CN109627763B - Method for preparing polyimide molding powder by solid-phase polymerization - Google Patents

Method for preparing polyimide molding powder by solid-phase polymerization Download PDF

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CN109627763B
CN109627763B CN201811420979.2A CN201811420979A CN109627763B CN 109627763 B CN109627763 B CN 109627763B CN 201811420979 A CN201811420979 A CN 201811420979A CN 109627763 B CN109627763 B CN 109627763B
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dianhydride
polyimide
anhydride
aromatic
diether
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CN109627763A (en
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陈海波
张鑫
仇伟
石耀东
杨开业
徐延伟
原博
郑福群
刘彪
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Wanhua Chemical Group Co Ltd
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    • 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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • 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
    • 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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids

Abstract

The invention provides a method for preparing polyimide molding powder by solid-phase polymerization, which comprises the following steps: respectively crushing aromatic binary primary amine, aromatic binary anhydride and toughening plasticizer maleic anhydride ester, and uniformly mixing in a high-speed mixer; continuously feeding the mixed materials in a continuous rotary screw type conveying device, and reacting to generate polyimide; the polyimide formed is rotated, extruded and temperature controlled by equipment, and polyimide particles are formed and are crushed to obtain the polyimide molding powder. The method does not use an organic solvent, belongs to a green production line, and the prepared polyimide plate has high strength, impact resistance and mechanical property superior to that of polyimide prepared by a solvent method.

