CN109265694B - Synthetic method of regulator for polyether type polycarboxylate superplasticizer - Google Patents

Synthetic method of regulator for polyether type polycarboxylate superplasticizer Download PDF

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CN109265694B
CN109265694B CN201810893003.0A CN201810893003A CN109265694B CN 109265694 B CN109265694 B CN 109265694B CN 201810893003 A CN201810893003 A CN 201810893003A CN 109265694 B CN109265694 B CN 109265694B
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polyether
integer
formula
regulator
oxygen atom
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CN109265694A (en
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傅雁
李国云
虞亚丽
刘俊平
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Suzhou Fuclear Technology Co ltd
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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
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • 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
    • C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
    • 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
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment

Abstract

The invention discloses a synthesis method of a regulator for a polyether type polycarboxylate superplasticizer. The regulator has a structure shown in formula I, wherein X represents- (CH)2‑CH2‑O)a-structural fragment with terminal oxygen atom linked to R, a is any integer from 65 to 115, R is methyl or ethyl; y represents- (CH)2‑CH2‑O)b-or- (CH)2‑CHCH3‑O)cA structural fragment in which the terminal oxygen atom is linked to a carbonyl group, b is an integer from 20 to 140, and c is an integer from 15 to 110. The modulator need only be prepared by (1) preparing a monoester intermediate; (2) preparing a mono-anhydride monoester intermediate; (3) the preparation method has the advantages of simple method, controllable process, stable and safe reaction process and the like, and the obtained product can solve the problems of high viscosity, delayed bleeding and the like of high-grade concrete and has great market value.

