CN109320710B - Macromonomer and method for preparing polycarboxylate superplasticizer by using macromonomer - Google Patents
Macromonomer and method for preparing polycarboxylate superplasticizer by using macromonomer Download PDFInfo
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- CN109320710B CN109320710B CN201811148253.8A CN201811148253A CN109320710B CN 109320710 B CN109320710 B CN 109320710B CN 201811148253 A CN201811148253 A CN 201811148253A CN 109320710 B CN109320710 B CN 109320710B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- 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
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- 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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
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- 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
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Abstract
The invention discloses a macromonomer and a method for preparing a polycarboxylate superplasticizer by using the macromonomer, wherein the preparation of the macromonomer comprises the steps of adding an initiator or a polyoxyethylene ether prepolymer thereof and a catalyst; alternately adding ethylene oxide and propylene oxide to carry out ring-opening polymerization reaction; the ring-opening polymerization reaction temperature of the ethylene oxide is 100-130 ℃; the ring-opening polymerization temperature of the propylene oxide is 115-150 ℃, and a polymerized macromonomer containing an initial unit and a polyoxyethylene ether and polyoxypropylene ether alternating chain segment is obtained; the preparation method comprises the following steps of (1) preparing a polycarboxylate water reducer, wherein the mole number of a single chain segment of polyoxyethylene ether is 20-60, the mole number of a single chain segment of polyoxypropylene ether is 1-10: and (2) carrying out free radical copolymerization reaction by using an oxidation-reduction system, dropwise adding the monomer b and the auxiliary agent into the macromonomer and kettle bottom water, and initiating the free radical polymerization reaction to obtain the polycarboxylic acid water reducing agent, wherein the product has the effects of water reducing rate of 25-50%, low mixing amount, low concrete cost and better slump retaining property.
Description
Technical Field
The invention relates to the technical field of polycarboxylic acid water reducing agents, and particularly relates to a macromonomer and a method for preparing a polycarboxylic acid water reducing agent by using the macromonomer.
Background
The polycarboxylate superplasticizer is prepared by copolymerizing active macromonomers and various active small monomers. The macromonomer provides polymerizable active double bonds in a molecular structure, and meanwhile, a long-chain structure of the macromonomer provides strong steric hindrance for the water reducing agent. Domestic polycarboxylic acid macromonomers have been popularized for more than ten years, but the problems of few macromonomers, slow technical updating and the like exist, and the method is not beneficial to the further development of the industry. The invention aims to innovate the polycarboxylic acid macromonomer from the aspects of improving the reaction activity of the polycarboxylic acid macromonomer, improving the side chain structure and improving the steric hindrance effect of the water supply and reduction agent.
Disclosure of Invention
The invention aims to improve the synthesis technology and performance of a polycarboxylate water reducer macromonomer and polycarboxylic acid thereof, and provides a macromonomer and a method for preparing a polycarboxylate water reducer by using the macromonomer.
The technical scheme of the invention is as follows:
a polycarboxylate water reducing agent macromonomer is a polymer formed by adding ethylene oxide and propylene oxide to an initiator ROH, and has a molecular structure as follows:
RO-(C2H4O)a1-(C3H60)b1-(C2H4O)a2-(C3H60)b2-…(C2H4O)ai-(C3H60)bi-(C2H4O)ai+1-H
wherein: ROH is a vinyl glycol ether compound consisting of a vinyl end cap, an alkyl glycol ether unit and a hydroxyl end;
r has a structural formula of H2C＝CH-0-(CH2-)n-，n＝2～4；
a1，a2，…ai，ai+1The addition mole number of each chain segment polyoxyethylene ether is 20-60, a1+a2+…+ai+1＝70～230；
b1，b2，…biThe number of moles of polyoxypropylene ether added to each segment is 1-10, b1+b2+…+bi＝2～16；
i is the number of chain segments and is an integer of 1 to 4.
Further, the ROH is vinyl glycol ether (H)2C＝CH-0-(CH2)2-OH), propylene glycol monovinyl ether (H)2C＝CH-0-(CH2)3-OH), 4-hydroxybutyl vinyl ether (H)2C＝CH-0-(CH2)4-OH) is selected from one or more.
Further, i is 2-4.
