CN111944089A - Cement containing polycarboxylate and polyhydroxy ester type grinding aid - Google Patents
Cement containing polycarboxylate and polyhydroxy ester type grinding aid Download PDFInfo
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- CN111944089A CN111944089A CN202010853078.3A CN202010853078A CN111944089A CN 111944089 A CN111944089 A CN 111944089A CN 202010853078 A CN202010853078 A CN 202010853078A CN 111944089 A CN111944089 A CN 111944089A
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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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
-
- 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
- C04B24/2641—Polyacrylates; Polymethacrylates
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
-
- 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
- C04B2103/52—Grinding aids; Additives added during grinding
-
- 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
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
Abstract
The invention relates to cement containing a polycarboxylic acid polyhydroxy ester type cement grinding aid, which comprises the following components in parts by weight: 5-10 parts of hydroxyethyl acrylate, 15-25 parts of monosodium itaconate, 2-4 parts of RAFT reagent, 0.2-0.4 part of initiator, 0.5-1 part of cosolvent and 70-100 parts of deionized water. The water-based group-polyhydroxy functional group in the grinding aid structure has good lubricating effect in the cement grinding process, greatly increases the thermal conversion efficiency in the grinding process, and simultaneously can not agglomerate due to the existence of a double electric layer when the cement grain size is smaller; the cement grinding aid is synthesized by adopting the RAFT technology, the molecular weight of the cement grinding aid is low (1800-4000), and the polydispersity is small (1.2-1.3); simple production process, stable performance and no chloride ion.
Description
The invention relates to a divisional application of a Chinese patent 'polycarboxylic acid polyhydroxy ester type cement grinding aid and a preparation method', wherein the application date is 2018, 2 and 28 days, and the application number is 201810168083.3.
Technical Field
The invention relates to a cement grinding aid, in particular to cement containing a polycarboxylic acid polyhydroxy ester type grinding aid.
Background
The cement grinding aid is also called cement process additive, and is a chemical substance which is added in the cement grinding process and has the functions of grinding aid and enhancement and can improve the cement performance. The cement production process can be summarized as two-mill one-firing, i.e. grinding of raw materials, calcination and grinding of cement. The energy consumption of the clinker grinding process accounts for 60 percent of the total energy consumption, the energy utilization rate is low, and about 97 percent of the consumed energy is converted into heat energy to be wasted. With the increase of the grinding fineness, the specific surface area of the material is increased, the adhesion force or the interfacial tension of the powder is increased, so that cracks generated on the particles can be healed again, the particles are adsorbed and adhered to each other, qualified fine powder cannot be timely blown out of the mill along with wind, and free electrovalence bonds on the new surface generated when the particles are broken drive the adjacent particles to be adhered and aggregated with each other, so that serious ball packing and package forging phenomena are caused, the output per machine hour of cement production is greatly reduced, and the utilization rate of energy is greatly reduced.
At present, a plurality of cement grinding aids usually ignore the difference between a grinding process and ground materials, do not adjust a grinding system, a grinding machine structure, a grinding body, process operation parameters and the like in a targeted manner, have single functions, have poor adaptability to cement production process conditions, and cause poor use effect and unstable product quality.
Chinese patent CN201210116601.X discloses an amide polyamine polycarboxylic acid polymer cement grinding aid and a preparation method thereof, wherein the amide polyamine polycarboxylic acid polymer cement grinding aid is prepared by free radical polymerization of maleic anhydride, acrylamide, acrylic acid and allyl ether in a certain molar ratio under the action of an initiator in an aqueous solution at a proper temperature. The amide polyamine polycarboxylic acid polymer cement grinding aid can improve the cement strength and the grinding efficiency. The invention has the defects of low grinding aiding effect, uneven distribution of the molecular weight of the polycarboxylic acid polymer and unstable grinding aiding effect.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a polycarboxylic acid polyol ester type cement grinding aid.
