CN114716678A - Preparation method of imide structure polymer - Google Patents
Preparation method of imide structure polymer Download PDFInfo
- Publication number
- CN114716678A CN114716678A CN202011524414.6A CN202011524414A CN114716678A CN 114716678 A CN114716678 A CN 114716678A CN 202011524414 A CN202011524414 A CN 202011524414A CN 114716678 A CN114716678 A CN 114716678A
- Authority
- CN
- China
- Prior art keywords
- polymer
- imide
- parts
- acid
- raw materials
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/14—Polyamide-imides
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
- C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
Abstract
The invention provides a preparation method of an imide structure polymer, which comprises the following steps of raw materials, by weight, 10-90 parts of a reactive dispersion medium amido bond polymer, 0-50 parts of a polymerized monomer diacid, 5-100 parts of diamine, and 5-100 parts of carboxylic acid capable of forming cyclic internal anhydride and/or a derivative formed by the carboxylic acid, wherein the carboxylic acid is at least one of a tribasic acid and a tetrabasic acid, and the derivative is at least one of anhydride and ester; the preparation method comprises the steps of mixing raw materials, taking a molten amido bond polymer as a dispersion medium, reacting and mixing a polymerization monomer in the dispersion medium, and polymerizing to obtain a polymer containing an imide structure. The problems of difficult processing of polyimide resin and cost and environment caused by solvent are solved.
Description
Technical Field
The invention relates to the technical field of engineering plastics, in particular to a preparation method of an imide structure polymer.
Technical Field
The polyamide is the most widely applied engineering plastic, has the advantages of high strength, good temperature resistance, corrosion resistance, excellent wear resistance, aging resistance and moderate cost, and is widely applied to the fields of electronic appliances, fibers, automobiles, mechanical manufacturing and the like. However, since the molecule contains a large number of hydrogen bonds, it tends to absorb water, and the mechanical strength is deteriorated. In addition, with the trend of light weight and intensification, various parts are smaller and thinner, higher requirements on the temperature resistance of the material are provided, and the important direction of material development is to further economically improve the temperature resistance of the material.
Polyimide is one of the best temperature resistant plastic varieties because of its stable rigid ring structure. And because of the molecular structure, the polyamide resin does not contain a hydrogen bond donor, the water absorption is obviously reduced compared with polyamide, and the polyamide resin is the most outstanding variety in the comprehensive performance of engineering plastics. The excessive cost and special processing limits the use of polyimides. The method combines the advantages of polyimide and polyamide to prepare the polyamide-imide copolymer or blend material by various methods, and is a method for combining the advantages of the two materials.
Patent CN 106188551 discloses a method for modifying polyamide with semi-aromatic polyimide, which comprises reacting dianhydride and diamine in solution to prepare amide, and then closing the ring to form polyimide. Finally, the modified polyamide is obtained by a method of blending the polyamide with polyamide, and the temperature resistance of the polyamide can be obviously improved. However, the two materials are mainly combined by means of physical blending, and phase separation is easy to generate in long-term use.
Patent CN 106336512 discloses a method for synthesizing amide imide copolymer, but the synthesis method requires the use of large amount of strong polar solvent, and the solvent is difficult to process and high in cost, which limits the application of the method.
Patent CN 103890042 a reports a process for preparing thermoplastic polyimides by diamines and anhydrides, wherein a large amount of alcoholic solvents is used, which are highly volatile and which add considerable additional costs for recovery and disposal.
Disclosure of Invention
In order to improve the temperature resistance and water absorption performance of polyamide resin, simultaneously improve the processing difficulty of polyimide resin and the cost caused by solvent and solve the environmental problems caused by the processing difficulty, the invention provides a method for preparing a polymer containing an imide structure by using an amido bond polymer as a reactive dispersion medium.
The method enables the condensation reaction of polyamide and the generation reaction of imide functional group to both occur in an amido bond polymer melting medium, can ensure the strong polarity environment required in the imide generation process, and can avoid the additional cost and environmental problems caused by the use of a volatile strong polarity solvent. The obtained amide imide copolymer has higher temperature resistance and lower water absorption performance than polyamide, and avoids the problem of difficult processing of traditional polyimide.
In order to achieve the purpose of the invention, the invention adopts the technical scheme that:
the preparation method of the imide structure polymer comprises the following steps of raw materials, by weight, 10-90 parts of reactive dispersion medium amido bond polymer, 0-50 parts of polymerized monomer diacid, 5-100 parts of diamine, and 5-100 parts of carboxylic acid capable of forming cyclic internal anhydride and/or derivatives formed by the carboxylic acid, wherein the carboxylic acid is at least one of tribasic acid and tetrabasic acid, and the derivatives are at least one of anhydride and ester; the preparation method comprises the steps of mixing raw materials, taking a molten amido bond polymer as a dispersion medium, reacting and mixing a polymerization monomer in the dispersion medium, and polymerizing to obtain a polymer containing an imide structure.
The invention selects the melted amido bond polymer to replace the traditional strong polar solvent as the dispersion medium of the reaction, utilizes the polarity of the amido bond polymer as the solvent in the melting state, and leads the polymerization monomer to be dissolved in the polymer in the melting state for reaction. Therefore, the imide generation reaction which needs to be carried out in a strong polar solvent can be smoothly carried out without introducing a volatile organic solvent, and the method is a green environment-friendly process.
