CN106883403A - The preparation method of maleic acid mono alkyl ester polyether - Google Patents
The preparation method of maleic acid mono alkyl ester polyether Download PDFInfo
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- CN106883403A CN106883403A CN201710229194.6A CN201710229194A CN106883403A CN 106883403 A CN106883403 A CN 106883403A CN 201710229194 A CN201710229194 A CN 201710229194A CN 106883403 A CN106883403 A CN 106883403A
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- maleic acid
- alkyl ester
- acid mono
- mono alkyl
- maleic anhydride
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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
- 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
- C08G65/2606—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 containing hydroxyl groups
- C08G65/2609—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 containing hydroxyl groups containing aliphatic hydroxyl groups
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
The present invention relates to a kind of preparation method of maleic acid mono alkyl ester polyether, it is characterised in that：Comprise the following steps：One, during maleic anhydride, alkylol and catalyst by proportion added into autoclave together, epoxides is added after vacuumized nitrogen three times, stirring is warming up to 65 70 DEG C, and exothermic heat of reaction makes temperature rise to 120 DEG C, continues to react to pressure keeping constant；Two, 120 130 DEG C of temperature is controlled, pressure is 2 4Kg, and epoxide reaction is persistently added dropwise, and continues to react 1 2h；Three, vacuumize removing residual epoxy compound and obtain maleic acid mono alkyl ester polyether.Process is simple, it is not necessary to solvent, it is not required that acidic catalyst, and base catalyst used can also act as nertralizer in last water reducer preparatory phase, and directly with epoxide and maleic anhydride polycondensation, low cost, molecular weight and structure adjustable extent are big.
Description
Technical field
The invention belongs to construction material field of chemicals, more particularly to a kind of preparation side of maleic acid mono alkyl ester polyether
Method.
Background technology
Water reducer is a kind of under conditions of maintaining concrete slump constant, can be reduced outside the concrete of mixing water amount
Plus agent.Belong to anion surfactant mostly, there is lignosulfonates, naphthalene sulphonate formaldehyde polymer etc..Add concrete
There is peptizaiton to cement granules after mixture, its workability can be improved, reduce unit consumption of water, improve concrete mix
Mobility；Or unit cement consumption is reduced, save cement.According to chemical composition composition is generally divided into：Lignin sulfonate diminishing
Agent, naphthalene series high-efficiency water-reducing agent, melamine superplasticizer, Amino-sulfonic Acid-based Water-reducer, fatty acid series diminishing high
Agent, polycarboxylic acid series high efficiency water reducing agent.Wherein polycarboxylic acid series high efficiency water reducing agent be early 1980s Japan take the lead in develop it is new
Generation water reducer, is that forefront, scientific and technological content highest, one kind that application prospect is best, combination property is optimal are high in the world at present
Effect water reducer.Polycarboxylic acid series high efficiency water reducing agent of new generation overcomes some drawbacks of conventional water reducing agents, with volume is low, slump retaining
Can good, concrete contraction percentage be low, adjustability is strong, high performance potentiality are big on molecular structure, do not use formaldehyde in production process
Deng outstanding advantages.
Poly carboxylic acid series water reducer is main by acrylic compounds unsaturation small molecule monomer and polyethers polymeric monomer copolymerization
Water soluble polymer with comb-type structure, a class is acrylic monomer and polyoxyethylene monomethyl ether in polyethers polymeric monomer
Esterification products such as polyalkylene glycol acrylate ester monomethyl ether a, class is such as pi-allyl polyoxy of the APEO containing double bond unsaturated alcohol
Vinethene, also a class are the esterification products such as maleic acid mono alkyl ester polyoxyethylene of maleic acid or maleic anhydride and polyethylene glycol
Ether.
Patent CN100465123C " a kind of method that maleic anhydride prepares polycarboxylate water-reducer ", with solid acid SO4 2-/
ZnO2It is catalyst, esterification occurs under 80-90 DEG C of reduced pressure by polyethylene glycol and maleic anhydride obtains poly- second two
Alcohol esterified object of maleic anhydride and the mixture of remaining maleic anhydride, polycarboxylic acids is prepared as copolymerization such as polyether macromonomer and acrylic acid
Water reducer.The technique is needed to use solid acid catalyst, and filtering is needed after reaction, and it is complete to be difficult esterification；In addition, remaining horse
Carry out acid anhydrides to be difficult to participate in copolymerization when water reducer is prepared.