Further, said a1+a2+…+ai+1＝100～200。
Further, b is1+b2+…+bi＝6～11。
Further, the number average molecular weight of the macromonomer is 3284 to 10816,
further, the number average molecular weight of the macromonomer is 4850-9554.
Further, the invention discloses a preparation method of a macromonomer, which comprises the following steps:
the method comprises the following steps: preparation of a prepolymer
Carrying out anhydrous treatment and vacuum pumping on the reaction kettle and the pipeline, and carrying out inert gas purging after vacuum pumping; adding an initiator and a catalyst into a reaction vessel, mixing, adding 5-12 mol of ethylene oxide e, adjusting the temperature in the reaction vessel to 105-130 ℃, then carrying out ring-opening polymerization reaction, controlling the pressure in the reaction vessel to be 0-0.45 MPa until the pressure in the reaction vessel is constant, stabilizing for 15-30 min, cooling to 65-80 ℃, and removing unreacted ethylene oxide; obtaining a prepolymer with the number average molecular weight of 308-630;
step two: preparation of macromonomers
Supplementing a catalyst into the reaction kettle in the step one; addition of ethylene oxide a1E, adjusting the temperature in the reaction kettle to 105-130 ℃, and then carrying out ring-opening polymerization reaction until the pressure in the kettle is constant and then stabilizing for 15-30 min; adjusting the temperature in the reaction kettle to 115-150 ℃ again, and adding epoxypropane b into the reaction kettle1Performing ring opening polymerization reaction until the pressure in the kettle is constant, and stabilizing for 15-30 min; alternatively adding ethylene oxide and propylene oxide to carry out ring-opening polymerization reaction, and finally adding ethylene oxide a oncei+1And (3) performing ring-opening polymerization reaction until the pressure in the kettle is constant and then stabilizing for 15-30 min, cooling to 65-80 ℃, and removing unreacted ethylene oxide to obtain the macromonomer.
Further, the catalyst is any one of sodium methoxide, potassium hydroxide, sodium hydride and sodium ethoxide.
Furthermore, in the first step, the mole number e of the ethylene oxide added to the prepolymer is equal to the mole number of the added initiator x the mole number of the ethylene oxide in 1 mole of the designed prepolymer.
Further, the adding amount of the catalyst in the step one is 0.05-0.15% of the sum of the weight of the initiator and the weight of the ethylene oxide in the prepolymer.
Furthermore, the adding amount of the catalyst in the second step is 0.05-0.15% of the sum of the weight of the ethylene oxide and the weight of the propylene oxide.
And further, after the macromonomer is prepared in the second step, adding a neutralizing agent, and adjusting the pH value to 5-6.5.
Further, the neutralizing agent is any one of glacial acetic acid and phosphoric acid.
Further, the ratio of ethylene oxide: the mol ratio of the propylene oxide added in portions is a1：b1：a2＝20～60：2～5：20～50。
Further, the ratio of ethylene oxide: the mol ratio of the propylene oxide added in portions is a1：b1：a2：b2：a3＝20～60：1～5：30～60：1～5：20～60。
Further, the ratio of ethylene oxide: the mol ratio of the propylene oxide added in portions is a1：b1：a2：b2：a3：b3：a4＝30～60：1～5：30～60：1～5：30～60：1～5：20～60。
Further, the ratio of ethylene oxide: the mol ratio of the propylene oxide added in portions is a1：b1：a2：b2：a3：b3：a4：b4：a5＝30～60：1～5：30～60：1～5：30～60：1～5：30～60：1～5：20～60。
Further, the invention discloses a method for preparing a polycarboxylate superplasticizer by using a macromonomer, which comprises the following steps:
radical copolymerization using a redox system:
adding a macromonomer into a reaction kettle with a stirrer, and adding water for stirring; and (3) dropwise adding an aqueous solution of the monomer b while adding an oxidant for 24-150 min, then dropwise adding a solution c for 30-150 min, continuously stirring, curing and preserving heat for 30-120 min after dropwise adding, adding an alkaline substance into the reaction kettle for neutralization, adjusting the pH to 5-7, finally adding water until the solid content accounts for 20-60% of the weight, and controlling the temperature to be 5-45 ℃ in the preparation process.
Further, the monomer b is monocarboxylic acid with unsaturated double bonds and derivatives thereof, including acrylic acid.