Description

Synthetic method of regulator for polyether type polycarboxylate superplasticizer
The invention belongs to a regulator for polyether type polycarboxylate superplasticizer and a synthesis method thereof, has application number of 201610487749.2, is a divisional application of invention application of 2016, 6 and 28, and belongs to the technical part of a product preparation method.
Technical Field
The invention belongs to the technical field of concrete materials, and relates to a regulator for a water reducer, in particular to a regulator for a polyether type polycarboxylate water reducer and a synthesis method thereof.
Background
At present, infrastructure construction in China is in a vigorous development stage, particularly development of high-speed rail and high-rise houses drives concrete-related industries to be greatly advanced, and high-performance concrete prepared by adding a polycarboxylic acid water reducer (polycarboxylate superplasticizer) serving as a concrete admixture is increasingly concerned by people.
As a result, polycarboxylic acid water reducing agents have been widely used in high grade concrete (usually, concrete with strength grade C60 or above), but some of the problems are becoming more and more prominent. Particularly, the polyether polycarboxylate superplasticizer has the problems of high viscosity, serious hysteresis bleeding and the like for high-grade concrete while realizing high water reducing rate.
Therefore, the research and development of a novel regulator for the polyether type polycarboxylate superplasticizer for improving the performance of high-grade concrete can greatly meet the requirement of economic construction, and has practical significance.
Disclosure of Invention
In one aspect, the invention provides a regulator (commonly called "polyether partner") for a polyether type polycarboxylate superplasticizer, which has a structure shown in a formula (I):
Figure 690635DEST_PATH_IMAGE001
wherein:
x represents- (CH)2-CH2-O)a-structural fragment with terminal oxygen atom linked to R, a is any integer from 65 to 115, R is methyl or ethyl;
y represents- (CH)2-CH2-O)b-or- (CH)2-CHCH3-O)cA structural fragment in which the terminal oxygen atom is linked to a carbonyl group, b is an integer from 20 to 140, and c is an integer from 15 to 110.
In another aspect, the invention provides a synthesis method of the regulator for the polyether type polycarboxylate superplasticizer, which comprises the following steps:
(1) preparation of monoester intermediate:
adding pyromellitic dianhydride shown in the formula (II) and monohydroxy polyether shown in the formula (III) into a reaction vessel according to the molar ratio of pyromellitic monoanhydride to monohydroxy polyether = 1-1.2: 1, wherein X represents- (CH)2-CH2-O)aA structural fragment, wherein a is an integer of 65-115, R is methyl or ethyl, and a terminal oxygen atom is connected with R, and the reaction is carried out for 2-4 hours at 100-120 ℃ under the stirring condition to obtain a monoester intermediate shown as a formula (IV);
Figure 247518DEST_PATH_IMAGE002
；
(2) preparation of the mono-anhydride monoester intermediate:
adding dibutyltin oxide serving as a catalyst and xylene serving as a solvent into a reaction container according to the molar ratio of dibutyltin oxide = 10-15: 1 serving as a monoester intermediate, heating and refluxing for 6-8 hours, removing water by a reflux water separation device, and evaporating xylene after water removal is finished to obtain a monoanhydride monoester intermediate shown as a formula (V);
Figure DEST_PATH_IMAGE003
；
(3) preparing a target product:
adding the dihydroxy polyether described as the formula (VI) into a reaction container according to the molar ratio of the mono-anhydride monoester intermediate to the dihydroxy polyether = 2-2.5: 1, wherein Y represents- (CH)2-CH2-O)b-or- (CH)2-CHCH3-O)cA structural segment, wherein a terminal oxygen atom is connected with a hydrogen atom, b is any integer from 20 to 140, c is any integer from 15 to 110, and the structural segment and the terminal oxygen atom are reacted for 3 to 4 hours at 100 to 120 ℃ under the stirring condition to obtain a target product, namely the regulator for the polyether polycarboxylic acid water reducer as shown in the formula (I);
Figure 452235DEST_PATH_IMAGE004
。
preferably, in the above synthesis method, the molar ratio of the pyromellitic monoanhydride to the monohydroxy polyether in the step (1) is 1: 1.
Preferably, in the above synthesis method, the monohydroxy polyether in step (1) is in a molten state.
Preferably, in the above synthesis method, the molar ratio of the monoester intermediate to dibutyltin oxide in the step (2) is 10: 1.
Preferably, in the above synthesis method, the reflux water separator in step (2).
Preferably, in the above synthesis method, the molar ratio between the monoanhydride monoester intermediate and the dihydroxy polyether in step (3) is 2: 1.
Preferably, in the above synthesis method, the stirring is performed by a mechanical stirring device or a magnetic stirring device.
Compared with the prior art, the invention adopting the technical scheme has the following advantages: the preparation method is simple, the process is controllable, the reaction process is stable and safe, the target product can be obtained by only three steps, and the obtained product can solve the problems of high viscosity, serious hysteresis bleeding and the like of high-grade concrete, and has great market value.
Drawings
FIG. 1 is a drawing showing the product obtained in example 11H-NMR spectrum.
FIG. 2 is a diagram of the product obtained in example 21H-NMR spectrum.
FIG. 3 shows the product obtained in example 31H-NMR spectrum.
Detailed Description
The technical solution of the present invention will be further described with reference to specific examples. Unless otherwise specifically stated, various reagents, materials, instruments and the like used in the following examples are commercially available.
