CN101768353B - Method for increasing molecular weight of polyamide/graphite composite material through solid-phase polymerization - Google Patents
Method for increasing molecular weight of polyamide/graphite composite material through solid-phase polymerization Download PDFInfo
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- CN101768353B CN101768353B CN200910028625A CN200910028625A CN101768353B CN 101768353 B CN101768353 B CN 101768353B CN 200910028625 A CN200910028625 A CN 200910028625A CN 200910028625 A CN200910028625 A CN 200910028625A CN 101768353 B CN101768353 B CN 101768353B
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Abstract
The invention discloses a method for increasing molecular weight of a polyamide/graphite composite material through solid-phase polymerization, which is characterized by comprising the following steps: adding the granular or powdered polyamide/graphite composite material into a reactor; in an oxygen-free atmosphere or under vacuum, and in the presence of a phosphorous catalyst, performing the solid-phase polymerization reaction on the polyamide/graphite composite material, and continuously stirring the material in the reactor or continuously rotating the reactor in the reaction process; and performing catalyst removing post-treatment on the polyamide/graphite composite material with the increased molecular weight. By using the solid-phase polymerization method, the molecular weight of the polyamide/graphite composite material can be effectively increased, so that the thermodynamic property of the material is improved.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of method that improves polyamide/graphite matrix material molecular weight through solid state polymerization.
Background technology
Polymeric amide is the widely used thermoplastic engineering plastic of a kind of excellent performance.But because its specific conductivity is 10
-15Below the S/cm, the antistatic property of goods is poor, has limited its range of application.The raising of specific conductivity normally through adding a certain amount of electro-conductive material, connects into conductive path by conductive filler material, thereby makes polymer materials have certain electroconductibility.Mostly the graphite-like conductive filler material is natural graphite, expanded graphite etc. in the prior art; Receive the influence of filler size and reunion situation; Need high amount of filler could form conductive network in the system; Percolation threshold is high, and is bigger to the intensity and the toughness infringement of matrix material, and caused the decline of conducing composite material processing characteristics.
Graphite is dispersed in the monomer of polyamide, can prepares the polyamide/graphite conducing composite material through in-situ polymerization.And graphite is disperseed in polyamide substrate with the nano level graphite wafer through the method for graphite oxide; The conduction percolation threshold of this polyamide/graphite conducing composite material is low; Promptly under the low situation of graphite consumption, just can in the polyamide/graphite conducing composite material, form the spatial conductive network; And show excellent conductivity, form polyamide/nano graphite composite material with high conduction performance.But through the method for in-situ polymerization, when the graphite addition is higher, be difficult for obtaining the polyamide compoiste material of higher molecular weight, therefore limited the application of graphite composite material in the conducing composite material field.
Solid state polymerization has been applied to fields such as polymeric amide, polyester at present, with the molecular weight that improves product to adapt to request for utilization.But being used for the polyamide/graphite field of compound material does not appear in the newspapers as yet.Solid state polymerization has following characteristics: (1) temperature of reaction obviously reduces, and side reaction and DeR can significantly reduce.Generally below the performed polymer melting temperature 5~40 ℃ of solid phase polymerization temperature, melt polymerization then must be at it more than fusing point.Thermal degradation reaction activation energy is high, and speed of response is obviously accelerated under the high temperature, and solid phase polymerization temperature reduces, and has suppressed thermal degradation process, can improve the quality of polymerisate so greatly; (2) the polymerization product relative molecular mass can improve greatly, thus make its machinery, mechanical property be improved significantly.The industry nylon 6 slice is when the vacuum solid state polymerization, and the low relative molecular mass compounds content can drop to 1%~2% from 12%; (3) energy consumption reduces.Solid phase polymerization temperature reduces, and has avoided the stirring of high sticking melt, and whole polymerization process energy consumption is reduced; (4) solid state polymerization need not to use solvent, is an eco-friendly polymerization process; (5) polymerization technique is simple, flexible.But polymerization methods is operate continuously both, but also periodical operation; Polymerization technique both can make preparatory crystallization, drying, solid state polymerization in same equipment, carry out, and also can separately carry out.Polymerization unit is polymerization reactor both, also can be moisture eliminator; (6) solid state polymerization processes exists the reaction transient equilibrium.Its general three stage of experience: reversible chemical reaction in the polymer particle, polycondensation small molecular by product such as water from particle inside to the diffusion of particle surface with from the diffusion of particle surface to the space inert protective gas; Its speed of reaction often receives chemical reaction, small molecular by product to spread the dual function of two speed; To onesize particle, high temperature is diffusion control often down, and low temperature is chemical reaction control down.The polymer crystallization degree constantly increases with the carrying out of solid state polymerization processes.In a word, solid state polymerization is acquisition high quality, high-performance, the high molecular weight polymkeric substance is important and effective means.
