CN115044196B - Preparation method of nylon alloy - Google Patents

Preparation method of nylon alloy Download PDF

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CN115044196B
CN115044196B CN202110248831.0A CN202110248831A CN115044196B CN 115044196 B CN115044196 B CN 115044196B CN 202110248831 A CN202110248831 A CN 202110248831A CN 115044196 B CN115044196 B CN 115044196B
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nylon
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CN115044196A (en
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李洋
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Chengdu 401 Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/36—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing nitrogen, e.g. by nitration
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyamides (AREA)

Abstract

The invention provides a preparation method of nylon alloy, which comprises the steps of continuously adding 5-100 parts of polymer, 5-100 parts of diamine and 5-100 parts of diacid and/or diacid ester into a screw extrusion device, uniformly mixing to form a continuously conveyed melt, and feeding the melt into a subsequent polymerization device to form the polymer alloy comprising nylon components. The steps and energy consumption from raw materials to products are reduced, and the product performance is better.

Description

Preparation method of nylon alloy
Technical Field
The invention relates to the technical field of engineering plastics, in particular to a preparation method of nylon alloy.
Background
Nylon is the most commonly used engineering plastic at present, has good mechanical property and temperature resistance, and is widely applied to various aspects of machinery, electric appliances, electronics, automobiles and the like. However, nylon polymers have the disadvantages of large polarity, high water absorption, deformation after water absorption and the like, and limit the application range. The water absorption rate of nylon can be reduced by preparing the polyesteramide through copolymerization, but the hydrolysis resistance of the polyester part is far lower than that of nylon, so that the stability of the polyesteramide material in a high-temperature and high-humidity environment is far lower than that of nylon.
Improving the properties of polymers by melt blending different types of polymers to form polymeric alloys is another important way to improve polymer properties. Two or more polymers commonly used to form alloys are incompatible and phase separation occurs during blending. The addition of a compatibilizer generally enables various polymers to form a relatively stable microscopic phase structure, thereby ensuring the stability of physical properties of the product. In particular, nylon polymers of some specific molecular structures, which have melting points or temperatures that can be melt processed even above their decomposition temperatures, are not capable of producing nylon alloys by conventional methods.
Disclosure of Invention
Aiming at the technical problems, the invention provides a preparation method of nylon alloy. The polymerization process of nylon and the formation process of alloy are synchronously carried out, so that the steps and energy consumption from raw materials to products are reduced, and the product performance is better.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of nylon alloy comprises the steps of continuously adding 5-100 parts of polymer, 5-100 parts of diamine and 5-100 parts of diacid and/or diacid ester into a screw extrusion device, uniformly mixing to form a continuously conveyed melt, and feeding the melt into a subsequent polymerization device to form the polymer alloy comprising nylon components.
The nylon alloy raw material of the invention uses the dibasic acid and/or dibasic acid ester and diamine small molecular monomer to replace polyamide raw material, the blending reaction contains nylon polymerization reaction, the dibasic acid or ester and diamine monomer are subjected to melt polymerization reaction in a screw extrusion device, the raw material continuously enters screw extrusion equipment, polymerization and blending reaction are completed in the flowing process of material transmission, the continuity of feeding, reaction and discharging in the polymerization reaction of the small molecular monomer is realized, the intermittent production defect of the traditional reaction kettle process is overcome, the step of preparing nylon salt in aqueous solution is omitted, the process of independently preparing nylon product is also omitted, and the modified nylon alloy is directly prepared from the small molecular monomer through one-step reaction.
The polymer raw material is used as a reactive dispersion medium, and the polymerization monomers are uniformly mixed in the dispersion medium of the polymer through melt reaction.
The polymer raw material is used as a reactive dispersion medium, the dibasic acid and the diamine meet in a molten dispersion system of the polymer to generate salt, and the salt undergoes polymerization reaction, so that the whole system is very uniform, the condition that a certain component is incompatible can not occur, and the uniform mixing of the raw materials can be realized rapidly.
On the other hand, the dispersion system has a certain melting point and viscosity, and can be suitable for the application of screw extrusion equipment, so that the material mixing and dispersing process can be carried out in the screw extrusion equipment, the advantages of high heat transfer and dispersing efficiency of the screw extrusion equipment are fully exerted, the continuous production of the polymerization of the small molecular monomers is realized, and the production efficiency is greatly improved.