The polycarboxylic acid polyolThe base ester type cement grinding aid is prepared by adopting an aqueous RAFT polymerization method, the relative molecular mass of the base ester type cement grinding aid is 1800-4000, and the molecular structural formula of the base ester type cement grinding aid is (m: 4-8, n: 8-15; R in the formula)1、R2is-H, -OH, -CH2OH、-CH3、-CH2CH3One of them) is as follows:
the polycarboxylic acid polyhydroxy ester type cement grinding aid comprises the following components in parts by weight: 5-10 parts of hydroxyethyl acrylate, 15-25 parts of monosodium itaconate, 2-4 parts of RAFT reagent, 0.2-0.4 part of initiator, 0.5-1 part of cosolvent and 70-100 parts of deionized water.
The water-soluble RAFT reagent is at least one of alpha-dithio-phenylmethyl-p-phenylmethylene pyridinium chloride, S ' -bis (alpha, alpha ' -dimethyl-alpha ' -acetic acid) trithiocarbonate and diethyl dithiocarbamate type quaternary ammonium salt.
The initiator is at least one of ammonium persulfate, potassium persulfate and sodium persulfate.
The cosolvent is at least one of sodium benzoate, sodium salicylate and p-aminobenzoic acid.
The hydroxyethyl acrylate is directly commercially available.
The preparation method of the monosodium itaconate mono-polyhydroxy ester comprises the following steps:
(1) preparing a monosodium itaconate solution: adding 26 parts by weight of itaconic acid and 40-60 parts by weight of water into a reactor, and stirring and dissolving to obtain an itaconic acid solution; dissolving 8 parts by weight of sodium hydroxide in 5-10 parts by weight of water to obtain an alkali solution; slowly dripping the alkali solution into the itaconic acid solution under the stirring condition, and continuously stirring and reacting for 0.5-1h after finishing dripping to obtain the monosodium itaconate solution.
(2) Esterification of monosodium itaconate: in a reaction kettle provided with a dropping device and a temperature control system, 18 to 27 weight parts of water-soluble polyhydric alcohol, 60 to 80 weight parts of water, 0.4 to 0.8 weight part of catalyst and 0.1 to 0.2 weight part of hydroquinone are added, the reaction temperature is heated and controlled to be 120-140 ℃, 79 to 104 weight parts of monosodium itaconate solution in the step (1) is dropwise added, the reaction is continued for 3 to 5 hours after the dropwise addition is finished, the low boiling point azeotrope generated in the reaction process is continuously fractionated out, and after the reaction is finished, the monosodium itaconate is cooled and granulated by a spray method to obtain the monosodium itaconate.
The water-soluble polyalcohol is at least one of glycerol, pentaerythritol, trimethylolpropane and trimethylolethane;
the catalyst is at least one of p-toluenesulfonic acid, hexadecyl trimethyl ammonium hydroxide, dodecyl trimethyl ammonium hydroxide and octadecyl trimethyl ammonium hydroxide.
The invention also aims to provide a preparation method of the polycarboxylic acid polyol ester type cement grinding aid. The preparation method of the polycarboxylic acid polyhydroxy ester type cement grinding aid comprises the following steps:
under the condition of introducing nitrogen, sequentially adding hydroxyethyl acrylate, monosodium itaconate, RAFT reagent, cosolvent, initiator with the formula amount of 30-40% and deionized water with the formula amount of 80-90% into a reaction kettle, stirring and heating the solution to 75-80 ℃ until the solution is completely dissolved, then slowly dropwise adding the rest of initiator and the rest of deionized water into the reaction kettle, after dropwise adding is finished for 20-30min, continuously reacting for 6-8h at 75-80 ℃, and cooling to room temperature to obtain the polycarboxylic acid polyhydroxy ester type cement grinding aid.