The raw material contains tribasic acid and tetrabasic acid, wherein the tribasic acid certainly has a carboxyl group which can not form internal anhydride, and the tetrabasic anhydride also has carboxyl group which can not form anhydride because the anhydride is very easy to hydrolyze. Carboxyl without anhydride in the system can perform exchange reaction with amido bond or imide bond in the amide polymer to form a product with uniform copolymerization to obtain amide-imide copolymer, and the polymer linked by covalent bond can not generate phase separation theoretically, so the durability is better than the traditional physical blending, thereby solving the problems of poor compatibility and unstable long-term use performance when blending amide and imide.
The dibasic acid is added into the raw materials, so that the reaction flexibility is better, more kinds of copolymers can be directly prepared, the reaction with the polymer raw materials can be more easily carried out in the dispersion process, the reduction of the molecular weight of the polymer is facilitated, the viscosity of the system is reduced, and the dispersion of the system is easier.
The raw materials are continuously added into a material mixing device according to a proportion, a polymerization monomer is enabled to react and mix uniformly in a molten reactive amide dispersion medium in the material mixing device, and the uniformly mixed materials enter a subsequent polymerization device to be polymerized until the nylon resin reaches the required molecular weight.
Due to the addition of the amido bond polymer, the dispersion system has a certain melting point and viscosity, can adapt to the application of a continuous flow material mixing device, and avoids the difficulty in controlling concentrated heat release caused by concentrated feeding. Make the joining of material be in during the state of continuous transport, mixing process and continuous transport process go on in step to make exothermic process disperse to the different positions of device along with the continuous forward transport of material, avoided traditional small molecule monomer raw materials viscosity low unable continuous feeding, can only melt polymerization and throw the material in the concentration, concentrate exothermic, reduce the problem of throwing material efficiency.
Various continuous flow material mixing devices can be used in the material mixing step of the present invention, preferably a screw extrusion device or a tubular reaction device.
The amide bond polymer is selected from at least one of polyamide, polyimide and amide imide copolymer. The raw material amido bond polymer can be polyamide, amide imide copolymer or thermoplastic polyimide, and different amide or imide groups are introduced by the method, so that the polymer structure can be flexibly designed according to the requirement, and products with different performance requirements can be obtained.
Preferably, the molecular weight of the amide bond polymer is not more than 100000. The low molecular weight polymer is selected, so that the melting and crystallization temperature of the whole system is reduced, the viscosity after melting is greatly reduced, and the dispersion of the polymerized monomer is easier. On the other hand, due to the limited boiling point of the organic amine, the system can be softened below the boiling point of the organic amine after the melting and crystallization temperature of the system is reduced, so that the organic amine and the organic amine can be dispersed more effectively.
Preferably, the amide linkage polymer does not crystallize or has a melting point of less than 400 ℃. A melting point below 400 ℃ ensures melting before decomposition of the polymer, and a molten polymer medium for the polymerization reaction is smoothly obtained.
The polymerization monomer of the invention is 0-50 parts of dibasic acid, 5-100 parts of diamine and 5-100 parts of anhydride. The monomers do not contain acid, acid anhydride is directly used as a polymerization monomer, the salt forming step can be reduced, precursor amic acid is directly generated for cyclization, and the heat release in the salt forming step can cause uneven dispersion.
The carboxylic acids of the present invention contain at least one of aliphatic or aromatic carboxylic acids of 9 to 32 carbon atoms and are capable of forming at least one internal anhydride. I.e., the tricarboxylic and tetracarboxylic acids should be capable of forming internal anhydrides having at least two carboxyl groups separated by two or three carbon atoms.
Preferably, the polymerized monomer is a diamine, a tetrabasic acid and/or a dianhydride formed from a tetrabasic acid. To obtain the homopolymerized polyimide product.
Further preferably, the polymerized monomer reacts in a molten amide bond polymer to obtain a polymer with an imide structure, and then the polymer is used as a dispersion medium for the reaction, and the reaction is repeated to increase the proportion of imide groups until an amide imide polymer with an amide bond proportion approaching zero is obtained. The copolymer product containing a certain proportion of imide functional groups is used as a polymer raw material, and is repeatedly reacted with the same dianhydride and diamine to gradually increase the proportion of the imide functional groups until a high-purity polyimide product with the proportion of amide groups close to zero can be obtained.
Further preferably, the diamine is an aliphatic diamine having a carbon chain length of not less than 8 carbon atoms. The rigidity of the monomers is mainly considered, and the long-chain diamine is selected as much as possible, so that the melting point of the polyimide is reduced to be lower than the decomposition temperature, and the thermoplastic polyimide product capable of being melted and processed is prepared.
The carboxylic acid and the derivative formed by the carboxylic acid cannot be dispersed with diamine in an amido bond polymer medium at the same time. Because the anhydride and the amine are both relatively active and react quickly, if the anhydride and the amine are simultaneously put into a polymer medium, the anhydride and the amine may not be dispersed yet, the anhydride and the amine react, physical blending is generated between the formed polyimide and the amido bond polymer medium, and certain influence is generated on the product performance.
