CN105524278A - Method for preparing linear macromolecules with controllable molecular weight by solution polycondensation reaction - Google Patents
Method for preparing linear macromolecules with controllable molecular weight by solution polycondensation reaction Download PDFInfo
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Abstract
The invention relates to a method for preparing linear macromolecules with controllable molecular weight by a solution polycondensation reaction. The method comprises five steps, i.e., preparing a reaction solution, controlling the reaction, computing product molecular weight, establishing a mathematical relation between reaction terminating current and the product molecular weight, and controlling the product molecular weight. Compared with the prior art, the method disclosed by the invention has the advantages that the viscosity of a solution polymerization system can be determined through the size of electric stirring device output current, and then, the molecular weight of a polymer is effectively controlled in a preparation process. The method has universality to solution polymerization reactions and is applicable to the preparation of various kinds of polymers such as polybenzimidazole, polyketone, polysulfone, polyether and polyamide. According to the method, the control on the molecular weight of the linear macromolecules to be prepared is accurate, and meanwhile, only a current measuring and displaying device (e.g., an ammeter) in series connection with an electric stirring device is additionally arranged outside a reaction device, so that the reaction device is simple, and the operation is easy. The method is of great significance for the preparation of the linear macromolecules with controllable molecular weight.
Description
Technical field
The present invention relates to macromolecule material preparation area, relate to the preparation method of the controlled linear polymeric of a kind of molecular weight specifically; The invention still further relates to the device adopting aforesaid method to prepare the controlled linear polymeric of molecular weight.
Background technology
Solution polycondensation is the method that monomer carries out polycondensation in inert solvent.It can make that do not melt or labile monomer carry out polycondensation, obtains heat-resisting aromatic heterocycle polymer, as polyimide, polysulfones, polyaramide, polyarylester etc.
The feature of solution polycondensation method is: carry out polycondensation in a solvent, and reaction system is even, and viscosity is little, as melt phase polycondensation, can not occur the situation stirring very difficulty because the polymerization degree increases.In addition, solvent absorbing reaction heat, can make up because after interpolation solvent, concentration diminishes, speed of reaction this weak point slack-off, favourable to the control of reaction.But solution polycondensation reaction is a kind of reversible process, and wherein the control of polymericular weight is very important.
Polybenzimidazole (PBI) is the resistant to elevated temperatures alkaline polymer of a class.PBI can pass through acid doping (HClO
4, H
2sO
4, HBr, HNO
3, and H
3pO
4deng) method improve the specific conductivity of film, as the electrolyte of fuel cell.The preparation of high molecular PBI mainly adopts solution polycondensation.The factor affecting molecular weight of product comprises temperature of reaction and time, monomer solid content (mass percent that polymerization single polymerization monomer is shared in polymer solvent and polymerization single polymerization monomer total amount), stir speed (S.S.) and monomer purity etc.The molecular weight of PBI is different, and character and utilization is also different.Up to the present, there is not yet gratifying report in polycondensation process molecular weight controllable method.Therefore, different batches PBI product cannot ensure to have stable molecular weight.