Compared with the prior art, the invention has the following advantages or beneficial results: (1) the cement grinding aid is of a polycarboxylic acid polyhydroxy ester type, carboxylate radicals in a grinding aid structure are adsorbed on the surfaces of cement grains (an electrostatic double electric layer is formed on the surface of cement) in the cement grinding process, and a water-based group-polyhydroxy functional group has a good lubricating effect in the cement grinding process, so that the heat conversion efficiency of the grinding process is greatly increased, and meanwhile, the cement grains cannot be agglomerated due to the existence of the electric double electric layer when the grain size of the cement is small, so that the strength of the cement grains after solidification is improved; (2) the cement grinding aid is synthesized by adopting the RAFT technology, the molecular weight of the cement grinding aid is low (1800-4000), and the polydispersity is small (1.2-1.3); (3) simple production process, stable performance and no chloride ion.
Detailed Description
A polycarboxylic acid polyol type cement grinding aid of the present invention is further described below with reference to the examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
Example 1
The polycarboxylic acid polyhydroxy ester type cement grinding aid comprises the following components in parts by weight: 9 parts of hydroxyethyl acrylate, 20 parts of monosodium itaconate, 4 parts of RAFT reagent alpha-dithiobenzyl p-phenylmethylene pyridinium chloride, 0.4 part of initiator potassium persulfate, 1 part of sodium salicylate and 100 parts of deionized water.
The preparation method of the monosodium itaconate mono-polyhydroxy ester comprises the following steps:
(1) preparing a monosodium itaconate solution: adding 26 parts by weight of itaconic acid and 60 parts by weight of water into a reactor, and stirring and dissolving to obtain an itaconic acid solution; dissolving 8 parts by weight of sodium hydroxide in 10 parts by weight of water to obtain an alkali solution; slowly dripping the alkali solution into the itaconic acid solution under the stirring condition, and continuously stirring and reacting for 0.5h after finishing dripping to obtain the monosodium itaconate solution.
(2) Esterification of monosodium itaconate: 27 parts by weight of pentaerythritol, 80 parts by weight of water, 0.4 part by weight of p-toluenesulfonic acid and 0.1 part by weight of hydroquinone are added into a reaction kettle provided with a dropping device and a temperature control system, the reaction temperature is heated and controlled to be 140 ℃, 104 parts by weight of (1) mesoxysodium itaconate solution is dropped into the reaction kettle dropwise, the reaction continues for 3 hours after the dropping is finished for 2 hours, low-boiling-point azeotrope generated in the reaction process is continuously fractionated out, and after the reaction is finished, the reaction is granulated by cooling and spraying to obtain the monosodium itaconate.
The preparation method of the polycarboxylic acid polyol ester type cement grinding aid comprises the following steps:
under the condition of introducing nitrogen, sequentially adding hydroxyethyl acrylate, monosodium itaconate, sodium salicylate, RAFT reagent alpha-dithiobenzyl p-phenylmethylene pyridinium chloride, 33% of initiator potassium persulfate and 85% of deionized water into a reaction kettle, stirring and heating the solution to 77 ℃ until the solution is completely dissolved, slowly dropwise adding the rest of initiator potassium persulfate and the rest of deionized water into the solution, after 26min dropwise adding is finished, continuously reacting at 77 ℃ for 6.5h, and cooling to room temperature to obtain the polycarboxylic acid polyhydroxy ester type cement grinding aid.
Example 2
The polycarboxylic acid polyhydroxy ester type cement grinding aid comprises the following components in parts by weight: 10 parts of hydroxyethyl acrylate, 15 parts of monosodium itaconate, 3 parts of RAFT reagent S, S ' -bis (alpha, alpha ' -dimethyl-alpha ' -acetic acid) trithiocarbonate, 0.3 part of initiator sodium persulfate, 0.71 part of cosolvent sodium benzoate and 80 parts of deionized water.
The preparation method of the monosodium itaconate mono-polyhydroxy ester comprises the following steps:
(1) preparing a monosodium itaconate solution: adding 26 parts by weight of itaconic acid and 40 parts by weight of water into a reactor, and stirring and dissolving to obtain an itaconic acid solution; dissolving 8 parts by weight of sodium hydroxide in 5 parts by weight of water to obtain an alkali solution; and slowly dripping the alkali solution into the itaconic acid solution under the stirring condition, and continuously stirring and reacting for 1h after dripping to obtain the monosodium itaconate solution.
