阅读说明：本技术 一种高强度自流平灌浆料 (High-strength self-leveling grouting material ) 是由 李向红 于 2020-05-29 设计创作，主要内容包括：本发明涉及一种高强度自流平灌浆料,所述高强度自流平灌浆料包括醚化纤维素和改性聚羧酸减水剂的复配成分,其中醚化纤维素是纤维素经醚化剂醚化后的产物；改性聚羧酸减水剂为四元共聚聚合物,所述四元共聚聚合物的单体分别为不饱和聚醚、不饱和羧酸、不饱和磺酸盐以及多元醇丙烯酸酯。当不饱和聚醚、不饱和羧酸、不饱和磺酸盐和多元醇丙烯酸酯以一定配比共聚,所得到的改性聚羧酸减水剂与醚化纤维素复配后,所得灌浆料配方可以兼有良好的抗折抗压的强度,以及较为理想的流动性能和膨胀性能。(The invention relates to a high-strength self-leveling grouting material, which comprises a compound component of etherified cellulose and a modified polycarboxylic acid water reducing agent, wherein the etherified cellulose is a product obtained by etherifying cellulose with an etherifying agent; the modified polycarboxylic acid water reducing agent is a quaternary copolymerization polymer, and monomers of the quaternary copolymerization polymer are respectively unsaturated polyether, unsaturated carboxylic acid, unsaturated sulfonate and polyol acrylate. When unsaturated polyether, unsaturated carboxylic acid, unsaturated sulfonate and polyol acrylate are copolymerized according to a certain proportion, and the obtained modified polycarboxylate water reducer is compounded with etherified cellulose, the obtained grouting material formula has good breaking and compression strength, and more ideal flowing property and expansion property.)

1. The high-strength self-leveling grouting material is characterized by comprising compound components of etherified cellulose and a modified polycarboxylic acid water reducing agent, wherein the etherified cellulose is a product obtained by etherifying cellulose with an etherifying agent; the modified polycarboxylate superplasticizer is a quaternary copolymerization polymer, and the monomers are respectively unsaturated polyether, unsaturated carboxylic acid, unsaturated sulfonate and polyol acrylate.

2. The high strength self-leveling grouting material of claim 1, wherein the polyol acrylate is obtained by esterifying a polyol and acrylic acid, the polyol is at least one selected from sorbitol, pentaerythritol, cyclohexanediol and glycerol, and the ratio of the amount of hydroxyl groups of the polyol to the amount of acrylic acid is 1: 1-1.2.

3. The high-strength self-leveling grouting material as claimed in claim 2, wherein the polyol is selected from a compound of cyclohexanediol and glycerol according to a molar ratio of 1-2: 1-2.

4. The high strength self-leveling grouting material of claim 1, wherein the unsaturated polyether is selected from at least one of allyl polyoxyethylene ether, isoamyl alcohol polyoxyethylene ether and methallyl alcohol polyoxyethylene ether; the unsaturated carboxylic acid is selected from acrylic acid and/or methacrylic acid; the unsaturated sulfonate is selected from propenyl sulfonate or styrene sulfonate.

5. The high strength self-leveling grouting material as claimed in claim 4, wherein the number average molecular weight of the unsaturated polyether is 500-4000, preferably 1500-3000.

6. The high-strength self-leveling grouting material as claimed in claim 1, wherein the mass ratio of the etherified cellulose to the modified polycarboxylic acid water reducing agent is 6-10: 2-5.

7. The high strength self-leveling grouting material of claim 1, wherein the etherifying agent is selected from 3-chloro-2-hydroxypropyl trimethyl ammonium chloride or 2, 3-epoxypropyl trimethyl ammonium chloride.

8. The high-strength self-leveling grouting material as claimed in claim 1, wherein the mass ratio of the unsaturated polyether, the unsaturated carboxylic acid, the unsaturated sulfonate and the polyol acrylate is 10-20:10-20:2-5: 0.5-1.

9. The high strength self-leveling grouting material of claim 1, wherein the preparation method of the etherified cellulose comprises the following steps:

s1, placing cellulose in alkali liquor, stirring for 1-3h, and drying;

s2, dissolving the product in the S1 in organic alcohol, adding an etherifying agent, and reacting at 50-70 ℃.