The invention has the beneficial effects that:
1. the invention selects the melted amido bond polymer to replace the traditional strong polar solvent as the dispersion medium of the reaction, utilizes the polarity of the amido bond polymer as the solvent in the melting state, and leads the polymerization monomer to be dissolved in the polymer in the melting state for reaction. Therefore, the imide generation reaction which needs to be carried out in a strong polar solvent can be smoothly carried out without introducing a volatile organic solvent, the raw materials do not contain water, a nylon salt does not need to be prepared in water or an alcohol solution in the polymerization reaction, the polymerization process is greatly simplified, the generation of waste liquid in the preparation process of the nylon salt is avoided, the imide precursor amic acid does not need to be prepared in the volatile solvent, and the process is a green environment-friendly process.
2. The amido bond polymer has wide raw material sources, can be finished polyamide, polyimide or amide imide copolymer purchased in the market, can also be prepolymer oligomer, and can take defective products generated in the manufacturing process as raw materials, so waste materials are not generated basically.
3. Selecting amido bond polymer with molecular weight not more than 100000. The low molecular weight polymer is selected, so that the melting and crystallization temperature of the whole system is reduced, the viscosity after melting is greatly reduced, and the dispersion of the polymerized monomer is easier. On the other hand, due to the limited boiling point of the organic amine, the system can be softened below the boiling point of the organic amine after the melting and crystallization temperature of the system is reduced, so that the organic amine and the organic amine can be dispersed more effectively. The reaction system has better dispersibility and higher product quality stability.
Detailed Description
In order to more clearly and specifically illustrate the technical solution of the present invention, the present invention is further described by the following embodiments. The following examples are intended to illustrate the practice of the present invention and are not intended to limit the scope of the invention.
Example 1
The preparation method of the imide structure polymer comprises the following steps of raw materials, by weight, 10-90 parts of reactive dispersion medium amido bond polymer, 0-50 parts of polymerized monomer diacid, 5-100 parts of diamine, and 5-100 parts of carboxylic acid capable of forming cyclic internal anhydride and/or derivatives formed by the carboxylic acid, wherein the carboxylic acid is at least one of tribasic acid and tetrabasic acid, and the derivatives are at least one of anhydride and ester; the preparation method comprises the steps of mixing raw materials, taking a molten amido bond polymer as a dispersion medium, reacting and mixing a polymerization monomer in the dispersion medium, and polymerizing to obtain a polymer containing an imide structure.
Example 1
The preparation method of the imide structure polymer comprises the following steps that raw materials comprise 10 parts of reactive dispersion medium amido bond polymer, 5 parts of polymerization monomer diamine and 5 parts of carboxylic acid capable of forming cyclic internal anhydride, wherein the carboxylic acid is at least one of tribasic acid and tetrabasic acid; the preparation method comprises the steps of mixing raw materials, taking a molten amido bond polymer as a dispersion medium, reacting and mixing a polymerization monomer in the dispersion medium, and polymerizing to obtain a polymer containing an imide structure.
Example 2
The preparation method of the imide structure polymer comprises the following steps that raw materials comprise 90 parts by weight of reactive dispersion medium amido bond polymer, 50 parts by weight of polymerized monomer diacid, 100 parts by weight of diamine and 100 parts by weight of carboxylic acid derivative capable of forming cyclic internal anhydride, wherein the derivative is at least one of anhydride and ester; the preparation method comprises the steps of mixing raw materials, taking a molten amido bond polymer as a dispersion medium, reacting and mixing a polymerization monomer in the dispersion medium, and polymerizing to obtain a polymer containing an imide structure.
The amide bond polymer is at least one selected from polyamide, polyimide and amide imide copolymer.
The molecular weight of the amide bond polymer is not more than 100000.
The amide bond polymer does not crystallize or has a melting point of less than 400 ℃.
The method is a universal method for preparing the imide polymer, and the used dibasic acid, diamine, amido bond polymer, tribasic acid, tetrabasic acid and derivative raw materials thereof can be selected at will according to performance requirements and cost factors.
The carbon chain length of the diamine is not less than 7 carbon atoms.
The dibasic acid is at least one of aliphatic or aromatic dibasic acid containing 2-30 carbon atoms. The carboxylic acid contains at least one of an aliphatic or aromatic carboxylic acid having 9 to 32 carbon atoms and is capable of forming at least one internal anhydride.
In the implementation process of the invention, the mixing sequence of the raw materials needs to be flexibly selected according to the requirements of equipment and final products, and the raw materials can be fed sequentially or simultaneously, and even the acid and the amine can be respectively dispersed into the polymer and then mixed for reaction.
Example 3
The preparation method of the imide structure polymer comprises the following steps that raw materials comprise, by weight, 50 parts of reactive dispersion medium amido bond polymer, 20 parts of polymerized monomer diacid, 50 parts of diamine, carboxylic acid capable of forming cyclic internal anhydride and 5 parts of derivative formed by the carboxylic acid, wherein the carboxylic acid is at least one of tribasic acid and tetrabasic acid, and the derivative is at least one of anhydride and ester; the preparation method comprises the steps of mixing raw materials, taking a molten amido bond polymer as a dispersion medium, reacting and mixing a polymerization monomer in the dispersion medium, and polymerizing to obtain a polymer containing an imide structure.
The amide bond polymer is at least one selected from polyamide, polyimide and amide imide copolymer.
The molecular weight of the amide bond polymer is not more than 100000.