(2) Esterification of monosodium itaconate: adding 18 parts by weight of glycerol, 60 parts by weight of water, 0.3 part by weight of hexadecyl trimethyl ammonium hydroxide, 0.5 part by weight of p-toluenesulfonic acid and 0.2 part by weight of hydroquinone into a reaction kettle provided with a dropping device and a temperature control system, heating and controlling the reaction temperature to be 120 ℃, dropwise adding 79 parts by weight of (1) mesoelkanoic acid monosodium solution, continuing to react for 5 hours after 1 hour of dropwise adding is finished, continuously fractionating low-boiling-point azeotrope generated in the reaction process, and cooling and granulating by a spraying method after the reaction is finished to obtain the monosodium itaconate.
The preparation method of the polycarboxylic acid polyol ester type cement grinding aid comprises the following steps:
under the condition of introducing nitrogen, sequentially adding hydroxyethyl acrylate, monosodium itaconate, sodium benzoate as a cosolvent, RAFT reagent S, S ' -bis (alpha, alpha ' -dimethyl-alpha ' -acetic acid) trithiocarbonate, initiator sodium persulfate with the formula amount of 30% and deionized water with the formula amount of 80% into a reaction kettle, stirring and heating the solution to 80 ℃ until the solution is completely dissolved, then slowly dropwise adding the rest of the initiator sodium persulfate and the rest of the deionized water into the solution, after 30min of dropwise addition, continuing to react for 6h at 80 ℃, and cooling to room temperature to obtain the polycarboxylic acid polyhydroxy ester type cement grinding aid.
Example 3
The polycarboxylic acid polyhydroxy ester type cement grinding aid comprises the following components in parts by weight: 5 parts of hydroxyethyl acrylate, 15 parts of monosodium itaconate, 2 parts of alpha-dithio-benzyl-p-phenylene pyridinium chloride, 0.2 part of ammonium persulfate, 0.5 part of p-aminobenzoic acid and 70 parts of deionized water.
The preparation method of the monosodium itaconate mono-polyhydroxy ester comprises the following steps:
(1) preparing a monosodium itaconate solution: adding 26 parts by weight of itaconic acid and 45 parts by weight of water into a reactor, and stirring and dissolving to obtain an itaconic acid solution; dissolving 8 parts by weight of sodium hydroxide in 7 parts by weight of water to obtain an alkali solution; slowly dripping the alkali solution into the itaconic acid solution under the stirring condition, and continuously stirring and reacting for 0.6h after finishing dripping to obtain the monosodium itaconate solution.
(2) Esterification of monosodium itaconate: 26 parts by weight of trimethylolpropane, 64 parts by weight of water, 0.2 part by weight of p-toluenesulfonic acid, 0.4 part by weight of dodecyl trimethyl ammonium hydroxide and 0.13 part by weight of hydroquinone are added into a reaction kettle provided with a dropping device and a temperature control system, the reaction temperature is heated and controlled to be 125 ℃, 86 parts by weight of (1) mesocozeb monosodium solution is dropped into the reaction kettle dropwise, the reaction is continued for 4.5 hours after the dropping is finished, low-boiling-point azeotrope generated in the reaction process is continuously fractionated out, and after the reaction is finished, the reaction kettle is cooled and granulated by a spray method to obtain the monosodium itaconate.
The preparation method of the polycarboxylic acid polyol ester type cement grinding aid comprises the following steps:
under the condition of introducing nitrogen, sequentially adding hydroxyethyl acrylate, monosodium itaconate, poly-hydroxy ester, p-aminobenzoic acid, alpha-dithio-benzyl-p-benzylidene pyridinium chloride, 40% of ammonium persulfate and 90% of deionized water into a reaction kettle, stirring and heating the solution to 75 ℃ until the solution is completely dissolved, then slowly dropwise adding the solution of the rest of ammonium persulfate and the rest of deionized water, finishing dropwise adding for 20min, continuously reacting for 8h at 75 ℃, and cooling to room temperature to obtain the polycarboxylic acid poly-hydroxy ester type cement grinding aid.
