CN105524278B - A kind of method that solution polycondensation reaction prepares the controllable linear polymeric of molecular weight - Google Patents
A kind of method that solution polycondensation reaction prepares the controllable linear polymeric of molecular weight Download PDFInfo
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Abstract
The foundation of mathematical relationship and five steps of control of molecular weight of product between a kind of method that solution polycondensation reaction prepares the controllable linear polymeric of molecular weight, including the control of configuration, reaction of reaction solution, the calculating of molecular weight of product, reaction terminating electric current and molecular weight of product.Compared with prior art, the method that the present invention uses can judge the viscosity of solution polymerization system, and then control effectively to the molecular weight of polymer in preparation process by the size of electric mixing device output current.This method has universality to solution polymerization, is suitable for all kinds of polybenzimidazoles, polyketone, the preparation of the polymer such as polysulfones, polyethers and polyamide.The present invention has the molecular weight precise control to standby linear polymeric of drawing up, the method of the invention need to only increase and the concatenated current measurement of electric mixing device and display device (such as ammeter) outside reaction unit simultaneously, reaction unit is simple, easy to operate.It is significant to linear polymeric molecular weight controllable preparation.
Description
Technical field
The present invention relates to macromolecule material preparation areas, more particularly to a kind of linear polymeric that molecular weight is controllable
Preparation method；The invention further relates to the devices that the controllable linear polymeric of molecular weight is prepared using the above method.
Background technology
Solution polycondensation is the method that monomer carries out polycondensation reaction in atent solvent.It can make insoluble or labile
Monomer carries out polycondensation, obtains heat-resisting aromatic heterocycle polymer, such as polyimides, polysulfones, Nomex, polyarylate.
The characteristics of solution polycondensation method is：Polycondensation reaction is carried out in a solvent, and reaction system is uniform, and viscosity is small, will not picture
Melt polycondensation is such, occurs stirring extremely difficult situation since the degree of polymerization increases.It, can be in addition, solvent absorption reaction heat
It makes up since concentration becomes smaller after addition solvent, this slack-off shortcoming of reaction rate is advantageous to the control of reaction.However, molten
Liquid polycondensation reaction is a kind of reversible process, and the control of wherein polymer molecular weight is particularly important.
Polybenzimidazoles (PBI) is a kind of heat safe alkaline polymer.PBI can pass through acid doping (HClO4、H2SO4、
HBr、HNO3And H3PO4Deng) method improve film conductivity, the electrolyte as fuel cell.High molecular weight PBI's
It prepares and mainly uses solution polycondensation.The factor for influencing molecular weight of product includes reaction temperature and the time, (polymerization of monomer solid content
Monomer mass percent shared in polymer solvent and polymerized monomer total amount), stir speed (S.S.) and monomer purity etc..Point of PBI
Son amount is different, and performance and purposes are also different.Up to the present, there is not yet crossing about polycondensation process molecular weight controllable method side
It satisfactorily reports in face.Therefore, different batches PBI products can not ensure with stable molecular weight.
Solution polycondensation prepares PBI often using polyphosphoric acids as solvent, and in early days, monomer disappears quickly for reaction, be transformed into two,
Three, the oligomer such as tetramer are then the polycondensation between oligomer later, molecular weight are made to gradually increase.The extension reaction time is conducive to
Improve molecular weight.However, polycondensation reaction is again simultaneously a reversible process, the PBI of high molecular weight has group elimination reaction (such as two
De- contracting reaction can occur for first carboxylic acid), chemical degradation (partial hydrolysis) and Exchange reaction of chain.Therefore, it is difficult to by the reaction time come
Judge the extent of reaction.The imidazole group of PBI forms a large amount of hydrogen bonds with polyphosphoric acids in polycondensation process, increases the viscosity of system.
Molecular weight is higher, and the effect of strand and solvent is bigger, and system viscosity is higher.Under identical monomer concentration and system temperature,
It is higher to reach the identical required output power of stir speed (S.S.).Therefore, contracting can be monitored by monitoring the output current of motor
The poly- extent of reaction.