Patent 100577591C synthesis setting time controllable high-performance polycarboxylic acids water reducing agents use a kind of polymeric monomer, and this is big
Monomer is formed by maleic anhydride with polyoxyethylene monoalkyl ethers condensation, and concrete technology is：Poly glycol monomethyl ether and maleic anhydride
Add together in reactor, add p-methyl benzenesulfonic acid class catalyst, reacted 5 hours under the conditions of 80-90 DEG C, obtain polymeric monomer.
The technique uses more acidic catalyst, and the amount of the alkali of neutralization, and small point for generating are increased when finally preparing water reducer
Alite is remained in water reducer, reduces the dispersiveness of polycarboxylate water-reducer.
Patent 101700964B " a kind of water reducer preparation method and maleic acid mono alkyl ester ", maleic acid or maleic anhydride with
Alkylol is under the acidic catalysts such as the concentrated sulfuric acid, antioxidant and solvent existence condition in 120-150 DEG C of esterification generation maleic acid list
Arrcostab, then reacts generation maleic acid mono alkyl ester and gathers with epoxide under caustic alcohol or BFEE catalysis again
Ether polymeric monomer, finally prepares polycarboxylate water-reducer with acrylic monomer copolymerization.The technique prepares maleic acid mono alkyl ester polyether
It is too complicated, not only need to have used acidic catalyst, but also antioxidant is used, antioxidant influences last polymerisation, increase
The consumption of initiator；Also solvent, reclaiming immediately also can be lossy, generally speaking causes the system of maleic acid mono alkyl ester polyether
Standby cost is higher.
A kind of patent CN102010487B " high-performance big for northwest region ground material high salinity, Gao Hanni, the weather temperature difference
Polycarboxylate water-reducer ", with poly glycol monomethyl ether and maleic anhydride as primary raw material, by esterification synthesizing polyethylene glycol horse
Carry out acid anhydrides surface-active macromonomer, then polycarboxylate water-reducer is prepared with the monomer copolymerization such as unsaturated acids, the technique esterification process is also used
Acidic catalyst, and inert gas band water process, process costs are high, and it is complete to be difficult reaction.
The content of the invention
The purpose of the present invention is to overcome the deficiencies in the prior art, there is provided a kind of preparation side of maleic acid mono alkyl ester polyether
Method.
To achieve the above object, the present invention is adopted the technical scheme that：
Polymeric monomer maleic acid mono alkyl ester polyether, its structural formula is as follows：
Wherein R1、R2It is H or CH3, R3It is C1~C6Alkyl, m, n are 20 ~ 50 integers.
Its preparation method is comprised the following steps：
The first step：To addition maleic anhydride, C in autoclave2-C6Alkylol and catalyst, after vacuum nitrogen gas replace three times
Oxirane or expoxy propane are added, the mol ratio of maleic anhydride, alkylol, oxirane or expoxy propane is 1:0.7-1:1-
3, catalyst is 0.0010.05 with the mol ratio of maleic anhydride, and agitating heating is warming up to 6570 DEG C, and exothermic heat of reaction is voluntarily warming up to
120 DEG C, when pressure is constant, first stage reaction terminates.
Second step：Under the conditions of 120-130 DEG C of insulation, oxirane or expoxy propane or alternate dropwise addition epoxy second is persistently added dropwise
Alkane and expoxy propane, addition are 20-50 with the mol ratio of maleic anhydride：1, process control pressure 2-4Kg is added dropwise, drip off follow-up
Continuous insulation reaction 1-2h.
3rd step：Vacuumize removing residual monomer, inflated with nitrogen cooling discharge.
The mol ratio of maleic anhydride, alkylol, oxirane or expoxy propane is preferably 1 in the first step:0.9-1:2-3.
Catalyst is potassium hydroxide, trimethylamine, preferably one kind of triethylamine, potassium hydroxide in the first step.
Catalyst is preferably 0.01-0.05 with the mol ratio of maleic anhydride in the first step.