The cement (70% of clinker, 5% of gypsum, 10% of slag and 15% of fly ash) with the same weight and formula amount is placed in a mill, the invention and a commercial liquid grinding aid (comparative example) with the total amount of 0.4% are added, the milling is carried out for the same time, and the performance parameters of the prepared cement are as follows:
while the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes, modifications and variations can be made therein without departing from the spirit and scope of the invention as defined in the following claims.
Claims (9)
1. A cement containing a polycarboxylic acid polyol ester type grinding aid is characterized in that: the formula of the polycarboxylic acid polyhydroxy ester type grinding aid comprises the following components in parts by weight: 5-10 parts of hydroxyethyl acrylate, 15-25 parts of monosodium itaconate, 2-4 parts of RAFT reagent, 0.2-0.4 part of initiator, 0.5-1 part of cosolvent and 70-100 parts of deionized water.
2. The cement containing the polycarboxylate polyol grinding aid as claimed in claim 1, wherein: the polycarboxylic acid polyhydroxy ester type grinding aid is prepared by adopting an aqueous RAFT polymerization method, the relative molecular mass is 1800-4000, and the molecular structural formula is as follows:
wherein m: 4-8, n: 8-15 parts of; r1、R2is-H, -OH, -CH2OH、-CH3、-CH2CH3One of them.
3. The cement containing the polycarboxylate polyol grinding aid as claimed in claim 1, wherein: the RAFT reagent is at least one of alpha-dithio-phenylmethyl-p-phenylmethylene pyridinium chloride, S ' -bis (alpha, alpha ' -dimethyl-alpha ' -acetic acid) trithiocarbonate and diethyl dithiocarbamate type quaternary ammonium salt.
4. The cement containing the polycarboxylate polyol grinding aid as claimed in claim 1, wherein: the initiator is at least one of ammonium persulfate, potassium persulfate and sodium persulfate.
5. The cement containing the polycarboxylate polyol grinding aid as claimed in claim 1, wherein: the cosolvent is at least one of sodium benzoate, sodium salicylate and p-aminobenzoic acid.
6. The cement containing the polycarboxylate polyhydroxy ester type grinding aid as claimed in claim 1, wherein the preparation method of the monosodium itaconate mono polyhydroxy ester is as follows:
(1) preparing a monosodium itaconate solution: adding 26 parts by weight of itaconic acid and 40-60 parts by weight of water into a reactor, and stirring and dissolving to obtain an itaconic acid solution; dissolving 8 parts of sodium hydroxide in 5-10 parts of water to obtain an alkali solution; slowly dripping the alkali solution into the itaconic acid solution under the stirring condition, and continuously stirring and reacting for 0.5-1h after dripping to obtain an itaconic acid monosodium solution;
(2) esterification of monosodium itaconate: adding 18-27 parts of water-soluble polyol, 60-80 parts of water, 0.4-0.8 part of catalyst and 0.1-0.2 part of hydroquinone into a reaction kettle provided with a dropping device and a temperature control system in parts by weight, heating and controlling the reaction temperature to be 120-140 ℃, dropping 79-104 parts of monosodium itaconate solution in the step (1) dropwise, continuing to react for 3-5h after the dropping is finished for 01-2h, continuously fractionating low-boiling-point azeotrope generated in the reaction process, and cooling and granulating by a spray method after the reaction is finished to obtain the monosodium itaconate.
7. The cement as claimed in claim 6, wherein the water-soluble polyhydric alcohol is at least one of glycerol, pentaerythritol, trimethylolpropane and trimethylolethane.
8. The cement as claimed in claim 6, wherein the catalyst is at least one of p-toluenesulfonic acid, cetyl trimethyl ammonium hydroxide, dodecyl trimethyl ammonium hydroxide and octadecyl trimethyl ammonium hydroxide.