The amide bond polymer does not crystallize or has a melting point of less than 400 ℃.
The carbon chain length of the diamine is not less than 7 carbon atoms.
The dibasic acid is at least one selected from aliphatic or aromatic dibasic acids containing 2-30 carbon atoms. The carboxylic acid contains at least one of an aliphatic or aromatic carboxylic acid of 9 to 32 carbon atoms and is capable of forming at least one internal anhydride.
The carboxylic acid and the derivative formed by the carboxylic acid cannot be dispersed simultaneously with the diamine in the amide bond polymer medium.
The raw materials are continuously added into a material mixing device according to a proportion, a polymerization monomer is uniformly mixed in a molten reactive amide dispersion medium in the material mixing device, and the uniformly mixed materials enter a subsequent polymerization device to be polymerized until the nylon resin reaches the required molecular weight.
Various continuous flow material mixing devices can be used in the material mixing step of the present invention, preferably a screw extrusion device or a tubular reaction device.
And the subsequent polymerization device is at least one of a screw extrusion device, a tubular reaction device and a kettle type reaction device, and after polymerization is finished, the subsequent polymerization device is extruded by the screw extrusion device for granulation. After various raw materials are uniformly mixed and dispersed in a material mixing device, a longer screw extrusion device can be directly added behind to continue polymerization and remove volatilized small molecules until the molecular weight reaches the target discharge. However, in order to achieve a sufficiently large molecular weight, sufficient reaction time is required, and thus a screw extruder having a particularly long length-diameter ratio is required, and multiple stages of screw extruders are usually required to be connected in series, which increases the capital investment and increases the equipment occupation. The volume of the apparatus can be reduced by connecting other polymerization apparatuses in series. A pipe reactor, a reaction tank polymerization apparatus, and a screw extrusion apparatus having a larger diameter can be used in the present invention. After the polymerization is complete, it is passed through an additional set of screw devices where the material is further homogenized and the small molecule volatiles are removed.
Preferably, the subsequent polymerization apparatus is a plug flow reactor or a screw extrusion apparatus connected in series. The plug flow reactor is a continuous polymerization reactor, can be in a pipeline type, can also be in a reaction kettle or tower type, and mainly ensures that the material inlet and outlet are in continuous flow, ideally, no backflow exists, and the retention time of all the materials in the material inlet and outlet is equal. The continuous flow reactor can control the time of material polymerization, thereby obtaining polymers with different molecular weights. After the materials pass through the continuous flow reactor, the device is preferably a polymerization device for continuously discharging the materials in a flowing way, and the continuous production is most favorably realized.
Example 4
The preparation method of the amide imide copolymer comprises the following steps of preparing raw materials, wherein the raw materials do not contain volatile organic solvents, and comprise 21.8 parts of polymeric monomer pyromellitic dianhydride, 11.6 parts of hexamethylene diamine and 80 parts of PA66 resin by weight;
the polymerization method comprises the following steps: placing 218g of monomer pyromellitic dianhydride and 800g of PA66 resin according to the formula amount in an internal mixer under the protection of nitrogen for dispersing for 15 minutes at the maximum temperature of 280 ℃, transferring the mixture into an autoclave with a condensing device, adding 116g of hexamethylene diamine and 1g of catalyst, replacing for 3 times by nitrogen, and carrying out closed reaction for 4 hours at the maximum temperature of 290 ℃. Slowly releasing pressure and discharging generated water. Then reacting for 0.5 hour under the conditions of 300 ℃ and 0.02 Mpa. Heating to 320 ℃ to discharge to obtain the amide imide copolymer, wherein the melting point is 285 ℃, the temperature is 25 ℃ higher than PA 66260 ℃, the water absorption is 0.8 percent, and the water absorption is 64 percent lower than PA 662.2 percent.
Example 5
The preparation method of the amide imide copolymer comprises the following steps of preparing raw materials, wherein the raw materials do not contain volatile organic solvents, and comprise 25.4 parts of polymeric monomer pyromellitic acid, 11.6 parts of hexamethylene diamine and 80 parts of PA66 resin by weight;
the polymerization method comprises the following steps: 254g of monomer pyromellitic acid and 800g of PA66 resin according to the formula amount are placed in an internal mixer under the protection of nitrogen for dispersing for 15 minutes at the maximum temperature of 280 ℃, then transferred into an autoclave with a condensing device, 116g of hexamethylene diamine and 1g of catalyst are added, and after 3 times of nitrogen replacement, the mixture is sealed and reacted for 4 hours at the maximum temperature of 290 ℃. Slowly releasing pressure and discharging generated water. Then, the reaction was carried out at 300 ℃ and 0.02MPa for 0.5 hour. Heating to 320 ℃ and discharging to obtain the amide imide copolymer with melting point of 383 ℃ and the basic performance consistent with that of the product in the example 1.