Furthermore, the monomer b also comprises one or two of hydroxyethyl acrylate and hydroxypropyl acrylate.
Further, the c solution comprises a chain transfer agent, a reducing agent and water.
Further, the chain transfer agent is one or more of mercaptopropionic acid, thioglycolic acid, mercaptoethanol and sodium hypophosphite.
Further, the chain transfer agent accounts for 0.31-0.64% of the total weight of the macromonomer and the monomer b.
Further, the macromonomer: the weight ratio of the monomer b is 350: 30 to 50.
Further, the oxidant is one or two of hydrogen peroxide and persulfate, and accounts for 0.64-1.28% of the total weight of the macromonomer and the monomer b.
Further, the reducing agent is one or more of L-ascorbic acid, D-erythorbic acid, sodium L-ascorbate, sodium D-erythorbate, sodium bisulfite and rongalite, and accounts for 0.18-0.51% of the total weight of the macromonomer and the monomer b.
Further, the alkaline substance is any one of sodium hydroxide, potassium hydroxide, calcium hydroxide and potassium permanganate.
The macromonomer of the present invention has the following novel characteristics: (1) the initiator is blocked by vinyl, has high activity, contains an ether bond after a vinyl double bond, ensures that a long side chain of a macromonomer structure is more free in the water reducing agent, and improves the slump retaining property of the water reducing agent and the wrapping property of cement paste. (2) The macromonomer contains long polyoxyethylene ether chain segments and short polyoxypropylene ether chain segments which are alternately embedded, and hydrophobic and hydrophilic chain segments are alternately meshed and interwoven, so that the steric hindrance effect is more prominent. The product of the invention has the water reducing rate of 25-50%, low mixing amount, low concrete cost and can produce the polycarboxylic acid water reducing agent with better slump retaining property.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The application discloses a method for preparing a large bill, which comprises the following steps:
the method comprises the following steps: preparation of a prepolymer
10 moles (880g) of vinyl glycol ether serving as an initiator and 2.77g (0.09% of the total amount of the materials) of sodium hydride serving as a catalyst are added into the reaction kettle and mixed; adding 50 mol (2200g) of ethylene oxide, adjusting the temperature in the reaction kettle to 110 ℃ to carry out ring-opening polymerization reaction, controlling the pressure in the reaction kettle to be 0-0.45 MPa until the pressure in the kettle is constant, stabilizing for 15-30 min, cooling to 65-80 ℃, and removing unreacted ethylene oxide; obtaining a prepolymer with the number average molecular weight of 308;
step two: preparation of macromonomers
Taking 1 mol (308g) of prepolymer, and supplementing and adding 2.68g (namely 2.96g-0.28g) of catalyst sodium hydride according to 0.09% of the quantity of supplemented materials; 15 moles (660g) of ethylene oxide are added, and the number of moles of ethylene oxide in the polyoxyethylene ether segment connected with the initiator is increased to 20 (a)1Adjusting the temperature in the reaction kettle to 110 ℃, and then carrying out ring-opening polymerization reaction until the pressure in the kettle is constant and then stabilizing for 15-30 min; regulating the temperature in the reaction kettle to 130 ℃ again, adding 2 mol (116g) of propylene oxide into the reaction kettle for ring-opening polymerization reaction until the temperature is controlled to 130 ℃ againStabilizing the pressure in the kettle for 15-30 min after the pressure is constant; finally, adjusting the temperature in the reaction kettle to 110 ℃, adding 50 mol (2200g) of propylene oxide into the reaction kettle for ring-opening polymerization reaction until the pressure in the kettle is constant and then stabilizing for 15-30 min, cooling to 65-80 ℃, removing unreacted ethylene oxide to obtain a macromonomer A with the number average molecular weight of 32841；
Step three: neutralizing macromonomers
And (5) after the macromonomer is prepared in the step two, adding glacial acetic acid into the reaction kettle, and adjusting the pH value to 6.