10. The high-strength self-leveling grouting material according to any one of claims 1 to 9, wherein the high-strength self-leveling grouting material comprises the following raw materials in parts by weight:

Technical Field

The invention belongs to the field of building materials, and particularly relates to a high-strength self-leveling grouting material.

Background

The fabricated concrete building refers to a fabricated building in which a structural system of the building is composed of concrete parts (prefabricated members). One of the key technologies of the fabricated concrete building structure is the connection of nodes, and the nodes are force transmission pivots of the fabricated structure system and are the weakest parts of the fabricated structure system. The stable connection between the nodes is an important guarantee for the shock resistance and the integrity of the assembled structural system. If the quality problem exists at the joint of the nodes, the transmission of force among the components is influenced, the components are cracked, and even the serious results of structural disintegration, collapse and the like are caused. The common connection mode between the upper prefabricated wallboard and the lower prefabricated wallboard in the construction is the steel bar sleeve grouting connection. The steel bar sleeve grouting connection is characterized in that ribbed steel bars are inserted into a metal sleeve, grouting material mixture is injected, and the mixture is hardened to form a whole body and realize force transmission. The performance of the steel bar sleeve grouting connection is determined by the sleeve and the sleeve grouting material. The sleeve grouting material is a dry mixture which is prepared by taking cement as a basic material, adding fine aggregate, a concrete additive and other materials, and has good fluidity, early strength, high strength, micro-expansion and other properties after being stirred by adding water.

Generally, the main technical properties of a good grouting material are shown in the following aspects: (1) high compressive strength: the grouting material needs to generate a bond force on the reinforcing steel bar, so that the reinforcing steel bar is not easy to pull out under a certain tensile force, and the safety of the structure is ensured; (2) fluidity: the grouting material is usually pre-buried in precast concrete component bottom, and the grouting material mixture is injected through the grouting pore after inserting ribbed steel bar in the grouting sleeve during connection, or the grouting sleeve is pre-buried at vertical precast component top, and the above-mentioned process must ensure that the grouting material has higher self-leveling property and expansibility, just can make the grouting material smoothly fill the sleeve, makes the filling of grout position full and even, does not have the gas pocket.

The sleeve grouting material comprises the following components: high performance water reducers, high strength aggregates, expanding agents, cellulose and other auxiliary materials (e.g., to prevent air bubble formation in the grout formulation, and also to incorporate defoamers). The water reducing agent structure is generally a polycarboxylate water reducing agent, and can provide great flow property for the grouting material, thereby preventing the grouting material from bleeding, and because the water reducing agent is a flexible structure, the mechanical properties of the grouting material, such as compressive strength, rupture strength and the like, are reduced to different degrees easily in the adding process.

Therefore, how to make the grouting material have high strength, good flowing performance and good expansion performance is a problem which needs to be solved urgently, and has great significance for better application of the grouting material in the field.

Disclosure of Invention

The invention aims to provide a high-strength self-leveling grouting material which comprises compound components of etherified cellulose and a modified polycarboxylic acid water reducing agent and can solve the problems.

The present invention is realized by the following technical means.

A high-strength self-leveling grouting material comprises a compound component of etherified cellulose and a modified polycarboxylic acid water reducing agent, wherein the etherified cellulose is a product of cellulose etherified by an etherifying agent; the modified polycarboxylic acid water reducing agent is a quaternary copolymerization polymer, and monomers of the quaternary copolymerization polymer are respectively unsaturated polyether, unsaturated carboxylic acid, unsaturated sulfonate and polyol acrylate.

Further, the polyol acrylate is obtained by esterifying polyol and polyacrylic acid, the polyol is selected from sorbitol, pentaerythritol, cyclohexanediol or glycerol, and the ratio of the hydroxyl groups of the polyol to the amount of acrylic acid is 1: 1-1.2.

Further, the polyalcohol is a compound of cyclohexanediol and glycerol according to a molar ratio of 1-2: 1-2.

Further, the unsaturated polyether is selected from at least one of allyl polyoxyethylene ether, isoamyl alcohol polyoxyethylene ether and methallyl alcohol polyoxyethylene ether. The number average molecular weight of the unsaturated polyether is 500-4000, preferably 1500-3000.

