CN107383358B - Hyperbranched synthetic method of unsaturated polyoxyethylene ether and products thereof and application - Google Patents
Hyperbranched synthetic method of unsaturated polyoxyethylene ether and products thereof and application Download PDFInfo
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- CN107383358B CN107383358B CN201710579599.2A CN201710579599A CN107383358B CN 107383358 B CN107383358 B CN 107383358B CN 201710579599 A CN201710579599 A CN 201710579599A CN 107383358 B CN107383358 B CN 107383358B
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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
- C08G65/2615—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 the other compounds containing carboxylic acid, ester or anhydride groups
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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
- 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
- C04B24/2605—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polyethers (AREA)
Abstract
The present invention provides a kind of synthetic methods of hyperbranched unsaturated polyoxyethylene ether, and using unsaturated polyoxyethylene ether and its application hyperbranched made from the synthetic method.The synthetic method specifically includes that firstly, making polyol and unsaturated carboxylic acid carry out esterification, carboxylate intermediate obtained remains a large amount of hydroxyl；Then, in the presence of anionic ring-opening polymerization catalysts, so that carboxylate intermediate is carried out anionic ring-opening polymerization with ethylene oxide and react to get target product.Using the polycarboxylate water-reducer with higher polyoxyethylene ether molecule chain density that the hyperbranched unsaturated polyoxyethylene ether is prepared as raw material, higher water-reducing rate, higher cement paste divergence are shown, to show superior retarding effect；Therefore, synthetic method provided by the present invention and using hyperbranched unsaturated polyoxyethylene ether made from the synthetic method, has broad application prospects and market potential.
Description
Technical field
The invention belongs to the additive field of concrete, in particular to a kind of conjunction of hyperbranched unsaturated polyoxyethylene ether
At method, and using unsaturated polyoxyethylene ether and its application hyperbranched made from the synthetic method.
Background technique
In modern concrete class architectural engineering, polycarboxylic acids dehydragent is usage amount maximum, most widely used one kind
Additive is built, the polycarboxylic acids dehydragent is different from acting on the lignosulfonic acid for improving concrete dispersibility by electrostatic repulsion
Salt water-reducing agent and naphthalene water reducer, polycarboxylic acids dehydragent have an electrostatic repulsion effect and steric hindrance effect simultaneously, and its
In steric hindrance effect mainly by straight chain polyoxyethylene ether structure provide, the Relative mole of straight chain polyoxyethylene ether molecular structure
Ratio and structural molecule amount directly influence the comprehensive performance of polycarboxylic acids dehydragent.
However, in the prior art, the unsaturated polyoxyethylene ether as polycarboxylic acids dehydragent reaction raw materials is generally
Single linear chain structure or double linear chain structures, the polycarboxylic acids dehydragent that this unsaturation polyoxyethylene ether is synthesized as reaction raw materials
The relative molar proportions of straight chain polyoxyethylene ether molecular structure can not further increase, and in other words, can not further promote polyoxy
The density of vinyl ether molecules chain, so as to cause there are performance bottlenecks as the polycarboxylic acids dehydragent prepared by it, accordingly, it is difficult to full
There is the demand of high target in full border architectural engineering to polycarboxylic acids dehydragent.
Summary of the invention
It is a kind of with higher polyoxyethylene the present invention is directed to obtain for various technological deficiencies existing in the prior art
The polycarboxylate water-reducer of ether molecule chain density；Therefore, inventor is to the polyoxy as the primary raw material for preparing polycarboxylate water-reducer
Vinethene is modified, firstly, making polyol and unsaturated carboxylic acid progress esterification, among carboxylate obtained
Body remains a large amount of hydroxyl；Then, in the presence of anionic ring-opening polymerization catalysts, make carboxylate intermediate and ring
Oxidative ethane carries out anionic ring-opening polymerization reaction, and target product is finally made.
