CN109734903A - A method of continuously preparing branched polyethylene imine - Google Patents
A method of continuously preparing branched polyethylene imine Download PDFInfo
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- CN109734903A CN109734903A CN201811588814.6A CN201811588814A CN109734903A CN 109734903 A CN109734903 A CN 109734903A CN 201811588814 A CN201811588814 A CN 201811588814A CN 109734903 A CN109734903 A CN 109734903A
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- branched polyethylene
- polyethylene imine
- aziridine
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Abstract
It is to solve the problems, such as that polymerization technology complexity, polymerization time length, polymerization temperature height and polymer molecular weight are distributed wide in the prior art the invention discloses a kind of method for continuously preparing branched polyethylene imine.Method includes the following steps: aziridine monomer and the mixed solution being made of catalyst and solvent are continuously squeezed into micro passage reaction with metering pump respectively by (1), the two is mixed in micro passage reaction entrance；(2) reaction mass stops 10~300s at a temperature of 50~100 DEG C in micro passage reaction in step (1), is down to after room temperature and is continuously discharged from reactor outlet；(3) the removing solvent of reaction solution obtained in collection step (2) and catalyst, are made branched polyethylene imine.Compared with prior art, preparing branched polyethylene imine using this method has the advantages that polymerization technique is simple, polymerization time is short, polymerization temperature is low and polyethyleneimine narrow molecular weight distribution.
Description
Technical field
The invention belongs to field of fine chemical, are related to a kind of method for continuously preparing branched polyethylene imine, and in particular to
A method of branched polyethylene imine is continuously prepared by the open loop auto polymerization reaction of aziridine monomer.
Background technique
Polyethyleneimine (Polyethyleneimine, PEI) is aziridine (EI) monomer in acidic catalyst, polymerization
Under object additive existence condition, through a kind of typical water-soluble cationic polymer, average molecular matter made from ring-opening polymerisation
Amount is from several hundred to hundreds of thousands etc..PEI can be divided into two kinds of straight chain type (L-PEI) and branching type (B-PEI) by its molecular structure, and two
Person is since there is also notable differences in physical property for structure difference: the molecule of L-PEI on a main chain, deposit by compound with regular structure
In amorphous and two kinds of forms of crystallization, and the characteristics of B-PEI shows highly -branched due to molecule, amorphous state is generally showed,
It is the polyethyleneimine being most widely used at present.B-PEI is colourless to faint yellow thick liquid in appearance, there is certain suction
Moist, miscible with water, commercially available product is usually the aqueous solution of 20%~50% concentration.Containing there are two C in each PEI monomer
With a N, wherein contain a large amount of primary amine, secondary amine and tertiary amine group on the strand of B-PEI, the ratio between these three amine groups are
1:2:1, and each can be protonated, and charge density when this protonates it completely is up to 23.3mmol/g, is mesh
The preceding known cationic polymer with highest charge density, can be widely applied to papermaking, petroleum, fiber, coating, ink,
Multiple technical fields such as adhesive, water process, new material, gas purification, biomedicine and Treatment of Metal Surface.
Currently, B-PEI is the open loop auto polymerization reaction preparation by monomer aziridine (EI).Patent
CN201380064522.1 discloses a kind of preparation method for producing the not polyethyleneimine of chloride, and this method is held in reaction
Polyethyleneimine is prepared by Semi-batch reaction in device, the reaction time 1~for 24 hours, 80~120 DEG C of reaction temperature, resulting polymers
Number-average molecular weight Mn is 500~500000, and dispersion degree (the ratio between weight average molecular weight Mw and number-average molecular weight Mn) is 1.3~5.0.Specially
Sharp CN201480044867.5 and CN201480082629.3 discloses a kind of ethyleneimine polymer and its manufacturing method, the party
Method usually prepares polyethyleneimine in still reaction container, 0.5~20h of reaction time, and 50~150 DEG C of reaction temperature, gained
Polymer number-average molecular weight Mn is greater than 13000, and dispersion degree is 1.4~5.0.