Invention content
The present invention in view of the deficiencies of the prior art, has invented and a kind of having prepared the controllable line of molecular weight using solution polycondensation reaction
The high molecular method and apparatus of property.A kind of method that solution polycondensation reaction prepares the controllable linear polymeric of molecular weight, including with
Lower step,
1) configuration of reaction solution：In equipped with the agitating paddle being connected with electric mixing device, thermometer and protective gas
Reaction vessel in be added wait for reactive material and reaction dissolvent, obtain reaction solution；Agitating device by conducting wire through current measurement and
Display unit is connected with DC power supply；Reaction solution is stirred by agitating paddle；
2) control reacted：Ascending step 1) gained reaction solution temperature, the current value of monitor current table, stirring fill
Set at the uniform velocity stirring under, when the temperature of reaction solution rises to required reaction temperature, with the carry out electric current meter reading of reaction start by
Gradually rise, the current value of monitor current table, reaction is terminated when electric current meter reading rises to a certain current value, removal reaction is molten
Agent obtains reaction product；
3) above-mentioned operating process 2 times or more is repeated, from step 2) the difference is that the current value for terminating reaction is different；
Obtain 3 or more the different current values and their corresponding reaction products for terminating reaction；
4) inherent viscosity of reaction product obtained by step 3) is measured using Ubbelohde viscometer；It is quasi- using mathematics three
Conjunction mode establishes the relationship between reaction terminating electric current and product property viscosity；
5) control of solution polycondensation resultants in reaction process molecular weight：The spy of required product is determined according to required product molecular weight
Property viscosity, according to relationship obtained by step 4), calculate needed for the termination electric current that reacts, repeat the operation of step 2)
Journey, the current value of monitor current table obtain required reaction product until terminating reaction when required termination electric current.
The control of the step 2) reaction and step 3)：May include following 3 processes：
a：The temperature of raising reaction solution, the current value of monitor current table, in the case where agitating device at the uniform velocity stirs, reaction solution
Temperature when rising to required reaction temperature, the initial current value of ammeter is A；With the carry out electric current meter reading of reaction start by
Gradually rise, when electric current meter reading is constant or occurs declining phenomenon, reaction terminates, and the current value of ammeter is B at this time；
b：Using reaction solution, identical mixing speed and the identical reaction temperature with step a same compositions, monitoring electricity
The current value of flow table react until being terminated when a certain current value between A and B, and removal reaction dissolvent obtains reaction product；
c：The operating process 2 times or more for repeating step b, from step b the difference is that the current value for terminating reaction is different；
Obtain 3 or more current values between A and B and their corresponding reaction products.
Mathematical Fitting formula by Origin softwares to step 2) reaction product inherent viscosity and terminate electric current
Fitting of a polynomial is carried out, the exponent number of fitting is 3.
The polycondensation product is polybenzimidazoles, polyimides, polyether sulphone, poly(aryl ether ketone), polyphenylene oxide, polyphenylene sulfide
One kind in ether；
The corresponding reactant of polybenzimidazoles be quaternary amine (four amine hydrochlorates) and binary acid (derivative of binary acid), or
Person is 3,4- diaminobenzoic acids, and corresponding solvent is polyphosphoric acids；
The corresponding reactant of polyimides be dianhydride (tetrabasic carboxylic acid) and diamine, corresponding solvent be dimethylacetylamide,
The intensive polar solvents such as dimethylformamide, dimethyl sulfoxide (DMSO)；
The corresponding reactant of polyarylsulfone (PAS) includes aromatic dicarboxylic phenol and 4, and 4 '-dichloro diphenyl sulfones, corresponding solvent is diformazan
The intensive polar solvents such as yl acetamide, dimethylformamide, dimethyl sulfoxide (DMSO), sulfolane；
The corresponding reactant of poly(aryl ether ketone) includes aromatic dicarboxylic phenol and difluoro benzophenone, and corresponding solvent is dimethyl
The intensive polar solvents such as acetamide, dimethylformamide, dimethyl sulfoxide (DMSO), sulfolane；
The corresponding reactant of polyphenylene oxide is 2,6- xylenols, and corresponding solvent is benzene；
The corresponding reactant of polyphenylene sulfide is diphenyl ether and sulfur dichloride (disulphur dichloride), corresponds to chloroform；
Mass fraction in reaction solution shared by reactant is that 3-30% is differed.