The polymer raw material is at least one of polyolefin, polyether, polyphenyl ether, polythioether, polyaromatic hydrocarbon, polystyrene, polysulfone, polysiloxane and vinyl polymer.
Preferably, at least one component of the polymer feed contains at least one of amino, carboxyl, anhydride, hydroxyl, epoxy, and oxazoline functional groups.
The functional group has extremely high polarity, can react with amino or carboxyl on nylon, has good bonding capability, can be used as a compatilizer, and can increase the bonding capability between a base polymer and the capability generated by polymerization to form a stable microscopic phase structure.
Polyethers, polythioethers, polysulfones have relatively high polarity per se and may have a certain compatibility with nylon, so that the introduction of polar functional groups to increase the compatibility is not necessary, other polyolefins, polyarenes, polystyrenes, polysiloxanes, vinyl polymers have relatively low polarity per se and nylon has relatively poor compatibility, so that the introduction of functional groups having relatively high polarity or capable of reacting with nylon in at least one component of the polymer raw material by copolymerization or the like is necessary, otherwise, the resulting polymer alloy has difficulty in achieving relatively high performance. Even if the polymer is polyether, polythioether or polysulfone, the performance of the alloy can be further improved by introducing proper functional groups.
The polymer and the raw materials of the dibasic acid and/or the dibasic acid ester are melted and mixed uniformly in the screw extrusion device before the diamine is added into the screw extrusion device, and a continuously conveyed melt is formed in the screw extrusion device. In the nylon polymerization process, a great deal of heat is released in the process of mixing diamine and diamine, the system temperature can far exceed the boiling point of water, and the water removed in the polymerization reaction forms high-temperature and high-pressure steam, so that before the diamine and diamine are mixed, a stable melt is required to be formed in the screw extrusion device, and at least one section of barrel of the extrusion device is filled with the melt, so that water and other volatile raw materials can be sealed in the system. And the volatility of the dibasic acid is far lower than that of diamine, so that the polymer raw material and the dibasic acid monomer are firstly mixed to form a continuously conveyed melt, and then the diamine is added, so that the uncontrollable leakage of high-pressure water vapor from a raw material inlet can be avoided.
Preferably, the diamine is continuously added to the screw extruder in liquid or solution form. It is easier to ensure the tightness of the equipment.
The subsequent polymerization device is a continuous conveying polymerization device.
The continuous conveying polymerization device is at least one of a screw extrusion device and a tubular reaction device.
The polymer raw material used in the invention does not undergo severe degradation under the condition of nylon polymerization, so that the polymer raw material has higher melt viscosity in the process of material melt conveying, and the polymer raw material accounts for not less than 2% and preferably 5% of the mass of nylon component in the final product in order to ensure sufficient sealing.
In the polymerization of diamine and diacid to form nylon, the molar ratio of the two monomers is generally comparable, as diamine is generally more volatile and slightly more volatile than diacid. In the present invention, since the polymer raw material may contain an amino group, a carboxylic acid or an acid anhydride, and may participate in the polymerization reaction of nylon, it is necessary to consider the amount of the amine or the acid in the polymer raw material, and the molar ratio of the diamine to the diacid is set to be larger than that of the usual nylon polymerization, and the polymerization ratio is adjusted according to the actual situation.
The mole ratio of the dibasic acid and/or dibasic acid ester to diamine in the raw materials is 0.66-1.5:1.
the highest temperature reached in the process of preparing the alloy is higher than the decomposition temperature of the nylon component in the product.
Preferably, the diacid raw material contains aromatic diacid, and the mole ratio of the aromatic diacid accounts for at least 20 percent of the mole ratio of the diacid raw material. The melting point of nylon prepared by the monomer is often higher than the decomposition temperature.
The invention has the beneficial effects that:
1. the traditional nylon alloy preparation method is that different kinds of polymers are respectively prepared, then the different kinds of polymers are blended, wherein energy consumption is required in the polymerization process of different raw material polymers, energy consumption is also required in the process of preparing raw material particles, then the raw material particles are fused and blended, and the energy consumption is repeatedly wasted. The invention adopts the micromolecule monomer to replace nylon as the raw material, and the polymerization and blending of the nylon occur simultaneously, so that the repeated energy consumption of granulating the nylon from a melt state and then melting particles can be reduced, and the invention has important significance for saving and reducing emission.