The above-mentioned reaction for preparing polyethyleneimine is usually interval or semi-batch progress, reaction in popular response container
Material is mixed by way of dropwise addition, has strict requirements to the dropwise addition mixing rate of material, the process is more complicated, the reaction time
Generally more than 8h, reaction temperature is usually above 100 DEG C, and gained polyethyleneimine product usually has wider molecular weight point
Cloth, dispersion degree are 1.3~5.0, and containing more small molecular weight polymer, it is unfavorable that this will be generated in its certain subsequent application
It influences.
Summary of the invention
In order to overcome deficiency present in background technique, polymerization technology in branched polyethylene imine preparation process is solved
Complicated, polymerization time length, polymerization temperature is high and polymer molecular weight is distributed wide problem.
The present invention provides a kind of method for continuously preparing branched polyethylene imine, this method used catalyst is water solubility
Acid compound or water-soluble halohydrin compound, dosage are the 0.2%~10% of aziridine quality, and solvent for use is alcohol
Or water, dosage are the 5%~50% of aziridine quality, specifically includes the following steps:
(1) aziridine monomer and the mixed solution being made of above-mentioned catalyst with solvent are continuously beaten with metering pump respectively
Enter micro passage reaction, the two is mixed in micro passage reaction entrance, and flow is by its stop in micro passage reaction
Time determines；
(2) reaction mass stops 10~300s, drop at a temperature of 50~100 DEG C in micro passage reaction in step (1)
It is continuously discharged from reactor outlet after to 20~30 DEG C；
(3) reaction solution obtained in collection step (2) removes solvent and catalyst, and branched polyethylene imine is made.
The preferred water-soluble inorganic acid of aqueous acidic compound, water solubility halohydrin compound preferably 3 carbon
Single chlorhydrin within atom.
The preferred hydrochloric acid of the water-soluble inorganic acid, dosage are the 0.5%~2% of aziridine quality, 3 carbon originals
The chloro- 1,2- propylene glycol of the preferred 3- of single chlorhydrin, the chloro- 1,3- propylene glycol of 2-, trimethylene chlorohydrin, the chloro- 2- propyl alcohol of 3- within son,
Ethylene chlorhydrin and ethylene chlorhydrin, dosage are the 0.5%~2% of aziridine quality.
The preferred water of solvent, dosage are the 10%~30% of aziridine quality.
Preferably 60~90 DEG C of temperature described in step (2).
Residence time preferably 30~120s described in step (2).
Removing solvent and catalyst can carry out under negative pressure, normal pressure or pressurized conditions in step (3), preferably in negative pressure item
It is carried out under part.
It is reacted by aziridine monomer through open loop auto polymerization it should be noted that above-mentioned branched polyethylene imine refers to
Polymer obtained.
Compared with prior art, the invention has the following advantages that
(1) branched polyethylene imine is prepared using continuous processing, polymerization reaction time is 30~120s, between traditional
It knocks off skill, polymerization technique is simple, polymerization time is short, polymerization efficiency is high；
(2) polymerization reaction is usually at 60~90 DEG C, and compared to traditional polymerization technique, polymerization temperature is low；
(3) use its dispersion degree of branched polyethylene imine prepared by the present invention for 1.5~3.0, narrow molecular weight distribution, low point
Sub- weight polymers content is low, product quality is high.
Specific embodiment
The invention will be further described by the following examples, but the present invention is not limited by the following example.
The present embodiment prepares branched polyethylene imine using the healthy and free from worry microchannel G1 glass reactor, uses two metering pumps point
Reactor is not squeezed by aziridine monomer and by the mixed solution that catalyst and solvent form, the two is mixed at Reactor inlet
It closes, is successively flowed out after three are held the reaction module that flow is 8.2mL, collect reaction solution, removed under reduced pressure after being cooled by water
Solvent both obtains branched polyethylene imine.
The molecular weight of above-mentioned branched polyethylene imine, chromatographic condition are measured using gel permeation chromatography (GPC) are as follows:
Ultrahydrogel 250 (300mm*7.8mm) chromatographic column, 2414 type differential refraction detectors, mobile phase is Acetic acid-sodium acetate
Buffer (0.2mol/L acetic acid -0.1mol/L sodium acetate), detector and column temperature are 40 DEG C, flow velocity 1mL/min, sample volume 20
μ L, sample is to flow phase dilution.