Further, the unsaturated carboxylic acid is selected from acrylic acid and/or methacrylic acid.

Further, the unsaturated sulfonate is selected from propenyl sulfonate or styrene sulfonate.

Further, the number average molecular weight of the unsaturated polyether is 500-4000, preferably 1500-3000.

Further, the mass ratio of the etherified cellulose to the modified polycarboxylic acid water reducing agent is 6-10: 2-5.

Further, the unsaturated carboxylic acid is selected from acrylic acid or methacrylic acid; the etherifying agent is selected from 3-chloro-2-hydroxypropyl trimethyl ammonium chloride or 2, 3-epoxypropyl trimethyl ammonium chloride.

Further, the ratio of the amounts of the unsaturated polyether, the unsaturated carboxylic acid, the unsaturated sulfonate and the polyol acrylate is 10-20:10-20:2-5: 0.5-1.

Further, the preparation method of the etherified cellulose comprises the following steps:

s1, placing cellulose in alkali liquor, stirring for 1-3h, and drying;

s2, dissolving the product in the S1 in organic alcohol, adding an etherifying agent, and reacting at 50-70 ℃.

The alkali liquor is sodium hydroxide solution, and the organic alcohol is ethanol. The amounts used are well known to those skilled in the art.

Further, the etherifying agent is selected from 3-chloro-2-hydroxypropyl trimethyl ammonium chloride or 2, 3-epoxypropyl trimethyl ammonium chloride.

Further, the high-strength self-leveling grouting material comprises the following raw materials in parts by weight:

preferably, the sand is common gravel, quartz sand, silicon carbide sand or a mixture thereof.

The cement is selected from ordinary portland cement, has no special requirement on strength, and is common in the field.

The specification of the sand is 30-100 meshes.

The invention has the following beneficial effects:

1. the self-leveling grouting material contains etherified cellulose, wherein the cellulose is subjected to etherification modification, so that the cellulose is grafted with ether groups with strong flexibility, the flexibility of the cellulose can be greatly improved, and the self-leveling performance of the grouting material containing the flexible etherified cellulose is remarkably improved.

2. The invention also contains a modified polycarboxylic acid water reducing agent which is a quaternary random copolymerization structure and consists of unsaturated polyether, unsaturated carboxylic acid, unsaturated sulfonate and polyol acrylate. The unsaturated polyether and the unsaturated carboxylic acid monomer belong to flexible chain segments, so that the flexibility of the modified polycarboxylate superplasticizer can be improved; the polyol acrylate can form a cross-linking structure and/or a certain branched chain structure among molecular chains through esterification reaction, so that the rigidity of the molecular chains is increased. The grouting material containing the modified polycarboxylate superplasticizer obtained by polymerizing the four chain segments has obviously improved mechanical strength.

3. Surprisingly, the etherified cellulose and the modified carboxylic acid water reducing agent in the formula have good synergistic effect. Specifically, after the quaternary copolymerization polycarboxylic acid water reducing agent obtained by the monomers according to a certain proportion is compounded with the etherified cellulose, the obtained grouting material has the characteristics of high strength, self-leveling property and expansibility.

Detailed Description

The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. The starting materials described in the examples of the present invention are commercially available and, unless otherwise specified, the starting materials and methods employed are those conventional in the art.

Wherein the cement is selected from common Portland cement purchased from Hangzhou Ruichen building materials Co., Ltd, and has model number of RC-5482;

the sand is purchased from Weichafang Tiancheng building materials Limited company and has the specification of 40-70 meshes;

the defoaming agent is purchased from Xiamen Rayman chemical technology Co., Ltd, is an organic silicon defoaming agent and has the model of RK-3366N;

UEA bulking agents are purchased from new materials ltd, build, beijing.

Preparation example 1

The preparation method of the etherified cellulose 1 comprises the following steps:

s1, in a 500ml beaker, 10g of carboxymethyl cellulose is placed in 500ml of NaOH alkali liquor with the concentration of 3 wt% and stirred for 1 hour, and then after filtration, the mixture is dried by a vacuum oven;

s2, in a three-neck flask, dissolving 20mmol of the product in S1 in 200ml of ethanol, adding 21mmol of etherifying agent 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, reacting at 50 ℃ for 2h, and then distilling under reduced pressure to remove the solvent to obtain etherified cellulose 1.

