CN110229329A - A kind of biomass-based furans polyamide continuous production device of high polymerization degree half and continuous producing method - Google Patents
A kind of biomass-based furans polyamide continuous production device of high polymerization degree half and continuous producing method Download PDFInfo
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- CN110229329A CN110229329A CN201910393714.6A CN201910393714A CN110229329A CN 110229329 A CN110229329 A CN 110229329A CN 201910393714 A CN201910393714 A CN 201910393714A CN 110229329 A CN110229329 A CN 110229329A
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/46—Post-polymerisation treatment
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Abstract
The present invention relates to the continuous production devices and production method of a kind of biomass-based furans polyamide of high polymerization degree half.Device used herein successively includes prepolymerization system, paradigmatic system, heat-exchange system；The continuous production processes of half biomass-based furans polyamide are the following steps are included: furans chloride compounds and aminated compounds are mixed；Prepolymerization is carried out, prepolymer product is obtained；Then polymerization reaction is carried out, polymerizate is obtained；Finally polymerizate is post-processed.It can be realized the continuous production of half biomass-based furans polyamide using the device of the invention, heat transfer is uniform, mass transfer effect is good, and it is high to adjust half biomass-based furans polyamide molecular weight obtained by the good and of the invention method of temperature effect, polydispersity is lower, molecular weight is easily-controllable, and polymer molecular weight is up to 300,000 or more, and breadth coefficient is less than 1.6, process flow is simple, entire production process three-waste free discharge, production system are stablized, high production efficiency.
Description
Technical field
The invention belongs to macromolecule synthesising technology fields, are related to the system of the biomass-based furans polyamide of high polymerization degree half
Preparation Method, and in particular to the method and reaction unit of the biomass-based furans polyamide of continuous production high polymerization degree half.
Background technique
Polyamide refers to the high polymer in macromolecular chain of repeat units containing amide group, has good chemical stabilization
Property, dielectricity and excellent mechanical property, are widely used in composite material, ballistic-resistant article, chemical industry equipment, special protecting clothing
The fields such as dress, electronic equipment.
Traditional monomer of polyamide from petroleum base, consumes a large amount of petroleum resources mostly, and not only raw material comes
Source is limited, and causes serious environmental pollution,
Biomass is as currently the only reproducible organic carbon resource, with distribution is wide, reserves are big, environmental-friendly, greenhouse
The advantages that gas zero-emission, will become the primary raw material of rear fossil economy era liquid fuel and organic chemicals, have substitution
The tremendous potential of traditional energy or petrochemical material.
Therefore, develop the amide of biological poly containing furan nucleus of reproducible novel green sustainable development to material science
Development and the utilization of biomass energy are of great significance.However using traditional polymerization it is difficult that high polymerization degree is prepared
The amide material of biological poly containing furan nucleus.It traces it to its cause because no matter using melt polymerization or using polymerisation in solution, furan
The carboxyl on ring of muttering is easy to that decarboxylic reaction (Huang Weijun, Zhu Ning etc., biology base containing furan nucleus occur under 195 DEG C of reaction temperatures
The synthesis of polyamide, chemical progress, 2018,30 (12): 1836--1843), therefore the furans of high polymerization degree can not be prepared
Based polyamide resin.
Polymer of the present invention belongs to a kind of novel biology base furans polyamide, by two formyl of organism-based raw material furans
Chlorine and aromatic diamines are prepared by continuous production method.Shown in general formula of the chemical structure such as formula (I):
There is heat-resisting furans aromatic group and amide flexible simultaneously on biological poly amide molecule chain described herein
Group, therefore there is excellent heat resistance, dielectricity, resistance to acid and alkali and good mechanical property；Simultaneously because molecule contains
Furan ring structure, therefore there is good biodegradability, bactericidal properties.And furan nucleus carbon atom number is fewer than phenyl ring, virtue
Fragrance is weaker than phenyl ring, and furan nucleus volume ratio benzene ring structure is small, and bulk density is just bigger than the material of furan structure, and mechanical property may
It is higher than benzene ring structure Fypro, compared with aromatic polyamide, biological poly amide may have it is similar or
More excellent material property.
At home, there are mainly two types of synthetic methods: 1. use furans dimethyl chloride and diamines low temperature polymerization (Chinese patent CN
104245793 A)；2. using furandicarboxylic acid and diamines high-temperature polycondensation (105801843 A of CN).Solution polymerization process production
The key of function admirable polymer is two o'clock: the first, material is uniformly mixed；The second, strict control reaction temperature.
