CN103131002A - Polyether amine and preparation method thereof - Google Patents
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- CN103131002A CN103131002A CN201310095868XA CN201310095868A CN103131002A CN 103131002 A CN103131002 A CN 103131002A CN 201310095868X A CN201310095868X A CN 201310095868XA CN 201310095868 A CN201310095868 A CN 201310095868A CN 103131002 A CN103131002 A CN 103131002A
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Abstract
The invention discloses a polyether amine and a preparation method thereof, and belongs to the technical field of high polymer material synthesis and preparation. According to the polyether amine and the preparation method thereof, a ketone, an aldehyde or an acid anhydride is reacted with primary amine for the first time to generate ketimine, aldimine or acyl protected amine compounds, and secondary amine or active hydroxyl and an alkylene oxide monomer are subjected to anionic polymerization so as to successfully synthesize polyether amine containing primary amine. The defects that the conventional method, namely, direct hydroxyl amination, requires harsh conditions of the equipment and the process, and side reaction is likely to happen when the amine compound is bonded with a polyether chain, are overcome, and polyether amine which is moderate in reaction condition and tidy in structure is successfully synthesized. The polyether amine has potential application in the fields of machine manufacturing, electrical equipment and electronic devices, communication and transportation, petrochemical engineering, national defense construction, electrophoretic paint, anticorrosive paint and the like.
Description
Technical field
The invention belongs to synthesis of polymer material and preparing technical field, be specifically related to a kind of polyetheramine and preparation method thereof.
Background technology
Polyetheramine is the toughness solidifying agent of a based epoxy resin and the main raw material of preparation polyurethane-urea and polyurea materials.When polyetheramine is used as the solidifying agent of epoxy resin, not only reduced the fragility of cured article, improved flexibility and the thermomechanical property of cured article, and overcome small molecules polyamine compounds volatile, easily absorb water in air and carbonic acid gas, shortcoming that toxicity is large.And as preparation polyurethane-urea and polyurea materials, can greatly improve reflection speed and and the physicals of material.
At present, the structure of polyetheramine mainly contains three kinds: (1) linear polyether amine, its main chain are polyethers, and molecule two ends are shortening by direct aminatin or after introducing itrile group or azido-, obtains amido, preparation technology are required stricter, and cost is large; (2) branching type polyetheramine, in its structure, polyethers section and amido are alternate, carry out polycondensation by polyamine and bis-epoxy monomer, and synthetic method is simple, is mainly used in medicament slow release and separation technology field; (3) pendant amine fundamental mode polyetheramine, its main chain are polyethers, and side group is contained aminated compounds and replaces, and introduce amido, but often contain reactive hydrogen in the aminated compounds structure, and a uncontrollable aminated compounds only reacts with a polyether backbone.Therefore, controlling desirable amine molecule structure, is this type of synthetic key.
CN102604072A discloses under highly basic or metal catalyst; by the still reaction at intermittence; utilize the amido of tertbutyloxycarbonyl (BOC) protection alcamine compound; cause epoxide and carry out the negatively charged ion ring-opening reaction; after removing the BOC protection; obtain polyetheramine, but BOC primary amine can be protected, also secondary amine can be protected.US005510535A discloses a kind of synthetic method of Amino Terminated polyether(ATPE), prepares under double metal cyanide-catalyzed condition by amine initiator and alkylene oxides compound to get, and productive rate is high, but strict to processing requirement, pollutes greatly, and cost is high.Therefore, by rational structure design, the polyetheramine of synthetic amido end-blocking has a wide range of applications.
Summary of the invention
The object of the present invention is to provide a kind of polyetheramine and preparation method thereof, the present invention has overcome the critical conditions requirement of traditional method hydroxyl direct aminatin to equipment and technique, the defectives such as side reaction easily occur when aminated compounds is connected with polyether chain, successfully synthesize the polyetheramine of reaction conditions gentleness, compound with regular structure.Polyetheramine of the present invention has potential application in fields such as machinofacture, electric appliance and electronic, communications and transportation, petrochemical complex, national defense construction, electrocoating paint, protective systems.
For achieving the above object, the present invention adopts following technical scheme:
A kind of polyetheramine has following structure:
M wherein, n is 1 ~ 20 natural number, R
2, R
3, R
4CH
2Or CH
2CH
2, R
1The alkoxyl group of general formula 2,
X wherein, y, z are respectively 0 ~ 100 integer.
A kind of method for preparing polyetheramine as above, the polyetheramine by amido " protection ", " deprotection " synthetic primary amine end-blocking comprises the following steps:
(1) successively polyamine, ketone or aldehydes or anhydride compound, aromatic hydrocarbons organic solvent are added reaction system, reaction under 60 ~ 130 ℃, underpressure distillation obtains the aminated compounds by ketoimine or aldimine or acyl group protection;
(2) with the aminated compounds of step (1) as initiator, add in polymerization reaction kettle with the catalyzer of metering, under protection of inert gas, drip continuously the epoxies monomer of metering, control temperature being 60 ~ 150 ℃ is 0.01 ~ 20MPa with reaction pressure, after reinforced complete, continue reaction 0.5 ~ 8h, obtain the polyetheramine by ketoimine or aldimine or acyl group protection;
(3) sorbent material, organic acid or mineral acid, deionized water are added in the polyetheramine of step (2), 20 ~ 150 ℃ of reaction 1 ~ 10h, deprotection, underpressure distillation is filtered, and namely obtains described polyetheramine product.
The described polyamine of step (1) is piperazine amido derivative, fatty amine or the aromatic amine compounds that contains secondary amine or hydroxyl and contain primary amine groups.
The described ketone of step (1) or aldehydes are aliphatics ketone, aliphatics aldehydes and derivative thereof.
The described catalyzer of step (2) is alkalimetal oxide, oxyhydroxide, alkoxide or alkaline earth metal oxide, oxyhydroxide, alkoxide.
The described epoxies monomer of step (2) is one or more the mixture in oxyethane, propylene oxide, tetrahydrofuran (THF), butylene oxide ring.
The described organic acid of step (3) or mineral acid are oxalic acid, propanedioic acid, hexanodioic acid, boric acid or phosphoric acid, and wherein acid is 0.1 ~ 2.0 with the mol ratio of metal ion.
The described sorbent material of step (3) is diatomite, gac, atlapulgite or silicates.
Remarkable advantage of the present invention is: compared with prior art, the present invention has not only realized the synthetic of target product, and reaction conditions is gentleer, has avoided shortening method or direct aminatin method to the harsh requirement of conversion unit and technique, reduces costs; And adopt imine group that primary amine groups is protected; effectively reduced the side reaction when aminated compounds is connected with polyether chain; thereby obtain the polyetheramine that contains primary amine groups of compound with regular structure, in fields such as machinofacture, electric appliance and electronic, communications and transportation, petrochemical complex, national defense construction, electrocoating paint, protective systems, potential application is arranged.
Description of drawings
Fig. 1 is polyetheramine product of the present invention
13The C nmr spectrum.
Fig. 2 is the gpc analysis of polyetheramine product of the present invention.
Embodiment
The present invention is further elaborated below in conjunction with concrete example, but embodiments of the present invention are not limited to this.
Embodiment 1
(1) in there-necked flask, with triethylene tetramine and acetone in molar ratio 1:2.5 be dissolved in toluene, control temperature of reaction at 90 ~ 130 ℃, reaction 6 ~ 10h, the separatory water outlet, transformation efficiency is 95%; Remove toluene, water and excessive acetone in system, obtain the triethylene tetramine of ketoimine protection;
(2) triethylene tetramine (2mol) and the sodium ethylate (0.3wt%) with the ketoimine protection adds in polymerization reaction kettle, pass into argon shield, dripping propylene oxide (50mol) reacts, control pressure is 0.1 ~ 10MPa, after reinforced the end, continue reaction 5h, obtain the polyetheramine of ketoimine protection; Then add phosphoric acid (0.4mol), deionized water (30mol) and sorbent material (5wt%); hydrolysis 1h removes the ketoimine blocking group under 60 ~ 150 ℃, then in 50 ~ 130 ℃ of temperature ranges, and the acetone in the removal system; filter at last, namely obtain described polyetheramine product.
(1) in there-necked flask, with tetraethylene pentamine and butyraldehyde in molar ratio 1:3 be dissolved in toluene, control temperature of reaction at 90 ~ 130 ℃, reaction 5 ~ 9h, the separatory water outlet, transformation efficiency is 93%; Remove toluene, water and excessive butyraldehyde in system, obtain the tetraethylene pentamine of aldimine protection;
(2) tetraethylene pentamine (1mol) and the potassium oxide (0.3wt%) with the aldimine protection adds in polymerization reaction kettle, passes into argon shield, drips oxyethane (20mol), control pressure is 0.1 ~ 10MPa, after reinforced the end, continue reaction 5h, obtain the polyetheramine of aldimine protection; Then add oxalic acid (0.5mol), deionized water (35mol) and sorbent material (5wt%); hydrolysis 1h removes the aldimine blocking group under 60 ~ 150 ℃, then in 50 ~ 130 ℃ of temperature ranges, and butyraldehyde in the removal system; filter, namely obtain described polyetheramine product.
(1) in there-necked flask, with N-aminoethyl piperazine and acetone in molar ratio 1:4 be dissolved in toluene, control temperature of reaction at 60 ~ 100 ℃, reaction 5 ~ 8h, separatory water outlet; Remove toluene, water and excessive acetone in system, obtain the aminoethyl piperazine of ketoimine protection;
(2) aminoethyl piperazine (1mol) and the sodium methylate (0.5wt%) with the ketoimine protection adds in polymerization reaction kettle, passes into argon shield, drips butylene oxide ring (40mol), control pressure is 0.1 ~ 10MPa, after reinforced the end, continue reaction 5h, obtain the polyetheramine of ketoimine protection; Then add oxalic acid (0.5mol), deionized water (40mol) and sorbent material (8wt%); hydrolysis 1h removes the ketoimine blocking group under 60 ~ 150 ℃, then in 50 ~ 130 ℃ of temperature ranges, and acetone in the removal system; filter, namely obtain described polyetheramine product.
Embodiment 4
(1) in there-necked flask, with Dyhard RU 100 and methylethylketone in molar ratio 1:1.5 be dissolved in toluene, control temperature of reaction at 60 ~ 120 ℃, reaction 7 ~ 9h, the separatory water outlet, transformation efficiency is 95%; Remove toluene, water and excessive methylethylketone in system, obtain the Dyhard RU 100 of ketoimine protection;
(2) Dyhard RU 100 (1mol) and the sodium Metal 99.5 (0.4wt%) with the ketoimine protection adds in polymerization reaction kettle, pass into argon shield, first drip propylene oxide (20mol) and drip again oxyethane (20mol), control pressure is 0.1 ~ 10MPa, after reinforced the end, continue reaction 5h, obtain the polyetheramine of ketoimine protection; Then add boric acid (0.5mol), deionized water (25mol) and sorbent material (10wt%); hydrolysis 1h removes the ketoimine blocking group under 60 ~ 150 ℃, then in 50 ~ 130 ℃ of temperature ranges, and methylethylketone in the removal system; filter, namely obtain described polyetheramine product.
Embodiment 5
(1) in there-necked flask, with thanomin and propionic aldehyde in molar ratio 1:3 be dissolved in toluene, control temperature of reaction at 90 ~ 130 ℃, reaction 6 ~ 10h, the separatory water outlet, transformation efficiency is 95%; Remove toluene, water and excessive propionic aldehyde in system, obtain the thanomin of aldimine protection;
(2) thanomin (3mol) and the sodium hydroxide (0.3wt%) with the aldimine protection adds in polymerization reaction kettle, pass into argon shield, first drip propylene oxide (20mol), drip again oxyethane (20mol), drip at last butylene oxide ring (20mol) and react, control pressure is 0.1 ~ 10MPa, after reinforced the end, continue reaction 6h, obtain the polyetheramine of aldimine protection; Then add phosphoric acid (1mol), deionized water (45mol) and sorbent material (12wt%); hydrolysis 1h removes the aldimine blocking group under 60 ~ 150 ℃, then in 50 ~ 130 ℃ of temperature ranges, and the propionic aldehyde in the removal system; filter at last, namely obtain described polyetheramine product.
Embodiment 6
(1) in there-necked flask, with triethylene tetramine and diacetyl oxide in molar ratio 1:2.5 be dissolved in toluene, control temperature of reaction at 90 ~ 130 ℃, reaction 6 ~ 10h; Remove toluene and acetic acid in system, obtain the triethylene tetramine of ethanoyl protection;
(2) triethylene tetramine (2mol) and the potassium metal (0.3wt%) with the ethanoyl protection adds in polymerization reaction kettle, pass into argon shield, dripping propylene oxide (40mol) reacts, control pressure is 0.1 ~ 10MPa, after reinforced the end, continue reaction 5h, obtain the polyetheramine of ethanoyl protection; Then add phosphoric acid (0.4mol), deionized water (30mol) and sorbent material (5wt%); hydrolysis 1h removes the ethanoyl blocking group under 60 ~ 150 ℃, then in 50 ~ 130 ℃ of temperature ranges, and the acetic acid in the removal system; filter at last, namely obtain described polyetheramine product.
Applicating superiority:
With polyetheramine at present commonly used, compare as D230, following superiority is arranged:
(1) curing speed is fast, can be faster approximately 30% than D230, because neoteric product has three reactive groups, and five reactive hydrogens are arranged.
(2) cured product hardness is also high than like product D230.
(3) snappiness and D230 are suitable.
The above is only preferred embodiment of the present invention, and all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (8)
1. polyetheramine, it is characterized in that: this polymkeric substance has following structure:
Or
(1)
M wherein, n is 1 ~ 20 natural number, R
2, R
3, R
4CH
2Or CH
2CH
2, R
1The alkoxyl group of general formula 2,
(2)
X wherein, y, z are respectively 0 ~ 100 integer.
2. method for preparing polyetheramine as claimed in claim 1 is characterized in that: the polyetheramine by amido " protection ", " deprotection " synthetic primary amine end-blocking comprises the following steps:
(1) successively polyamine, ketone or aldehydes or anhydride compound, aromatic hydrocarbons organic solvent are added reaction system, reaction under 60 ~ 130 ℃, underpressure distillation obtains the aminated compounds by ketoimine or aldimine or acyl group protection;
(2) with the aminated compounds of step (1) as initiator, add in polymerization reaction kettle with the catalyzer of metering, under protection of inert gas, drip continuously the epoxies monomer of metering, control temperature being 60 ~ 150 ℃ is 0.01 ~ 20MPa with reaction pressure, after reinforced complete, continue reaction 0.5 ~ 8h, obtain the polyetheramine by ketoimine or aldimine or acyl group protection;
(3) sorbent material, organic acid or mineral acid, deionized water are added in the polyetheramine of step (2), 20 ~ 150 ℃ of reaction 1 ~ 10h, deprotection, underpressure distillation is filtered, and namely obtains described polyetheramine product.
3. the preparation method of polyetheramine according to claim 2, it is characterized in that: the described polyamine of step (1) is piperazine amido derivative, fatty amine or the aromatic amine compounds that contains secondary amine or hydroxyl and contain primary amine groups.
4. the preparation method of polyetheramine according to claim 2, it is characterized in that: the described ketone of step (1) or aldehydes are aliphatics ketone, aliphatics aldehydes and derivative thereof.
5. the preparation method of polyetheramine according to claim 2, it is characterized in that: the described catalyzer of step (2) is alkalimetal oxide, oxyhydroxide, alkoxide or alkaline earth metal oxide, oxyhydroxide, alkoxide.
6. the preparation method of polyetheramine according to claim 2 is characterized in that: the described epoxies monomer of step (2) is one or more the mixture in oxyethane, propylene oxide, tetrahydrofuran (THF), butylene oxide ring.
7. the preparation method of polyetheramine according to claim 2, it is characterized in that: the described organic acid of step (3) or mineral acid are oxalic acid, propanedioic acid, hexanodioic acid, boric acid or phosphoric acid, wherein acid is 0.1 ~ 2.0 with the mol ratio of metal ion.
8. the preparation method of polyetheramine according to claim 2, it is characterized in that: the described sorbent material of step (3) is diatomite, gac, atlapulgite or silicates.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104140454A (en) * | 2013-10-29 | 2014-11-12 | 中国石油化工股份有限公司 | Polyether amine based alkyl glycoside for drilling fluid and preparation method thereof |
| CN106279470A (en) * | 2016-08-08 | 2017-01-04 | 上海交通大学 | Amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine and preparation method thereof |
| CN107207722A (en) * | 2015-01-26 | 2017-09-26 | 巴斯夫欧洲公司 | Polyetheramine with low melting point |
| CN112625230A (en) * | 2017-08-15 | 2021-04-09 | 长春人造树脂厂股份有限公司 | Reactive epoxy compound, core-shell epoxy resin particle, aqueous epoxy resin composition, and coating composition |
| CN115518401A (en) * | 2022-10-26 | 2022-12-27 | 万华节能科技(烟台)有限公司 | Production process of latent curing agent required for producing single-component polyurea |
| CN115785434A (en) * | 2022-12-12 | 2023-03-14 | 江西百盛精细化学品有限公司 | A kind of preparation method of polyether amine |
| CN115838337A (en) * | 2022-11-23 | 2023-03-24 | 广州天润新材料科技有限公司 | Polyhydroxy branched polyether amine and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003034797A (en) * | 2001-05-16 | 2003-02-07 | Asahi Denka Kogyo Kk | Water-based lubricant |
| JP2006206847A (en) * | 2005-01-31 | 2006-08-10 | Sanyo Chem Ind Ltd | Polyoxyalkylene polyamine composition |
| CN101885832A (en) * | 2010-07-12 | 2010-11-17 | 中科院广州化灌工程有限公司 | Preparation and application of latent nonionic self-emulsifying epoxy curing agent |
| CN102604072A (en) * | 2012-03-02 | 2012-07-25 | 无锡阿科力化工有限公司 | Preparation method of polyether amine |
-
2013
- 2013-03-25 CN CN201310095868XA patent/CN103131002A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003034797A (en) * | 2001-05-16 | 2003-02-07 | Asahi Denka Kogyo Kk | Water-based lubricant |
| JP2006206847A (en) * | 2005-01-31 | 2006-08-10 | Sanyo Chem Ind Ltd | Polyoxyalkylene polyamine composition |
| CN101885832A (en) * | 2010-07-12 | 2010-11-17 | 中科院广州化灌工程有限公司 | Preparation and application of latent nonionic self-emulsifying epoxy curing agent |
| CN102604072A (en) * | 2012-03-02 | 2012-07-25 | 无锡阿科力化工有限公司 | Preparation method of polyether amine |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104140454A (en) * | 2013-10-29 | 2014-11-12 | 中国石油化工股份有限公司 | Polyether amine based alkyl glycoside for drilling fluid and preparation method thereof |
| CN104140454B (en) * | 2013-10-29 | 2017-06-30 | 中国石油化工股份有限公司 | A kind of drilling fluid polyethers amido APG and preparation method thereof |
| CN107207722A (en) * | 2015-01-26 | 2017-09-26 | 巴斯夫欧洲公司 | Polyetheramine with low melting point |
| CN107207722B (en) * | 2015-01-26 | 2021-04-30 | 巴斯夫欧洲公司 | Polyetheramines with low melting points |
| CN106279470A (en) * | 2016-08-08 | 2017-01-04 | 上海交通大学 | Amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine and preparation method thereof |
| CN112625230A (en) * | 2017-08-15 | 2021-04-09 | 长春人造树脂厂股份有限公司 | Reactive epoxy compound, core-shell epoxy resin particle, aqueous epoxy resin composition, and coating composition |
| CN115518401A (en) * | 2022-10-26 | 2022-12-27 | 万华节能科技(烟台)有限公司 | Production process of latent curing agent required for producing single-component polyurea |
| CN115838337A (en) * | 2022-11-23 | 2023-03-24 | 广州天润新材料科技有限公司 | Polyhydroxy branched polyether amine and preparation method and application thereof |
| CN115785434A (en) * | 2022-12-12 | 2023-03-14 | 江西百盛精细化学品有限公司 | A kind of preparation method of polyether amine |
| CN115785434B (en) * | 2022-12-12 | 2025-06-06 | 江西百盛精细化学品有限公司 | A kind of preparation method of polyetheramine |
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Application publication date: 20130605 |