The preparation method of the modified polycarboxylate superplasticizer 1 comprises the following steps:

and P1, mixing 5mmol of cyclohexanediol, 5mmol of glycerol and 30mmol of acrylic acid in a three-neck flask, and carrying out esterification reaction for 2 hours at 80 ℃ under the catalysis of concentrated sulfuric acid containing 0.3 wt% of sorbitol to obtain the sorbitol acrylate.

P2. three-necked flask, allyl polyoxyethylene ether, acrylic acid, sodium acrylate sulfonate and sorbitol acrylate were mixed at 10mmol, 2mmol and 0.5mmol, respectively, and 200ml of water was added. And 0.1 wt% of allyl polyoxyethylene ether BPO, and reacting for 5h at 80 ℃. Wherein the number average molecular weight of the allyl polyoxyethylene ether is 3000.

And P3, after the reaction is finished, adjusting the pH to 7 by using a 20% NaOH solution to obtain the modified polycarboxylic acid water reducing agent 1.

Preparation example 2

The preparation method of the modified polycarboxylate superplasticizer 2 comprises the following steps:

and P1, mixing 7mmol of cyclohexanediol, 3mmol of glycerol and 25mmol of acrylic acid in a three-neck flask, and carrying out esterification reaction for 2 hours at 80 ℃ under the catalysis of concentrated sulfuric acid containing 0.3 wt% of sorbitol to obtain the sorbitol acrylate.

P2. three-necked flask, allyl polyoxyethylene ether, acrylic acid, sodium acrylate sulfonate and sorbitol acrylate were mixed at 10mmol, 2mmol and 0.5mmol, respectively, and 200ml of water was added. And 0.1 wt% of allyl polyoxyethylene ether BPO, and reacting for 5h at 80 ℃. Wherein the number average molecular weight of the allyl polyoxyethylene ether is 3000.

And P3, after the reaction is finished, adjusting the pH to 7 by using a 20% NaOH solution to obtain the modified polycarboxylic acid water reducing agent 2.

Preparation example 3

The preparation method of the modified polycarboxylate superplasticizer 3 comprises the following steps:

and P1, mixing 3mmol of cyclohexanediol, 7mmol of glycerol and 30mmol of acrylic acid in a three-neck flask, and carrying out esterification reaction for 2 hours at 80 ℃ under the catalysis of concentrated sulfuric acid containing 0.3 wt% of sorbitol to obtain the sorbitol acrylate.

P2. three-necked flask, allyl polyoxyethylene ether, acrylic acid, sodium acrylate sulfonate and sorbitol acrylate were mixed at 10mmol, 2mmol and 0.5mmol, respectively, and 200ml of water was added. And 0.1 wt% of allyl polyoxyethylene ether BPO, and reacting for 5h at 80 ℃. Wherein the number average molecular weight of the allyl polyoxyethylene ether is 3000.

And P3, after the reaction is finished, adjusting the pH to 7 by using a 20% NaOH solution to obtain the modified polycarboxylic acid water reducing agent 3.

Preparation example 4

The preparation method of the modified polycarboxylate superplasticizer 4 comprises the following steps:

and P1, mixing 5mmol of sorbitol, 5mmol of cyclohexanediol and 30mmol of acrylic acid in a three-neck flask, and carrying out esterification reaction for 2 hours at 80 ℃ under the catalysis of concentrated sulfuric acid containing 0.3 wt% of sorbitol to obtain the sorbitol acrylate.

P2. three-necked flask, allyl polyoxyethylene ether, acrylic acid, sodium acrylate sulfonate and sorbitol acrylate were mixed at 10mmol, 2mmol and 0.5mmol, respectively, and 200ml of water was added. And 0.1 wt% of allyl polyoxyethylene ether BPO, and reacting for 5h at 80 ℃. Wherein the number average molecular weight of the allyl polyoxyethylene ether is 3000.