But the consersion unit of existing polyamide is still reaction polymerizer.Because the viscosity of polymerization reaction system compared with
Height, the whipped form of tank polymerization device keep material mixing uneven, in particular to rise up to reaction later period polymerization system viscosity, object
Material mixing difficulty further increases, and causes local monomer concentration is excessively high perhaps too low polymer is made local implode or office occur
Portion's degree of polymerization is too low, causes polymer mother liquor molecular weight distribution uneven；Simultaneously as polymerization reaction system exotherm rate is quickly,
Tank reactor only has external jacket heat exchange, and the heat of reaction system cannot quickly be taken away, it cannot be guaranteed that the low temperature of reaction system
And the temperature uniformity of W-response system, local high temperature cause and the polyamides that decarboxylic reaction makes generation occur on furan nucleus
Amine is degraded, and reaction synchronism is very poor, and there are many side reaction, and polymer molecular weight is difficult to control.
Summary of the invention
In order to overcome the above problem, present inventor has performed sharp studies, as a result, it has been found that: using including static microring array
The continuous production device of the microdevices such as device, microreactor and multi-stage screw device and heat-exchange system, improve pre-polymerization system and
The heat transfer of paradigmatic system, mass transfer effect, can continuous production furans polyamide, and the molecular weight of gained resin is high, more points
Scattered property is low, and the method products obtained therefrom quality of the biomass-based furans polyamide of continuous production half is stablized, energy consumption and investment
It is at low cost, apparatus structure is simple, process flow is succinct, high production efficiency, be suitable for heavy industrialization continuous production.
In a first aspect, the purpose of the present invention is to provide the continuous productions of a kind of half biomass-based furans polyamide
Device, the device include sequentially connected prepolymerization system, polymer reactor.
On the other hand, it is continuously given birth to the purpose of the present invention is to provide a kind of using method described in first aspect present invention
The method for producing furans polyamide, method includes the following steps:
Step 1 mixes furans chloride compounds and aminated compounds；
Step 2 carries out prepolymerization reaction, obtains prepolymer；
Step 3 carries out polymerization reaction, obtains polymerizate；
Step 4 post-processes polymerizate.
The advantageous effect of present invention is that:
(1) the present invention provides the continuous production devices of a kind of half biomass-based furans polyamide, using microring array
Device and microreactor prepare furans polyamide, the heat transfer efficiency for solving prepolymerisation stage in its preparation process is low, heat transfer not
Uniform problem enables the heat generated in reaction process quickly to remove, to avoid caused by reaction system hot-spot
Implode and the generation of low molecular weight by-products；
(2) continuous production device of the invention using multi-stage screw polymerizing reactor and pre-polymerization system micro-mixer and
Microreactor is mating, guarantees being continuously conveyed for the high viscosity resins that polymerization reaction generates, while by adjusting multi-stage screw polymerization
Revolving speed, diameter and the draw ratio of screw rod at different levels are in reaction unit come when meeting the stop of the reactant of polymerization stage in preparation process
Between, accurate temperature controlling, heat transfer efficiency and mass transfer stability；
(3) the present invention provides a kind of method for preparing furans polyamide using continuous production device continuous production,
Pass through the mixing of raw material, prepolymerization reaction, polymerization reaction, the spray drying of furans polyamide, centrifuge washing, filtering, drying
Furans polyamide can be efficiently prepared with processes such as moldings, the molecular weight of gained furans polyamide is high, such as molecular weight
Greater than 300,000, and its polydispersity it is small < 1.6, for example, 1.52, gained furans polyamide quality is stablized, energy consumption and artificial
Investment reduces, process stabilizing and energy large-scale industrial production.
(4) offer of the present invention prepares the continuous reaction apparatus of furans polyamide, and spray drying device can lead in device
It is dry to guarantee that resin powder can clean for the mean particle size for overregulating the control furans polyamide such as temperature, pressure, flow
Only, to guarantee that the capability and performance of half prepared biomass-based furans polyamide is stablized；
(5) compared to the enlarge-effect of traditional reaction kettle, the present invention continuously prepares the method for furans polyamide using micro- mixed
Clutch, microreactor and multi-stage screw polymerizing reactor etc., these devices are easily achieved, produce without obvious enlarge-effect
High-efficient, save the cost is suitble to industrialization large-scale continuous production furans polyamide.