Example 6
The preparation method of the amide imide copolymer comprises the following steps of preparing raw materials, wherein the raw materials do not contain volatile organic solvents, and comprise 21.8 parts of polymeric monomer pyromellitic dianhydride, 20.0 parts of dodecanediamine and 39.4 parts of PA1212 resin by weight;
the polymerization method comprises the following steps: dispersion A was obtained by dispersing 218g of pyromellitic anhydride and 200g of PA1212 resin in an internal mixer set at a maximum temperature of 280 ℃ for 10 minutes;
200g of dodecanediamine and 194g of PA1212 resin were dispersed in an internal mixer set at a maximum temperature of 220 ℃ for 10 minutes to obtain dispersion B;
adding the dispersion A and the dispersion B into an autoclave, adding 0.8g of catalyst, pumping nitrogen for 3 times, reacting for 4 hours at 260 ℃, and then reacting for 0.5 hour at 260 ℃ and 0.02 Mpa. Heating to 280 ℃ and discharging to obtain the amide imide copolymer with the melting point of 220 ℃.
Example 7
The preparation method of the amide imide copolymer comprises the following steps of preparing raw materials, wherein the raw materials do not contain volatile organic solvents, and comprise 21.8 parts of polymeric monomer pyromellitic dianhydride, 20.0 parts of dodecanediamine and 42.3 parts of the amide imide copolymer obtained in example 3 by weight;
the polymerization method comprises the following steps: 218g of pyromellitic anhydride and 223g of the amide imide copolymer obtained in example 3 were dispersed in an internal mixer with the maximum temperature set at 280 ℃ for 10 minutes to obtain dispersion C;
200g of dodecanediamine and 200g of the amide imide copolymer obtained in example 3 were dispersed in an internal mixer with the maximum temperature set at 250 ℃ for 10 minutes to give dispersion D;
adding the dispersion C and the dispersion D into an autoclave, adding 0.8g of catalyst, pumping nitrogen for 3 times, reacting for 4 hours at 260 ℃, and then reacting for 0.5 hour at 280 ℃ and 0.02 Mpa. Heating to 290 ℃ and discharging to obtain the amide imide copolymer with the melting point of 253 ℃.
Example 8
The process for producing a polyimide using the product of example 7 as a polymer raw material was repeated 4 times in accordance with the procedures of examples 6 and 7 described above, each time using the product of the previous time as a polymer raw material, to obtain a high-purity polyimide having an amide bond ratio of about 1/64, a melting point of 303 ℃ being in agreement with 303 ℃ reported in document CN 103890042A, indicating that a high-purity polyimide can be obtained by the process of the present invention and is a melt-processable thermoplastic product.
In this example, in order to obtain an imide group with a higher proportion, the amide imide copolymer obtained by the reaction is used as an amide bond polymer raw material, and the reaction is repeated until a high-purity polyimide with an amide bond proportion approaching zero is obtained.
Example 9
The preparation method of polyimide comprises the steps of using 40 parts of high-purity polyimide prepared by using NMP as a solvent through a traditional process, 21.8 parts of pyromellitic dianhydride and 20.0 parts of dodecanediamine as raw materials, putting the raw materials into a co-rotating twin-screw extruder, setting the temperature of each section to be 150 ℃ and 320 ℃, keeping the residence time for 20 minutes, performing reactive extrusion and granulation to obtain the polyimide, wherein the melting point of the polyimide is 305 ℃, the melting point of the polyimide is consistent with the melting point of 303 ℃ reported by the document CN 103890042A, and the basic performance of the polyimide is consistent with that of the product of the example 8.
Example 10
The preparation method of the amide imide copolymer comprises the following steps of preparing raw materials, wherein the raw materials do not contain volatile organic solvents, and comprise 21.0 parts of polymerized monomer trimellitic acid, 11.6 parts of hexamethylene diamine and 80 parts of PA66 resin by weight;
the polymerization method comprises the following steps: 210g of monomer trimellitic acid monomer and 800g of PA66 resin are placed in an internal mixer protected by nitrogen for 15 minutes at the maximum temperature of 280 ℃, then the mixture is transferred into an autoclave with a condensing device, 116g of hexamethylene diamine and 1g of catalyst are added, after 3 times of nitrogen replacement, the mixture is sealed and reacted for 4 hours at the maximum temperature of 290 ℃. Slowly releasing pressure and discharging generated water. Then reacting for 0.5 hour under the conditions of 300 ℃ and 0.02 Mpa. Heating to 320 ℃ for discharging to obtain the amide imide copolymer, wherein the melting point is 279 ℃, the temperature is increased by 19 ℃ compared with PA 66260 ℃, the water absorption is 1.0 percent, and the water absorption is reduced by 55 percent compared with PA 662.2 percent.
Firstly, dispersing dibasic acid and the carboxylic acid and/or the carboxylic acid derivative into a molten amido bond polymer for reaction, and then adding diamine for reaction to obtain the amide imide copolymer. The acid and polyamide are first reacted at high temperature to produce homogeneously dispersed intermediate containing amido bond and terminal carboxyl group. In this step, a portion of the acid reacts with the amide linkages and residual amino groups in the polyamide to form a low molecular weight polymer, and the mixture contains a large number of amide linkages, so that the system is sufficiently polar to uniformly disperse the unreacted acid. And because the molecular weight of the polymer is low, the melting and crystallization temperature of the whole system is reduced, the viscosity after melting is greatly reduced, the uniform mixing of the neutralization amine in the next step is facilitated, the dispersibility is good, and the stability of the product is higher.