Description

Method for preparing polyimide molding powder by solid-phase polymerization
Technical Field
The invention belongs to the technical field of polyimide synthesis, and particularly relates to a method for preparing polyimide molding powder by solid-phase polymerization.
Background
Polyimide is a special high-performance heat-resistant material which can be used under high-temperature extreme conditions. Due to the extremely high use temperature, most polyimide products are molded by means of pressing, and even sintering is needed after primary molding by pressing to finally form the polyimide products, for example, the classic polyimide resin VESPLE is sintered (US 3179631).
There are several methods for the synthesis of polyimide molding powders or molding pellets, and US3179631 discloses the polycondensation of aprotic polar solvents to polyimides: and performing low-temperature polycondensation on dianhydride and diamine in N, N-dimethylacetamide, N-dimethylformamide or N-methylpyrrolidone to obtain a polyamic acid solution, and adding acetic anhydride and a tertiary amine catalyst to obtain the polyimide. The dianhydrides and diamines used in VESPEL of the classical structure are respectively pyromellitic dianhydride and diaminodiphenyl ether.
The creative chemical method comprises the steps of preparing a polymer with a polymerized seven-membered ring structure in an aprotic polar solvent by a dianhydride and diisocyanate method, and then removing carbon dioxide to obtain the PI2080 polyimide resin with the glass transition temperature of more than 340 ℃ (EP1354926), wherein the dianhydride is benzophenone dianhydride, and the diisocyanate is MDI and TDI.
Linear polyimides can be prepared by a DIELS-ALDER reaction using maleic anhydride and a diamine. The main reaction is two steps, wherein firstly, maleic anhydride reacts with diamine to generate bismaleimide, and secondly, the bismaleimide continuously reacts with the diamine, and the bismaleimide is opened through double bonds of the bismaleimide and is connected with amino to form polyimide resin. Imide substances containing double bonds are prone to regular crosslinking at high temperature to form thermosetting resins.
In addition, polyimide was synthesized from tetracarboxylic acid and diamine as raw materials in a polar phenol solvent with a high boiling point (US 5378420).
However, all of the above synthetic methods involve the treatment with organic solvents. The use of a large amount of organic solvents causes the problems of non-environmental-friendliness, high VOC, difficult solvent recovery and high cost in the production process of polyimide.
The company GE, USA, in 1976, disclosed a process for the preparation of polyetherimides by reaction melt extrusion using a co-rotating twin screw extruder (US 4073773). The method adopts a temperature step rising method at different feeding sections, solid materials are uniformly mixed and then are directly fed into an extruder, and the polyetherimide melt can be prepared by extrusion under the condition of vacuumizing. The method has an advantage in that the polyimide is synthesized without using a solvent. But the extruded material is a molten resin.
At present, a method for directly preparing solid polyimide by using a screw type reaction device is not found, the solid phase preparation method can avoid the environmental problem caused by using a solvent, and the complicated operations of polymer precipitation, filtration, washing, solvent recovery, drying and the like after the monomer is polymerized in the solvent are avoided, so that the production efficiency and the labor intensity are greatly improved.
Disclosure of Invention
The invention aims to provide a method for preparing polyimide molding powder by solid-phase polymerization, which solves the problems of longer polyimide synthesis process, difficult solvent recovery treatment, low production efficiency and the like.
In order to achieve the above purpose and achieve the above technical effects, the invention adopts the following technical scheme:
a method for preparing polyimide molding powder by solid-phase polymerization comprises the following steps:
a) respectively crushing aromatic binary primary amine, aromatic binary anhydride and toughening plasticizer maleic anhydride ester, and uniformly mixing in a high-speed mixer;
b) continuously feeding the mixed materials in a continuous rotary screw type conveying device, and reacting to generate polyimide;
c) the produced polyimide is rotated and extruded by equipment to form polyimide particles, and the polyimide particles are crushed to obtain the polyimide molding powder.
In the present invention, the aromatic primary diamine in step a) is an aromatic primary diamine having 6 to 27 carbon atoms, preferably one or more of diaminodiphenyl ether, diaminodiphenyl sulfone, diaminodiphenyl methane, dimethyldiaminodiphenyl methane, bisphenol a diether diamine, bisphenol S diether diamine, p-phenylenediamine and m-phenylenediamine, more preferably one or more of p-phenylenediamine, m-phenylenediamine, diaminodiphenyl ether, diaminodiphenyl sulfone, triphendiether diamine, bisphenol a diether diamine and biphenol diether diamine.
In the present invention, the aromatic dicarboxylic anhydride in step a) is an aromatic dicarboxylic anhydride having 10 to 31 carbon atoms, preferably one or more of pyromellitic dianhydride, benzophenone dianhydride, biphenyl dianhydride, diphenyl ether dianhydride, diphenyl sulfide dianhydride, triphenyl diether dianhydride, bisphenol a diether dianhydride, bisphenol S diether dianhydride, biphenyl diphenol diether dianhydride and diphenyl sulfone dianhydride, more preferably one or more of pyromellitic dianhydride, biphenyl dianhydride, diphenyl ether dianhydride, triphenyl diether dianhydride, biphenyl diphenol diether dianhydride, bisphenol a diether dianhydride and bisphenol S diether dianhydride.