Beneficial effect of the invention is：Process is simple, it is not necessary to solvent, it is not required that acidic catalyst, and alkalescence used is urged
Agent can also act as nertralizer in last water reducer preparatory phase, and directly use epoxide and maleic anhydride polycondensation, into
This is very low, and molecular weight and structure adjustable extent are big, and only need to adjust formula under the conditions of same process is easy to prepare different molecular
The maleic acid mono alkyl ester APEO of amount, polyethenoxy ether, can also prepare maleic acid mono alkyl ester polyoxyethylene polyoxy
Polypropylene block polyethers, easily prepares a series of polymeric monomer of functionalization.
Specific embodiment
Below by embodiment, the invention will be further described, but not thereby limiting the invention.
Embodiment 1
To adding 49g in 1L autoclaves（0.5mol）Maleic anhydride, 27g（0.45mol）Isopropanol and 0.28g（0.005mol）Hydrogen
Potassium oxide, vacuum nitrogen gas add 44g after replacing 3 times（1mol）Oxirane, stirring is warming up to 65 DEG C, exothermic heat of reaction nature
120 DEG C are warming up to, are gradually reduced after pressure to peak；Continue that oxirane is added dropwise after pressure no longer changes, in control kettle
Pressure 3Kg, adds 660g altogether（15mol）Oxirane, 120 DEG C of insulation reaction 1h after dripping off, pressure is invariable；Vacuumize
Removing residual ethylene, cooling discharge after inflated with nitrogen obtains maleic acid list isopropyl ester APEO, gel permeation chromatography
Weight average molecular weight 1472 is measured, chemical analysis measure double bond retention rate 97.5%.
Embodiment 2
To adding 49g in 1L autoclaves（0.5mol）Maleic anhydride, 30g（0.5mol）Isopropanol and 0.28g（0.005mol）Hydrogen
Potassium oxide, other are with embodiment 1.Experimental result：Product weight average molecular weight 1472, double bond retention rate 97.6%.
Embodiment 3
To adding 49g in 1L autoclaves（0.5mol）Maleic anhydride, 30g（0.5mol）Isopropanol and 0.56g（0.01mol）Hydrogen-oxygen
Change potassium, other are with embodiment 1.Experimental result：Product weight average molecular weight 1516, double bond retention rate 93.4%.
Embodiment 4
To adding 49g in 1L autoclaves（0.5mol）Maleic anhydride, 37g（0.5mol）N-butanol and 0.28g（0.005mol）Hydrogen
Potassium oxide, other are with embodiment 1.Experimental result：Product weight average molecular weight 1486, double bond retention rate 96.6%.
Embodiment 5
To adding 49g in 1L autoclaves（0.5mol）Maleic anhydride, 30g（0.5mol）Isopropanol and 0.69g（0.01mol）Front three
Amine, other are with embodiment 1.Experimental result：Product weight average molecular weight 1472, double bond retention rate 95.1%.
Embodiment 6
To adding 49g in 1L autoclaves（0.5mol）Maleic anhydride, 30g（0.5mol）Isopropanol and 0.28g（0.005mol）Hydrogen
Potassium oxide, vacuum nitrogen gas add 66g after replacing 3 times（1.5mol）Oxirane, stirring is warming up to 65 DEG C, and exothermic heat of reaction is certainly
120 DEG C so are warming up to, are gradually reduced after pressure to peak；Continue that oxirane is added dropwise after pressure no longer changes, control kettle
Interior pressure 3Kg, adds 880g altogether（20mol）Oxirane, 120 DEG C of insulation reaction 2h after dripping off, pressure is invariable；Take out true
Sky removing residual ethylene, cooling discharge after inflated with nitrogen obtains maleic acid list isopropyl ester APEO,.Experimental result：Produce
Thing weight average molecular weight 1918, double bond retention rate 96.2%.
Embodiment 7
To adding 49g in 1L autoclaves（0.5mol）Maleic anhydride, 30g（0.5mol）Isopropanol and 0.28g（0.005mol）Hydrogen
Potassium oxide, vacuum nitrogen gas add 58g after replacing 3 times（1mol）Expoxy propane, stirring is warming up to 65 DEG C, exothermic heat of reaction nature
120 DEG C are warming up to, are gradually reduced after pressure to peak；Continue that expoxy propane is added dropwise after pressure no longer changes, in control kettle
Pressure 3Kg, adds 870g altogether（15mol）Expoxy propane, 130 DEG C of insulation reaction 1.5h after dripping off, pressure is invariable；Take out true
Sky removing residual ethylene, cooling discharge after inflated with nitrogen obtains maleic acid list isopropyl ester polyethenoxy ether,.Experimental result：Produce
Thing weight average molecular weight 1898, double bond retention rate 95.8%.
