.5% industrial grade hydrogen peroxide at one time after the temperature is stable;
3) after 5min, beginning to drip the solution B, after finishing dripping the solution B, beginning to drip the solution A within 10min, wherein the dripping time of the solution A is 4 hours, and the dripping time of the solution B is 4.5 hours; the solution B consists of 0.5 part of ascorbic acid, 0.55 part of mercaptopropionic acid and 85 parts of water, and the solution A consists of 34 parts of acrylic acid, 2 parts of sodium methallyl sulfonate and 60 parts of water;
4) after the dropwise addition is finished, keeping the temperature constant, curing for 2.8 hours, slowly adding 6 parts of sodium methoxide and triisopropanolamine in a mass ratio of 1:1 when the temperature of the reaction solution is lower than 30 ℃, and replenishing water to 1000 parts to obtain the anti-mud polycarboxylic acid water reducing agent based on 3000 molecular weight polyether with the mass fraction of 40%.
Example 6
An anti-mud polycarboxylate superplasticizer based on 3000 molecular weight polyether is mainly prepared from the following components: 3000 molecular weight polyether macromonomer, hydrogen peroxide, acrylic acid, unsaturated sulfonate, ascorbic acid, phenyl carboxylic acid functional monomer, phosphate functional monomer, chain transfer agent, neutralizer and water; the total mass is 1000 parts, the mass fraction of the prepared finished product is 40%, and the preparation method comprises the following steps:
1) adding 345 parts of oke 702, 7 parts of a composition of methacryloyloxyethyl trimellitic anhydride and methacryloyloxyethyl phthalic monoester in a mass ratio of 1:1, 1.5 parts of a composition of methacryloyloxyethyl phosphate and ethylene glycol methacrylate phosphate in a mass ratio of 2:3 and 180 parts of water into a reaction kettle, stirring and heating until the materials are dissolved;
2) measuring the temperature in the kettle, controlling the temperature at 52 ℃, and adding 1.5 parts of 27.5% industrial grade hydrogen peroxide at one time after the temperature is stable;
3) after 5min, beginning to drip the solution B, and after finishing dripping the solution B, beginning to drip the solution A within 10 min; the dropping time of the solution A is 4.5 hours, and the dropping time of the solution B is 5 hours; the solution B consists of 0.55 part of ascorbic acid, 0.3 part of a composition of thioglycolic acid and mercaptopropanol in a mass ratio of 1:1 and 100 parts of water, and the solution A consists of 33 parts of acrylic acid, 5 parts of a composition of sodium propenyl sulfonate and sodium methyl propylene sulfonate in a mass ratio of 1:1 and 50 parts of water;
4) after the dropwise addition is finished, keeping the temperature constant, curing for 3 hours, slowly adding 8 parts of triethanolamine when the temperature of the reaction solution is lower than 30 ℃, and replenishing water to 1000 parts to obtain the anti-mud polycarboxylate superplasticizer based on 3000 molecular weight polyether with the mass fraction of 40%.
The mud-resistant type polycarboxylate superplasticizers based on 3000 molecular weight polyether of the above examples 1, 2, 3, 4, 5, 6 were tested for their initial fluidity of neat paste, fluidity of 1h, initial slump/extension of concrete and slump/extension over time at the same concentration as that of the ordinary polycarboxylate superplasticizers in different cements. The cement used in the experiment is Huaxin 42.5 ordinary silica cement, and the test standard GB/8076-.