2. The initial material mixing of the traditional alloy preparation is the mixing of macromolecules and macromolecules, molecular chains are entangled and are harder to move and disperse, the initial mixing stage of the invention is the mixing of small molecules and macromolecules, the small molecules can enter between the macromolecular chains, the mixing is more uniform, the physical properties are more stable, and the product performance is better.
3. For nylon with a melting point or a temperature capable of being melt-processed which is higher than the decomposition temperature of the nylon, the nylon alloy cannot be prepared by the traditional method, but the melt processing temperature of the whole material adopting the method can still be lower than the decomposition temperature of the nylon, and the nylon alloy can still be prepared by the method. The method is particularly suitable for the situation that the highest temperature in the alloy preparation process is higher than the decomposition temperature of nylon in the product.
Detailed Description
The invention will be further described by the following examples for the purpose of more clearly and specifically describing the object of the invention. The following examples are only for specific illustration of the implementation method of the present invention and do not limit the protection scope of the present invention.
Example 1
The preparation method of the nylon alloy comprises the steps of continuously adding 5 parts of polymer, 5 parts of diamine and 5 parts of dibasic acid into a screw extrusion device for uniform mixing to form a continuously conveyed melt, and feeding the melt into a subsequent polymerization device to form the polymer alloy comprising nylon components.
Example 2
The preparation method of the nylon alloy comprises the steps of continuously adding 100 parts of polymer, 90 parts of diamine and 90 parts of dibasic acid ester into a screw extrusion device, uniformly mixing to form a continuously conveyed melt, and feeding the melt into a subsequent polymerization device to form the polymer alloy comprising nylon components.
The polymer raw material is used as a reactive dispersion medium, and the polymerization monomer is melted and mixed uniformly in the dispersion medium of the polymer.
The polymer raw material is at least one of polyolefin, polyether, polyphenyl ether, polythioether, polyaromatic hydrocarbon, polystyrene, polysulfone, polysiloxane and vinyl polymer.
At least one component of the polymer feed contains at least one of amino, carboxyl, anhydride, hydroxyl, epoxy, and oxazoline functional groups.
The mole ratio of the dibasic acid and/or dibasic acid ester to diamine in the raw materials is 1:1.
the highest temperature reached during the preparation of the alloy is above the decomposition temperature of the nylon component of the product.
Example 3
The preparation method of the nylon alloy comprises the steps of continuously adding 50 parts of polymer, 100 parts of diamine and 100 parts of dibasic acid into a screw extrusion device, uniformly mixing to form a continuously conveyed melt, and feeding the melt into a subsequent polymerization device to form the polymer alloy comprising nylon components.
The polymer raw material is used as a reactive dispersion medium, and the polymerization monomer is melted and mixed uniformly in the dispersion medium of the polymer.
The polymer raw material is at least one of polyolefin, polyether, polyphenyl ether, polythioether, polyaromatic hydrocarbon, polystyrene, polysulfone, polysiloxane and vinyl polymer.
At least one component of the polymer feed contains at least one of amino, carboxyl, anhydride, hydroxyl, epoxy, and oxazoline functional groups.
The polymer raw material accounts for not less than 2%, preferably 5% of the mass of the nylon component in the final product.
The mole ratio of the dibasic acid and/or dibasic acid ester to diamine in the raw materials is 0.66:1.
the diacid raw material contains aromatic diacid, and the mole ratio of the aromatic diacid accounts for at least 20 percent of the mole ratio of the diacid raw material.
Example 4
The preparation method of the nylon alloy comprises the steps of continuously adding 20 parts of polymer, 60 parts of diamine and 50 parts of diacid into a screw extrusion device, uniformly mixing to form a continuously conveyed melt, and feeding the melt into a subsequent polymerization device to form the polymer alloy comprising nylon components.
The polymer raw material is used as a reactive dispersion medium, and the polymerization monomer is melted and mixed uniformly in the dispersion medium of the polymer.
The polymer raw material is at least one of polyolefin, polyether, polyphenyl ether, polythioether, polyaromatic hydrocarbon, polystyrene, polysulfone, polysiloxane and vinyl polymer.
At least one component of the polymer feed contains at least one of amino, carboxyl, anhydride, hydroxyl, epoxy, and oxazoline functional groups.
The polymer raw material and the diacid monomer are firstly mixed to form a continuously conveyed melt, and then diamine is added, so that the uncontrollable leakage of high-pressure water vapor from a raw material inlet can be avoided.