Summary of the invention
The objective of the invention is for the range of application of widening material, the thermomechanical property of improving material; A kind of solid state polymerization that passes through is provided; Improve the method for the molecular weight of polyamide/graphite matrix material effectively, thereby make it to possess good mechanical performance and processing characteristics.
The object of the invention can reach through following measure:
A kind of method through solid state polymerization raising polyamide/graphite matrix material molecular weight is characterized in that, may further comprise the steps:
A) particulate state or powdered polyamide/graphite matrix material are joined in the reactor drum;
B) at oxygen-free atmosphere or vacuum condition, and make the polyamide/graphite matrix material carry out solid-phase polymerization under the condition that exists of phosphorus-containing catalyst, constantly stir in the reactor drum in the reaction process or reactor drum constantly rotates, so as reactant its fully react;
The polyamide/graphite matrix material that improves molecular weight that c) will obtain carries out the denitrating catalyst aftertreatment.
Wherein polyamide/oxidized graphite composite material is made up of polyamide substrate and nano-graphite, makes through in-situ polymerization, and its staple is: graphite 0.25~5 mass parts, polymeric amide 100 mass parts.Described polymeric amide is selected from one or more in nylon 6, nylon 66, Ni Long11, nylon 12, nylon 1010, NYLON610 or the nylon 612; The starting material polyamide/oxidized graphite composite material can only be made up of graphite and polymeric amide, can also contain other auxiliary agents, also can contain little amount of catalyst, like catalyzer of adding when the polymerizing polyamide etc.
Oxygen-free atmosphere is nitrogen, carbonic acid gas or helium atmosphere, and vacuum condition is absolute pressure 0.5~20torr.
Used phosphorus-containing catalyst is one or more in phosphoric acid, sodium hypophosphite, inferior sodium phosphate, tolyl hypophosphite, the manganous hypophosphite; Addition is 0.0005~0.005mol/100g polymkeric substance, and the adding of catalyzer can effectively improve the speed of reaction of solid-phase polymerization.
The temperature of solid-phase polymerization is that the solid-phase polymerization time is 2~48 hours between the second-order transition temperature and fusing point of polymeric amide, is preferably 8~24 hours, but in this preferable range, effectively improves the molecular weight of polymkeric substance within a short period of time.
Initial polyamide/graphite matrix material can have any suitable molecular weight; But in order more preferably to bring into play effect of the present invention; Starting material preferably has viscosity-average molecular weight in 2000~20000 scopes, and 10000~18000 starting molecule amount is more suitable; Certainly the present invention also can use the material of higher molecular weight, and this depends on the purposes that product is final.
The method of aftertreatment denitrating catalyst by: the material behind the solid state polymerization is placed pure water heating, stirs and get final product (is water-soluble catalyst because of adopting catalyzer), and the temperature of pure water is 15~100 ℃, preferred 50 ℃; And stirring velocity 10~300rpm, preferred 100rpm.
After adopting method of the present invention, resulting polyamide/oxidized graphite conducing composite material has higher molecular weight, thereby makes polymkeric substance possess the good mechanical performance, and the original specific conductivity of matrix material is uninfluenced.
Embodiment
Related concrete pharmaceutical chemicals among the present invention:
Phosphoric acid (analytical pure), sodium hypophosphite (analytical pure), inferior sodium phosphate (analytical pure), Hypophosporous Acid, 50 amine (CP): Chemical Reagent Co., Ltd., Sinopharm Group.
Polyamide/graphite matrix material: self-control.
Polymericular weight utilizes five-spot to record through Ubbelohde viscometer.