TABLE 1 Effect of different water reducing agents on the flow of neat cement slurries (Huaxin 42.5 ordinary silica cement)
| Classes of water reducing agents | Initial flow/mm | 1h flowability/mm |
| Common water reducing agent | 240 | 200 |
| Example 1 | 245 | 210 |
| Example 2 | 250 | 220 |
| Example 3 | 240 | 215 |
| Example 4 | 245 | 210 |
| Example 5 | 245 | 220 |
| Example 6 | 255 | 225 |
TABLE 2 influence of different water-reducing agents on the flowability of ordinary concrete (Huaxin 42.5 ordinary portland cement)
TABLE 3 influence of different water-reducing agents on the flowability of the concrete with a high mud content (Huaxin 42.5 ordinary silica cement)
| Classes of water reducing agents | Initial slump/slump mm | Slump/slump with time of passage in mm |
| Common water reducing agent | 175/370 | 130/350 |
| Example 1 | 215/490 | 190/475 |
| Example 2 | 210/490 | 200/480 |
| Example 3 | 220/500 | 185/475 |
| Example 4 | 225/495 | 190/485 |
| Example 5 | 210/505 | 185/490 |
| Example 6 | 230/485 | 190/480 |
According to the comparison of the initial fluidity and the 1h fluidity of the cement paste, the initial fluidity and the time-lapse fluidity of the concrete, the cement paste initial fluidity and the 1h fluidity of the cement paste are slightly different from those of the common water reducing agent in the experiment of the mud-resistant polycarboxylate water reducing agent based on the 3000 molecular weight polyether in the examples 1, 2, 3, 4, 5 and 6, and the examples 1, 2, 3, 4, 5 and 6 are only slightly better than those of the common water reducing agent. When the water reducer is applied to ordinary concrete, the initial slump/expansion and the time-dependent slump/expansion of the examples 1, 2, 3, 5 and 6 are better than those of the ordinary water reducer, when the water reducer is applied to concrete with a large mud content, the initial slump/expansion and the time-dependent slump/expansion of the ordinary water reducer are greatly reduced, and the initial slump/expansion and the time-dependent slump/expansion of the examples 1, 2, 3, 4, 5 and 6 still keep higher levels. In conclusion, the mud-resistant polycarboxylate superplasticizer based on the polyether with the molecular weight of 3000 can show good adaptability in raw materials with large mud content, and the water reducing performance is not influenced by the quality of the raw materials.
Claims (7)
1. A preparation method of a mud-resistant polycarboxylate superplasticizer based on 3000 molecular weight polyether is characterized by comprising the following steps: the water reducing agent is mainly prepared from the following components: 3000 molecular weight polyether macromonomer, hydrogen peroxide, acrylic acid, unsaturated sulfonate, ascorbic acid, phenyl carboxylic acid functional monomer, phosphate functional monomer, chain transfer agent, neutralizer and water; the total mass is 1000 parts, the mass fraction of the prepared finished product is 40%, and the preparation method comprises the following steps:
1) adding 335-350 parts of 3000 molecular weight polyether macromonomer, 2-7 parts of phenylcarboxylic acid functional monomer, 1.5-5.5 parts of phosphate functional monomer and 180-220 parts of water into a reaction kettle, stirring and heating until the monomers are dissolved;
2) measuring the temperature in the kettle, controlling the temperature at 46-52 ℃, and adding 0.8-1.5 parts of hydrogen peroxide at one time after the temperature is stable;
3) after 5min, the solution B is sequentially dripped, and after the dripping of the solution B is finished, the solution A is dripped within 10 min; the dripping time of the solution A is a hours, the value of a is 2-4, and the dripping time of the solution B is a +0.5 hour; the solution B consists of 0.35 to 0.55 part of ascorbic acid, 0.3 to 0.6 part of chain transfer agent and 80 to 100 parts of water, and the solution A consists of 33 to 40 parts of acrylic acid, 1.5 to 5 parts of unsaturated sulfonate and 50 to 70 parts of water;
4) after the dropwise addition is finished, keeping the temperature constant, curing for 1-3 hours, slowly adding 6-12 parts of neutralizing agent when the temperature of the reaction solution is lower than 30 ℃, and replenishing water to 1000 parts to obtain the anti-mud polycarboxylate superplasticizer based on 3000 molecular weight polyether with the mass fraction of 40%;
the phenyl carboxylic acid functional monomer is composed of one or more of methacryloyloxyethyl trimellitic anhydride, methacryloyloxyethyl phthalic monoester and pyromellitic dianhydride hydroxyethyl dimethacrylate.
2. The method of claim 1, wherein: the polyether macromonomer with the molecular weight of 3000 comprises one or more of allyl polyoxyethylene ether, methyl allyl polyoxyethylene ether, prenol polyoxyethylene ether and vinyl butyl ether polyoxyethylene ether with the molecular weight of 3000.
3. The method of claim 1, wherein: the unsaturated sulfonate is composed of one or more of sodium vinyl sulfonate, sodium propenyl sulfonate, sodium methyl propylene sulfonate and sodium styrene sulfonate.
4. The method of claim 1, wherein: the phosphate functional monomer is composed of one or two of methacryloyloxyethyl phosphate and ethylene glycol methacrylate phosphate.
5. The method of claim 1, wherein: the chain transfer agent is composed of one or more of thioglycolic acid, mercaptopropionic acid, mercaptoethanol and mercaptopropanol.
6. The method of claim 1, wherein: the neutralizing agent is composed of one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, sodium ethoxide, ethanolamine, diethanolamine, triethanolamine and triisopropanolamine.
7. The method of claim 1, wherein: the hydrogen peroxide is 27.5 percent of industrial grade hydrogen peroxide by mass percent.
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