Detailed description of the invention
Fig. 1 is a kind of structural schematic diagram of the continuous production device of preferred furans polyamide of the present invention.
Specific embodiment
Below by attached drawing and preferred embodiment, the present invention is described in more detail.Illustrated by these, the present invention
The characteristics of and advantage will become more apparent from it is clear.
According to the present invention, a kind of continuous reaction apparatus for preparing furans polyamide is provided, which includes successively
Prepolymerization system, the paradigmatic system of connection.
In one embodiment, prepolymerization system includes sequentially connected feedstock storage unit, micro-mixer and micro- anti-
Answer device.In a preferred embodiment, micro-mixer is static micro-mixer.
In one embodiment, feedstock storage unit includes raw material storage tanks to delivery pump, and raw material storage tanks include furans
Chloride compounds storage tank and aromatic diamines storage tank, for storage of raw materials furans chloride compounds and aromatic diamines and solvent.?
In one embodiment, furans chloride compounds are furans dimethyl chlorides, and aromatic diamines are m-phenylene diamine (MPD), p-phenylenediamine, 4,4-
Diaminodiphenyl ether, 4,4 '-diaminodiphenylmethane and 1,5- naphthylenediamine.
In one embodiment, prepolymerization system includes sequentially connected furans dimethyl chloride storage tank and aromatic diamines storage
Tank, triple valve, furans dimethyl chloride precision delivery pump, aromatic diamines precision delivery pump, micro-mixer and microreactor.
In the present invention, micro-mixer effect is to be blended in initial monomers furan starting material chloride compounds and aromatic diamines
Together, it prepares to carry out polymerization reaction.
In one embodiment, furans dimethyl chloride storage tank first passes through pipeline and is connected with triple valve, using threeway
Valve output end is connect with micro-mixer.
In one embodiment, aromatic diamines storage tank first passes through pipeline and is connected with triple valve, defeated using triple valve
Outlet is connect with micro-mixer.In one embodiment, furans chloride compounds storage tank, aromatic diamines storage tank, furans acyl chlorides
It is equipped on compound precision delivery pump, aromatic diamines precision delivery pump and conveyance conduit and enters microring array for adjusting raw material
The insulation jacket of temperature before device.
In one embodiment, half biomass-based furans polyamide is prepared using chloride method, preferably by furans acyl
It is prepared by chlorine compound and aminated compounds.In preferred embodiments, aminated compounds is aromatic diamine compound.
In one embodiment, furans chloride compounds are added in furans acyl chlorides storage tank, and aminated compounds is added to
In aromatic diamines storage tank, furans chloride compounds are conveyed from furans chloride compounds storage tank by furans chloride compounds precision
Pump is transported in micro-mixer, and aminated compounds is transported to from aromatic diamines storage tank by aromatic diamines precision delivery pump micro- mixed
In clutch.
In one embodiment, to furans chloride compounds storage tank, furans chloride compounds precision delivery pump and between
Conveyance conduit on insulation jacket in be passed through thermal medium (such as ethylene glycol), make the furans acyl in furans chloride compounds storage tank
Chlorine compound raw material is in the molten condition of higher temperatures (as being higher than 85 DEG C), conveys in aromatic diamines storage tank, aromatic diamines precision
Pump and between conveyance conduit on insulation jacket in be equipped with cold medium (such as ethyl alcohol), this method pass through furans chloride compounds
Accurate delivery pump and aromatic diamines precision delivery pump control raw material enter the flow velocity of micro-mixer, to control mixing micro-mixer
The proportion and reaction speed of middle raw material.
According to the present invention, process units further includes raw material purge tank, and raw material purge tank passes through conveyance conduit and threeway respectively
Valve is connected, then is connected through pipeline with raw material storage tanks.Preferably, the delivery pipe of furans chloride compounds storage tank and raw material purge tank
Road is equipped with triple valve, and the one outlet of raw material purge tank is connect by conveyance conduit with the triple valve；Simultaneously in aromatic diamines
Also is provided with triple valve on the conveyance conduit of storage tank and raw material purge tank, another outlet of raw material purge tank by conveyance conduit with
Triple valve connection.
In one embodiment, maintenance or raw material storage tanks and material of the raw material purge tank for continuous production device are defeated
Send the cleaning of pipeline.