Embodiment 1
With granular graphite content is that 1.5% nylon 6/ graphite composite material (viscosity-average molecular weight is 1.79E+04) joins in the reaction flask of Rotary Evaporators; At vacuum condition (absolute pressure 1torr); Under 160 ℃ of conditions, be catalyzer with the inferior sodium phosphate, addition is 1.3*10
-5Mol/g makes the reactant solid state polymerization, makes it abundant reaction with 100rpm revolving reaction bottle in the reaction process.Certain hour (be respectively 4 hours, 8 hours, 12 hours, 24 hours) after, place 50 ℃ of pure water to stir the material behind the solid state polymerization, reclaim the polyamide/graphite matrix material that has improved molecular weight.
Gained result such as following table:
After the result can know 24 hours from table, the matrix material viscosity-average molecular weight can be increased to 2.50E+4 by 1.79E+04, and its tensile strength is increased to 73.6MPa by 61.8MPa, and is uninfluenced through the specific conductivity that detects matrix material.
Embodiment 2:
With granular graphite content is that nylon 612/graphite composite material (viscosity-average molecular weight is 1.95E+04) of 1.5% joins in the reaction flask of Rotary Evaporators; At vacuum condition (absolute pressure 1torr); Under 160 ℃ of conditions, be catalyzer with the inferior sodium phosphate, addition is 1.3*10
-5Mol/g makes the reactant solid state polymerization, makes it abundant reaction with 100rpm revolving reaction bottle in the reaction process.Certain hour (be respectively 4 hours, 8 hours, 12 hours, 24 hours) after, place 40 ℃ of pure water to stir the material behind the solid state polymerization, reclaim the polyamide/graphite matrix material that has improved molecular weight.
Gained result such as following table:
After the result can know 24 hours from table, the matrix material viscosity-average molecular weight can be increased to 2.71E+4 by 1.95E+04, and its tensile strength is increased to 60.2MPa by 55.7MPa.
Embodiment 3
With granular graphite content is that 1% nylon 66/ graphite composite material (viscosity-average molecular weight is 1.55E+04) joins in the reaction flask of Rotary Evaporators, at vacuum condition (absolute pressure 1torr), under 160 ℃ of conditions, is catalyzer with phosphoric acid, and addition is 1.0*10
-5Mol/g makes the reactant solid state polymerization, makes it abundant reaction with 100rpm revolving reaction bottle in the reaction process.Certain hour (be respectively 4 hours, 8 hours, 12 hours, 24 hours) after, place 60 ℃ of pure water to stir the material behind the solid state polymerization, reclaim the polyamide/graphite matrix material that has improved molecular weight.
Gained result such as following table:
After the result can know 24 hours from table, the matrix material viscosity-average molecular weight can be increased to 2.61E+4 by 1.55E+04, and its tensile strength is increased to 80.3MPa by 69.5MPa.
Embodiment 4
With granular graphite content is that nylon 1010/graphite composite material (viscosity-average molecular weight is 1.79E+04) of 2% joins in the reaction flask of Rotary Evaporators, in condition of nitrogen gas, under 140 ℃ of conditions, is catalyzer with the sodium hypophosphite, and addition is 1.5*10
-5Mol/g makes the reactant solid state polymerization, makes it abundant reaction with 100rpm revolving reaction bottle in the reaction process.Certain hour (be respectively 4 hours, 12 hours, 24 hours, 48 hours) after, place 50 ℃ of pure water to stir the material behind the solid state polymerization, reclaim the polyamide/graphite matrix material that has improved molecular weight.
Gained result such as following table:
After the result can know 48 hours from table, the matrix material viscosity-average molecular weight can be increased to 2.41E+4 by 1.79E+04, and its tensile strength is increased to 56.1MPa by 47.9MPa.
Embodiment 5
With granular graphite content is that NYLON610/graphite composite material (viscosity-average molecular weight is 1.86E+04) of 1.5% joins in the reaction flask of Rotary Evaporators, at helium atmosphere, under 180 ℃ of conditions, is catalyzer with the inferior sodium phosphate, and addition is 2.0*10
-5Mol/g makes the reactant solid state polymerization, makes it abundant reaction with 100rpm revolving reaction bottle in the reaction process.Behind the certain hour, place 50 ℃ of pure water to stir the material behind the solid state polymerization, reclaim the polyamide/graphite matrix material that has improved molecular weight.
Gained result such as following table:
After the result can know 24 hours from table, the matrix material viscosity-average molecular weight can be increased to 2.40E+4 by 1.86E+04, and its tensile strength is increased to 56.4MPa by 45.3MPa.