And P3, after the reaction is finished, adjusting the pH to 7 by using a 20% NaOH solution to obtain a modified polycarboxylic acid water reducing agent 4.

Preparation example 5

The preparation method of the etherified cellulose 2 comprises the following steps:

s1, in a 500ml beaker, 10g of carboxymethyl cellulose is placed in 500ml of NaOH alkali liquor with the concentration of 3 wt% and stirred for 3 hours, and then after filtration, the mixture is dried by a vacuum oven;

s2, in a three-neck flask, dissolving 20mmol of the product in S1 in 200ml of ethanol, adding 24mmol of etherifying agent 2, 3-epoxypropyltrimethylammonium chloride, reacting at 70 ℃ for 2h, and then distilling under reduced pressure to remove the solvent to obtain etherified cellulose 2.

The preparation method of the modified polycarboxylate superplasticizer 5 comprises the following steps:

and P1, mixing 10mmol of pentaerythritol and 40mmol of acrylic acid in a three-neck flask, and carrying out esterification reaction for 3 hours at the temperature of 80 ℃ under the catalysis of concentrated sulfuric acid containing 0.2 wt% of pentaerythritol to obtain pentaerythritol acrylate.

P2. three-necked flask, mixing Ensoprenol polyoxyethylene, acrylic acid, sodium acrylate sulfonate and pentaerythritol acrylate at 20mmol, 5mmol and 1mmol, respectively, and adding 300ml of water. And 0.2 wt% of BPO of isoamyl alcohol polyoxyethylene, and reacting for 5 hours at 80 ℃. Wherein the number average molecular weight of the isoprenol polyoxyethylene is 500.

And P3, after the reaction is finished, adjusting the pH to 7 by using a 20% NaOH solution to obtain the modified polycarboxylic acid water reducing agent 5.

Preparation example 6

The preparation method of the etherified cellulose 3 comprises the following steps:

s1, in a 500ml beaker, 10g of hydroxypropyl methyl cellulose is placed in 500ml of NaOH alkali liquor with the concentration of 3 wt% and stirred for 3 hours, and then after filtration, the mixture is dried by a vacuum oven;

s2, in a three-neck flask, dissolving 20mmol of the product in S1 in 200ml of ethanol, adding 22mmol of etherifying agent 2, 3-epoxypropyltrimethylammonium chloride, reacting at 60 ℃ for 2h, and then distilling under reduced pressure to remove the solvent to obtain etherified cellulose 3.

The preparation method of the modified polycarboxylate superplasticizer 6 comprises the following steps:

and P1, mixing 10mmol of glycerol and 30mmol of acrylic acid in a three-neck flask, and carrying out esterification reaction for 3 hours at 80 ℃ under the catalysis of concentrated sulfuric acid containing 0.2 wt% of glycerol to obtain glycerol acrylate.

P2. three-necked flask, methallyl alcohol polyoxyethylene ether, acrylic acid, sodium acrylate sulfonate and glycerol acrylate were mixed at 15mmol, 12mmol, 3mmol and 0.7mmol, respectively, and 300ml of water was added. And 0.2 wt% of methallyl alcohol polyoxyethylene ether BPO, at 85 ℃ for 4 h. Wherein the number average molecular weight of the methallyl alcohol polyoxyethylene ether is 4000.

And P3, after the reaction is finished, adjusting the pH to 7.5 by using a 20% NaOH solution to obtain a modified polycarboxylic acid water reducing agent 6.

Preparation example 7

The preparation method of the modified polycarboxylate superplasticizer 7 comprises the following steps:

and P1, mixing 10mmol of glycerol and 30mmol of acrylic acid in a three-neck flask, and carrying out esterification reaction for 3 hours at 80 ℃ under the catalysis of concentrated sulfuric acid containing 0.2 wt% of glycerol to obtain glycerol acrylate.

P2. three-necked flask, methallyl alcohol polyoxyethylene ether, acrylic acid, sodium acrylate sulfonate and glycerol acrylate were mixed at 25mmol, 3mmol and 0.3mmol, respectively, and 300ml of water was added. And 0.2 wt% of methallyl alcohol polyoxyethylene ether BPO, at 85 ℃ for 4 h. Wherein the number average molecular weight of the methallyl alcohol polyoxyethylene ether is 4000.