In one embodiment, organic solvent is housed, organic solvent is preferably commonly used in the art in raw material purge tank
Organic solvent is preferably selected from n,N-Dimethylformamide, n,N-dimethylacetamide tetrahydrofuran, chlorobenzene, N- crassitude
One or more of ketone, methylisobutylketone, methyl isopropyl ketone dimethyl sulfoxide.
In one embodiment, it is passed on micro-mixer equipped with the temperature for monitoring reaction mass temperature in micro-mixer
Sensor, it is stringent monitor temperature consequently facilitating temperature adjusting.
In one embodiment, the volume of micro-mixer is smaller, and preferable volume is less than 200ml, or even only several milliliters
To tens milliliters, for example, 2ml.Preferably, micro-mixer contains the microchannel structure of Y type and/or T-type, and material is in microring array
It is uniformly mixed in device by pressure.The micro-mixer heat transfer of smaller volume is fast, and mass transfer is uniform, so that material mixing is more equal
Even, compared with existing batch reactor, micro-mixer mixing efficiency is higher than traditional reaction kettle mixing efficiency.
In one embodiment, pressure gauge is housed in the connecting pipe of micro-mixer and microreactor, for monitoring
Pressure in production process in pipeline.
In one embodiment, raw material monomer carries out prepolymerization reaction first in microreactor, generates prepolymer.
In one embodiment, paradigmatic system includes multi-stage screw polymerizing reactor, preferably microreactor and multistage
The connection of screw rod polymerizing reactor.
In one embodiment, multi-stage screw polymerizing reactor includes sequentially connected level-one screw rod polymerization reaction
Device, second level screw rod polymer reactor and three-level screw rod polymer reactor.
In one embodiment, it is each that control is cased on level-one screw rod polymer reactor to three-level screw rod polymer reactor
The temperature collet of grade screw rod polymer reactor.
In one embodiment, screw diameter, spiral shell of the level-one screw rod polymer reactor to three-level screw rod polymer reactor
Bar draw ratio, screw speed, jacket temperature can be adjusted according to production requirement.
In one embodiment, the screw diameter of level-one screw rod polymer reactor to three-level screw rod polymer reactor is
10mm~30mm, screw slenderness ratio are 20~60, and screw speed is 50~300rpm, and jacket temperature is 10~50 DEG C.
In one embodiment, the screw diameter of level-one screw rod polymer reactor be 10~20mm, draw ratio be 45~
60, revolving speed is 180~250rpm, and jacket temperature is 10~30 DEG C, the screw diameter of second level screw rod polymer reactor is 15~
20mm, draw ratio are 35~45, and revolving speed is 120~180rpm, and jacket temperature is 30~40 DEG C, three-level screw rod polymer reactor
Screw diameter is 20~25mm, draw ratio is 20~35, and revolving speed is 80~120rpm, and jacket temperature is 40~50 DEG C,.
In one embodiment, the screw diameter of level-one screw rod polymer reactor be 10mm, draw ratio 60, revolving speed is
300rpm, jacket temperature are 10 DEG C, and the screw diameter of second level screw rod polymer reactor is 20mm, draw ratio 45, and revolving speed is
160rpm, jacket temperature are 38 DEG C, and the screw diameter of three-level screw rod polymer reactor is 25mm, draw ratio 25, and revolving speed is
120rpm, jacket temperature are 50 DEG C.
In one embodiment, the screw rod of level-one screw rod polymer reactor to three-level screw rod polymer reactor is single head
Screw rod, double threaded screw or three screw rods.
In one embodiment, the prepolymer in microreactor enters in multi-stage screw polymerizing reactor and is gathered
Reaction is closed, polymerizate is obtained.
In one embodiment, multi-stage screw polymerizing reactor is compact multi-level screw rod polymer reactor, multistage spiral shell
Bar polymerizing reactor is higher compared with the mass-transfer efficiency of common screw reactor, and polymerizate can be reached by the less residence time
It is required to polymerization, mass-and heat-transfer efficiency is higher compared with common screw reactor, so that obtained furans polyamide dispersibility
More preferably, multi-stage screw polymerizing reactor can avoid that implode occurs in polymerization process.
In one embodiment, can be in parallel using multiple multi-stage screw polymerizing reactors, expand reaction scale.
The present invention prepares furans polyamide using furans chloride compounds and aromatic diamine compound reaction, first will
Furans chloride compounds and aromatic diamine compound prepare polyamide, are then handled polyamide to obtain furans polyamide resin
Rouge, furans chloride compounds directly with aminated compounds occur amidation process during, hydrogen chloride can be generated
(HCl), HCl is remained not only in system can hinder reaction to carry out to forward direction, can also cause to corrode to equipment.