Example 11
The preparation method of the amide imide copolymer comprises the following steps of preparing raw materials, wherein the raw materials do not contain volatile organic solvents, and comprise 31.0 parts of polymeric monomer diethyl pyromellitate, 11.6 parts of dodecanediamine and 80 parts of PA66 resin by weight;
the polymerization method comprises the following steps: the raw materials in the above proportion are fed into a co-rotating twin-screw extruder with each stage set at 150-300 ℃ for reactive extrusion, granulation and retention time of 22 minutes to obtain the amide imide copolymer with a melting point of 259 ℃ close to PA66, water absorption of 0.3 percent and water absorption of 86 percent lower than PA 662.2.
Example 12
The preparation method of the amide imide copolymer comprises the following steps of preparing raw materials, wherein the raw materials do not contain volatile organic solvents, and comprise 21.8 parts of polymeric monomer pyromellitic dianhydride, 21.6 parts of p-phenylenediamine, 16.6 parts of terephthalic acid and 100 parts of PA66 resin by weight;
the polymerization method comprises the following steps: the raw materials with the proportion are led to a double-screw extruder to be extruded in a reaction type with the temperature of 150-330 ℃ in each section, and are granulated and stay for 18 minutes to obtain the amide imide copolymer with the melting point of 318 ℃.
Example 13
The preparation method of the amide imide copolymer comprises the following steps of preparing raw materials, wherein the raw materials do not contain volatile organic solvents, and comprise 21.8 parts of polymeric monomer pyromellitic dianhydride, 20.0 parts of dodecanediamine and 80 parts of PA66 resin by weight;
the polymerization method comprises the following steps: adding 218g of monomer pyromellitic dianhydride, 800g of PA66 resin, 200g of dodecanediamine and 1g of catalyst into a high-pressure reaction kettle according to the formula ratio, replacing 3 times with nitrogen, and carrying out closed reaction for 4 hours at the maximum temperature of 290 ℃. Slowly releasing pressure and discharging generated water. Then reacting for 0.5 hour under the conditions of 300 ℃ and 0.02 Mpa. The temperature is increased to 320 ℃, and the amide imide copolymer is obtained, wherein the melting point is 261 ℃ and the performance of the product is close to that of the product obtained in example 8.
Example 14
The preparation method of the amide imide copolymer comprises the following steps of preparing raw materials, wherein the raw materials do not contain volatile organic solvents, and comprise 21.8 parts of polymeric monomer pyromellitic dianhydride, 2.92 parts of adipic acid, 24.0 parts of dodecane diamine and 80 parts of PA66 resin by weight;
the polymerization method comprises the following steps: the monomer pyromellitic dianhydride with the formula amount of 218g, PA66 resin of 800g and adipic acid of 29.2g are put into an autoclave to react for 30 minutes at 280 ℃, dodecane diamine of 240g and catalyst of 1g are added to replace 3 times by nitrogen, and then the sealed reaction is carried out for 4 hours at the maximum temperature of 290 ℃. Slowly releasing pressure and discharging generated water. Then reacting for 0.5 hour under the conditions of 300 ℃ and 0.02 Mpa. Heating to 320 ℃ and discharging to obtain the amide imide copolymer with the melting point of 263 ℃.
Example 15
The preparation method of the amide imide copolymer comprises the following steps of raw materials, wherein the raw materials do not contain volatile organic solvents, and comprise 21.8 parts of polymeric monomer pyromellitic dianhydride, 2.92 parts of adipic acid, 24.0 parts of 4, 4' -diaminodiphenyl ether and 80 parts of PA66 resin by weight;
the polymerization method comprises the following steps: the monomer pyromellitic dianhydride with the formula amount of 218g, PA66 resin of 800g and adipic acid of 29.2g are put into an autoclave to react for 30 minutes at 280 ℃, dodecane diamine of 240g and catalyst of 1g are added to replace 3 times by nitrogen, and then the sealed reaction is carried out for 4 hours at the maximum temperature of 290 ℃. Slowly releasing pressure and discharging generated water. Then reacting for 0.5 hour under the conditions of 300 ℃ and 0.02 Mpa. Heating to 320 ℃ and discharging to obtain the amide imide copolymer, wherein the glass transition temperature is 120 ℃, and is increased by 70 ℃ compared with PA 6650 ℃.
Example 16
The preparation method of the amide imide copolymer comprises the following steps of preparing raw materials without volatile organic solvents, wherein the raw materials comprise 20 parts of polymeric monomer trimellitic acid, 2.92 parts of adipic acid, 24.0 parts of dodecane diamine and 80 parts of PA66 resin by weight;
the polymerization method comprises the following steps: 200g of monomer trimellitic acid, 800g of PA66 resin and 29.2g of adipic acid in the formula are placed in an autoclave to react for 30 minutes at 280 ℃, 240g of dodecanediamine and 1g of catalyst are added to the autoclave, nitrogen is substituted for 3 times, and then the mixture is sealed and reacted for 4 hours at 290 ℃ of the maximum temperature. Slowly releasing pressure and discharging generated water. Then reacting for 0.5 hour under the conditions of 300 ℃ and 0.02 Mpa. Heating to 320 ℃ and discharging to obtain the amide imide copolymer with the melting point of 242 ℃.