And P3, after the reaction is finished, adjusting the pH to 7.5 by using a 20% NaOH solution to obtain a modified polycarboxylic acid water reducing agent 7.

Preparation example 8

The preparation method of the modified polycarboxylate superplasticizer 8 comprises the following steps:

and P1, mixing 10mmol of glycerol and 30mmol of acrylic acid in a three-neck flask, and carrying out esterification reaction for 3 hours at 80 ℃ under the catalysis of concentrated sulfuric acid containing 0.2 wt% of glycerol to obtain glycerol acrylate.

P2. three-necked flask, methallyl alcohol polyoxyethylene ether, acrylic acid, sodium acrylate sulfonate and glycerol acrylate were mixed at 20mmol, 7mmol and 3mmol, respectively, and 300ml of water was added. And 0.2 wt% of methallyl alcohol polyoxyethylene ether BPO, at 85 ℃ for 4 h. Wherein the number average molecular weight of the methallyl alcohol polyoxyethylene ether is 800.

And P3, after the reaction is finished, adjusting the pH to 7.5 by using a 20% NaOH solution to obtain a modified polycarboxylic acid water reducing agent 8.

Preparation example 9

The preparation method of the modified polycarboxylate superplasticizer 9 comprises the following steps:

and P1, mixing 10mmol of glycerol and 30mmol of acrylic acid in a three-neck flask, and carrying out esterification reaction for 3 hours at 80 ℃ under the catalysis of concentrated sulfuric acid containing 0.2 wt% of glycerol to obtain glycerol acrylate.

P2. three-necked flask, methallyl alcohol polyoxyethylene ether, acrylic acid, sodium acrylate sulfonate and glycerol acrylate were mixed at 15mmol, 8mmol, 1mmol and 0.6mmol, respectively, and 300ml of water was added. And 0.2 wt% of methallyl alcohol polyoxyethylene ether BPO, at 85 ℃ for 4 h. Wherein the number average molecular weight of the methallyl alcohol polyoxyethylene ether is 1200.

And P3, after the reaction is finished, adjusting the pH to 7.5 by using a 20% NaOH solution to obtain the modified polycarboxylic acid water reducing agent 9.

Preparation example 10

The preparation method of the modified polycarboxylate superplasticizer 10 comprises the following steps:

p1. three-necked flask, methallyl alcohol polyoxyethylene ether, acrylic acid and sodium acrylate sulfonate were mixed at 15mmol, 15mmol and 1mmol, respectively, and 300ml of water was added. And 0.2 wt% of methallyl alcohol polyoxyethylene ether BPO, at 85 ℃ for 4 h. Wherein the number average molecular weight of the methallyl alcohol polyoxyethylene ether is 1200.

And P2, after the reaction is finished, adjusting the pH to 7.5 by using a 20% NaOH solution to obtain the modified polycarboxylic acid water reducing agent 10.

Preparation example 11

The preparation method of the modified polycarboxylic acid water reducing agent 11 comprises the following steps:

p1. three-necked flask, acrylic acid, sodium acrylate sulfonate and glycerol acrylate were mixed at 15mmol, 5mmol and 1mmol, respectively, and 300ml of water was added. And 0.2 wt% of acrylic acid, BPO, at 85 ℃ for 4 h.

And P2, after the reaction is finished, adjusting the pH to 7.5 by using a 20% NaOH solution to obtain the modified polycarboxylic acid water reducing agent 11.

Preparation example 12

The preparation method of the modified polycarboxylate superplasticizer 12 comprises the following steps:

p1. three-necked flask, methallyl alcohol polyoxyethylene ether, sodium acrylate sulfonate and glycerol acrylate were mixed at 15mmol, 5mmol and 1mmol, respectively, and 300ml of water was added. And 0.2 wt% of methallyl alcohol polyoxyethylene ether BPO, at 85 ℃ for 4 h. Wherein the number average molecular weight of the methallyl alcohol polyoxyethylene ether is 200.

And P2, after the reaction is finished, adjusting the pH to 7.5 by using a 20% NaOH solution to obtain the modified polycarboxylic acid water reducing agent 12.