Example 1: the method is used for preparing the regulator of the polyether polycarboxylic acid water reducing agent.
Into a 1000 mL four-necked flask was added molten polyethylene glycol monomethyl ether3000 (MPEG-3000, 300 g, 0.1 mol) and pyromellitic monoanhydride (23.6 g, 0.1 mol), heated to 100 ℃ with stirring, and reacted at this temperature for 2 h; then adding xylene (100 g) and dibutyltin oxide (2.49 g, 0.01 mol), heating and refluxing for 6 h, removing water by a water separator, and removing xylene by reduced pressure distillation; adding polyethylene glycol 6000 (PEG-6000, 300 g, 0.05 mol), adjusting temperature to 100 deg.C, reacting at the temperature for 3.5 h, and cooling to obtain target product1The H-NMR spectrum is shown in FIG. 1.
Example 2: the method is used for preparing the regulator of the polyether polycarboxylic acid water reducing agent.
A1000 mL four-necked flask was charged with molten polyethylene glycol monoethyl ether 5000 (EPEG-5000, 500 g, 0.1 mol) and pyromellitic dianhydride (23.6 g, 0.1 mol), heated to 110 ℃ with stirring, and reacted at this temperature for 3 hours; then adding dimethylbenzene (160 g) and dibutyltin oxide (2.5 g, 0.01 mol), heating and refluxing for 7 h, removing water through a water separator, and removing dimethylbenzene by reduced pressure distillation; adding polypropylene glycol 2000 (PPG-2000, 100 g, 0.05 mol), adjusting temperature to 110 deg.C, reacting at the temperature for 3 h, and cooling to obtain target product1The H-NMR spectrum is shown in FIG. 2.
Example 3: the method is used for preparing the regulator of the polyether polycarboxylic acid water reducing agent.
A1000 mL four-necked flask was charged with molten polyethylene glycol monomethyl ether 4000 (MPEG-4000, 400 g, 0.1 mol) and pyromellitic dianhydride (23.6 g, 0.1 mol), heated to 120 ℃ with stirring, and reacted at this temperature for 4 hours; then adding xylene (130 g) and dibutyltin oxide (2.5 g, 0.01 mol), heating and refluxing for 8 h, removing water by a water separator, and removing xylene by reduced pressure distillation; adding polyethylene glycol 4000 (PEG-4000, 200 g, 0.05 mol), adjusting temperature to 120 deg.C, reacting at the temperature for 4 h, and cooling to obtain the final product1The H-NMR spectrum is shown in FIG. 3.
Example 4: the regulator obtained by the invention is compounded with the water reducing agent to influence the performance of concrete.
The method for testing the bleeding rate of the concrete comprises the following steps: taking fresh concrete, measuring according to a bleeding rate ratio method specified in GB 8076-2008, recording the bleeding amount of each time period, and calculating the bleeding rate of each time period from the bleeding amount of each time period.
Method for testing concrete viscosity: determined by measuring the flow-down time of an inverted slump cone (cone: 20 cm in large-mouth diameter, 10 cm in small-mouth diameter, 30 cm in height): wetting a slump cone and a bottom plate (without open water), putting the slump cone upside down (with a large opening facing upwards) on the bottom plate, righting and stabilizing, adding newly-mixed high-grade concrete by a small shovel in two layers, filling the concrete into each layer with the height being half of the cone height, inserting and tamping each layer for 15 times by an inserting and tamping rod, inserting and tamping, and performing inserting and tamping along the spiral direction from the outside to the center, wherein the inserting and tamping are uniformly distributed on the cross section. When the concrete at the side of the cylinder is inserted and tamped, the tamping rod can be slightly inclined. When the bottom layer is inserted and tamped, the tamping rod penetrates through the whole depth, and when the top layer is inserted and tamped, the tamping rod penetrates through the top layer to the surface of the bottom layer; when the top layer is poured, the concrete should be poured to a position higher than the opening of the barrel. During the tamping process, if the concrete sinks to a position lower than the opening of the cylinder, the concrete should be added at any time. And after the top layer is inserted and pounded, scraping the redundant concrete and trowelling the concrete. After the concrete on the bottom plate at the side of the cylinder is removed, the slump cylinder is vertically and stably lifted, timing is started by using a stopwatch while lifting is started, the slump cylinder is lifted to 30 cm within 3-5 s, and the timing is stopped after the concrete in the slump cylinder completely flows, so that the time is the flowing-down time of the concrete. The entire process from the start of the loading to the lifting of the slump cone should be carried out without interruption and should be completed within 150 s.
The three regulators (polyether mate) in the embodiments 1 to 3 are respectively compounded with the polyether polycarboxylic acid water reducing agent to form the composite water reducing agent, and the compounding method is that the regulator replaces the polyether polycarboxylic acid water reducing agent, and the replacing amount is 4 percent. C60 concrete is prepared under the test conditions of the same mixing proportion, water consumption, water reducer mixing amount and the like, the performance of the concrete is measured, meanwhile, the C60 concrete prepared by using a polyether polycarboxylic acid water reducer without a regulator (polyether partner) is used as a control experiment material, and the detection results of various performances are shown in Table 1.
Figure 369244DEST_PATH_IMAGE005
The slump, the expansion degree and the falling time of the reverse slump cone of the concrete mixed with the regulator and the polyether polycarboxylic acid water reducing agent show that the viscosity of the concrete is greatly reduced; from the bleeding rate and the bleeding rate after 1 hour, it can be seen that the bleeding and the delayed bleeding of the concrete are both greatly reduced. In addition, the 28-day compressive strength is also improved to a certain extent.