Wherein, the general formula: n (amount of substance) M (mass)/M (molar mass);
the initiator is vinyl glycol ether, propylene glycol vinyl ether and 4-hydroxybutyl vinyl ether, which can achieve good effect in the invention;
the neutralizing agent is glacial acetic acid to adjust the pH value, and phosphoric acid can be used to adjust the pH value, so that the effect of adjusting the pH value can be obtained;
the catalyst in the invention refers to one or a combination mode of several of sodium methoxide, potassium hydroxide, sodium hydride and sodium ethoxide, the adding amount of the catalyst in the first step is 0.05-0.15% of the sum of the weight of the initiator and the weight of ethylene oxide in the prepolymer, and the adding amount of the catalyst in the second step is 0.05-0.15% of the sum of the weight of ethylene oxide and propylene oxide, and the reaction temperature and the adding speed can be adjusted according to the using amount of the catalyst, so that the same reaction effect can be obtained.
Examples 1 to 13 Process control conditions for preparation of macromonomers (see Table 1)
Table 1:
in the present invention, when the number average molecular weight of the macromonomer exceeds 9554, the conventional industrial production can be realized, but the production efficiency is lowered, the viscosity is increased, the cost is correspondingly increased, and the practical significance in application is not achieved.
Preparation of reference example of macromonomer (see Table 2)
Table 2:
examples JS _1 to JS _13
This group of examples is an example of the process for the preparation of a polycarboxylic acid water reducing agent using a macromonomer according to the present invention (radical copolymerization with a redox system).
The principle of synthesizing the polycarboxylate superplasticizer by an oxidation-reduction system is that free radicals are generated by oxidation-reduction reaction, an oxidant substance is added into the system firstly, then a reducing agent is dripped into the system to generate oxidation-reduction reaction with the oxidant in a solution, and the free radicals are generated to initiate monomer polymerization to synthesize the polycarboxylate superplasticizer.
The application discloses a method for preparing a polycarboxylate superplasticizer by using a macromonomer, which comprises the following steps:
adding a part of water into the reaction kettle, adding the macromonomer in the embodiment, and stirring and dissolving; dropwise adding the aqueous solution of b while adding an oxidant for 24-150 min, then dropwise adding the solution of c for 30-150 min, continuously stirring, curing and preserving heat for 30-150 min after dropwise adding, adding an alkaline substance into the reaction kettle for neutralization, adjusting the pH to 5-7, and finally adding water until the solid content accounts for 20-60% of the weight, wherein the reaction temperature is as follows: and (5) obtaining the colorless transparent liquid water reducing agent at the temperature of 5-45 ℃.
The invention only provides 40% of solid content, the specific dosage is adjusted according to different working conditions at that time, and water is added until the solid content accounts for 20-60% of the weight;
the monomer b is prepared from acrylic acid, acrylic acid and hydroxyethyl acrylate in a matching way, or acrylic acid and hydroxypropyl acrylate in a matching way, the specific dosage is adjusted according to different conditions at that time, and the final effect is as good;
the chain transfer agent is one or a combination mode of several of mercaptopropionic acid, thioglycolic acid, mercaptoethanol and sodium hypophosphite, wherein the sodium hypophosphite is added in a dropping mode and a kettle bottom mode, the using amount of the sodium hypophosphite accounts for 0.31-0.64% of the total weight of the macromonomer and the monomer b, the specific using amount is adjusted according to different conditions at that time, and the effect of adjusting the molecular weight is achieved;
the oxidant in the invention refers to any one or a combination mode of two of hydrogen peroxide and persulfate, the dosage of the oxidant accounts for 0.64-1.28% of the total weight of the macromonomer and the monomer b, and the specific dosage is adjusted according to different conditions at that time, so that the same initiating effect can be achieved;
the reducing agent in the invention is one or a combination mode of more of L ascorbic acid, D erythorbic acid, rongalite, L sodium ascorbate, D sodium erythorbate and sodium bisulfite, the dosage of the reducing agent accounts for 0.18-0.51% of the total weight of the macromonomer and the monomer b, the specific dosage is adjusted according to different conditions at that time, and the effect of each mode meets the product requirement;
the alkaline substance can be any one of sodium hydroxide, potassium hydroxide and calcium hydroxide, which all play a role in neutralization, and the specific dosage is adjusted according to different conditions at the time, so that the effect of the invention is as good as that of the invention.
Examples JS _1 to JS _13 are the Process control conditions for preparing the polycarboxylic acid Water-reducing agent (see Table 3)
Table 3:
the above table shows the material ratios of examples JS _1 to JS _ 13.
Comparative example of polycarboxylic acid water reducing agent
The polycarboxylate superplasticizer comparative examples 1 to 7 are methods for synthesizing polycarboxylate superplasticizers by using the monomers of comparative examples 1 to 7 through an oxidation-reduction method.
Comparative examples 1 to 7
Adding part of water into the reaction kettle, adding the monomers of comparative examples 1-5, and stirring for dissolving; dropwise adding a solution of a monomer b while adding an oxidant for 90-150 min, then dropwise adding a solution c for 120-150 min, keeping the temperature for 60min after dropwise adding is finished, adding an alkaline substance into a reaction kettle for neutralization, adjusting the pH value to 5-7, and finally adding water until the solid content accounts for 20-60% of the weight, wherein the reaction temperature is as follows: and (5) obtaining the colorless transparent liquid water reducing agent at the temperature of 5-45 ℃.
Comparative examples 1 to 7 Synthesis methods of Water reducing Agents (see Table 5)
Table 5:
performance test comparison table:
as can be seen from the comparison of the performances of the above examples and the comparative examples, the macromonomer of the invention adopts vinyl glycol ether as an initiator, and adopts a polyoxypropylene ether point-type multi-segment hybrid to form the macromonomer, and the fluidity and the plasticity retention property over time of 60min (the initial fluidity of cement paste is 270-295 mm, and the fluidity over 60min is 260-295 mm) of the cement paste of the polycarboxylic acid water reducer prepared by the macromonomer are obviously better than those of polyoxyethylene ether (the initial fluidity of cement paste is 250-255 mm, and the fluidity over 60min is 190-240 mm) using methallyl alcohol or isoamylol as an initiator and that of polyoxyethylene ether polyoxypropylene ether block polymerization monomer (the initial fluidity of cement paste is 265-285 mm, and the fluidity over 60min is 245-250 mm) using methallyl alcohol or isoamylol as an initiator in the comparative examples. The fluidity of the cement paste of the embodiment is also obviously better than that of a polyoxyethylene ether macromonomer (the initial fluidity of the cement paste is 250-255 mm, and the fluidity at 60min is 230-245 mm) taking a vinyl glycol ether compound as an initiator. The initial fluidity of the cement paste reaches 290-305 mm in the embodiment that the macromonomer molecular weight is 4850-9554, the fluidity of 60min reaches 285-295 mm, the performance of the water reducing agent is better, and a better technical effect can be achieved.
The above-described embodiments of the present invention are merely examples for clearly illustrating the invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that various changes and modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious changes and modifications belonging to the technical solutions of the present invention are within the scope of the present invention.
Claims (17)
1. A macromonomer is a polymer obtained by adding ethylene oxide and propylene oxide to an initiator ROH, and has a molecular structure of:
RO-(C2H4O)a1-(C3H6O)b1-(C2H4O)a2-(C3H60)b2-…(C2H4O)ai-(C3H6O)bi-(C2H4O)ai+1-H
wherein: a1, a2, … ai and ai +1 are the addition mole number of each segment of polyoxyethylene ether, the addition mole number of each segment is 20-60, and a1+ a2+ … + ai +1= 100-180; b1, b2 and … bi are the addition mol number of the polyoxypropylene ether in each chain segment, the addition mol number of each chain segment is 1-10, b1+ b2+ … + bi = 6-11, and a 1: b 1: a 2: b 2: a3 = 20-60: 1-2: 30-60: 5-7: 20-45 or a 1: b 1: a 2: b 2: a 3: b 3: a4= 20-60: 1-2: 30-60: 5-7: 20-45: 1-7: 20-60, i is the number of chain segments and is an integer from 2 to 3, and the ROH is propylene glycol vinyl ether H2C = CH-O- (CH2) 3-OH.
2. The macromonomer according to claim 1, wherein the macromonomer has a number average molecular weight of 3284 to 10816.
3. The macromonomer according to claim 2, wherein the macromonomer has a number average molecular weight of 4850 to 9554.