Solution polycondensation prepares PBI often using polyphosphoric acid as solvent, and reaction is early stage, and monomer disappears very soon, be transformed into two, three, the oligopolymer such as the tetramer, be then the polycondensation between oligopolymer later, molecular weight increased gradually.The prolongation reaction times is conducive to improving molecular weight.But polycondensation is again a reversing process simultaneously, the PBI of high molecular has group elimination reaction (as de-contracting reaction can occur di-carboxylic acid), chemical degradation (partial hydrolysis) and Exchange reaction of chain.Therefore, be difficult to judge level of response by the reaction times.In polycondensation process, the imidazole group of PBI and polyphosphoric acid form a large amount of hydrogen bond, add the viscosity of system.Molecular weight is higher, and the effect of molecular chain and solvent is larger, and system viscosity is higher.Under identical monomer concentration and system temperature, the output rating reached required for identical stir speed (S.S.) is higher.Therefore, the outward current by monitoring electric motor can monitor the level of response of polycondensation.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, invented a kind of solution polycondensation that adopts and reacted the method and apparatus preparing the controlled linear polymeric of molecular weight.A method for the controlled linear polymeric of molecular weight is prepared in solution polycondensation reaction, comprises the following steps,
1) configuration of reaction soln: in being equipped with the stirring rake be connected with electric mixing device, adding question response material and reaction solvent in the reaction vessel of thermometer and shielding gas, obtaining reaction soln; Whipping appts is connected with direct supply through current measurement and display unit by wire; By stirring rake, reaction soln is stirred;
2) control of reacting: ascending step 1) temperature of gained reaction soln, the current value of monitor current table, under whipping appts at the uniform velocity stirs, when the temperature of reaction soln rises to desired reaction temperature, along with the reometer reading that carries out of reaction starts to rise gradually, the current value of monitor current table, the termination reaction when reometer reading rises to a certain current value, remove reaction solvent, obtain reaction product;
3) above-mentioned operating process more than 2 times is repeated, from step 2) difference is that the current value of termination reaction is different; Obtain more than 3 different current values of termination reaction, and the reaction product of their correspondences;
4) to step 3) limiting viscosity of gained reaction product utilizes Ubbelohde viscometer to measure; Mathematics three fit approach are utilized to set up relationship between reaction terminating electric current and product property viscosity;
5) control of solution polycondensation resultants in reaction process molecular weight: the limiting viscosity determining required product according to required molecular weight of product, according to step 4) gained relationship, calculate the termination electric current of required reaction, repeating step 2) operating process, the current value of monitor current table, until termination reaction during required termination electric current, obtain required reaction product.
Described step 2) control of reacting and step 3): 3 following processes can be comprised:
A: the temperature raising reaction soln, the current value of monitor current table, under whipping appts at the uniform velocity stirs, when the temperature of reaction soln rises to desired reaction temperature, the initial current value of reometer is A; Along with the reometer reading that carries out of reaction starts to rise gradually, when reometer reading is constant or occur decline phenomenon, reaction terminates, and now the current value of reometer is B;
B: adopt and the reaction soln of step a same composition, identical stirring velocity and identical temperature of reaction, the current value of monitor current table, until termination reaction during a certain current value between A and B, removal reaction solvent, obtains reaction product;
From step b difference, the operating process of c: repeating step b more than 2 times, is that the current value of termination reaction is different; Obtain more than 3 current values between A and B, and the reaction product of their correspondences.
Mathematical Fitting formula by Origin software to step 2) reaction product limiting viscosity and stop electric current carry out polynomial fitting, the exponent number of matching is 3.
Described polycondensation product is the one in polybenzimidazole, polyimide, polyether sulphone, polyaryletherketone, polyphenylene oxide, polyphenylene sulfide;
The reactant that polybenzimidazole is corresponding is quaternary amine (four amine hydrochlorates) and diprotic acid (derivative of diprotic acid), or 3,4-diaminobenzoic acid, and corresponding solvent is polyphosphoric acid;
The reactant that polyimide is corresponding is dianhydride (tetracarboxylic acid) and diamine, and corresponding solvent is the intensive polar solvents such as N,N-DIMETHYLACETAMIDE, dimethyl formamide, dimethyl sulfoxide (DMSO);
The reactant that polyarylsulphone is corresponding comprises aromatic dicarboxylic phenol and 4,4 '-dichloro diphenyl sulfone, and corresponding solvent is the intensive polar solvents such as N,N-DIMETHYLACETAMIDE, dimethyl formamide, dimethyl sulfoxide (DMSO), tetramethylene sulfone;
The reactant that polyaryletherketone is corresponding comprises aromatic dicarboxylic phenol and difluoro benzophenone, and corresponding solvent is the intensive polar solvents such as N,N-DIMETHYLACETAMIDE, dimethyl formamide, dimethyl sulfoxide (DMSO), tetramethylene sulfone;
The reactant that polyphenylene oxide is corresponding is 2,6-xylenol, and corresponding solvent is benzene;
The reactant that polyphenylene sulfide is corresponding is phenyl ether and sulfur dichloride (disulphur dichloride), corresponds to chloroform;
Massfraction in reaction soln shared by reactant be 3-30% not etc.