The reaction vessel equipped with agitating device includes reaction vessel main body, and temperature measures and display unit, electronic
Stirring rod, current measurement and display unit；
Driven stirring rod is connected with DC power supply again after being connected in series with current measurement and display unit；
Temperature measures and display unit is used to measure and show that the temperature of reaction system in reaction vessel main body, stirring rod to be used
In to the reaction system progress mechanical agitation in reaction vessel main body.
Temperature measures and display unit is thermometer, and current measurement and display unit are ammeter.
The reaction vessel main body is equipped with gas feed and outlet.Compared with prior art, the method that the present invention uses
It can judge the viscosity of solution polymerization system, and then to poly- in preparation process by the size of electric mixing device output current
The molecular weight for closing object control effectively.This method has universality to solution polymerization.It therefrom can be determined that, the present invention
The polycondensation reaction that the method for use is suitable for includes：All kinds of polybenzimidazoles, polyketone, polysulfones, polyethers and polyamide etc..The present invention
With the molecular weight precise control to standby linear polymeric of drawing up, accuracy is up to 90% or more advantage, while the present invention
The method need to only increase and the concatenated current measurement of electric mixing device and display device (such as ammeter) outside reaction unit
, reaction unit is simple, easily operated.It is significant to linear polymeric molecular weight controllable preparation.
Description of the drawings
A kind of schematic devices preparing the controllable linear polymeric of molecular weight using solution polycondensation reaction of Fig. 1.In figure, 1
For ammeter；2 be motor；3 be governor；4 be heating device.
The corresponding multiphase formula matched curve for terminating electric current and inherent viscosity of Fig. 2 Examples 1 to 4.
Specific implementation mode
Embodiment 1：
Weigh 500.0g polyphosphoric acids, 29.9g P2O5(0.211mol) and 33.8g 3,3`- diaminobenzidines
(0.158mol), sequentially adds 500mL, in the four-hole bottle equipped with nitrogen inlet, mechanical agitation, condensing reflux pipe and thermometer,
It is gradually heating to 210 DEG C using electric heating cover.210 DEG C of temperature is controlled, 26.2g isophthalic two is added in 390-410 revs/min of rotating speed
Formic acid (0.158mol).It is maintained in the case that 210 DEG C or so rotating speeds maintain 400rap/min in temperature, when electric current reaches
When 2.50A, 15mL deionized waters are rapidly added into solution, and rapidly pour into solution in deionized water.After left undisturbed overnight, take
Go out drying, crush, deionized water is used in combination to elute repeatedly, until solution becomes neutral.Solid is dried, that is, is obtained powdered
mPBI.It is 0.82dL/g using the inherent viscosity that Ubbelohde viscometer measures, the molecular weight being calculated is viscosity-average molecular weight
38307。
Embodiment 2：
Weigh 500.0g polyphosphoric acids, 29.9g P2O5(0.211mol) and 33.8g 3,3`- diaminobenzidines
(0.158mol), sequentially adds 500mL, in the four-hole bottle equipped with nitrogen inlet, mechanical agitation, condensing reflux pipe and thermometer,
It is gradually heating to 210 DEG C using electric heating cover.210 DEG C of temperature is controlled, 26.2g isophthalic two is added in 390-410 revs/min of rotating speed
Formic acid (0.158mol).It is maintained in the case that 210 DEG C or so rotating speeds maintain 400rap/min in temperature, when electric current reaches
When 2.66A, 15mL deionized waters are rapidly added into solution, and rapidly pour into solution in deionized water.After left undisturbed overnight, take
Go out drying, crush, deionized water is used in combination to elute repeatedly, until solution becomes neutral.Solid is dried, that is, is obtained powdered
mPBI.It is 0.90dL/g using the inherent viscosity that Ubbelohde viscometer measures, the viscosity-average molecular weight being calculated is 41352.