Example 17
The preparation method of the polyimide comprises the steps of using 40 parts of high-purity polyimide prepared by using NMP as a solvent through a traditional process, 21.8 parts of pyromellitic dianhydride and 20.0 parts of octane diamine as raw materials, performing reactive extrusion and granulation through a co-rotating double-screw extruder with the temperature of 150-320 ℃ in each section, and obtaining the polyimide with the melting point of 335 ℃. Specifically, polyimide raw materials are added from a machine head, pyromellitic anhydride is added into a 5 th barrel after a polymer is melted, then melted octane diamine is added into a ninth barrel, the materials continue to react, and the length-diameter ratio of a total screw is 180: 1, staying for 20 minutes, and extruding and granulating to obtain the polyimide resin.
Example 18
The preparation method of the amide imide copolymer comprises the following steps of preparing raw materials, wherein the raw materials do not contain volatile organic solvents, and comprise 21 parts of polymerized monomer 4, 4' -oxydiphthalic anhydride, 21.6 parts of p-phenylenediamine, 16.6 parts of terephthalic acid and 100 parts of PA66 resin by weight;
the polymerization method comprises the following steps: the raw materials with the proportion are led to a double-screw extruder for reactive extrusion and granulation through each section of which is set to be 150-330 ℃, so as to obtain the amide imide copolymer with the melting point of 338 ℃.
Specifically, a polyamide raw material PA66 is added from a machine head, after a polymer is melted, acid anhydride is added into a cylinder body in the 5 th section, then melted p-phenylenediamine is added into a cylinder body in the ninth section, the materials continue to react, and the length-diameter ratio of a total screw is 180: and (1) keeping for 20 minutes, and extruding and granulating to obtain the polyimide resin.
Example 19
The molten polyimide resin prepared in example 13 was fed into a pipe reactor equipped with a static mixing device, dodecanediamine and pyromellitic dianhydride were then added in succession, the materials continued to stay in the pipe reactor for 30 minutes and continuously flowed out of the pipe, after passing through a pipe having a length-to-diameter ratio of 20: 1 to a double-screw extruder to obtain the polyimide resin, wherein the melting point of the polyimide resin is 303 ℃.
Example 20
The polyimide resin obtained in example 19 was fed from the head of a co-rotating twin-screw extruder, pyromellitic anhydride was fed into the fifth barrel after melting, dodecanediamine was fed into the ninth barrel, and then the material was fed into a reaction vessel, two reaction vessels were set to receive the continuously extruded material from the extruder in turn, the material was reacted in the reaction vessels for 30 minutes, and extruded by a melt pump for granulation to obtain a polyimide resin having a melting point of 301 ℃.
The polymerization method does not need the process of preparing nylon salt in water or alcohol solution, does not need to prepare the imide precursor polyamic acid in a volatile polar solvent, saves a large amount of water resources and energy, does not need to introduce a volatile organic solvent, and is a novel green and environment-friendly new process. The method can easily introduce various monomers to prepare copolyamide imide and polyimide, and can adjust the performance of products in a large range.
The conventional method blends polyimide and polyamide to obtain modified polyamide, the two materials are mainly combined in a physical blending mode, phase separation is easy to generate after long-term use, and particularly the impact strength of a product placed for a long time is greatly influenced. According to the invention, the amide imide polymer is obtained through imide-generating chemical bonds, the product stability is high, the uniformity is good, the conventional melt conveying and die discharging can be used, the material strips are smooth and uniform and are continuous, the sample is full and uniform after being granulated, the product produced continuously has stable performance and high yield, the phase separation can not be generated after the product is placed for a long time, and the impact strength is not changed.
The preparation method of the invention can add one or more of conventional catalysts synthesized by polyamide and amide imide copolymer, antioxidants, lubricants, molecular weight regulators and the like according to the needs, and can also directly complete the polymerization reaction without adding any auxiliary agent. The preparation method is suitable for synthesizing various amide imide copolymer resins, is not limited to the types listed in the examples, and has wide application range.
The above embodiments only express specific embodiments of the present invention, and the description is specific and detailed, but not to be understood as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (11)
1. The preparation method of the imide structure polymer is characterized in that raw materials comprise, by weight, 10-90 parts of reactive dispersion medium amido bond polymer, 0-50 parts of polymerized monomer diacid, 5-100 parts of diamine, and 5-100 parts of carboxylic acid capable of forming cyclic internal anhydride and/or derivatives formed by the carboxylic acid, wherein the carboxylic acid is at least one of tribasic acid and tetrabasic acid, and the derivatives are at least one of anhydride and ester; the preparation method comprises the steps of mixing raw materials, taking a molten amido bond polymer as a dispersion medium, reacting and mixing a polymerization monomer in the dispersion medium, and polymerizing to obtain a polymer containing an imide structure.
2. The method for preparing the imide structural polymer as claimed in claim 1, wherein the raw materials are continuously added to a material mixing device in proportion, the polymerized monomers are uniformly mixed in the molten reactive amide dispersion medium by reaction in the material mixing device, and the uniformly mixed materials are polymerized in a subsequent polymerization device until the nylon resin reaches the required molecular weight.
3. The method for producing an imide structural polymer according to claim 1 wherein said amide bond polymer is at least one selected from the group consisting of polyamide, polyesteramide, polyimide and amide imide copolymer.
4. The process for producing an imide structural polymer according to claim 3, wherein the molecular weight of the amide bond polymer is not more than 100000.
5. The process for producing the imide structural polymer according to claim 3, wherein the amide bond polymer is not crystallized or has a melting point of less than 400 ℃.