Specifically, the first aspect of the present invention provides a kind of synthetic method of hyperbranched unsaturated polyoxyethylene ether,
The following steps are included:
S1: polyol and unsaturated carboxylic acid X are added into reaction vessel:
Wherein, R is the alkyl of H or C1~C8；And esterification catalyst, polymerization inhibitor is added, in 65 DEG C~95 DEG C of reaction temperature
Degree is lower to carry out esterification, and intermediate A is made；Wherein, the esterification catalyst is p-methyl benzenesulfonic acid, and the polymerization inhibitor is to benzene
Diphenol or/and benzoquinone；Wherein, the effect of polymerization inhibitor is to prevent unsaturated carboxylic acid X from self-polymeric reaction occurs, to avoid a large amount of
The generation of by-product；Wherein, in the molecular structure of the intermediate A, the terminal hydroxy group of each no esterification can be anti-by polymerizeing
Straight chain polyoxyethylene ether branched structure should be generated；
S2: the intermediate A, ethylene oxide, anionic ring-opening polymerization catalysts being added into compressive reaction device,
In 160 DEG C~185 DEG C of reaction temperature and the reaction vessel of 0.15Mpa~0.25Mpa under pressure, it is poly- to carry out anion open loop
Reaction is closed, the hyperbranched unsaturated polyoxyethylene ether is obtained.
Preferably, in above-mentioned synthetic method, the polyol is selected from following any one or more: erythrol,
Pentaerythrite, pentitol, mannitol, inositol.
Preferably, in above-mentioned synthetic method, the anionic ring-opening polymerization catalysts be selected from it is following any or
It is a variety of: sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide.
Preferably, in above-mentioned synthetic method, the molar ratio of the polyol and the unsaturated carboxylic acid X are 1:
1.1~1:1.5；It is the hydroxyl hair in order to enable few as far as possible in the polyol using this preferred molar ratio range
Raw esterification, generates ester group, it is also desirable to which only a hydroxyl generates ester group, and remaining hydroxyl is then reserved, and is used
Reaction in subsequent step S2 is realized hyperbranched to finally extend highly branched chain.
Preferably, in above-mentioned synthetic method, the quality that adds of the esterification catalyst is reactant gross mass in S1
0.5%~2.5%.
Preferably, in above-mentioned synthetic method, the quality that adds of the polymerization inhibitor is reactant gross mass in S1
0.02%~0.20%.
Preferably, in above-mentioned synthetic method, the quality that adds of the anionic ring-opening polymerization catalysts is in S2
The 0.5%~2.5% of reactant gross mass.
Preferably, the duration of the esterification in the S1 of above-mentioned synthetic method is 3~8 hours.
Preferably, the duration of the anionic ring-opening polymerization reaction in the S2 of above-mentioned synthetic method is 3.5~7.5 small
When.
In addition, the second aspect of the present invention provide it is hyperbranched made from a kind of synthetic method according to first aspect
Unsaturated polyoxyethylene ether.Since in above-mentioned synthetic method, obtained intermediate A (carboxylate intermediate) is remained largely
Hydroxyl, these hydroxyls polymerize with ethylene oxide respectively, to generate several branches, that is, complete hyperbranched.
Exist finally, the third aspect of the present invention additionally provides unsaturated polyoxyethylene ether hyperbranched described in second aspect
The application in polycarboxylate water-reducer is prepared, specifically, the hyperbranched unsaturated polyoxyethylene ether and unsaturated carboxylic acid carry out
Free radicals copolymerization reaction is to be made polycarboxylate water-reducer；It is noted that since the free radicals copolymerization reaction process can lead to
It crosses known conventional method to realize, so concrete operation step and reaction condition repeat no more herein.According to the third aspect
The application has been obviously improved the dispersibility of cement granules, same time delay when polycarboxylate water-reducer therein is used for cement
Presetting period and final setting time are grown, consolidated statement reveals excellent retarding effect.
Compared with the common polycarboxylate water-reducer (or commercially available common polycarboxylate water-reducer) synthesized under same reaction conditions,
There is higher polyoxyethylene ether strand using hyperbranched unsaturated polyoxyethylene ether of the present invention as prepared by raw material
The polycarboxylate water-reducer of density shows higher water-reducing rate, higher cement paste divergence, to show superior
Retarding effect；In conclusion synthetic method provided by the present invention and using hyperbranched insatiable hunger made from the synthetic method
And polyoxyethylene ether, it has broad application prospects and market potential.
Specific embodiment
The present invention is further elaborated With reference to embodiment, but the present invention is not limited to following embodiment party
Formula.
According to the synthetic method of the hyperbranched unsaturated polyoxyethylene ether of first aspect, comprising the following steps: S1: to anti-
It answers and polyol and unsaturated carboxylic acid X is added in container:
Wherein, R is the alkyl of H or C1~C8；And esterification catalyst, polymerization inhibitor is added, in 65 DEG C~95 DEG C of reaction temperature
Degree is lower to carry out esterification, and intermediate A is made；Wherein, the esterification catalyst is p-methyl benzenesulfonic acid, and the polymerization inhibitor is to benzene
Diphenol or/and benzoquinone；S2: the intermediate A, ethylene oxide, anionic ring-opening polymerization are added into compressive reaction device
Catalysts in 160 DEG C~185 DEG C of reaction temperature and the reaction vessel of 0.15Mpa~0.25Mpa under pressure, carry out
Anionic ring-opening polymerization reaction, obtains the hyperbranched unsaturated polyoxyethylene ether.
In a preferred embodiment, the polyol is selected from following any one or more: erythrol, Ji Wusi
Alcohol, pentitol, mannitol, inositol.
In a preferred embodiment, the anionic ring-opening polymerization catalysts are selected from following any one or more:
Sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide.
In a preferred embodiment, the molar ratio of the polyol and the unsaturated carboxylic acid X be 1:1.1~
1:1.5.
In a preferred embodiment, the esterification catalyst add quality be S1 in reactant gross mass 0.5%
~2.5%.
In a preferred embodiment, the polymerization inhibitor add quality be S1 in reactant gross mass 0.02%~
0.20%.
In a preferred embodiment, the quality that adds of the anionic ring-opening polymerization catalysts is reactant in S2
The 0.5%~2.5% of gross mass.
According to the hyperbranched unsaturated polyoxyethylene ether of second aspect, the synthetic method system as described in first aspect
?.
The application in polycarboxylate water-reducer is being prepared according to the hyperbranched unsaturated polyoxyethylene ether of the third aspect,
Specifically, the hyperbranched unsaturated polyoxyethylene ether and unsaturated carboxylic acid carry out free radicals copolymerization reaction so that polycarboxylic acids is made
Water-reducing agent.Unsaturated carboxylic acid therein includes acrylic acid, methacrylic acid etc..
Synthesis step in following each embodiments is routine operation unless otherwise instructed, and reaction raw materials therein are such as without spy
Bright equal can obtain from public commercial source is not mentionleted alone.
Embodiment 1
S1: 500g erythrol, 380g acrylic acid, 10g p-methyl benzenesulfonic acid and 1.2g hydroquinone being added into reaction vessel,
The mechanical stirring 5h under 80 DEG C of reaction temperature completes esterification, and intermediate A 1 is made；
S2: intermediate A 1,2000g ethylene oxide, 20g sodium ethoxide described in 150g are added into compressive reaction device, 170
DEG C reaction temperature and 0.15Mpa reaction vessel under pressure, carry out anionic ring-opening polymerization reaction, reaction time 6h,
Hyperbranched unsaturated polyoxyethylene ether P1 is made.
Embodiment 2
S1: addition 550g pentaerythrite, 500g methacrylic acid, 15g p-methyl benzenesulfonic acid and 1.8g pairs into reaction vessel
Benzene diquinone, the mechanical stirring 4.5h under 90 DEG C of reaction temperature complete esterification, and intermediate A 2 is made；
S2: intermediate A 2,3000g ethylene oxide, 25g potassium ethoxide described in 175g are added into compressive reaction device, 165
DEG C reaction temperature and 0.20Mpa reaction vessel under pressure, carry out anionic ring-opening polymerization reaction, the reaction time is
Hyperbranched unsaturated polyoxyethylene ether P2 is made in 5.5h.
Embodiment 3
S1: 800g pentitol, 600g acrylic acid, 25g p-methyl benzenesulfonic acid, 2g hydroquinone and 2g are added into reaction vessel
Benzoquinone, the mechanical stirring 4.5h under 75 DEG C of reaction temperature complete esterification, and intermediate A 3 is made；
S2: intermediate A 3,4000g ethylene oxide, 20g potassium ethoxide described in 200g are added into compressive reaction device, 175
DEG C reaction temperature and 0.18Mpa reaction vessel under pressure, carry out anionic ring-opening polymerization reaction, the reaction time is
Hyperbranched unsaturated polyoxyethylene ether P3 is made in 6.5h.
Embodiment 4
S1: 1000g mannitol, 650g methacrylic acid, 35g p-methyl benzenesulfonic acid, 5.5g are added into reaction vessel to benzene
Diphenol, the mechanical stirring 6h under 75 DEG C of reaction temperature complete esterification, and intermediate A 4 is made；
S2: intermediate A 4,7500g ethylene oxide, 75g potassium methoxide described in 350g are added into compressive reaction device, 175
DEG C reaction temperature and 0.22Mpa reaction vessel under pressure, carry out anionic ring-opening polymerization reaction, reaction time 6h,
Hyperbranched unsaturated polyoxyethylene ether P4 is made.
Embodiment 5
S1: 1000g inositol, 550g acrylic acid, 30g p-methyl benzenesulfonic acid, 5.5g are added into reaction vessel to benzene two
Quinone, the mechanical stirring 6.5h under 80 DEG C of reaction temperature complete esterification, and intermediate A 5 is made；
S2: intermediate A 5,8000g ethylene oxide, 70g sodium methoxide described in 350g are added into compressive reaction device, 180
DEG C reaction temperature and 0.25Mpa reaction vessel under pressure, carry out anionic ring-opening polymerization reaction, the reaction time is
Hyperbranched unsaturated polyoxyethylene ether P5 is made in 6.5h.
Inventor is also respectively with hyperbranched unsaturated polyoxyethylene ether P1~P5, methyl allyl polyoxyethylene ether
(HPEG), isopentene group polyoxyethylene ether (TPEG) is reaction raw materials, under identical material ratio and same reaction conditions and not
Saturated carboxylic acid synthesizes polycarboxylate water-reducer (i.e. according to a conventional method), and has carried out the measurement of correlated performance.
Testing cement used is 42.5 ordinary portland cement of Shanghai conch, tests water-reducing rate with reference to GB/8076-2008 and cement is net
Divergence is starched, extension diameter units are millimeter (mm), and test temperature is 25 DEG C, testing humidity 55%；Test result is as follows table 1
It is shown:
Table 1
It can be seen that the polycarboxylate water-reducer performance further synthesized with hyperbranched unsaturated polyoxyethylene ether P1~P5
Higher water-reducing rate and cement paste divergence out.Due to the molecular structure of corresponding unsaturated polyoxyethylene ether in the prior art
In often only include one to two polyoxyethylene ether branches, so in final polycarboxylate water-reducer product, polyoxyethylene
The density of ether strand can not be promoted further；Unlike this, synthetic method provided by the present invention can obtain higher poly-
Ethylene oxide ether molecule chain density, therefore obtained polycarboxylate water-reducer has superior retarding effect.
Specific embodiments of the present invention are described in detail above, but it is merely an example, the present invention is simultaneously unlimited
It is formed on particular embodiments described above.To those skilled in the art, any couple of present invention carries out equivalent modifications and
Substitution is also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by equal transformation and
Modification, all should be contained within the scope of the invention.
Claims (7)
1. a kind of synthetic method of hyperbranched unsaturated polyoxyethylene ether, which comprises the following steps:
S1: polyol and unsaturated carboxylic acid X are added into reaction vessel:
Wherein, R is the alkyl of H or C1~C8；And esterification catalyst, polymerization inhibitor is added, under 65 DEG C~95 DEG C of reaction temperature
Esterification is carried out, intermediate A is made；Wherein, the esterification catalyst is p-methyl benzenesulfonic acid, and the polymerization inhibitor is hydroquinone
Or/and benzoquinone；
S2: the intermediate A, ethylene oxide, anionic ring-opening polymerization catalysts being added into compressive reaction device,
In 160 DEG C~185 DEG C of reaction temperature and the reaction vessel of 0.15Mpa~0.25Mpa under pressure, anionic ring-opening polymerization is carried out
Reaction, obtains the hyperbranched unsaturated polyoxyethylene ether；
Wherein, the polyol be selected from it is following any one or more: erythrol, pentaerythrite, pentitol, mannitol,
Inositol；
Wherein, the molar ratio of the polyol and the unsaturated carboxylic acid X are 1:1.1~1:1.5.
2. synthetic method according to claim 1, which is characterized in that the anionic ring-opening polymerization catalysts are selected from
It is any one or more below: sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide.
3. synthetic method according to claim 1, which is characterized in that the quality that adds of the esterification catalyst is anti-in S1
Answer the 0.5%~2.5% of object gross mass.
4. synthetic method according to claim 1, which is characterized in that the quality that adds of the polymerization inhibitor is reactant in S1
The 0.02%~0.20% of gross mass.
5. synthetic method according to claim 1, which is characterized in that the throwing of the anionic ring-opening polymerization catalysts
Adding quality is 0.5%~2.5% of reactant gross mass in S2.
6. hyperbranched unsaturated polyoxyethylene ether made from a kind of synthetic method according to any of the above-described claim.
7. hyperbranched unsaturated polyoxyethylene ether according to claim 6 is preparing the application in polycarboxylate water-reducer,
It is characterized in that, the hyperbranched unsaturated polyoxyethylene ether and unsaturated carboxylic acid carry out free radicals copolymerization reaction to be made poly-
Carboxylic acid water reducer.
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| CN110643005B (en) * | 2018-06-26 | 2022-01-04 | 科之杰新材料集团有限公司 | Preparation method of ester viscosity-reducing polycarboxylic acid superplasticizer |
| CN110642987B (en) * | 2018-06-26 | 2022-01-04 | 科之杰新材料集团有限公司 | Ether ester copolymerization viscosity-reduction type polycarboxylate superplasticizer and preparation method thereof |
| CN110642990B (en) * | 2018-06-26 | 2022-01-04 | 科之杰新材料集团有限公司 | Preparation method of low-sensitivity viscosity-reduction type polycarboxylic acid superplasticizer |
| CN108975747B (en) * | 2018-08-01 | 2021-05-07 | 上海台界化工有限公司 | Synthesis method of retarding polycarboxylate superplasticizer |
| CN110105494B (en) * | 2019-05-28 | 2021-03-30 | 安徽天润化学工业股份有限公司 | Preparation method of hyperbranched zwitterionic polyacrylamide and application of hyperbranched zwitterionic polyacrylamide in oilfield exploitation |
| CN111040146A (en) * | 2019-12-05 | 2020-04-21 | 上海台界化工有限公司 | Synthesis method of phosphorus-containing unsaturated polyoxyethylene ether, product and application thereof |
| CN114230775B (en) * | 2021-12-27 | 2023-08-04 | 厦门德丰行塑胶工业有限公司 | Hyperbranched ester compound and nylon fiber composite material and preparation method thereof |
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| CN102887979B (en) * | 2012-10-22 | 2014-02-05 | 北京工业大学 | Preparation method of star polycarboxylic acid high-performance water reducing agent |
| CN104710606A (en) * | 2013-12-12 | 2015-06-17 | 辽宁奥克化学股份有限公司 | Alkenyl terminated polyether ester and preparation method thereof, and water reducing agent prepared by using alkenyl terminated polyether ester and preparation method thereof |
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