9. The cement containing a polycarboxylate polyol type grinding aid as set forth in claims 1 to 8, wherein the preparation method of the polycarboxylate polyol type cement grinding aid comprises the steps of:
under the condition of introducing nitrogen, sequentially adding hydroxyethyl acrylate, monosodium itaconate, poly-hydroxy ester, RAFT reagent, cosolvent, initiator with the formula amount of 30-40% and deionized water with the formula amount of 80-90% into a reaction kettle, stirring and heating the solution to 75-80 ℃ until the solution is completely dissolved, then slowly dropwise adding the rest initiator and the rest deionized water solution, after dropwise adding is finished for 20-30min, continuously reacting for 6-8h at 75-80 ℃, and cooling to room temperature to obtain the polycarboxylic acid poly-hydroxy ester type cement grinding aid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010853078.3A CN111944089A (en) | 2018-02-28 | 2018-02-28 | Cement containing polycarboxylate and polyhydroxy ester type grinding aid |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810168083.3A CN108467456B (en) | 2018-02-28 | 2018-02-28 | Polycarboxylic acid polyhydroxy ester type cement grinding aid and preparation method thereof |
| CN202010853078.3A CN111944089A (en) | 2018-02-28 | 2018-02-28 | Cement containing polycarboxylate and polyhydroxy ester type grinding aid |
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| CN201810168083.3A Division CN108467456B (en) | 2018-02-28 | 2018-02-28 | Polycarboxylic acid polyhydroxy ester type cement grinding aid and preparation method thereof |
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| CN111944089A true CN111944089A (en) | 2020-11-17 |
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| CN202010853078.3A Withdrawn CN111944089A (en) | 2018-02-28 | 2018-02-28 | Cement containing polycarboxylate and polyhydroxy ester type grinding aid |
| CN201810168083.3A Expired - Fee Related CN108467456B (en) | 2018-02-28 | 2018-02-28 | Polycarboxylic acid polyhydroxy ester type cement grinding aid and preparation method thereof |
| CN202010853088.7A Withdrawn CN111909309A (en) | 2018-02-28 | 2018-02-28 | Preparation method of polycarboxylic acid polyhydroxy ester type cement grinding aid |
| CN202010853079.8A Withdrawn CN111943847A (en) | 2018-02-28 | 2018-02-28 | Monosodium itaconate mono-polyhydroxy ester and application thereof in cement grinding aid |
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| CN201810168083.3A Expired - Fee Related CN108467456B (en) | 2018-02-28 | 2018-02-28 | Polycarboxylic acid polyhydroxy ester type cement grinding aid and preparation method thereof |
| CN202010853088.7A Withdrawn CN111909309A (en) | 2018-02-28 | 2018-02-28 | Preparation method of polycarboxylic acid polyhydroxy ester type cement grinding aid |
| CN202010853079.8A Withdrawn CN111943847A (en) | 2018-02-28 | 2018-02-28 | Monosodium itaconate mono-polyhydroxy ester and application thereof in cement grinding aid |
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| US11597859B2 (en) | 2020-01-24 | 2023-03-07 | Oatey Co. | Solvent cement formulations having extended shelf life |
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| GB9602084D0 (en) * | 1996-02-02 | 1996-04-03 | Sandoz Ltd | Improvements in or relating to organic compounds |
| SE526347C2 (en) * | 2003-09-18 | 2005-08-30 | Perstorp Specialty Chem Ab | New copolymer and cement additive comprising the same |
| EP2699526B1 (en) * | 2011-04-21 | 2021-09-01 | BASF Construction Additives GmbH | Accelerator composition, process for producing it and its uses |
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2018
- 2018-02-28 CN CN202010853078.3A patent/CN111944089A/en not_active Withdrawn
- 2018-02-28 CN CN201810168083.3A patent/CN108467456B/en not_active Expired - Fee Related
- 2018-02-28 CN CN202010853088.7A patent/CN111909309A/en not_active Withdrawn
- 2018-02-28 CN CN202010853079.8A patent/CN111943847A/en not_active Withdrawn
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| Publication number | Publication date |
|---|---|
| CN111909309A (en) | 2020-11-10 |
| CN108467456A (en) | 2018-08-31 |
| CN108467456B (en) | 2021-01-19 |
| CN111943847A (en) | 2020-11-17 |
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