6. The method for preparing imide structural polymers as claimed in claim 1, wherein the polymerizable monomers include 0 to 50 parts of dibasic acid, 5 to 100 parts of diamine and 5 to 100 parts of acid anhydride.
7. The method for producing the imide structural polymer of claim 1 wherein the carboxylic acid is at least one of aliphatic or aromatic carboxylic acids having 9 to 32 carbon atoms and is capable of forming at least one internal acid anhydride.
8. The method for preparing imide structural polymers of claim 7 wherein the polymeric monomer is diamine, tetrabasic acid and/or dianhydride of tetrabasic acid.
9. The method for preparing the imide-structured polymer according to claim 8, wherein the polymerization monomer is reacted in a molten amide bond polymer to obtain an imide-structured polymer, and the imide-structured polymer is used as a dispersion medium for the reaction, and the reaction is repeated to increase the proportion of imide groups until an imide polymer with an amide bond proportion close to zero is obtained.
10. The method for producing an imide structural polymer as claimed in claim 8, wherein said diamine is an aliphatic diamine having a carbon chain length of not less than 8 carbon atoms.
11. The method for producing an imide structural polymer as claimed in claim 1, wherein the carboxylic acid and the derivative thereof are not dispersed simultaneously with the diamine in the amide bond polymer medium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011524414.6A CN114716678A (en) | 2020-12-22 | 2020-12-22 | Preparation method of imide structure polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011524414.6A CN114716678A (en) | 2020-12-22 | 2020-12-22 | Preparation method of imide structure polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114716678A true CN114716678A (en) | 2022-07-08 |
Family
ID=82230224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011524414.6A Pending CN114716678A (en) | 2020-12-22 | 2020-12-22 | Preparation method of imide structure polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114716678A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332766A (en) * | 1998-10-29 | 2002-01-23 | 住友胶木株式会社 | Imide containing polymers made by bulk polymerization |
| CN102099398A (en) * | 2008-06-12 | 2011-06-15 | 罗地亚管理公司 | Process for preparing a polyamideimide, a polyamideimide and composition comprising this polyamideimide |
| CN111518270A (en) * | 2019-05-17 | 2020-08-11 | 成都肆零壹科技有限公司 | Preparation method of environment-friendly polyamide resin |
| CN112062950A (en) * | 2020-03-28 | 2020-12-11 | 成都肆零壹科技有限公司 | Continuous nylon polymerization process |
-
2020
- 2020-12-22 CN CN202011524414.6A patent/CN114716678A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332766A (en) * | 1998-10-29 | 2002-01-23 | 住友胶木株式会社 | Imide containing polymers made by bulk polymerization |
| CN102099398A (en) * | 2008-06-12 | 2011-06-15 | 罗地亚管理公司 | Process for preparing a polyamideimide, a polyamideimide and composition comprising this polyamideimide |
| CN111518270A (en) * | 2019-05-17 | 2020-08-11 | 成都肆零壹科技有限公司 | Preparation method of environment-friendly polyamide resin |
| CN112062950A (en) * | 2020-03-28 | 2020-12-11 | 成都肆零壹科技有限公司 | Continuous nylon polymerization process |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112390945B (en) | Continuous nylon polymerization method | |
| CN1116341C (en) | Method for producing polyamide | |
| WO2018120702A1 (en) | Method for producing semi-aromatic polyamide and semi-aromatic polyamide | |
| CN111363144B (en) | Polymerization process of polyesteramide | |
| JP2010530458A (en) | Process for producing polyamide in an extruder | |
| CN106188551B (en) | A kind of preparation method of semi-aromatic polyimide modified nylon dragon and preparation method thereof and semi-aromatic polyimides | |
| WO2020233497A1 (en) | Method for preparing environmentally friendly polyamide resin | |
| JPS59155433A (en) | Polycondensation | |
| JPS6164718A (en) | Reactive composition based on polyamide oligomer and epoxideresin | |
| CN114316255A (en) | High-temperature-resistant nylon continuous melt polymerization method | |
| EP2726536A1 (en) | Branched polyamide | |
| CN111057233A (en) | Copolymerized semi-aromatic polyamide and preparation method thereof | |
| CN114716678A (en) | Preparation method of imide structure polymer | |
| CN109666143A (en) | Polyamic acid solution preparation method | |
| EP2658897A1 (en) | Amino functionalised oligoimides with enhanced storage stability | |
| CN115044196B (en) | Preparation method of nylon alloy | |
| JPS63275632A (en) | Novel curable wholly aromatic polyamide | |
| JP2010215682A (en) | Method for solid state polymerization of polyamide | |
| JPS62225531A (en) | Amorphous aromatic copolyamide and its production | |
| CN113667119B (en) | Polyacetamide-imide film and preparation method thereof | |
| CN109337056A (en) | Graphene oxide modification of nylon/PI alloy and preparation method | |
| CN114605633B (en) | Bulk flame-retardant nylon and preparation method and application thereof | |
| CN109627763B (en) | Method for preparing polyimide molding powder by solid-phase polymerization | |
| EP1217027B1 (en) | Melt-processible, thermoplastic random copolyimides having recoverable crystallinity and associated processes | |
| CN117186402A (en) | Ethynyl aniline end capped isoamide material and its prepn process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |