CN106565506A - Method for preparing polyhydric alcohol amine ester - Google Patents
Method for preparing polyhydric alcohol amine ester Download PDFInfo
- Publication number
- CN106565506A CN106565506A CN201610977193.5A CN201610977193A CN106565506A CN 106565506 A CN106565506 A CN 106565506A CN 201610977193 A CN201610977193 A CN 201610977193A CN 106565506 A CN106565506 A CN 106565506A
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- Prior art keywords
- polyhydric alcohol
- alcohol amine
- cmp
- catalyst
- amine ester
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/063—Polymers comprising a characteristic microstructure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for preparing polyhydric alcohol amine ester. Under existence of a catalyst, hydroxyl in polyhydric alcohol amine and carboxyl in organic acid are subject to esterification to obtain a compound, unesterified hydroxyl is contained in an obtained product, and the utilized catalyst is solid superacid loaded by conjugated microporous polymers (CMPs). According to the method, the conversion rate of the polyhydric alcohol amine reaches 95.6%, and the yield of the polyhydric alcohol amine can reach 88.9%. The activity of the catalyst adopted in the method is high, and is easily separated and recycled.
Description
Technical field
The present invention relates to a kind of method for preparing polyhydric alcohol amine ester, and in particular to a kind of to exist in solid super acid catalyst
The lower method for preparing polyhydric alcohol amine ester.
Background technology
A small amount of abrasion-aided additive is added in manufacture of cement, cement production consumption not only can be effectively reduced, and
The intensity of cement can be improved, therefore adds cement grinding aid reduce cement clinker consumption, increase solid waste building resource
Utilization rate, is one of Important Action for cement industry energy-saving and emission-reduction.The work of the main component triethanolamine of cement grinding aid
With.Triethanolamine can promote the dissolving of calcium phase, aluminium phase and iron phase in cement, so as to promote C in clinker3A、C4The ore deposits such as AF
The aquation of thing, therefore cement early strength can be improved, however triethanolamine there is also some it is influential on cement quality should
With drawback, mainly have：(1) late-enhancement effect is not obvious.Generally triethanolamine can only increase cement early strength, to the later stage
The growth effect of intensity is not obvious, even results in cement later strength retraction.Research shows that triethanolamine is in the aquation later stage
Slurry solution in, almost (2) affect setting time.As triethanolamine promotes C3A、C4The fast hydration of the mineral such as AF,
Cause shorten setting time.(3) with additive competitive Adsorption.Triethanolamine is a kind of highly polar Organic substance, easily and cement surface
Complexing of metal ion formed organic chelate, with concrete admixture occur competitive Adsorption, make additive useful effect volume
Reduce.
The drawbacks of triethanolamine, constrains the development of grinding aid.Later research using polyhydric alcohol amine ester replace triethanolamine or
With triethanolamine synergism.Polyhydric alcohol amine ester is prepared with organic acid reaction by polyhydric alcohol amine, but the reaction is main at present
Concentrated sulphuric acid, concentrated hydrochloric acid, strong phosphoric acid and to liquid acid such as methylbenzene sulphurs are used, has that corrosivity are big, environmental pollution is big, reaction
Conversion ratio and the low problem of yield.
The content of the invention
The technical problem to be solved is that prior art prepares polyhydric alcohol amine with polyhydric alcohol amine and organic acid reaction
There is a problem of in ester technique that catalyst reaction efficiency is low, be not easily recycled utilization, environmental pollution is big, corrosivity are big, there is provided be a kind of
The method that new polyhydric alcohol amine prepares polyhydric alcohol amine ester with organic acid reaction.The method has catalyst high income, reaction condition
Gently, be easily recycled, the advantage that environmental pollution is little.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of side for preparing polyhydric alcohol amine ester
Method, in the presence of a catalyst, the carboxyl in hydroxyl in polyhydric alcohol amine and organic acid be esterified obtained by compound, and
Contain nonesterified hydroxyl in products obtained therefrom, wherein catalyst used is the solid super strong for being conjugated microporous polymer CMPs loads
Acid, polyhydric alcohol amine for triethanolamine, triisopropanolamine and diethanolamine one or two, organic acid be propanoic acid, ethanedioic acid,
One kind of succinic acid and maleic anhydride.
Concrete operations are to sequentially add polyhydric alcohol amine, organic acid and catalyst in a kettle., wherein in polyhydric alcohol amine
The mol ratio of the carboxyl in hydroxyl and organic acid is 1.1-10:1, at -150 DEG C of temperature 60 C, add water entrainer, and by cold
Condenser except the water of dereaction production, after reaction 2-5 hours, is separated by filtration catalyst, that is, obtains polyhydric alcohol amine ester with water knockout drum.
Preferably, catalyst in terms of weight fraction including following components：A) 20～60 parts of carrier, carrier are micro- selected from conjugation
At least one during pore polymer CMPs is serial in CMP-0, CMP-1,4, CMP-5 superhigh cross-linking polymer；Be loaded in thereon
B) 40～80 parts are selected from SO4 2-、Cl-、S2O8 2-In at least one solid super-strong acid.