The described reaction vessel of whipping appts that is equipped with comprises reaction vessel main body, temperature survey and display unit, driven stirring rod, current measurement and display unit;
Driven stirring rod is connected with direct supply after being connected in series current measurement and display unit again;
Temperature survey and display unit are for measuring and show the temperature of reaction system in reaction vessel main body, and stirring rod is used for carrying out mechanical stirring to the reaction system in reaction vessel main body.
Temperature survey and display unit are thermometer, and current measurement and display unit are reometer.
Described reaction vessel main body is provided with gas feed and outlet.Compared with prior art, the method that the present invention adopts, by the size of electric mixing device outward current, judges the viscosity of solution polymerization system, and then control effectively to the molecular weight of polymkeric substance in preparation process.This method has universality to solution polymerization.Therefrom can judge, the polycondensation that the method that the present invention adopts is applicable to comprises: all kinds of polybenzimidazole, polyketone, polysulfones, polyethers and polymeric amide etc.It is accurate that the present invention has the molecular weight control of standby linear polymeric of drawing up, accuracy up to more than 90% advantage, the method of the invention only need increase the current measurement and display unit (as reometer) of connecting with electric mixing device outside reaction unit simultaneously, reaction unit is simple, easy handling.Significant to linear polymeric molecular weight controlled synthesis.
Accompanying drawing explanation
A kind of solution polycondensation that adopts of Fig. 1 reacts the device schematic diagram preparing the controlled linear polymeric of molecular weight.In figure, 1 is reometer; 2 is electric motor; 3 is speed regulator; 4 is heating unit.
The termination electric current of Fig. 2 embodiment 1 ~ 4 correspondence and the heterogeneous formula matched curve of limiting viscosity.
Embodiment
Embodiment 1:
Take 500.0g polyphosphoric acid, 29.9gP
2o
5(0.211mol) and 33.8g3,3`-diaminobenzidine (0.158mol), add 500mL successively, be equipped with in the four-hole bottle of nitrogen inlet, mechanical stirring, condensing reflux pipe and thermometer, adopt electric heating cover to be warming up to 210 DEG C gradually.Control temperature 210 DEG C, rotating speed 390-410 rev/min, adds 26.2g m-phthalic acid (0.158mol).Remain on about 210 DEG C, when rotating speed maintains 400rap/min in temperature, when electric current reaches 2.50A, in solution, add rapidly 15mL deionized water, and rapidly solution is poured in deionized water.After left undisturbed overnight, take out oven dry, pulverize, and with deionized water drip washing repeatedly, until solution becomes neutrality.Solid is dried, namely obtains Powdered mPBI.The limiting viscosity utilizing Ubbelohde viscometer to record is 0.82dL/g, and the molecular weight calculated is viscosity-average molecular weight 38307.
Embodiment 2:
Take 500.0g polyphosphoric acid, 29.9gP
2o
5(0.211mol) and 33.8g3,3`-diaminobenzidine (0.158mol), add 500mL successively, be equipped with in the four-hole bottle of nitrogen inlet, mechanical stirring, condensing reflux pipe and thermometer, adopt electric heating cover to be warming up to 210 DEG C gradually.Control temperature 210 DEG C, rotating speed 390-410 rev/min, adds 26.2g m-phthalic acid (0.158mol).Remain on about 210 DEG C, when rotating speed maintains 400rap/min in temperature, when electric current reaches 2.66A, in solution, add rapidly 15mL deionized water, and rapidly solution is poured in deionized water.After left undisturbed overnight, take out oven dry, pulverize, and with deionized water drip washing repeatedly, until solution becomes neutrality.Solid is dried, namely obtains Powdered mPBI.The limiting viscosity utilizing Ubbelohde viscometer to record is 0.90dL/g, and the viscosity-average molecular weight calculated is 41352.