In one embodiment, it is added acid binding agent in polycondensation process, acid binding agent is preferably inorganic base or organic base,
More preferably one or more of lithium hydroxide, calcium hydroxide, diisopropylamine, triethylamine, tert-butylamine, tetramethylethylenediamine.
In one embodiment, paradigmatic system further includes the acid binding agent tank connecting with multi-stage screw polymerizing reactor,
Acid binding agent is housed in acid binding agent tank, acid binding agent is added in polycondensation to adsorb the HCl of generation.
In one embodiment, which further includes heat-exchange system, heat-exchange system respectively with pre-polymerization collaboration
System is connected with paradigmatic system, to adjust the temperature of prepolymerization system and paradigmatic system.
In one embodiment, heat-exchange system includes refrigerating circulatory device and heat cycles device.
In one embodiment, refrigerating circulatory device includes that media storage tank, medium equipped with cold medium convey circulation
Media storage tank, micro-mixer and microreactor are coupled shape by pump, spinner flowmeter and medium delivery pipe road, medium delivery pipe road
At circulation loop.
In one embodiment, heat cycles device includes that media storage tank, medium equipped with thermal medium convey circulation
Pump, spinner flowmeter and medium delivery pipe road, multi-stage screw polyplant connect to form circulation loop by conveyance conduit.
In one embodiment, after-treatment system include spray dryer, centrifugal scrubber, filter, drying box, at
Type machine.
In one embodiment, furans polyamide, which is taken away solvent by high temperature gas flow in spray dryer, obtains
Half biomass-based furans polyamide powder is obtained, passes through and adjusts the adjustable furans polyamide resins such as temperature, pressure, flow, air quantity
The speed and powder morphology that rouge is precipitated.
In one embodiment, centrifugal scrubber by high speed centrifugation power to by washing furans polyamide slurry into
Row centrifugal dehydration removes remaining a small amount of water in half biomass-based furans polyamide resin resin system, and then guarantees furans polyamide
Toner has good form.
In one embodiment, drying box obtains dry furan for removing moisture contained by furans polyamide
It mutters polyamide, is formed through molding machine, finally obtain the biomass-based furans polyamide resin fat prod of form uniform half.
Another aspect of the present invention provides a kind of continuous producing method of furans polyamide, it is preferred to use the present invention the
Continuous reaction apparatus described in one side carries out, method includes the following steps:
Step 1 mixes furans chloride compounds and aminated compounds, carries out preferably in micro-mixer.
In one embodiment, half biomass-based furans polyamide is synthesized using chloride method, using biology base acyl
Chlorine or derivatives thereof and aromatic diamine or derivatives thereof reaction obtain.
In one embodiment, in step 1, furans chloride compounds are selected from 2,5- furans dimethyl chloride, 2,3- furans
It mutters dimethyl chloride and 3,4- furans dimethyl chloride.
In one embodiment, in step 1, aminated compounds is selected from m-phenylene diamine (MPD), p-phenylenediamine, 4,4- diamino
One or both of diphenyl ether, 4,4 '-diaminodiphenylmethane and 1,5- naphthylenediamine.
In one embodiment, in step 1, furans chloride compounds storage tank stores furans chloride compounds, fragrance
Diamines storage tank storage is dissolved in the aromatic diamine compound of organic solvent.
In one embodiment, in step 1, furans chloride compounds and aminated compounds carry out in micro-mixer
Mixing, preferably mixes the furans chloride compounds of molten condition with the aminated compounds of solution state.
In one embodiment, by adjusting furans chloride compounds storage tank, furans chloride compounds precision delivery pump
And the heat medium temperature in the insulation jacket on the conveyance conduit between furans chloride compounds storage tank and microreactor, make furan
Chloride compounds of muttering are transmitted with molten condition through piping, preferably 80~90 DEG C of molten condition.
The furans chloride compounds of molten condition pass through furans acyl chlorides by conveyance conduit by furans chloride compounds storage tank
Compound precision delivery pump is transported in micro-mixer.
Triple valve, triple valve and raw material purge tank are equipped on conveyance conduit between furans acyl chlorides storage tank and micro-mixer
Connection is equipped with organic solvent in raw material purge tank, for the clear of continuous polymerization system maintenance or raw material storage tank and conveyance conduit
It washes.