Claims (8)

1. A synthetic method of a regulator for a polyether type polycarboxylate superplasticizer comprises the following steps:
1) preparation of monoester intermediate:
adding pyromellitic dianhydride shown in the formula II and monohydroxy polyether shown in the formula III into a reaction vessel according to the molar ratio of pyromellitic dianhydride to monohydroxy polyether = 1-1.2: 1, wherein X represents- (CH)2-CH2-O)aA structural fragment, wherein a is an integer of 65-115, R is methyl or ethyl, and a terminal oxygen atom is connected with R, and the reaction is carried out for 2-4 hours at 100-120 ℃ under the stirring condition to obtain a monoester intermediate shown as a formula IV;
Figure RE-343640DEST_PATH_IMAGE001
；
2) preparation of the mono-anhydride monoester intermediate:
adding dibutyltin oxide serving as a catalyst and xylene serving as a solvent into a reaction container according to the molar ratio of dibutyltin oxide = 10-15: 1 serving as a monoester intermediate, heating and refluxing for 6-8 hours, removing water by a reflux water separation device, and evaporating xylene after water removal is finished to obtain a monoanhydride monoester intermediate shown as a formula V;
Figure RE-729622DEST_PATH_IMAGE002
；
3) preparing a target product:
adding the dihydroxy polyether described as formula VI into a reaction container according to the molar ratio of the mono-anhydride monoester intermediate to the dihydroxy polyether = 2-2.5: 1, wherein Y represents- (CH)2-CH2-O)b-or- (CH)2-CHCH3-O)cA structural segment, wherein a terminal oxygen atom is connected with a hydrogen atom, b is any integer from 20 to 140, c is any integer from 15 to 110, and the structural segment and the terminal oxygen atom are reacted for 3 to 4 hours at 100 to 120 ℃ under the stirring condition to obtain the regulator shown as the formula I for the polyether polycarboxylic acid water reducer;
Figure RE-493047DEST_PATH_IMAGE003
。
2. the method of synthesis according to claim 1, characterized in that: the regulator for the polyether type polycarboxylate superplasticizer has a structure shown as a formula I:
Figure RE-357098DEST_PATH_IMAGE004
wherein:
x represents- (CH)2-CH2-O)a-structural fragment with terminal oxygen atom linked to R, a is any integer from 65 to 115, R is methyl or ethyl;
y represents- (CH)2-CH2-O)b-or- (CH)2-CHCH3-O)cA structural fragment in which the terminal oxygen atom is linked to a carbonyl group, b is an integer from 20 to 140, and c is an integer from 15 to 110.
3. The method of synthesis according to claim 1, characterized in that: the molar ratio of the pyromellitic dianhydride to the monohydroxy polyether in the step 1) is 1: 1.
4. The method of synthesis according to claim 1, characterized in that: in step 1), the monohydroxy polyether is in a molten state.
5. The method of synthesis according to claim 1, characterized in that: the molar ratio of the monoester intermediate to dibutyltin oxide in the step 2) is 10: 1.
6. The method of synthesis according to claim 1, characterized in that: the reflux water diversion device in the step 2) is a water diversion device.
7. The method of synthesis according to claim 1, characterized in that: the molar ratio of the monoanhydride monoester intermediate to the dihydroxy polyether in step 3) is 2: 1.
8. The method of synthesis according to claim 1, characterized in that: the stirring is accomplished by a mechanical stirring device or a magnetic stirring device.
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