Embodiment 1
Aziridine monomer is conveyed using metering pump A, flow 19.7mL/min (16.4g/min) will be defeated using metering pump B
Water is sent, is not added catalyst, flow 4.9mL/min (water consumption be about aziridine quality 30%), the two is in Reactor inlet
Place's mixing, successively holds the reaction module that flow is 8.2mL by three, the residence time is about 60s, polymeric reaction temperature 80
DEG C, reaction solution is collected after being cooled by water, does not obtain branched polyethylene imine after removed under reduced pressure light component.
Embodiment 2
Aziridine monomer is conveyed using metering pump A, flow 19.7mL/min (16.4g/min) will be defeated using metering pump B
The mixed solution for sending HCl and water to form, HCl content 2%, (water consumption is about aziridine quality to flow 4.9mL/min
30%), the two mixes at Reactor inlet, successively holds the reaction module that flow is 8.2mL by three, the residence time is about
For 60s, 80 DEG C of polymeric reaction temperature, reaction solution is collected after being cooled by water, and branched polyethylene Asia is obtained after removed under reduced pressure light component
Amine.Its molecular weight, Mn=17865, Mw/Mn=2.6 are measured using GPC.
Embodiment 3
Change catalyst HCl in embodiment 2 into ethylene chlorhydrin, remaining condition is constant, and the branching using GPC measurement preparation is poly-
The molecular weight of aziridine, Mn=16347, Mw/Mn=2.8.
Embodiment 4
It will be 0.5% by catalyst HCl usage amount in embodiment 2, remaining condition is constant, using the branch of GPC measurement preparation
Change the molecular weight of polyethyleneimine, Mn=7683, Mw/Mn=2.0.
Embodiment 5
Reaction temperature in embodiment 2 is risen to 90 DEG C, remaining condition is constant, using the branched polyethylene of GPC measurement preparation
The molecular weight of imines, Mn=20543, Mw/Mn=2.9.
Embodiment 6
It will be 1.0% by catalyst ethylene chlorhydrin usage amount in embodiment 3, remaining condition is constant, is measured and is prepared using GPC
Branched polyethylene imine molecular weight, Mn=10942, Mw/Mn=2.3.
Embodiment 7
Reaction temperature in embodiment 3 is down to 60 DEG C, remaining condition is constant, using the branched polyethylene of GPC measurement preparation
The molecular weight of imines, Mn=6332, Mw/Mn=2.1.
Embodiment 8
The usage amount of water in embodiment 2 is down to the 10% of aziridine dosage, i.e. the flow of metering pump A is 22.7mL/
Min (18.9g/min) is 1.9mL/min using the flow of metering pump B, remaining condition is constant, using the branch of GPC measurement preparation
Change the molecular weight of polyethyleneimine, Mn=12369, Mw/Mn=2.8.
Embodiment 9
Aziridine monomer is conveyed using metering pump A, flow 136.3mL/min (113.1g/min) will using metering pump B
The mixed solution of transport of H Cl and water composition, HCl content 1%, (water consumption is about aziridine quality to flow 11.3mL/min
10%), the two mixes at Reactor inlet, successively holds the reaction module that flow is 8.2mL by three, the residence time is about
For 10s, 60 DEG C of polymeric reaction temperature, reaction solution is collected after being cooled by water, and branched polyethylene Asia is obtained after removed under reduced pressure light component
Amine.Its molecular weight, Mn=1766, Mw/Mn=1.5 are measured using GPC.
Embodiment 10
Aziridine monomer is conveyed using metering pump A, flow 42.2mL/min (35.0g/min) will be defeated using metering pump B
The mixed solution for sending HCl and water to form, HCl content 2%, (water consumption is about aziridine quality to flow 7.0mL/min
20%), the two mixes at Reactor inlet, successively holds the reaction module that flow is 8.2mL by three, the residence time is about
For 30s, 70 DEG C of polymeric reaction temperature, reaction solution is collected after being cooled by water, and branched polyethylene Asia is obtained after removed under reduced pressure light component
Amine.Its molecular weight, Mn=5733, Mw/Mn=1.9 are measured using GPC.
