CN107383358A - Hyperbranched synthetic method of unsaturated APEO and products thereof and application - Google Patents
Hyperbranched synthetic method of unsaturated APEO and products thereof and application Download PDFInfo
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- CN107383358A CN107383358A CN201710579599.2A CN201710579599A CN107383358A CN 107383358 A CN107383358 A CN 107383358A CN 201710579599 A CN201710579599 A CN 201710579599A CN 107383358 A CN107383358 A CN 107383358A
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- synthetic method
- apeo
- hyperbranched
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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
-
- 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
Abstract
The invention provides a kind of synthetic method of hyperbranched unsaturated APEO, and using unsaturated APEO hyperbranched made from the synthetic method and its application.The synthetic method mainly includes：First, polyol is made to carry out esterification with unsaturated carboxylic acid, obtained carboxylate intermediate remains substantial amounts of hydroxyl；Then, in the presence of anionic ring-opening polymerization catalysts, carboxylate intermediate is carried out anionic ring-opening polymerization reaction with oxirane, produce target product.The polycarboxylate water-reducer with higher APEO molecule chain density prepared using the hyperbranched unsaturated APEO as raw material, shows higher water-reducing rate, higher cement paste divergence, so as to show more excellent retarding effect；Therefore, synthetic method provided by the present invention and using hyperbranched unsaturated APEO made from the synthetic method, has broad application prospects and market potential.
Description
Technical field
The invention belongs to the additive field of concrete, more particularly to a kind of conjunction of hyperbranched unsaturated APEO
Into method, and using unsaturated APEO hyperbranched made from the synthetic method and its application.
Background technology
In modern concrete class architectural engineering, polycarboxylic acids dehydragent is that usage amount is maximum, most widely used one kind
Additive is built, the polycarboxylic acids dehydragent is different from acting on the lignosulfonic acid for improving concrete dispersiveness by electrostatic repulsion
There is electrostatic repulsion effect and steric hindrance to act on simultaneously for salt water reducer and naphthalene water reducer, polycarboxylic acids dehydragent, and its
In steric hindrance effect mainly by straight chain polyoxyethylene ether structure provide, the Relative mole of straight chain APEO molecular structure
Ratio and structural molecule amount directly influence the combination property of polycarboxylic acids dehydragent.
However, in the prior art, the unsaturated APEO as polycarboxylic acids dehydragent reaction raw materials is generally
Single linear chain structure or double linear chain structures, the polycarboxylic acids dehydragent that this unsaturated APEO synthesizes as reaction raw materials
The relative molar proportions of straight chain APEO molecular structure can not be improved further, in other words, can not further lift polyoxy
The density of vinyl ether molecules chain, so as to cause performance bottleneck be present 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.
The content of the invention
For a variety of technological deficiencies present in prior art, it is contemplated that acquisition is a kind of to have higher polyoxyethylene
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, and first, polyol and unsaturated carboxylic acid is carried out esterification, among obtained carboxylate
Body remains substantial amounts of hydroxyl；Then, in the presence of anionic ring-opening polymerization catalysts, carboxylate intermediate and ring are made
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 APEO,
Comprise the following steps：
S1：Polyol and unsaturated carboxylic acid X are added into reaction vessel：
Wherein, R is H or C1~C8 alkyl；And esterification catalyst, polymerization inhibitor are 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, a large amount of so as to avoid
The generation of accessory substance；Wherein, in the molecular structure of the intermediate A, the terminal hydroxy group of each no esterification can be anti-by polymerizeing
Straight chain APEO branched structure should be generated；
S2：The intermediate A, oxirane, anionic ring-opening polymerization catalysts are added into compressive reaction device,
In 160 DEG C~185 DEG C of reaction temperature and 0.15Mpa~0.25Mpa reaction vessel under pressure, carry out anion open loop and gather
Reaction is closed, that is, the hyperbranched unsaturated APEO is made.
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, caustic alcohol, potassium ethoxide.
Preferably, in above-mentioned synthetic method, the polyol and the unsaturated carboxylic acid X mol ratio are 1：
1.1~1：1.5；It is in order that obtaining hydroxyl hair as far as possible few in the polyol using this preferable molar ratio range
Raw esterification, generates ester group, it is also desirable to an only hydroxyl generation ester group, and remaining hydroxyl is then reserved, and is used
Reaction in follow-up step S2, so as to finally extend highly branched chain, realize hyperbranched.
Preferably, in above-mentioned synthetic method, the esterification catalyst adds quality as reactant gross mass in S1
0.5%~2.5%.
Preferably, in above-mentioned synthetic method, the polymerization inhibitor adds quality as reactant gross mass in S1
0.02%~0.20%.
Preferably, in above-mentioned synthetic method, the anionic ring-opening polymerization catalysts add quality as 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 small for 3.5~7.5
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 APEO.Because in above-mentioned synthetic method, obtained intermediate A (carboxylate intermediate) remains largely
Hydroxyl, these hydroxyls polymerize with oxirane, so as to generate some side chains, that is, complete hyperbranched respectively.
Finally, the hyperbranched unsaturated APEO that the third aspect of the present invention is additionally provided described in second aspect exists
The application in polycarboxylate water-reducer is prepared, specifically, the hyperbranched unsaturated APEO is carried out with unsaturated carboxylic acid
Free radicals copolymerization reaction is with obtained polycarboxylate water-reducer；It is noted that because the free radicals copolymerization reaction process can lead to
Cross known conventional method to realize, so concrete operation step and reaction condition repeat no more herein.According to the third aspect
Described application, when polycarboxylate water-reducer therein is used for cement, the dispersiveness of cement granules, same time delay have been obviously improved it
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 APEO strand using hyperbranched unsaturated APEO of the present invention as prepared by raw material
The polycarboxylate water-reducer of density, higher water-reducing rate, higher cement paste divergence are shown, it is more excellent so as to show
Retarding effect；In summary, synthetic method provided by the present invention and using hyperbranched insatiable hunger made from the synthetic method
And APEO, have broad application prospects and market potential.
Embodiment
With reference to embodiment, the present invention is further elaborated, but the present invention is not limited to following embodiment party
Formula.
According to the synthetic method of the hyperbranched unsaturated APEO of first aspect, comprise the following steps：S1：To anti-
Answer and polyol and unsaturated carboxylic acid X are added in container：
Wherein, R is H or C1~C8 alkyl；And esterification catalyst, polymerization inhibitor are 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, oxirane, anionic ring-opening polymerization are added into compressive reaction device
Catalysts, in 160 DEG C~185 DEG C of reaction temperature and 0.15Mpa~0.25Mpa reaction vessel under pressure, carry out
Anionic ring-opening polymerization reacts, that is, the hyperbranched unsaturated APEO is made.
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, caustic alcohol, potassium ethoxide.
In a preferred embodiment, the polyol and the unsaturated carboxylic acid X mol ratio are 1：1.1~
1：1.5.
In a preferred embodiment, the esterification catalyst adds quality as 0.5% of reactant gross mass in S1
~2.5%.
In a preferred embodiment, the polymerization inhibitor add quality for reactant gross mass in S1 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 APEO of second aspect, it is as the synthetic method system described in first aspect
.
According to application of the hyperbranched unsaturated APEO of the third aspect in polycarboxylate water-reducer is prepared,
Specifically, the hyperbranched unsaturated APEO carries out free radicals copolymerization reaction so that polycarboxylic acids is made with unsaturated carboxylic acid
Water reducer.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
Do not mentionlet alone bright can obtain from open commercial sources.
Embodiment 1
S1：500g erythrol, 380g acrylic acid, 10g p-methyl benzenesulfonic acid and 1.2g hydroquinones are added into reaction vessel,
The mechanical agitation 5h under 80 DEG C of reaction temperature, esterification is completed, intermediate A 1 is made；
S2：Intermediate A 1,2000g oxirane, 20g caustic alcohols 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 APEO P1 is made.
Embodiment 2
S1：Addition 550g pentaerythrites, 500g methacrylic acids, 15g p-methyl benzenesulfonic acid and 1.8g pairs into reaction vessel
Benzene diquinone, the mechanical agitation 4.5h under 90 DEG C of reaction temperature, esterification is completed, intermediate A 2 is made；
S2：Intermediate A 2,3000g oxirane, 25g potassium ethoxides 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
5.5h, hyperbranched unsaturated APEO P2 is made.
Embodiment 3
S1：800g pentitols, 600g acrylic acid, 25g p-methyl benzenesulfonic acid, 2g hydroquinones and 2g are added into reaction vessel
Benzoquinone, the mechanical agitation 4.5h under 75 DEG C of reaction temperature, esterification is completed, intermediate A 3 is made；
S2：Intermediate A 3,4000g oxirane, 20g potassium ethoxides 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
6.5h, hyperbranched unsaturated APEO P3 is made.
Embodiment 4
S1：1000g mannitol, 650g methacrylic acids, 35g p-methyl benzenesulfonic acid, 5.5g are added into reaction vessel to benzene
Diphenol, the mechanical agitation 6h under 75 DEG C of reaction temperature, esterification is completed, intermediate A 4 is made；
S2：Intermediate A 4,7500g oxirane, 75g potassium methoxides 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 APEO 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 agitation 6.5h under 80 DEG C of reaction temperature, esterification is completed, intermediate A 5 is made；
S2：Intermediate A 5,8000g oxirane, 70g sodium methoxides 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
6.5h, hyperbranched unsaturated APEO P5 is made.
Inventor is also respectively with hyperbranched unsaturated APEO P1~P5, methyl allyl polyoxyethylene ether
(HPEG), isopentene group APEO (TPEG) is reaction raw materials, under identical material ratio and same reaction conditions and not
Saturated carboxylic acid synthesis polycarboxylate water-reducer (i.e. according to a conventional method), and carried out the measure of correlated performance.
Cement used in experiment is the ordinary portland cement of Shanghai conch 42.5, 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 such as table 1 below
It is shown：
Table 1
As can be seen here, the polycarboxylate water-reducer further synthesized with hyperbranched unsaturated APEO P1~P5 shows
Go out higher water-reducing rate and cement paste divergence.Due to the molecular structure of corresponding unsaturated APEO in the prior art
In often only include one to two APEO side chains, so in final polycarboxylate water-reducer product, its polyoxyethylene
The density of ether strand can not be lifted further；Unlike this, synthetic method provided by the present invention can obtain higher gather
Oxygen vinyl ether molecules chain density, therefore obtained polycarboxylate water-reducer has more excellent retarding effect.
The specific embodiment of the present invention is described in detail above, but it is intended only as example, it is of the invention and unlimited
It is formed on particular embodiments described above.To those skilled in the art, it is any to the equivalent modifications that carry out of the present invention and
Substitute also all among scope of the invention.Therefore, the impartial conversion made without departing from the spirit and scope of the invention and
Modification, all should be contained within the scope of the invention.
Claims (9)
1. a kind of synthetic method of hyperbranched unsaturated APEO, it is characterised in that comprise the following steps：S1：To anti-
Answer and polyol and unsaturated carboxylic acid X are added in container：
Wherein, R is H or C1~C8 alkyl；And esterification catalyst, polymerization inhibitor are 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 hydroquinones
Or/and benzoquinone；
S2：The intermediate A, oxirane, anionic ring-opening polymerization catalysts are added into compressive reaction device,
In 160 DEG C~185 DEG C of reaction temperature and 0.15Mpa~0.25Mpa reaction vessel under pressure, anionic ring-opening polymerization is carried out
Reaction, that is, the hyperbranched unsaturated APEO is made.
2. synthetic method according to claim 1, it is characterised in that the polyol be selected from it is following any or
It is a variety of：Erythrol, pentaerythrite, pentitol, mannitol, inositol.
3. synthetic method according to claim 1, it is characterised in that the anionic ring-opening polymerization catalysts are selected from
It is any one or more below：Sodium methoxide, potassium methoxide, caustic alcohol, potassium ethoxide.
4. synthetic method according to claim 1, it is characterised in that the polyol and the unsaturated carboxylic acid
X mol ratio is 1：1.1~1：1.5.
5. synthetic method according to claim 1, it is characterised in that the quality that adds of the esterification catalyst is anti-in S1
Answer the 0.5%~2.5% of thing gross mass.
6. synthetic method according to claim 1, it is characterised in that the polymerization inhibitor adds quality as reactant in S1
The 0.02%~0.20% of gross mass.
7. synthetic method according to claim 1, it is characterised in that the throwing of the anionic ring-opening polymerization catalysts
Add 0.5%~2.5% that quality is reactant gross mass in S2.
A kind of 8. hyperbranched unsaturated APEO made from synthetic method according to any of the above-described claim.
9. application of the hyperbranched unsaturated APEO according to claim 8 in polycarboxylate water-reducer is prepared,
Characterized in that, the hyperbranched unsaturated APEO carries out free radicals copolymerization reaction to be made poly- with unsaturated carboxylic acid
Carboxylic acid water reducer.
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Cited By (7)
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| CN108975747A (en) * | 2018-08-01 | 2018-12-11 | 上海台界化工有限公司 | A kind of synthetic method of slow-setting polycarboxylic acid water reducing agent |
| CN110105494A (en) * | 2019-05-28 | 2019-08-09 | 安徽天润化学工业股份有限公司 | A kind of preparation method of hyperbranched amphoteric ionic polyacrylamide and its application in oilfield exploitation |
| CN110642987A (en) * | 2018-06-26 | 2020-01-03 | 科之杰新材料集团有限公司 | Ether ester copolymerization viscosity-reduction type polycarboxylate superplasticizer and preparation method thereof |
| CN110642990A (en) * | 2018-06-26 | 2020-01-03 | 科之杰新材料集团有限公司 | Preparation method of low-sensitivity viscosity-reduction type polycarboxylic acid superplasticizer |
| CN110643005A (en) * | 2018-06-26 | 2020-01-03 | 科之杰新材料集团有限公司 | Preparation method of ester viscosity-reducing polycarboxylic acid superplasticizer |
| 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 |
| CN114230775A (en) * | 2021-12-27 | 2022-03-25 | 厦门德丰行塑胶工业有限公司 | Hyperbranched ester compound and nylon fiber-adding composite material and preparation method thereof |
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| CN108975747A (en) * | 2018-08-01 | 2018-12-11 | 上海台界化工有限公司 | A kind of synthetic method of slow-setting polycarboxylic acid water reducing agent |
| CN108975747B (en) * | 2018-08-01 | 2021-05-07 | 上海台界化工有限公司 | Synthesis method of retarding polycarboxylate superplasticizer |
| CN110105494A (en) * | 2019-05-28 | 2019-08-09 | 安徽天润化学工业股份有限公司 | A kind of preparation method of hyperbranched amphoteric ionic polyacrylamide and its application 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 |
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