Embodiment 3：
Weigh 500.0g polyphosphoric acids, 29.9g P2O5(0.211mol) and 33.8g 3,3`- diaminobenzidines
(0.158mol), sequentially adds 500mL, in the four-hole bottle equipped with nitrogen inlet, mechanical agitation, condensing reflux pipe and thermometer,
It is gradually heating to 210 DEG C using electric heating cover.210 DEG C of temperature is controlled, 26.2g isophthalic two is added in 390-410 revs/min of rotating speed
Formic acid (0.158mol).It is maintained in the case that 210 DEG C or so rotating speeds maintain 400rap/min in temperature, when electric current reaches
When 3.01A, 15mL deionized waters are rapidly added into solution, and rapidly pour into solution in deionized water.After left undisturbed overnight, take
Go out drying, crush, deionized water is used in combination to elute repeatedly, until solution becomes neutral.Solid is dried, that is, is obtained powdered
mPBI.It is 1.04dL/g using the inherent viscosity that Ubbelohde viscometer measures, the viscosity-average molecular weight being calculated is 43163.
Embodiment 4：
Weigh 500.0g polyphosphoric acids, 29.9g P2O5(0.211mol) and 33.8g 3,3`- diaminobenzidines
(0.158mol), sequentially adds 500mL, in the four-hole bottle equipped with nitrogen inlet, mechanical agitation, condensing reflux pipe and thermometer,
It is gradually heating to 210 DEG C using electric heating cover.210 DEG C of temperature is controlled, 26.2g isophthalic two is added in 390-410 revs/min of rotating speed
Formic acid (0.158mol).It is maintained in the case that 210 DEG C or so rotating speeds maintain 400rap/min in temperature, when electric current reaches
When 3.35A, 15mL deionized waters are rapidly added into solution, and rapidly pour into solution in deionized water.After left undisturbed overnight, take
Go out drying, crush, deionized water is used in combination to elute repeatedly, until solution becomes neutral.Solid is dried, that is, is obtained powdered
mPBI.It is 1.12dL/g using the inherent viscosity that Ubbelohde viscometer measures, the molecular weight being calculated is 51820.
Embodiment 5：
Weigh 500.0g polyphosphoric acids, 29.9g P2O5(0.211mol) and 33.8g 3,3`- diaminobenzidines
(0.158mol), sequentially adds 500mL, in the four-hole bottle equipped with nitrogen inlet, mechanical agitation, condensing reflux pipe and thermometer,
It is gradually heating to 210 DEG C using electric heating cover.210 DEG C of temperature is controlled, 26.2g isophthalic two is added in 390-410 revs/min of rotating speed
Formic acid (0.158mol).It is maintained in the case that 210 DEG C or so rotating speeds maintain 400 revs/min in temperature, when electric current reaches
When close to 3.55A, electric current meter reading starts shakiness.This is because system viscosity is excessive, solution is presented under the promotion of agitating paddle
Mass motion trend.The viscosity of the reading no longer reaction system of ammeter at this time.Mixed solution is poured into deionized water rapidly.
It after left undisturbed overnight, takes out drying, crush, deionized water is used in combination to elute repeatedly, until solution becomes neutral.Solid is dried, i.e.,
Obtain powdered mPBI.It is 1.34dL/g using the inherent viscosity that Ubbelohde viscometer measures, the molecular weight being calculated is
71392。
MPBI under the monitoring of 1 same current table of table synthesizes situation
Embodiment 5 is excluded, termination electric current corresponding to Examples 1 to 4 and inherent viscosity carry out multiphase formula fitting, three times phase
The curve of formula fitting is as shown in Fig. 2.Fitting formula is：
Y=-0.73014+0.3994*X+0.21363*X2-0.05015*X3。
Embodiment 6
Weigh 500.0g polyphosphoric acids, 29.9g P2O5(0.211mol) and 33.8g 3,3`- diaminobenzidines
(0.158mol), sequentially adds 500mL, in the four-hole bottle equipped with nitrogen inlet, mechanical agitation, condensing reflux pipe and thermometer,
It is gradually heating to 210 DEG C using electric heating cover.210 DEG C of temperature is controlled, 26.2g isophthalic two is added in 390-410 revs/min of rotating speed
Formic acid (0.158mol).It is maintained in the case that 210 DEG C or so rotating speeds maintain 400rap/min in temperature, when electric current reaches
When 2.60A, 15mL deionized waters are rapidly added into solution, and rapidly pour into solution in deionized water.After left undisturbed overnight, take
Go out drying, crush, deionized water is used in combination to elute repeatedly, until solution becomes neutral.Solid is dried, that is, is obtained powdered
mPBI.It is 0.87dL/g using the inherent viscosity that Ubbelohde viscometer measures, the viscosity-average molecular weight being calculated is 41352.