Comparative example 1
With granular graphite content is that 1.5% nylon 6/ graphite composite material (viscosity-average molecular weight is 1.86E+04) joins in the reaction flask of Rotary Evaporators, at CO
2Atmosphere, under 140 ℃ of conditions, catalyst-free makes the reactant solid state polymerization, makes it abundant reaction with 100rpm revolving reaction bottle in the reaction process.Behind the certain hour, reclaim the polyamide/graphite matrix material that has improved molecular weight.
Gained result such as following table:
After the result can know 48 hours from table, the matrix material viscosity-average molecular weight can be increased to 2.11E+4 by 1.86E+04, and the amplitude that the material molecule amount improves is very little.
Comparative example 2:
With granular graphite content is that nylon 612/graphite composite material (viscosity-average molecular weight is 1.95E+04) of 1.5% joins in the reaction flask of Rotary Evaporators; At vacuum condition (absolute pressure 5torr); Under 180 ℃ of conditions; Catalyst-free makes the reactant solid state polymerization, makes it abundant reaction with 100rpm revolving reaction bottle in the reaction process.Behind the certain hour, reclaim the polyamide/graphite matrix material that has improved molecular weight.
Gained result such as following table:
After the result can know 24 hours from table, the matrix material viscosity-average molecular weight can be increased to 2.26E+4 by 1.95E+04, and the amplitude that the material molecule amount improves is very little.
Claims (8)
1. the method through solid state polymerization raising polyamide/graphite matrix material molecular weight is characterized in that, may further comprise the steps:
A) particulate state or powdered polyamide/graphite matrix material are joined in the reactor drum;
B) at vacuum condition, and make the polyamide/graphite matrix material carry out solid-phase polymerization under the condition of phosphorus-containing catalyst existence, interior constantly stirring of reactor drum or reactor drum constantly rotate in the reaction process; Wherein, vacuum condition is absolute pressure 0.5~20torr;
The polyamide/graphite matrix material that improves molecular weight that c) will obtain carries out the denitrating catalyst aftertreatment.
2. method according to claim 1 is characterized in that, polyamide/graphite matrix material staple is:
Graphite 0.25~5 mass parts
Polymeric amide 100 mass parts.
3. method according to claim 1 and 2 is characterized in that, described polymeric amide is selected from one or more in nylon 6, nylon 66, Ni Long11, nylon 12, nylon 1010, NYLON610 or the nylon 612.
4. method according to claim 1 is characterized in that, described phosphorus-containing catalyst is selected from one or more in phosphoric acid, sodium hypophosphite, inferior sodium phosphate, tolyl hypophosphite or the manganous hypophosphite.
5. according to claim 1 or 4 described methods, it is characterized in that the addition of described phosphorus-containing catalyst is 0.0005~0.005mol/100g polymkeric substance.
6. method according to claim 1 is characterized in that, the temperature of solid-phase polymerization is between the second-order transition temperature and fusing point of polymeric amide.
7. method according to claim 1 is characterized in that, the solid-phase polymerization time is 2h~48h.
8. method according to claim 1 is characterized in that, the method for aftertreatment denitrating catalyst is: the polyamide/graphite matrix material that improves molecular weight that will obtain places 15~100 ℃ pure water to stir and gets final product.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1238790A (en) * | 1996-11-27 | 1999-12-15 | 纳幕尔杜邦公司 | Method for solid phase polymerization |
CN1277218A (en) * | 1999-06-11 | 2000-12-20 | 中国科学院化学研究所 | Composite nanometer-level polyamide/graphite material and its preparation |
WO2006079890A1 (en) * | 2005-01-27 | 2006-08-03 | Ems-Chemie Ag | Highly viscose thermoplastic polymer-based moulding compounds and the use thereof |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN1238790A (en) * | 1996-11-27 | 1999-12-15 | 纳幕尔杜邦公司 | Method for solid phase polymerization |
CN1277218A (en) * | 1999-06-11 | 2000-12-20 | 中国科学院化学研究所 | Composite nanometer-level polyamide/graphite material and its preparation |
WO2006079890A1 (en) * | 2005-01-27 | 2006-08-03 | Ems-Chemie Ag | Highly viscose thermoplastic polymer-based moulding compounds and the use thereof |
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