Method for synthesizing polycarboxylate high-performance water reducer by copolymerization reaction of benzenesulfonate ester active macromonomer

Abstract

The invention discloses a method for synthesizing a high-performance polycarboxylic acid water reducing agent by copolymerization of benzenesulfonate active macromonomers, and belongs to the field of water reducing agents. The method comprises the following steps: modifying styrene sulfonate to obtain benzene sulfonyl halide, mixing high-value cerate and alcohol to form an oxidation-reduction initiator system to initiate polymerization of unsaturated cationic quaternary ammonium monomers to obtain a hydroxyl-terminated cationic long chain, respectively putting the hydroxyl-terminated cationic long chain and methoxy polyethylene glycol into the benzene sulfonyl halide for sulfonylation to prepare the benzenesulfonate active macromonomers with different structures, and performing free radical copolymerization on the benzenesulfonate active macromonomers and carboxylic acid small monomers to obtain the high-performance polycarboxylic acid water reducing agent. According to the method, the styrene sulfonate is modified to obtain the benzene sulfonyl halide, and a mode for performing sulfonylation on a cationic side chain and an ether side chain is adopted, so that the benzenesulfonate active macromonomers with different structures and different functions are synthesized, and the novel comb structured high-performance polycarboxylic acid water reducing agent with polycarboxylic acid serving as a main chain and cations and polyether which serve as multi-element side chains is obtained. The process is continuous and easy to control, and has multiple excellent effect of reducing water, retaining slumps, resisting clays and the.

Description

technical field

[0001] The invention relates to the technical field of a benzenesulfonate-based polycarboxylic acid high-performance water reducer for concrete, in particular to a method of first modifying benzenesulfonyl halide with benzenesulfonate and then polymerizing cationic chains and sulfonylation reaction A specific preparation method of becoming a benzenesulfonate macromonomer and then copolymerizing with a carboxylic acid small monomer to form a polycarboxylate high-performance water reducer. Background technique

[0002] Polycarboxylate high-performance water reducer is the third generation of high-performance water reducer developed after lignosulfonate-based water-reducers and naphthalene-based high-performance water-reducers. It has the highest technological content and the best application prospects at present. , an application-type superplasticizer with the best comprehensive performance. The superplasticizer has the advantages of low dosage, high water red...

Examples

Embodiment 1

[0029] First, add 4.45g potassium p-styrenesulfonate and 32.06g 1,4-dioxane to the reactor successively, stir for 8 minutes, add 3.57g thionyl chloride dropwise to the reactor within 1 hour under ice-water bath conditions, and control After constant temperature reaction at 2°C for 16 hours, add 3.78g of ice water and 40.08g of toluene in sequence, vacuum-dry the extracted organic phase at 80°C to constant weight to obtain p-styrenesulfonyl chloride; Add dimethyl diallyl ammonium chloride and 1g cyclohexanol into another reactor, then add 775.54g water to prepare an aqueous solution with a mass concentration of 6%. The reactor is filled with nitrogen and repeatedly deoxygenated 4 times and then sealed for 18 minutes. , add 0.16g of cerium ammonium nitrate, stir for 28 minutes until it is evenly mixed, continue to heat up to 10°C for polymerization reaction, and react for 16 hours to obtain a long-chain hydroxyl-terminated cation aqueous solution; vacuumize the obtained long-chai...

Embodiment 2

[0031] The polycarboxylate superplasticizer solution with a mass fraction of 30% obtained in Example 1 was stored at 7° C. for 30 days, and its implementation effect was measured.

Embodiment 3

[0033] First, add 4.12g sodium p-styrene sulfonate, 14.43g dimethyl sulfoxide successively in the reactor, stir for 15 minutes, add 3.09g thionyl chloride dropwise to the reactor in 0.6 hours under ice-water bath conditions, control the temperature at After 13 hours of constant temperature reaction at 3.5°C, 2.81g of ice water and 25.26g of toluene were added in sequence, and the extracted organic phase was vacuum-dried at 60°C to constant weight to obtain p-styrenesulfonyl chloride; 40.69g of trimethyl Allyl ammonium chloride and 0.37g n-butanol are added in another reactor, then add 472.22g water and be mixed with the aqueous solution that mass concentration is 8%, the reactor is filled with nitrogen repeatedly 4 times and deoxygenated and sealed after 20 minutes, add 0.89g ammonium cerium sulfate, stir for 10 minutes until it is mixed evenly, continue to heat up to 35°C for polymerization reaction, and react for 13 hours to obtain an aqueous solution of long-chain hydroxyl-t...

technical field

[0001] The invention relates to the technical field of a benzenesulfonate-based polycarboxylic acid high-performance water reducer for concrete, in particular to a method of first modifying benzenesulfonyl halide with benzenesulfonate and then polymerizing cationic chains and sulfonylation reaction A specific preparation method of becoming a benzenesulfonate macromonomer and then copolymerizing with a carboxylic acid small monomer to form a polycarboxylate high-performance water reducer. Background technique

[0002] Polycarboxylate high-performance water reducer is the third generation of high-performance water reducer developed after lignosulfonate-based water-reducers and naphthalene-based high-performance water-reducers. It has the highest technological content and the best application prospects at present. , an application-type superplasticizer with the best comprehensive performance. The superplasticizer has the advantages of low dosage, high water red...

Examples

Embodiment 1

[0029] First, add 4.45g potassium p-styrenesulfonate and 32.06g 1,4-dioxane to the reactor successively, stir for 8 minutes, add 3.57g thionyl chloride dropwise to the reactor within 1 hour under ice-water bath conditions, and control After constant temperature reaction at 2°C for 16 hours, add 3.78g of ice water and 40.08g of toluene in sequence, vacuum-dry the extracted organic phase at 80°C to constant weight to obtain p-styrenesulfonyl chloride; Add dimethyl diallyl ammonium chloride and 1g cyclohexanol into another reactor, then add 775.54g water to prepare an aqueous solution with a mass concentration of 6%. The reactor is filled with nitrogen and repeatedly deoxygenated 4 times and then sealed for 18 minutes. , add 0.16g of cerium ammonium nitrate, stir for 28 minutes until it is evenly mixed, continue to heat up to 10°C for polymerization reaction, and react for 16 hours to obtain a long-chain hydroxyl-terminated cation aqueous solution; vacuumize the obtained long-chai...

Embodiment 2

[0031] The polycarboxylate superplasticizer solution with a mass fraction of 30% obtained in Example 1 was stored at 7° C. for 30 days, and its implementation effect was measured.

Embodiment 3

[0033] First, add 4.12g sodium p-styrene sulfonate, 14.43g dimethyl sulfoxide successively in the reactor, stir for 15 minutes, add 3.09g thionyl chloride dropwise to the reactor in 0.6 hours under ice-water bath conditions, control the temperature at After 13 hours of constant temperature reaction at 3.5°C, 2.81g of ice water and 25.26g of toluene were added in sequence, and the extracted organic phase was vacuum-dried at 60°C to constant weight to obtain p-styrenesulfonyl chloride; 40.69g of trimethyl Allyl ammonium chloride and 0.37g n-butanol are added in another reactor, then add 472.22g water and be mixed with the aqueous solution that mass concentration is 8%, the reactor is filled with nitrogen repeatedly 4 times and deoxygenated and sealed after 20 minutes, add 0.89g ammonium cerium sulfate, stir for 10 minutes until it is mixed evenly, continue to heat up to 35°C for polymerization reaction, and react for 13 hours to obtain an aqueous solution of long-chain hydroxyl-t...

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