Preferably, catalyst amount is the 0.5～5% of polyhydric alcohol amine and organic acid gross weight.
Preferably, the catalyst is selected from SO4 2-/CMP-0、SO4 2-/CMP-1,4、SO4 2-/CMP-5、Cl-/CMP-0、Cl-/
CMP-1,4、Cl-/CMP-5、S2O8 2-/CMP-1,4、S2O8 2-At least one in/CMP-5.
Preferably, reaction temperature is 80 DEG C～130 DEG C, and the response time is 2-3h.
The present invention has the advantages that：
1）To be conjugated the acid of capillary copolymer material CMPs supported solid superacids as catalyst, conjugation microporous polymer CMPs carriers can
With higher heat stability and chemical stability while making catalyst that there is very big specific surface area and porosity, so as to improve
The conversion ratio and the yield of polyhydric alcohol amine ester of polyhydric alcohol amine, the wherein conversion ratio of phenol up to 95.6%, the product of polyhydric alcohol amine ester
Rate is up to 88.9%.
2）By the present invention in that be catalyst with conjugation capillary copolymer material CMPs supported solid superacid acid, reaction condition
Relatively mild, the requirement to equipment is relatively low, while catalyst is recyclable, is used for multiple times, and reduces production cost；
3）Catalyst is separated with product simply, and eliminates neutralization operation, and the catalyst is used 5 times in addition, its catalytic
Can not be decreased obviously.Therefore, achieve preferable technique effect.
Specific embodiment
Below by embodiment, the present invention is further elaborated, but protection scope of the present invention is not limited to the reality
Apply example.
Embodiment 1
Triethanolamine 149g, propanoic acid 40g will be sequentially added in a kettle. will（The mol ratio of hydroxyl and carboxyl is 6:1）And 0.5g
Catalyst SO4 2-/ CMP-0, at 100 DEG C of temperature, using toluene as water entrainer, by condenser with water knockout drum except dereaction is given birth to
The water of product, after 2 hours of reaction, is separated by filtration catalyst, obtains polyhydric alcohol amine ester.Jing is analyzed, and the conversion ratio of triethanolamine reaches
92.8%, the yield of polyhydric alcohol amine ester is 86.5%.
Embodiment 2
Triethanolamine 149g, propanoic acid 40g will be sequentially added in a kettle. will（The mol ratio of hydroxyl and carboxyl is 6:1）And 0.5g
Catalyst Cl-/ CMP-5, at 100 DEG C of temperature, using toluene as water entrainer, by condenser with water knockout drum except dereaction is produced
Water, reaction 2 hours after, be separated by filtration catalyst, obtain polyhydric alcohol amine ester.Jing is analyzed, and the conversion ratio of triethanolamine reaches
92.1%, the yield of polyhydric alcohol amine ester is 84.7%.
Embodiment 3
Triisopropanolamine 191g, the ethanedioic acid 90g (mol ratio 3 of hydroxyl and carboxyl will be sequentially added in a kettle. will:1) and
1.5g catalyst S2O8 2-/ CMP-5, at 120 DEG C of temperature, using toluene as water entrainer, is removed with water knockout drum by condenser
The water of reaction production, after 2 hours of reaction, is separated by filtration catalyst, obtains polyhydric alcohol amine ester.Jing is analyzed, triisopropanolamine
Up to 95.6%, the yield of polyhydric alcohol amine ester is 88.9% to conversion ratio.
Embodiment 4
Diethanolamine 210g, the succinic acid 118g (mol ratio 2 of hydroxyl and carboxyl will be sequentially added in a kettle. will:And 1.5g 1)
Catalyst S2O8 2-/ CMP-5, at 120 DEG C of temperature, using toluene as water entrainer, by condenser with water knockout drum except dereaction is given birth to
The water of product, after 2 hours of reaction, is separated by filtration catalyst, obtains polyhydric alcohol amine ester.Jing is analyzed, and the conversion ratio of diethanolamine reaches
93.7%, the yield of polyhydric alcohol amine ester is 86.8%.
Embodiment 5
Catalyst in embodiment 3 is separated into taking-up after the completion of reaction, after drying process according to embodiment 3 reaction condition
5 reuses are carried out, catalyst is separated by filtration, is obtained polyhydric alcohol amine ester.Jing is analyzed, wherein the 1st time three different when reusing
Up to 93.2%, the yield of polyhydric alcohol amine ester is 85.9% to the conversion ratio of Propanolamine；When the 5th is reused, triisopropanolamine turns
Up to 91.7%, the yield of polyhydric alcohol amine ester is 83.5% to rate
Comparative example 1
Triisopropanolamine 191g, the ethanedioic acid 90g (mol ratio 3 of hydroxyl and carboxyl will be sequentially added in a kettle. will:1) and
1.5g catalyst concentrated sulphuric acids, at 120 DEG C of temperature, using toluene as water entrainer, by condenser with water knockout drum except dereaction is given birth to
The water of product, after 2 hours of reaction, adds potassium hydroxide solution to adjust pH value to neutrality, obtains polyhydric alcohol amine ester.Jing is analyzed, and three
Up to 70.4%, the yield of polyhydric alcohol amine ester is 66.8% to the conversion ratio of isopropanolamine.