Embodiment 3:
Take 500.0g polyphosphoric acid, 29.9gP
2o
5(0.211mol) and 33.8g3,3`-diaminobenzidine (0.158mol), add 500mL successively, be equipped with in the four-hole bottle of nitrogen inlet, mechanical stirring, condensing reflux pipe and thermometer, adopt electric heating cover to be warming up to 210 DEG C gradually.Control temperature 210 DEG C, rotating speed 390-410 rev/min, adds 26.2g m-phthalic acid (0.158mol).Remain on about 210 DEG C, when rotating speed maintains 400rap/min in temperature, when electric current reaches 3.01A, in solution, add rapidly 15mL deionized water, and rapidly solution is poured in deionized water.After left undisturbed overnight, take out oven dry, pulverize, and with deionized water drip washing repeatedly, until solution becomes neutrality.Solid is dried, namely obtains Powdered mPBI.The limiting viscosity utilizing Ubbelohde viscometer to record is 1.04dL/g, and the viscosity-average molecular weight calculated is 43163.
Embodiment 4:
Take 500.0g polyphosphoric acid, 29.9gP
2o
5(0.211mol) and 33.8g3,3`-diaminobenzidine (0.158mol), add 500mL successively, be equipped with in the four-hole bottle of nitrogen inlet, mechanical stirring, condensing reflux pipe and thermometer, adopt electric heating cover to be warming up to 210 DEG C gradually.Control temperature 210 DEG C, rotating speed 390-410 rev/min, adds 26.2g m-phthalic acid (0.158mol).Remain on about 210 DEG C, when rotating speed maintains 400rap/min in temperature, when electric current reaches 3.35A, in solution, add rapidly 15mL deionized water, and rapidly solution is poured in deionized water.After left undisturbed overnight, take out oven dry, pulverize, and with deionized water drip washing repeatedly, until solution becomes neutrality.Solid is dried, namely obtains Powdered mPBI.The limiting viscosity utilizing Ubbelohde viscometer to record is 1.12dL/g, and the molecular weight calculated is 51820.
Embodiment 5:
Take 500.0g polyphosphoric acid, 29.9gP
2o
5(0.211mol) and 33.8g3,3`-diaminobenzidine (0.158mol), add 500mL successively, be equipped with in the four-hole bottle of nitrogen inlet, mechanical stirring, condensing reflux pipe and thermometer, adopt electric heating cover to be warming up to 210 DEG C gradually.Control temperature 210 DEG C, rotating speed 390-410 rev/min, adds 26.2g m-phthalic acid (0.158mol).Remain on about 210 DEG C in temperature, when rotating speed maintains 400 revs/min, when electric current reaches close to 3.55A, reometer reading starts shakiness.This is because system viscosity is excessive, and solution presents mass motion trend under the promotion of stirring rake.The now viscosity of the reading of reometer no longer reaction system.Mixing solutions is poured into rapidly in deionized water.After left undisturbed overnight, take out oven dry, pulverize, and with deionized water drip washing repeatedly, until solution becomes neutrality.Solid is dried, namely obtains Powdered mPBI.The limiting viscosity utilizing Ubbelohde viscometer to record is 1.34dL/g, and the molecular weight calculated is 71392.
MPBI under the monitoring of table 1 same current table synthesizes situation
Get rid of embodiment 5, carry out heterogeneous formula matching to the termination electric current of embodiment 1 ~ 4 correspondence and limiting viscosity, the curve of three phase formulas matching as shown in Figure 2.Fitting formula is:
Y＝-0.73014+0.3994*X+0.21363*X
2-0.05015*X
3。
Embodiment 6
Take 500.0g polyphosphoric acid, 29.9gP
2o
5(0.211mol) and 33.8g3,3`-diaminobenzidine (0.158mol), add 500mL successively, be equipped with in the four-hole bottle of nitrogen inlet, mechanical stirring, condensing reflux pipe and thermometer, adopt electric heating cover to be warming up to 210 DEG C gradually.Control temperature 210 DEG C, rotating speed 390-410 rev/min, adds 26.2g m-phthalic acid (0.158mol).Remain on about 210 DEG C, when rotating speed maintains 400rap/min in temperature, when electric current reaches 2.60A, in solution, add rapidly 15mL deionized water, and rapidly solution is poured in deionized water.After left undisturbed overnight, take out oven dry, pulverize, and with deionized water drip washing repeatedly, until solution becomes neutrality.Solid is dried, namely obtains Powdered mPBI.The limiting viscosity utilizing Ubbelohde viscometer to record is 0.87dL/g, and the viscosity-average molecular weight calculated is 41352.