Termination electric current 2.60 in embodiment 6 is brought into fitting formula, the inherent viscosity of gained is 0.872, with reality
Result is tested to match.The result shows that：In certain current range, using the ammeter monitoring method of this patent to control polymer point
Son amount is effective.
Claims (5)
1. a kind of method that solution polycondensation reaction prepares the controllable linear polymeric of molecular weight, it is characterised in that：Including following step
Suddenly, the 1) configuration of reaction solution：In equipped with the agitating paddle being connected with electric mixing device, temperature measurement and display unit and guarantor
It protects to be added in the reaction vessel of gas and waits for reactive material and reaction dissolvent, obtain reaction solution；Agitating device is by conducting wire through electric current
It measures and display unit is connected with DC power supply；Reaction solution is stirred by agitating paddle；2) control reacted：It increases
The temperature of reaction solution obtained by step 1), the current value of monitor current table, in the case where agitating device at the uniform velocity stirs, the temperature of reaction solution
When degree rises to required reaction temperature, start to be gradually increasing with the carry out electric current meter reading of reaction, the current value of monitor current table,
Reaction is terminated when electric current meter reading rises to a certain current value, is removed reaction dissolvent, is obtained reaction product；3) above-mentioned behaviour is repeated
Make process 2 times or more, from step 2) the difference is that the current value for terminating reaction is different；Obtain terminate reaction 3 or more
Different current values and their corresponding reaction products；4) viscous using Ubbelohde to the inherent viscosity of reaction product obtained by step 3)
Degree meter is measured；The mathematical relationship between reaction terminating electric current and product property viscosity is established using three fit approach of mathematics
Formula；5) control of solution polycondensation resultants in reaction process molecular weight：Determine that the characteristic of required product is viscous according to required product molecular weight
Degree calculates the required termination electric current reacted according to relationship obtained by step 4), repeats the operating process of step 2), prison
The current value of ammeter is controlled, until terminating reaction when required termination electric current, obtains required reaction product；The polycondensation product is
One kind in polybenzimidazoles, polyimides, polyether sulphone, poly(aryl ether ketone), polyphenylene oxide, polyphenylene sulfide；Polybenzimidazoles corresponds to
Reactant be A and B or 3,4- diaminobenzoic acids, A be quaternary amine or four amine hydrochlorates, B be binary acid or binary acid
Derivative；Corresponding solvent is polyphosphoric acids；The corresponding reactant of polyimides is dianhydride and diamine or tetrabasic carboxylic acid
With diamine, corresponding solvent is one kind in dimethylacetylamide, dimethylformamide, dimethyl sulfoxide (DMSO)；Polyarylsulfone (PAS) corresponds to
Reactant include aromatic dicarboxylic phenol and 4,4 '-dichloro diphenyl sulfones, corresponding solvent is dimethylacetylamide, dimethyl methyl
One kind in amide, dimethyl sulfoxide (DMSO), sulfolane；The corresponding reactant of poly(aryl ether ketone) includes aromatic dicarboxylic phenol and difluorodiphenyl
Ketone, corresponding solvent are one kind in dimethylacetylamide, dimethylformamide, dimethyl sulfoxide (DMSO), sulfolane；Polyphenylene oxide pair
The reactant answered is 2,6- xylenols, and corresponding solvent is benzene；The corresponding reactant of polyphenylene sulfide is diphenyl ether and dichloro
Change sulphur or diphenyl ether and disulphur dichloride, corresponding solvent is chloroform.