Comparative example 2
Triisopropanolamine 191g, the ethanedioic acid 90g (mol ratios 3 of hydroxyl and carboxyl are sequentially added in a kettle.:1) with dense sulfur
Sour 3.9g, at 150 DEG C of temperature, using benzene as water entrainer, removes water by condenser and water knockout drum, after 2 hours of reaction, plus
Entering potassium hydroxide solution and pH value being adjusted to neutrality, that is, obtain polyhydric alcohol amine ester, Jing analyses, the conversion ratio of triisopropanolamine reach
75.6%, the yield of polyhydric alcohol amine ester is 71.3%.
Embodiment described above only expresses embodiments of the present invention, and its description is more concrete and detailed, but can not
Therefore the restriction to the scope of the claims of the present invention is interpreted as, as long as the skill obtained in the form of equivalent or equivalent transformation
Art scheme, all should fall within the scope and spirit of the invention.
Claims (5)
1. a kind of method for preparing polyhydric alcohol amine ester, it is characterised in that：In the presence of a catalyst, the hydroxyl in polyhydric alcohol amine with have
Carboxyl in machine acid be esterified obtained by compound, and containing nonesterified hydroxyl in products obtained therefrom, wherein used
Catalyst is the solid super-strong acid for being conjugated microporous polymer CMPs loads, and polyhydric alcohol amine is triethanolamine, triisopropanolamine and two
Ethanolamine one or two, organic acid for propanoic acid, ethanedioic acid, succinic acid and maleic anhydride one kind.
2. it is according to claim 1 prepare polyhydric alcohol amine ester method, it is characterised in that：Concrete operations are in a kettle.
Sequentially add polyhydric alcohol amine, organic acid and catalyst, the wherein mol ratio of the hydroxyl in polyhydric alcohol amine and the carboxyl in organic acid
For 1.1-10:1, at -150 DEG C of temperature 60 C, preferably 80 DEG C～130 DEG C, add water entrainer, and pass through condenser and Fen Shui
Device after reaction 2-5 hours, is separated by filtration catalyst, that is, obtains polyhydric alcohol amine ester except the water of dereaction production.
3. it is according to claim 1 prepare polyhydric alcohol amine ester method, it is characterised in that：Catalyst is wrapped in terms of weight fraction
Include：A) 20～60 parts of carrier, carrier selected from conjugation microporous polymer CMPs it is serial in CMP-0, CMP-1,4, CMP-5 superelevation friendship
At least one in linked polymer；Be loaded in b thereon) 40～80 parts selected from SO4 2-、Cl-、S2O8 2-In at least one solid
Super acids.
4. it is according to claim 1 prepare polyhydric alcohol amine ester method, it is characterised in that：Catalyst amount is polyhydric alcohol
The 0.5～5% of amine and organic acid gross weight.
5. it is according to claim 1 prepare polyhydric alcohol amine ester method, it is characterised in that：Catalyst is selected from SO4 2-/CMP-
0、SO4 2-/CMP-1,4、SO4 2-/CMP-5、Cl-/CMP-0、Cl-/CMP-1,4、Cl-/CMP-5、S2O8 2-/CMP-1,4、S2O8 2-/
At least one in CMP-5.
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| CN201610977193.5A CN106565506A (en) | 2016-11-08 | 2016-11-08 | Method for preparing polyhydric alcohol amine ester |
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| CN201610977193.5A CN106565506A (en) | 2016-11-08 | 2016-11-08 | Method for preparing polyhydric alcohol amine ester |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078407A (en) * | 2019-05-21 | 2019-08-02 | 扬州大学 | A kind of morning strong hyperbranched poly carboxylic acid water reducer and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103833549A (en) * | 2012-11-23 | 2014-06-04 | 中国石油天然气股份有限公司 | Preparation method of fatty acid polyol ester |
| CN104311435A (en) * | 2014-09-12 | 2015-01-28 | 北京工业大学 | Polyolamine ester and its synthesis method and use |
| CN105294411A (en) * | 2014-07-24 | 2016-02-03 | 中国石油化工股份有限公司 | Method for producing PODE (polyoxymethylene dimethyl ethers) through paraformaldehyde |
-
2016
- 2016-11-08 CN CN201610977193.5A patent/CN106565506A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103833549A (en) * | 2012-11-23 | 2014-06-04 | 中国石油天然气股份有限公司 | Preparation method of fatty acid polyol ester |
| CN105294411A (en) * | 2014-07-24 | 2016-02-03 | 中国石油化工股份有限公司 | Method for producing PODE (polyoxymethylene dimethyl ethers) through paraformaldehyde |
| CN104311435A (en) * | 2014-09-12 | 2015-01-28 | 北京工业大学 | Polyolamine ester and its synthesis method and use |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078407A (en) * | 2019-05-21 | 2019-08-02 | 扬州大学 | A kind of morning strong hyperbranched poly carboxylic acid water reducer and preparation method thereof |
| CN110078407B (en) * | 2019-05-21 | 2021-06-25 | 扬州大学 | Early-strength hyperbranched polycarboxylate superplasticizer and preparation method thereof |
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