Termination electric current 2.60 in embodiment 6 is brought in fitting formula, and the limiting viscosity of gained is 0.872, matches with experimental result.Result shows: in certain range of current, adopts the reometer of this patent monitoring method effective to control polymericular weight.
Claims (6)
1. a method for the controlled linear polymeric of molecular weight is prepared in solution polycondensation reaction, it is characterized in that: comprise the following steps,
1) configuration of reaction soln: in being equipped with the stirring rake be connected with electric mixing device, adding question response material and reaction solvent in the reaction vessel of temperature survey and display unit and shielding gas, obtaining reaction soln; Whipping appts is connected with direct supply through current measurement and display unit by wire; By stirring rake, reaction soln is stirred;
2) control of reacting: ascending step 1) temperature of gained reaction soln, the current value of monitor current table, under whipping appts at the uniform velocity stirs, when the temperature of reaction soln rises to desired reaction temperature, along with the reometer reading that carries out of reaction starts to rise gradually, the current value of monitor current table, the termination reaction when reometer reading rises to a certain current value, remove reaction solvent, obtain reaction product;
3) above-mentioned operating process more than 2 times is repeated, from step 2) difference is that the current value of termination reaction is different; Obtain more than 3 different current values of termination reaction, and the reaction product of their correspondences;
4) to step 3) limiting viscosity of gained reaction product utilizes Ubbelohde viscometer to measure; Mathematics three fit approach are utilized to set up relationship between reaction terminating electric current and product property viscosity;
5) control of solution polycondensation resultants in reaction process molecular weight: the limiting viscosity determining required product according to required molecular weight of product, according to step 4) gained relationship, calculate the termination electric current of required reaction, repeating step 2) operating process, the current value of monitor current table, until termination reaction during required termination electric current, obtain required reaction product.
2. in accordance with the method for claim 1, it is characterized in that:
Mathematical Fitting formula by software to step 2) limiting viscosity of all reaction product and stop electric current and carry out polynomial fitting.
3. in accordance with the method for claim 1, it is characterized in that:
Described polycondensation product is the one in polybenzimidazole, polyimide, polyether sulphone, polyaryletherketone, polyphenylene oxide, polyphenylene sulfide.
4. in accordance with the method for claim 1, it is characterized in that:
The described reaction vessel of whipping appts that is equipped with comprises reaction vessel main body, temperature survey and display unit, driven stirring rod, current measurement and display unit;
Driven stirring rod is connected with direct supply after being connected in series current measurement and display unit again;
Temperature survey and display unit are for measuring and show the temperature of reaction system in reaction vessel main body, and stirring rod is used for carrying out mechanical stirring to the reaction system in reaction vessel main body.
5. in accordance with the method for claim 4, it is characterized in that: temperature survey and display unit are thermometer, current measurement and display unit are reometer.
6. in accordance with the method for claim 4, it is characterized in that: described reaction vessel main body is provided with gas feed and outlet.
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| CN106220853A (en) * | 2016-09-12 | 2016-12-14 | 李涛 | A kind of polysulfone resin industrialized producing technology |
| 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 |
| CN110709446A (en) * | 2017-11-24 | 2020-01-17 | 株式会社Lg化学 | Process for producing polyarylene sulfide |
| CN114752056A (en) * | 2022-03-02 | 2022-07-15 | 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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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) |
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