2. according to the method for claim 1, it is characterised in that：Mathematical Fitting formula passes through anti-all to step 2) of software
It answers the inherent viscosity of product and terminates electric current and carry out fitting of a polynomial.
3. according to the method for claim 1, it is characterised in that：The reaction vessel equipped with agitating device includes reaction
Container body, temperature measures and display unit, driven stirring rod, current measurement and display unit；Driven stirring rod is connected in series with
It is connected again with DC power supply after current measurement and display unit；Temperature measures and display unit is for measuring and showing that reaction is held
The temperature of reaction system in device main body, stirring rod are used to carry out mechanical agitation to the reaction system in reaction vessel main body.
4. according to the method for claim 3, it is characterised in that：Temperature measures and display unit is thermometer, current measurement
And display unit is ammeter.
5. according to the method for claim 3, it is characterised in that：The reaction vessel main body is equipped with gas feed and goes out
Mouthful.
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| CN106220853B (en) * | 2016-09-12 | 2018-09-28 | 李涛 | A kind of polysulfone resin industrialized producing technology |
| KR102173641B1 (en) * | 2017-11-24 | 2020-11-03 | 주식회사 엘지화학 | Process for preparing polyarylene sulfide |
| CN109554059A (en) * | 2018-11-28 | 2019-04-02 | 韶关市合众化工有限公司 | A kind of polyarylsulfone (PAS) modified acroleic acid aqueous industrial coating |
| CN114752056B (en) * | 2022-03-02 | 2024-01-26 | 双驱智能科技(宁波)有限公司 | Device and method for repeatedly and stably producing polyaryletherketone with narrow molecular weight distribution |
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| CN102199247A (en) * | 2010-03-26 | 2011-09-28 | 中国石油化工股份有限公司 | Method for preparing polyacrylonitrile spinning solution |
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| CN1415685A (en) * | 2001-10-30 | 2003-05-07 | 中国石油化工股份有限公司 | Method for controlling the melt index of polyamide hot-melt adhesive |
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Effective date of registration: 20211129 Address after: 116023 No. 457, Zhongshan Road, Liaoning, Dalian Patentee after: DALIAN INSTITUTE OF CHEMICAL PHYSICS, CHINESE ACADEMY OF SCIENCES Patentee after: Sun Gongquan Patentee after: Wang Suli Address before: 116023 No. 457, Zhongshan Road, Liaoning, Dalian Patentee before: DALIAN INSTITUTE OF CHEMICAL PHYSICS, CHINESE ACADEMY OF SCIENCES |
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Effective date of registration: 20211213 Address after: 116023 No. 457, Zhongshan Road, Liaoning, Dalian Patentee after: DALIAN INSTITUTE OF CHEMICAL PHYSICS, CHINESE ACADEMY OF SCIENCES Patentee after: Zhongke Jiayuan (Foshan) new energy partnership (limited partnership) Address before: 116023 No. 457, Zhongshan Road, Liaoning, Dalian Patentee before: DALIAN INSTITUTE OF CHEMICAL PHYSICS, CHINESE ACADEMY OF SCIENCES Patentee before: Sun Gongquan Patentee before: Wang Suli |
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Effective date of registration: 20211223 Address after: 528216 room 1, building D3, No. 1, Xiangda Road, Danzao logistics center, Danzao Town, Nanhai District, Foshan City, Guangdong Province Patentee after: Zhongke Jiahong (Foshan) New Energy Technology Co.,Ltd. Address before: 116023 No. 457, Zhongshan Road, Liaoning, Dalian Patentee before: DALIAN INSTITUTE OF CHEMICAL PHYSICS, CHINESE ACADEMY OF SCIENCES Patentee before: Zhongke Jiayuan (Foshan) new energy partnership (limited partnership) |