The diamine is continuously added into the screw extrusion device in a liquid state or a solution state. It is easier to ensure the tightness of the equipment.
The subsequent polymerization device is a continuous conveying polymerization device.
The continuous conveying polymerization device is at least one of a screw extrusion device and a tubular reaction device.
The polymer raw material accounts for not less than 2%, preferably 5% of the mass of the nylon component in the final product.
The mole ratio of the dibasic acid and/or dibasic acid ester to diamine in the raw materials is 1.5:1.
the diacid raw material contains aromatic diacid, and the mole ratio of the aromatic diacid accounts for at least 20 percent of the mole ratio of the diacid raw material.
Example 5
According to 20:10 weight percent of mixed maleic anhydride grafted POE, terephthalic acid, 0.5 percent of antioxidant and 0.2 percent of catalyst accounting for the total weight are fed into a co-rotating double screw extruder from the front end through a weightlessness metering device. Setting the temperature of a screw, the temperature of a feeding section is 100-180 ℃, the temperature of a melting and dispersing section is 180-220 ℃, and continuously adding liquid hexamethylenediamine into a section 7 barrel through a liquid pump after the materials are melted and uniformly mixed, wherein the weight ratio of the hexamethylenediamine to the terephthalic acid is 118:166. the materials are uniformly mixed in a screw extrusion device and enter a continuous flow reactor with a stirring device, the temperature is controlled to be 280-310 ℃, and the effective volume of the reactor is 50 liters. And continuously flowing out of the continuous flow reactor, and then, feeding the material into a co-rotating double-screw extruder with the length-diameter ratio of 48:1 to extrude and granulate, thereby obtaining the PA6T/POE alloy. The average residence time of the material in the polymerization apparatus was 20 minutes.
The melting point of the nylon component PA6T exceeds 370 ℃, the decomposition temperature of the PA6T is exceeded, the nylon component PA6T cannot be directly melt-processed, the alloy cannot be prepared by the traditional method, and the PA6T/POE alloy prepared by the method can be melt-processed within 320 ℃. The water absorption rate of the PA6T/POE is 0.2 percent, which is far lower than that of the PA6T/66 by 1.2 percent.
Example 6
According to 20:10 weight percent of branch POE, terephthalic acid, 0.5 percent of antioxidant and 0.2 percent of catalyst accounting for the total weight are mixed, and the mixture is sent into a co-rotating double screw extruder from the front end through a weightlessness metering device. Setting the temperature of a screw, the temperature of a feeding section is 100-180 ℃, the temperature of a melting and dispersing section is 180-220 ℃, and after materials are melted and mixed uniformly, continuously adding liquid pentanediamine into a section 7 barrel through a liquid pump, wherein the weight ratio of the pentanediamine to the terephthalic acid is 104:166. the materials are uniformly mixed in a screw extrusion device and enter a continuous flow reactor with a stirring device, the temperature is controlled to be 280-310 ℃, and the effective volume of the reactor is 50 liters. And continuously flowing out of the continuous flow reactor, and then, feeding the material into a co-rotating double-screw extruder with the length-diameter ratio of 48:1 to extrude and granulate, thereby obtaining the PA5T/POE alloy. The average residence time of the material in the polymerization apparatus was 20 minutes.
The melting point of the nylon component PA5T is close to the decomposition temperature of the PA5T, the nylon component PA5T cannot be directly melt-processed, the alloy cannot be prepared by the traditional method, and the PA5T/POE alloy prepared by the method can be melt-processed within 310 ℃. The water absorption rate of PA5T/POE is 0.2 percent, which is far lower than that of PA5T/56 by 1.3 percent.
Example 7
According to 20:10 weight ratio mixing oxazoline branch PP, terephthalic acid, 0.5 percent of antioxidant and 0.2 percent of catalyst, and sending the mixture into a co-rotating double screw extruder from the front end through a weightlessness metering device. Setting the temperature of a screw, the temperature of a feeding section is 100-180 ℃, the temperature of a melting and dispersing section is 180-220 ℃, and after materials are melted and mixed uniformly, continuously adding liquid pentanediamine into a section 7 barrel through a liquid pump, wherein the weight ratio of the pentanediamine to the terephthalic acid is 104:166. the materials are uniformly mixed in a screw extrusion device and enter a continuous flow reactor with a stirring device, the temperature is controlled to be 280-310 ℃, and the effective volume of the reactor is 50 liters. And continuously flowing out of the continuous flow reactor, and then, feeding the material into a co-rotating double-screw extruder with the length-diameter ratio of 48:1 for extrusion granulation to obtain the PA5T/PP alloy. The average residence time of the material in the polymerization apparatus was 20 minutes.
The melting point of the nylon component PA5T is close to the decomposition temperature of the PA5T, the nylon component PA5T cannot be directly melt-processed, the alloy cannot be prepared by the traditional method, and the PA5T/PP alloy prepared by the method can be melt-processed within 310 ℃. The water absorption rate of the PA5T/PP alloy is 0.3 percent and is far lower than that of the PA5T/56 by 1.4 percent.
Example 8
According to 10:10:7.3 weight percent of PPS, terephthalic acid, adipic acid, 0.5 percent of antioxidant and 0.2 percent of catalyst which account for the total weight are mixed and fed into a co-rotating double screw extruder from the front end through a weightlessness metering device. Setting the temperature of a screw, the temperature of a feeding section is 150-230 ℃, the temperature of a melting and dispersing section is 270-305 ℃, and continuously adding liquid hexamethylenediamine into a section 7 barrel through a liquid pump after the materials are melted and uniformly mixed, wherein the molar ratio of the hexamethylenediamine to the diacid is 1.02:1, 13 parts by weight, uniformly mixing materials in a screw extrusion device, and feeding the materials into a continuous flow reactor with a stirring device, wherein the temperature is controlled to be 280-310 ℃, and the effective volume of the reactor is 50 liters. The material continuously flows out of the continuous flow reactor and then enters into the homodromous double-screw extrusion with the length-diameter ratio of 48:1Extruding and granulating by a machine to obtain PA6T/66/PPS alloy, wherein the average retention time of materials is 20 minutes, the melting point is 305 ℃, and the impact strength of no-notch is 33kj/m 2 。
Example 9
30 parts of PPS, 70 parts of PA6T/66 and 0.5% of antioxidant are combined from aspect ratio 48: adding the front end of a1 double-screw extruder, setting the temperature of each section to 270-320 ℃, extruding and granulating to obtain PA6T/66/PPS alloy, wherein the melting point is 303 ℃, and the impact strength without gaps is 22kj/m 2 . The average residence time of the material in the polymerization apparatus was 20 minutes.
The example is a traditional nylon alloy preparation method, compared with the example 8, the impact strength is improved by 50%, and the compatibility of the synthesized alloy is better.
Example 10
According to 30:1.5:10, uniformly mixing PPO, maleic anhydride grafting PS and adipic acid, continuously adding the mixture into an extruder from the front end of a double-screw extrusion device to melt materials, and continuously adding liquid hexamethylenediamine into a section 7 barrel, wherein the molar ratio of the hexamethylenediamine to the adipic acid is 1.03: the method comprises the steps of 1, uniformly mixing materials in a screw extrusion device, feeding the materials into a continuous flow reactor with a stirring device, controlling the temperature to be 280-310 ℃ and the effective volume of the reactor to be 50 liters, continuously flowing the materials out of the continuous flow reactor, feeding the materials into a homodromous double screw extruder with the length-diameter ratio of 48:1, continuously feeding glass fiber accounting for 30% of the weight of resin on the side of a section 6 barrel of the extruder, extruding and granulating to obtain the glass fiber reinforced PPO/PA66 alloy, wherein the impact strength of no gap is 32kj/m 2 The heat distortion temperature is 182 ℃. The average residence time of the material in the polymerization apparatus was 20 minutes.
In the embodiment, other components such as glass fiber and the like are added in the process of screw extrusion granulation, so that a modified product which can be directly applied is prepared in one step.
Example 11
30 parts of PPO,1.5 parts of maleic anhydride-grafted PS and 15 parts of PA66 are added continuously to an aspect ratio of 48:1, continuously adding glass fiber accounting for 30 percent of the weight of resin into a side feed of a section 6 cylinder after the material is melted, controlling the temperature to be 250-310 ℃, extruding and granulating to obtain the glass fiber reinforced PPO/PA66 alloy, and ensuring the notch impact strength25kj/m 2 The heat distortion temperature is 175 ℃. The average residence time of the material in the polymerization apparatus was 20 minutes.
The example is a traditional nylon alloy preparation method, compared with the example 10, the impact strength is obviously improved, and the compatibility of the synthesized alloy is better.
Example 12
According to 10:10:7.3 weight percent of mixed amino polysiloxane, terephthalic acid, adipic acid, 0.5 percent of antioxidant and 0.2 percent of catalyst which account for the total weight are fed into a co-rotating double screw extruder from the front end through a weightlessness metering device. Setting the temperature of a screw, the temperature of a feeding section is 150-230 ℃, the temperature of a melting and dispersing section is 270-305 ℃, and continuously adding liquid hexamethylenediamine into a section 7 barrel through a liquid pump after the materials are melted and uniformly mixed, wherein the molar ratio of the hexamethylenediamine to the diacid is 1.02:1, 13 parts by weight, uniformly mixing materials in a screw extrusion device, and feeding the materials into a continuous flow reactor with a stirring device, wherein the temperature is controlled to be 280-310 ℃, and the effective volume of the reactor is 50 liters. The material continuously flows out of the continuous flow reactor and enters a homodromous double-screw extruder with the length-diameter ratio of 48:1 to be extruded and granulated to obtain the PA 6T/66/silica gel alloy, the average residence time of the material is 20 minutes, the water absorption is as low as 0.1 percent and is far lower than 1.5 percent of PA6T/66, and the notch impact strength is 43kj/m 2 。
Example 13
According to 10:15 weight percent of PPS, terephthalic acid, 0.5 percent of antioxidant and 0.2 percent of catalyst accounting for the total weight are mixed and sent into a co-rotating double screw extruder from the front end through a weightlessness metering device. Setting the temperature of a screw, the temperature of a feeding section is 150-230 ℃, the temperature of a melting and dispersing section is 270-305 ℃, and after materials are melted and mixed uniformly, continuously adding liquid decanediamine into a section 7 barrel through a liquid pump, wherein the molar ratio of the decanediamine to terephthalic acid is 1.02:1, 16 parts by weight, uniformly mixing materials in a screw extrusion device, and feeding the materials into a continuous flow reactor with a stirring device, wherein the temperature is controlled to be 280-310 ℃, and the effective volume of the reactor is 50 liters. The materials continuously flow out of the continuous flow reactor and then enter a homodromous double-screw extruder with the length-diameter ratio of 48:1 to be extruded and granulated to obtain PA10T/PPS, the average residence time of the materials is 20 minutes, the water absorption is as low as 0.1%, and the water absorption is far as low as 0.1 percentBelow 0.5% of PA10T, no-notch impact strength 43kj/m 2 。
Example 14
According to 10: PPS, terephthalic acid and decanediamine are mixed in a weight ratio of 15:16, an antioxidant accounting for 0.5 percent of the total weight and a catalyst accounting for 0.2 percent of the total weight are fed into a co-rotating double screw extruder from the front end through a weight loss metering device. Setting the temperature of a screw, the temperature of a feeding section is 150-230 ℃, the temperature of a melting and dispersing section is 270-305 ℃, and after materials are melted and mixed uniformly, the materials enter a continuous flow reactor with a stirring device, the temperature is controlled to be 280-310 ℃, and the effective volume of the reactor is 50 liters. The material continuously flows out of the continuous flow reactor and enters a homodromous double-screw extruder with the length-diameter ratio of 48:1 to be extruded and granulated to obtain PA10T/PPS, the average residence time of the material is 20 minutes, the water absorption is as low as 0.1 percent and is far lower than 0.5 percent of PA10T, and the unnotched impact strength is 38kj/m 2 。
In this example, diamine and other raw materials can be directly added from the beginning to prepare alloy materials, so that the operation is more convenient for solid diamine, but the performance of the prepared materials is slightly poorer because the amine is more easily volatilized and lost. In actual production, the method can be flexibly selected according to the equipment and the requirements on the physical properties of materials.
Example 15
According to 20:5:10 weight percent of mixed maleic anhydride grafted POE, PA66, terephthalic acid, 0.5 percent of antioxidant and 0.2 percent of catalyst accounting for the total weight are fed into a co-rotating double screw extruder from the front end through a weightlessness metering device. Setting the temperature of a screw, the temperature of a feeding section is 100-180 ℃, the temperature of a melting and dispersing section is 180-220 ℃, and continuously adding liquid hexamethylenediamine into a section 7 barrel through a liquid pump after the materials are melted and uniformly mixed, wherein the weight ratio of the hexamethylenediamine to the terephthalic acid is 118:166. the materials are uniformly mixed in a screw extrusion device and enter a continuous flow reactor with a stirring device, the temperature is controlled to be 280-310 ℃, and the effective volume of the reactor is 50 liters. And continuously flowing out of the continuous flow reactor, and then, feeding the material into a co-rotating double-screw extruder with the length-diameter ratio of 48:1 to extrude and granulate to obtain the PA6T/66/POE alloy. The average residence time of the material in the polymerization apparatus was 20 minutes, the notched impact strength was 35j/m 2 。
The alloy prepared by the invention has functional groups capable of reacting with nylon, and part of the polymers and nylon in the formed alloy are covalently bonded together, so that at least two polymers are well compatible. Therefore, the alloy can be polymerized and blended with other polymers to adjust the proportion of each component in the alloy, so that the adjustment of the polymer performance can be more flexible. The alloy prepared by the invention can also be used as a compatilizer for other polymers during blending to enhance the performance of other alloys, and the application field of the material obtained by the invention can be expanded.
The preparation method of the invention can add certain or a plurality of auxiliary agents such as conventional antioxidants, catalysts, toughening agents, molecular weight regulators, lubricants and the like for polymerization reaction according to the requirement, and can also directly complete the polymerization reaction without adding the auxiliary agents. The preparation method is suitable for synthesizing various nylon alloys, is not limited to the types listed in the examples, and has wide application range.
The foregoing examples merely illustrate specific embodiments of the invention, which are described in greater detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention.

Claims (10)

1. A preparation method of nylon alloy is characterized in that: according to mass, the raw materials comprise 5-100 parts of polymer, 5-100 parts of diamine and 5-100 parts of dibasic acid and/or dibasic acid ester, the raw materials are continuously added into a screw extrusion device to be uniformly mixed to form a continuously conveyed melt, and the continuously conveyed melt enters a subsequent polymerization device to form a polymer alloy comprising nylon components;
the polymer raw material is at least one of polyolefin, polyether, polythioether, polyaromatic hydrocarbon, polysulfone and vinyl polymer;
at least one component of the polymer feed contains at least one of amino, carboxyl, anhydride, hydroxyl, epoxy, and oxazoline functional groups.
2. The method for preparing the nylon alloy according to claim 1, wherein: the polymer raw material is used as a reactive dispersion medium, and the polymerization monomer is melted and mixed uniformly in the dispersion medium of the polymer.
3. The method for preparing the nylon alloy according to claim 1, wherein: the polymer and the diacid and/or diacid ester raw materials are melted and mixed uniformly in the screw extrusion device before diamine is added into the screw extrusion device, and a continuously conveyed melt is formed in the screw extrusion device.
4. A method of producing a nylon alloy as claimed in claim 3, wherein the diamine is continuously fed into the screw extruder in a liquid or solution form.
5. The method for producing a nylon alloy according to claim 1, wherein the subsequent polymerization apparatus is a continuously-fed polymerization apparatus.
6. The method of producing a nylon alloy according to claim 1, wherein the polymer raw material accounts for not less than 2% by mass of the nylon component in the final product.
7. The method of producing a nylon alloy according to claim 6, wherein the polymer raw material accounts for not less than 5% by mass of the nylon component in the final product.
8. The method for preparing nylon alloy according to claim 1, wherein the molar ratio of the dibasic acid and/or dibasic acid ester to diamine in the raw material is 0.66-1.5:1.
9. the method of producing nylon alloy according to claim 1, wherein the highest temperature reached during the production of the alloy is higher than the decomposition temperature of the nylon component in the product.
10. The method for producing a nylon alloy according to claim 9, wherein the diacid raw material contains an aromatic diacid, and the molar ratio of the aromatic diacid is at least 20% of the molar ratio of the diacid raw material.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111363144A (en) * 2020-04-30 2020-07-03 成都肆零壹科技有限公司 Polymerization process of polyesteramide
CN112390945A (en) * 2020-03-28 2021-02-23 成都肆零壹科技有限公司 Continuous nylon polymerization method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112390945A (en) * 2020-03-28 2021-02-23 成都肆零壹科技有限公司 Continuous nylon polymerization method
CN111363144A (en) * 2020-04-30 2020-07-03 成都肆零壹科技有限公司 Polymerization process of polyesteramide

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