Embodiment 8
To adding 49g in 2L autoclaves（0.5mol）Maleic anhydride, 30g（0.5mol）Isopropanol and 0.56g（0.01mol）Hydrogen-oxygen
Change potassium, vacuum nitrogen gas add 87g after replacing 3 times（1.5mol）Expoxy propane, stirring is warming up to 65 DEG C, exothermic heat of reaction nature
120 DEG C are warming up to, are gradually reduced after pressure to peak；Continue that expoxy propane is added dropwise after pressure no longer changes, in control kettle
Pressure 3Kg, adds 1160g altogether（20mol）Expoxy propane, 130 DEG C of insulation reaction 2h after dripping off, pressure is invariable；Take out true
Sky removing residual ethylene, cooling discharge after inflated with nitrogen obtains maleic acid list isopropyl ester polyethenoxy ether,.Experimental result：Produce
Thing weight average molecular weight 2478, double bond retention rate 91.5%.
Embodiment 9
To adding 49g in 2L autoclaves（0.5mol）Maleic anhydride, 30g（0.5mol）Isopropanol and 0.56g（0.01mol）Hydrogen-oxygen
Change potassium, vacuum nitrogen gas add 66g after replacing 3 times（1.5mol）Oxirane, stirring is warming up to 65 DEG C, exothermic heat of reaction nature
120 DEG C are warming up to, are gradually reduced after pressure to peak；Continue that 440g is added dropwise after pressure no longer changes（10mol）Epoxy second
Alkane, pressure 3Kg in control kettle, oxirane drips off and 580g is being added dropwise（10mol）Expoxy propane, 130 DEG C of insulation reactions after dripping off
2h, pressure is invariable；Removing residual ethylene is vacuumized, cooling discharge after inflated with nitrogen obtains maleic acid list isopropyl ester and gathers
Oxygen ethene polyethenoxy ether,.Experimental result：Product weight average molecular weight 2198, double bond retention rate 92.0%.
Embodiment 10
To adding 49g in 2L autoclaves（0.5mol）Maleic anhydride, 30g（0.5mol）Isopropanol and 0.56g（0.01mol）Hydrogen-oxygen
Change potassium, vacuum nitrogen gas add 87g after replacing 3 times（1.5mol）Expoxy propane, stirring is warming up to 65 DEG C, exothermic heat of reaction nature
120 DEG C are warming up to, are gradually reduced after pressure to peak；Continue that 580g is added dropwise after pressure no longer changes（10mol）Epoxy third
Alkane, pressure 3Kg in control kettle, expoxy propane drips off and 440g is added dropwise again（10mol）Oxirane, 130 DEG C of insulation reactions after dripping off
2h, pressure is invariable；Removing residual ethylene is vacuumized, cooling discharge after inflated with nitrogen obtains maleic acid list isopropyl ester and gathers
Oxypropylene APEO,.Experimental result：Product weight average molecular weight 2198, double bond retention rate 92.3%.
Embodiment 11
To adding 196g in 5L autoclaves（2mol）Maleic anhydride, 120g（2mol）Isopropanol and 1.12g（0.02mol）Hydroxide
Potassium, vacuum nitrogen gas add 264g after replacing 3 times（6mol）Oxirane, stirring is warming up to 65 DEG C, and exothermic heat of reaction rises naturally
Temperature is gradually reduced to 120 DEG C after pressure to peak；Continue that oxirane is added dropwise after pressure no longer changes, control kettle internal pressure
Power 3Kg, adds 3520g altogether（80mol）Oxirane, 120 DEG C of insulation reaction 2h after dripping off, pressure is invariable；Vacuumize
Removing residual ethylene, cooling discharge after inflated with nitrogen obtains maleic acid list isopropyl ester APEO,.Experimental result：Product
Weight average molecular weight 1918, double bond retention rate 96.5%.