Embodiment 11
Aziridine monomer is conveyed using metering pump A, flow 12.7mL/min (10.5g/min) will be defeated using metering pump B
The mixed solution for sending ethylene chlorhydrin and water to form, ethylene chlorhydrin content 1%, (water consumption is about aziridine to flow 2.1mL/min
The 20% of quality), the two mixes at Reactor inlet, successively holds the reaction module that flow is 8.2mL by three, stops
Time is about 100s, 70 DEG C of polymeric reaction temperature, collects reaction solution after being cooled by water, and it is poly- that branching is obtained after removed under reduced pressure light component
Aziridine.Its molecular weight, Mn=15323, Mw/Mn=2.4 are measured using GPC.
Embodiment 12
Aziridine monomer is conveyed using metering pump A, flow 9.8mL/min (8.2g/min) will be conveyed using metering pump B
The mixed solution of ethylene chlorhydrin and water composition, ethylene chlorhydrin content 3%, (water consumption is about aziridine matter to flow 2.5mL/min
The 30% of amount), the two mix at Reactor inlet, successively passes through three and holds the reaction module that flow is 8.2mL, when stop
Between about 120s, 90 DEG C of polymeric reaction temperature, collect reaction solution after being cooled by water, the poly- second of branching obtained after removed under reduced pressure light component
Alkene imines.Its molecular weight, Mn=22439, Mw/Mn=3.0 are measured using GPC.
Claims (8)
1. a kind of method for continuously preparing branched polyethylene imine, it is characterised in that used catalyst is aqueous acidic compound
Or water-soluble halohydrin compound, dosage are the 0.2%~10% of aziridine quality, solvent for use is alcohol or water, is used
Amount is the 5%~50% of aziridine quality, specifically includes the following steps:
(1) aziridine monomer and the mixed solution being made of above-mentioned catalyst and solvent are continuously squeezed into metering pump respectively micro-
Channel reactor, the two are mixed in micro passage reaction entrance, and flow is by its residence time in micro passage reaction
It determines；
(2) reaction mass stops 10~300s in micro passage reaction, is down to 20 at a temperature of 50~100 DEG C in step (1)
It is continuously discharged from reactor outlet after~30 DEG C；
(3) reaction solution obtained in collection step (2) removes solvent and catalyst, and branched polyethylene imine is made.
2. a kind of method for continuously preparing branched polyethylene imine according to claim 1, it is characterised in that described water-soluble
Property acid compound be water-soluble inorganic acid, the water solubility halohydrin compound is single chlorhydrin within 3 carbon atoms.
3. a kind of method for continuously preparing branched polyethylene imine according to claim 1 or 2, it is characterised in that the water
Insoluble inorganic acid is hydrochloric acid, and dosage is the 0.5%~2% of aziridine quality, single chlorhydrin within 3 carbon atoms
For 3- chlorine-1,2-propylene glycol, the chloro- 1,3-PD of 2-, trimethylene chlorohydrin, the chloro- 2- propyl alcohol of 3-, ethylene chlorhydrin and ethylene chlorhydrin,
Its dosage is the 0.5%~2% of aziridine quality.
4. a kind of method for continuously preparing branched polyethylene imine according to claim 1, it is characterised in that the solvent
For water, dosage is the 10%~30% of aziridine quality.
5. a kind of method for continuously preparing branched polyethylene imine according to claim 1, it is characterised in that in step (2)
The temperature is 60~90 DEG C.
6. a kind of method for continuously preparing branched polyethylene imine according to claim 1, it is characterised in that in step (2)
The residence time is 30~120s.
7. a kind of method for continuously preparing branched polyethylene imine according to claim 1, it is characterised in that in step (3)
Removing solvent and catalyst can carry out under negative pressure, normal pressure or pressurized conditions.
8. a kind of method for continuously preparing branched polyethylene imine according to claim 1, it is characterised in that removing solvent
It is to be carried out under condition of negative pressure.
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| CN114479449A (en) * | 2022-03-16 | 2022-05-13 | 山东交通学院 | Composite material for ground restoration and bearing reinforcement engineering, preparation method and application |
| CN114539522A (en) * | 2022-03-04 | 2022-05-27 | 四川大学 | Method for synthesizing branched polyethyleneimine without adding catalyst |
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| CN114479449A (en) * | 2022-03-16 | 2022-05-13 | 山东交通学院 | Composite material for ground restoration and bearing reinforcement engineering, preparation method and application |
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