4. A process for the preparation of a macromonomer according to any one of claims 1 to 3 comprising the steps of:
the method comprises the following steps: preparation of a prepolymer
Carrying out anhydrous treatment and vacuum pumping on the reaction kettle and the pipeline, and carrying out inert gas purging after vacuum pumping; adding an initiator and a catalyst into a reaction vessel for mixing, adding ethylene oxide e = 5-12 mol, adjusting the temperature in the reaction vessel to 105-130 ℃, then carrying out ring-opening polymerization reaction, controlling the pressure in the reaction vessel to 0-0.45 MPa until the pressure in the reaction vessel is constant, stabilizing for 15-30 min, cooling to 65-80 ℃, and removing unreacted ethylene oxide; obtaining a prepolymer with the number average molecular weight of 308-630;
step two: preparation of macromonomers
Supplementing a catalyst into the reaction kettle in the step one; addition of ethylene oxide a1E, adjusting the temperature in the reaction kettle to 105-130 ℃, and then carrying out ring-opening polymerization reaction until the pressure in the kettle is constant and then stabilizing for 15-30 min; adjusting the temperature in the reaction kettle to 115-150 ℃ again, and adding epoxypropane b into the reaction kettle1Performing ring opening polymerization reaction until the pressure in the kettle is constant, and stabilizing for 15-30 min; ring-opening polymerization by alternately adding ethylene oxide and propylene oxideThe reaction is carried out, and finally, the ethylene oxide a is added oncei+1And (3) performing ring-opening polymerization reaction until the pressure in the kettle is constant and then stabilizing for 15-30 min, cooling to 65-80 ℃, and removing unreacted ethylene oxide to obtain the macromonomer.
5. The method of claim 4, wherein the catalyst is any one of sodium methoxide, potassium hydroxide, sodium hydride, and sodium ethoxide.
6. The method of claim 4, wherein the mole of ethylene oxide added to the prepolymer in step one, e = mole of initiator added x mole of ethylene oxide in 1 mole of prepolymer designed.
7. The method of claim 4, wherein the amount of catalyst added in step one is 0.05-0.15% of the total weight of the initiator and the ethylene oxide in the prepolymer.
8. The method for preparing a macromonomer according to claim 4, wherein the catalyst is added in an amount of 0.05 to 0.15% by weight of the sum of the weight of ethylene oxide and propylene oxide in the second step.
9. The method for preparing a macromonomer according to claim 4, wherein after the macromonomer is obtained in the second step, a neutralizing agent is added to adjust pH =5 to 6.5.
10. The method of claim 9, wherein the neutralizing agent is any one of glacial acetic acid and phosphoric acid.
11. A method for preparing a polycarboxylic acid water reducing agent by using the macromonomer according to any one of claims 1 to 3, comprising the steps of:
adopting a redox system to carry out free radical copolymerization:
adding a macromonomer into a reaction kettle with a stirrer, and adding water for stirring; dropwise adding the aqueous solution of the monomer b while adding an oxidant for 24-150 min, then dropwise adding the solution c for 30-150 min, continuously stirring, curing and preserving heat for 30-120 min after dropwise adding, adding an alkaline substance into the reaction kettle for neutralization, adjusting the pH = 5-7, and finally adding water until the solid content accounts for 20-60% of the weight, wherein the reaction temperature is as follows: 5-45 ℃;
the monomer b is monocarboxylic acid with unsaturated double bonds and derivatives thereof, including acrylic acid;
the c solution comprises a chain transfer agent, a reducing agent and water.
12. The method for preparing the water reducing agent according to claim 11, wherein the oxidant is one or two of hydrogen peroxide and persulfate, and the oxidant accounts for 0.64-1.28% of the total weight of the macromonomer and the monomer b.
13. The method for preparing the water reducing agent according to claim 11, wherein the monomer b further comprises one or two of hydroxyethyl acrylate and hydroxypropyl acrylate.
14. The method for preparing the water reducing agent according to claim 11, wherein the chain transfer agent is one or more of mercaptopropionic acid, mercaptoacetic acid, mercaptoethanol and sodium hypophosphite.
15. The method for preparing the water reducing agent according to claim 11, wherein the chain transfer agent accounts for 0.31-0.64% of the total weight of the macromonomer and the monomer b.
16. The method for preparing the water reducing agent according to claim 11, wherein the reducing agent is one or more of L ascorbic acid, D erythorbic acid, L sodium ascorbate, D sodium erythorbate, sodium bisulfite and rongalite, and the reducing agent accounts for 0.18-0.51% of the total weight of the macromonomer and the monomer b.
17. The method for preparing a water reducing agent according to claim 11, wherein the macromonomer: the weight ratio of the monomer b is 350: 30 to 50.
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