Claims (4)
1. a kind of preparation method of maleic acid mono alkyl ester polyether, it is characterised in that：Comprise the following steps：
The first step：During maleic anhydride, alkylol and catalyst by proportion added into autoclave together, vacuumized nitrogen three times
After add epoxides, stirring is warming up to 65-70 DEG C, and exothermic heat of reaction makes temperature rise to 120 DEG C, continues to react to pressure keeping
Constant, maleic anhydride, alkylol, the mol ratio of epoxides are 1:0.7-1:1-3, catalyst is with the mol ratio of maleic anhydride
0.001-0.05；
Second step：120-130 DEG C of temperature of control, pressure condition is 2-4Kg, and epoxide reaction is persistently added dropwise, and continues to react
1-2h, epoxide is 20-50 with the mol ratio of maleic anhydride：1
3rd step：Vacuumize removing residual epoxy compound and obtain maleic acid mono alkyl ester polyether.
2. the preparation method of maleic acid mono alkyl ester polyether according to claim 1, it is characterised in that：Alkylol is C2-C6
Saturated monohydroxy alcohol.
3. the preparation method of maleic acid mono alkyl ester polyether according to claim 1, it is characterised in that：What the first step was added
Epoxide is oxirane or expoxy propane, and the epoxide that second step is added is oxirane or expoxy propane or friendship
For the oxirane and expoxy propane that are added dropwise.
4. the preparation method of maleic acid mono alkyl ester polyether according to claim 1, it is characterised in that：The catalyst is
One or two in trimethylamine, triethylamine, potassium hydroxide.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109574840A (en) * | 2018-11-27 | 2019-04-05 | 四川奥克石达化学股份有限公司 | A kind of maleic acid ester and its synthetic method and its preparing the application in polycarboxylate water-reducer |
| CN110078910A (en) * | 2018-01-25 | 2019-08-02 | 北京砼帮汇科技有限公司 | A kind of poly carboxylic acid series water reducer branch polyether monomer and its synthetic method |
| CN115141366A (en) * | 2021-03-30 | 2022-10-04 | 中国石油化工股份有限公司 | Method for improving safety of maleic anhydride macromonomer in synthesis process and application |
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| CN1948209A (en) * | 2006-11-23 | 2007-04-18 | 河南理工大学 | Method of preparing poly carboxylic acid series water reducer using maleic anhydride |
| CN101700964A (en) * | 2009-11-26 | 2010-05-05 | 辽宁科隆精细化工股份有限公司 | Water reducing agent, preparation method thereof and maleic acid mono alkyl ester polyether |
| CN102010487A (en) * | 2010-10-21 | 2011-04-13 | 安徽中铁工程材料科技有限公司 | Method for preparing polycarboxylate water reducing agent |
| CN105622920A (en) * | 2014-11-05 | 2016-06-01 | 中国石油化工集团公司 | Macromolecule monomer preparation method |
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| CN1948209A (en) * | 2006-11-23 | 2007-04-18 | 河南理工大学 | Method of preparing poly carboxylic acid series water reducer using maleic anhydride |
| CN101700964A (en) * | 2009-11-26 | 2010-05-05 | 辽宁科隆精细化工股份有限公司 | Water reducing agent, preparation method thereof and maleic acid mono alkyl ester polyether |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110078910A (en) * | 2018-01-25 | 2019-08-02 | 北京砼帮汇科技有限公司 | A kind of poly carboxylic acid series water reducer branch polyether monomer and its synthetic method |
| CN110078910B (en) * | 2018-01-25 | 2022-03-04 | 福建钟山化工有限公司 | Branched polyether monomer for polycarboxylic acid water reducing agent and synthesis method thereof |
| CN109574840A (en) * | 2018-11-27 | 2019-04-05 | 四川奥克石达化学股份有限公司 | A kind of maleic acid ester and its synthetic method and its preparing the application in polycarboxylate water-reducer |
| CN115141366A (en) * | 2021-03-30 | 2022-10-04 | 中国石油化工股份有限公司 | Method for improving safety of maleic anhydride macromonomer in synthesis process and application |
| CN115141366B (en) * | 2021-03-30 | 2023-08-08 | 中国石油化工股份有限公司 | Method for improving safety in synthesis process of maleic anhydride type macromer and application |
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Application publication date: 20170623 |