In one embodiment, organic solvent is selected from n,N-Dimethylformamide, n,N-dimethylacetamide tetrahydro furan
It mutters, one or more of chlorobenzene, N-Methyl pyrrolidone, methylisobutylketone, methyl isopropyl ketone dimethyl sulfoxide
In one embodiment, by adjusting aromatic diamines storage tank, aromatic diamines precision delivery pump and aromatic diamines
Cold medium temperature in the insulation jacket on conveyance conduit between storage tank and microreactor, make amine aqueous solution enter micro-mixer it
The preceding solution state for low temperature, preferably -30~10 DEG C of solution state.
The aminated compounds of solution state is transported to microring array by aromatic diamines precision delivery pump by aromatic diamines storage tank
In device.
The furans chloride compounds of molten condition are mixed in micro-mixer with amine aqueous solution.
In one embodiment, enter the flow velocity of micro-mixer by adjusting furans chloride compounds and amine aqueous solution to control
Micro-mixer raw material proportioning processed.
In one embodiment, furan starting material chloride compounds are with the flow velocity of 30~100ml/min through furans chloride
Object precision delivery pump is closed to enter in micro-mixer；Aromatic diamines solution is with the flow velocity of 100~150ml/min through aromatic diamines essence
Close delivery pump enters in micro-mixer.
In one embodiment, in step 1, the furans chloride compounds of the molten condition of higher temperatures and the amine of low temperature
Solution is sufficiently mixed in micro-mixer, can prevent acyl chlorides and amine from mixing by the temperature in control micro-mixer
When react.
In one embodiment, using the temperature of refrigerating circulatory device control micro-mixer, the temperature of micro-mixer is controlled
Degree is -30~0 DEG C, preferably -25~-5 DEG C, such as -25 DEG C.
Step 2 carries out prepolymerization, obtains prepolymer, carries out preferably in microreactor.
In one embodiment, in step 2, the uniformly mixed material in micro-mixer enters in micro- reaction, raw
At prepolymer.
In one embodiment, in step 2, to make mixture that the polymerization reaction of generation macromolecular chain not occur,
Need the temperature of strict control microreactor.In one embodiment, in step 2, it is controlled using refrigerating circulatory device micro-
The temperature of reactor, the temperature for controlling microreactor is 5~35 DEG C, preferably 10~30 DEG C, such as 15 DEG C.
Step 3 carries out polymerization reaction, obtains polymerizate, preferably carries out in multi-stage screw polymerizing reactor.
In one embodiment, in step 3, the prepolymer generated in microreactor is successively in level-one to three-level spiral shell
Polymerization reaction is carried out in bar polymer reactor, obtains half biomass based polyamide resin.
In one embodiment, the temperature of polymerization reaction is 10-50 DEG C.
In one embodiment, the temperature of screw rod polymer reactor is controlled by heating circulation system in polymerization reaction
System.
Step 4 post-processes polymer.
In one embodiment, in step 4, post processor are as follows: half biomass-based furans polyamide enters
To spray dryer, resin is taken away solvent by high temperature gas flow spray dryer to obtain furans polyamide powder, is led to
Overregulating temperature, resin flow, air quantity etc. can control the speed and powder morphology of resin precipitation, from half biomass-based furan of control
It mutters the granular size of polyamide, guarantees that half biomass-based furans polyamide resin powders clean up, had excellent performance
Half biomass-based furans polyamide.
In one embodiment, furans polyamide resin is obtained after the cleaned filtering of gained furans polyamide, drying
Cosmetics end, then by being formed in molding machine, obtain half biomass-based furans polyamide resin fat prod.
In one embodiment, furans polyamide is dried, removes resin contained humidity, obtain half
Biomass-based furans polyamide resin powders, dry temperature are 150-250 DEG C, drying time 5-10h.
In one embodiment, the average grain of gained furans polyamide resin powders preferably exists less than 300 μm
150 μm or less.
The molecular weight of half biomass-based furans polyamide of method preparation is high according to a second aspect of the present invention,
Preferred molecular weight is greater than 300,000, such as can reach 326794, and polydispersity index is low, and polydispersity index, such as can less than 1.8
Down to 1.6.
Embodiment
In the present embodiment, furans acyl chlorides is provided by Hefei Li Fu Biotechnology Co., Ltd, other reagents are purchased from traditional Chinese medicines
Chemical reagent Co., Ltd, equipment are provided by Guizhou Micro Technology Co., Ltd..
The volume 50L of furans acyl chlorides storage tank, the volume 300L of aromatic diamines storage tank, micro-mixer volume 2ml, microreactor
Volume 30ml, pressure 0.0.1Mpa.
2,5- furans dimethyl chloride is packed into furans chloride compounds storage tank, 4,4- diaminodiphenyl ether is dissolved in DMAC
The 4,4- diaminodiphenyl ether solution that concentration is 15% is made into be fitted into aromatic diamines storage tank；
Conveying between furans acyl chlorides storage tank, furans acyl chlorides precision delivery pump and furans acyl chlorides storage tank and micro-mixer
Thermal medium is inputted in insulation jacket on pipeline, 2,5- furans dimethyl chloride is made to be in 85 DEG C of molten condition；
Conveying between aromatic diamines storage tank, aromatic diamines precision delivery pump and aromatic diamines storage tank and micro-mixer
Cold medium is inputted in insulation jacket on pipeline, 4,4- diaminodiphenyl ether solution is made to be in -30 DEG C of solution state；Molten
2, the 5- furans dimethyl chloride of state is entered in micro-mixer with the flow velocity of 25ml/min through furans dimethyl chloride precision delivery pump,
The DMAC solution of the 4,4- diaminodiphenyl ether of solution state is entered with the flow velocity of 100ml/min through aromatic diamines precision delivery pump
Into micro-mixer, it is -5 DEG C by the temperature that cooling cycle system controls micro-mixer, makes 2,5- furans dimethyl chloride and 4,
4- diaminodiphenyl ether solution is sufficiently mixed, and subsequently into prepolymerization is carried out in microreactor, passes through cooling cycle system
The temperature for controlling microreactor is 15 DEG C, obtains prepolymer；
Prepolymer, which enters in multi-stage screw polymerizing reactor, occurs polymerization reaction, and prepolymer successively flows into level-one screw rod
Polycondensation reaction, the polymerization of level-one screw rod are carried out in polymer reactor, second level screw rod polymer reactor and three-level screw rod polymer reactor
Screw rod of the reactor into three-level screw rod polymer reactor is double threaded screw, wherein the screw rod of level-one screw rod polymer reactor
Diameter is 10mm, draw ratio 60, revolving speed 300rpm, and jacket temperature is 10 DEG C, and the screw rod of second level screw rod polymer reactor is straight
Diameter is 20mm, draw ratio 45, revolving speed 160rpm, and jacket temperature is 38 DEG C, the screw diameter of three-level screw rod polymer reactor
For 25mm, draw ratio 25, revolving speed 120rpm, jacket temperature is 50 DEG C；
Polyamic acid resin is obtained after twin-screw polymerizing reactor is polymerize, into spray dryer, is obtained
Then furans polyamide resin powders carry out repeatedly washing using hot water and remove contained salinity in resin, dry by 120 DEG C
To furans polyamide resin powders, furans polyamide is obtained through Granulation Equipments, extrusion forming obtains the furans of required shape
Polyamide resin fat prod.
Molecular weight test is carried out to furans polyamide obtained using gel permeation chromatography (Waters 1515GPC),
Measuring its molecular weight is 326794, polydispersity 1.60.
Biology base furans polyamide is prepared using this continuous polymerization reaction unit, production capacity was to pass up to 1000kg/ days
3-5 times of interval synthesising biological base furans polyamide production capacity of uniting.
Preferred embodiment and exemplary example is combined to describe the invention in detail above.But need to state
It is that these specific embodiments are only not constitute any limit to protection scope of the present invention to illustrative explanations of the invention
System.Without departing from spirit of that invention and protection scope, the technology of the present invention content and embodiments thereof can be carried out
Various improvement, equivalencing or modification, these fall within the protection scope of the present invention.Protection scope of the present invention is with appended power
Subject to benefit requires.
Claims (10)
1. a kind of continuous production device of the biomass-based furans polyamide of high polymerization degree half, which is characterized in that the continuous production
Device includes sequentially connected prepolymerization system and polymer reactor, wherein the prepolymerization system includes sequentially connected raw material
Equipment, static micro-mixer and microreactor are stored, and the polymer reactor includes the multistage for carrying out polymerization reaction
Screw rod polymer reactor.
2. continuous production device according to claim 1, which is characterized in that the static micro-mixer is used for furans acyl chlorides
The mixing of compound and aminated compounds, the operating temperature range of the static micro-mixer are -30~0 DEG C, and described micro-
Reactor is mainly used for furans chloride compounds and aminated compounds carries out prepolymerization, the operating temperature range of microreactor
It is 5~35 DEG C.
3. continuous production device according to claim 1 or 2, which is characterized in that the raw material storage equipment includes furans
Acyl chlorides storage tank and aromatic diamines storage tank, the furans acyl chlorides storage tank are connect by furans acyl chlorides delivery pump with the micro-mixer,
The aromatic diamines storage tank is connect by aromatic diamines delivery pump with the micro-mixer, in the furans acyl chlorides storage tank, furans
Conveyance conduit between acyl chlorides delivery pump and micro-mixer is equipped with the insulation jacket equipped with thermal medium；Described fragrant two
The insulation jacket of cold medium is housed on the conveyance conduit between amine storage tank, aromatic diamines delivery pump and micro-mixer.
4. continuous production device according to claim 3, which is characterized in that the microreactor and the multi-stage screw are poly-
Reactor connection is closed, the multi-stage screw polymer reactor is preferably one to three-level screw rod polymer reactor, the multi-stage screw
Polymer reactor is equipped with the insulation jacket equipped with thermal medium, and one to three-level screw rod polymer reactor screw diameter range exists
10mm~30mm, screw slenderness ratio are 20~60, and screw speed is adjusted in 50~300rpm, and jacket temperature is controlled 10~50
℃。
5. continuous production device according to claim 3, which is characterized in that the continuous production device further includes heat exchange system
System, the heat-exchange system include the cooling recirculation system for controlling the prepolymerization system and the heating for controlling the polymer reactor
The circulatory system, the cooling recirculation system and the micro-mixer and the microreactor form circulation loop, the heating
The circulatory system and the polymer reactor form circulation loop.
6. a kind of use the biomass-based furan of continuous production device continuous production half according to any one of claim 1 to 5
It mutters the method for polyamide, which is characterized in that the described method comprises the following steps:
Step 1 mixes furans chloride compounds and aminated compounds, carries out preferably in micro-mixer；
Step 2 carries out prepolymerization, obtains prepolymer product, preferably carries out in microreactor；
Step 3 carries out polymerization reaction, obtains polymerization liquid, preferably carries out in multi-stage screw polymer reactor；
Step 4 post-processes polymerization reaction system.
7. according to the method described in claim 6, it is characterized in that, in step 1, the furans chloride compounds with 80~
100 DEG C of molten condition enters in micro-mixer, and the furans chloride compounds are defeated through acyl chlorides with the flow velocity of 30~100ml/min
Pump is sent to enter in micro-mixer；
Aminated compounds is dissolved in the solution that amine is formed in organic solvent, and -30~0 DEG C of amine aqueous solution passes through aromatic diamines delivery pump
Accurate measurement enters in micro-mixer, and amine aqueous solution is entered with the flow velocity of 150~300ml/min through aromatic diamines delivery pump micro-
In mixer；And/or
The organic solvent be selected from N,N-dimethylformamide, tetrahydrofuran, chlorobenzene, N-Methyl pyrrolidone, methylisobutylketone,
One or more of methyl isopropyl ketone, DMAC N,N' dimethyl acetamide and dimethyl sulfoxide.
8. according to the method described in claim 6, it is characterized in that, in step 3, alkaline matter is added in polymerization process
As acid binding agent, the acid binding agent is preferably selected from lithium hydroxide, calcium hydroxide, methylamine, dimethylamine, diisopropylamine, di-n-propylamine, three
One or more of ethamine, trimethylamine, tripropyl amine (TPA), isobutyl amine, tert-butylamine, N-methylmorpholine, piperidines and tetramethylethylenediamine.
9. the method according to any one of claim 6 to 8, which is characterized in that in step 4, the post-processing includes
Spray drying, the half biomass-based furans polyamide that preceding polymerization is obtained obtain solid, powdery tree by spray drying device
Then rouge washs away salinity contained in resin using hot water wash, obtains the biomass-based furans polyamide of pure half after dry
Resin.
10. the method according to any one of claim 6 to 8, which is characterized in that half biomass-based furans polyamides obtained
The molecular weight of polyimide resin is greater than 300,000, and polydispersity index is less than 1.6.
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