In the present invention, the preparation method of aromatic dicarboxylic acid anhydrides such as diphenol diether dianhydride is referred to US 4417044.
In the invention, the maleic anhydride ester in the step a) is maleic anhydride terpene alcohol ester, and the structural general formula is as follows:
Figure BDA0001880554970000041
the substance is a compound containing R1And a compound containing R2Is generated by esterification reaction, and the maleic anhydride terpene alcohol ester is preferably
Figure BDA0001880554970000042
Figure BDA0001880554970000043
One or more of (a) or (b),
wherein R is1Is H or-CH3Containing R2The terpene alcohol of (A) has at least 2 unsaturated bonds, and the terpene alcohol is preferably geraniol
Figure BDA0001880554970000044
Nerol
Figure BDA0001880554970000045
Linalool
Figure BDA0001880554970000046
Farnesol
Figure BDA0001880554970000047
And linalool
Figure BDA0001880554970000048
One or more of (a).
In the invention, the principle of the toughening plasticizer of the butenedioic anhydride terpene alcohol ester is as follows: the structure of the maleic anhydride terpene alcohol ester contains unsaturated bonds of a butenedioic acid unit and binary unsaturated bonds of terpene alcohol, and when a plurality of unsaturated bonds are heated, the unsaturated bonds can be regularly and repeatedly crosslinked with diamine and polyimide, so that the material forms a space network structure. The principle is as follows:
Figure BDA0001880554970000051
in the reaction process, a plurality of double bonds (1 and 2) in the molecules are opened during heating, and the double bonds of the butenedioic acid in other molecules can also be opened to form a space network structure together, so that the toughness of the resin is improved.
The preparation method of the butenedioic anhydride terpene alcohol ester comprises the following steps: adding equimolar amounts of butenedioic anhydride and terpene alcohol, dried DMAC, toluene or o-xylene into a three-neck flask equipped with a water separator and a condenser tube. Starting stirring and heating reflux (the temperature is between about 135 ℃ and 150 ℃), opening the water separator when no water drops appear in the water separator, discharging a water layer, evaporating most of benzene series and solvent in the three-mouth bottle, and stopping heating. Adding the residual viscous substance in the three-necked bottle into ethanol, stirring, adding water into the mixture, stirring, layering, adding the liquid into a separating funnel, extracting with dichloroethane, discharging water, discharging the organic phase, extracting with water to obtain ethanol, and discharging the water layer. Evaporating the organic layer, and cooling to below 10 ℃ to obtain the maleic anhydride terpene alcohol ester solid.
In the invention, the aromatic dibasic primary amine and the aromatic dibasic acid anhydride in the step a) are in equal molar ratio; the butene diacid anhydride ester is 0.01-5 wt%, preferably 0.5-4 wt% of the mass sum of the aromatic dibasic primary amine and the aromatic dibasic acid anhydride.
In the present invention, the continuous rotary screw type conveying device in the step b) is a continuous extrusion reaction device with internal rotation and conveyance, and preferably one or more of a single screw extruder, a twin screw extruder, a continuous double-blade dryer and a rake dryer.
In the present invention, when a screw extruder is used in step b), the screw length-diameter ratio is (42-66):1, preferably (50-60): 1.
In the invention, the process temperatures of the continuous extrusion reaction equipment in the step b) are respectively as follows: the feeding section is between room temperature and 100 ℃, the temperature of the first section is 160-; step b) needs normal pressure or vacuum pumping, the vacuum degree is 0 to-0.095 MPa, and the number of vacuum pumping holes is 0-4. When the number of the air exhaust holes is 0, the air exhaust holes also need to be opened and cannot be closed.
In the present invention, the feeding rate in step b) is 18-60g/min, preferably 19.8-48 g/min; the screw speed is 60-150rpm, preferably 70-120 rpm; the retention time is 4.2-15 min.
In the invention, the polyimide particles in the step c) continuously drop onto a material receiving conveyor belt from a discharge port of a screw extruder, and the materials are taken into a storage bin through air cooling and crushed to finish the preparation of the polyimide molding powder.
In the present invention, the vacuum pressures are gauge pressures.
The preparation process of the present invention is used for the preparation of high molecular weight, moldable polyimides, polyetherimides, polyesterimides, polyamideimides, and also for structural modification with rigid polyimides.
The invention has the beneficial effects that:
1. the preparation method can directly prepare the particles of the polyimide, and the particles are directly used as the molding compound after being crushed, so that the continuous production can be realized, and the production efficiency of the polyimide is improved.
2. The high molecular weight thermoplastic polyimide (such as polyetherimide) particles prepared by the method can be blended and modified with polyimide used under high temperature conditions, so that the problem that high temperature resistant polyimide powder of polyetherimide and pyromellitic dianhydride cannot be well modified is solved.
3. The mechanical properties of the polyimide sheet prepared by the method are better than those of the polyimide prepared in the solvent (see examples 1-5 in particular).
4. The invention does not use organic solvent, has no three wastes, and belongs to a typical green production route.
Drawings
FIG. 1: polyimide particles prepared in example 1
FIG. 2: polyimide particles prepared in example 2
FIG. 3: example 1 IR spectrum of polyimide resin prepared by extrusion
FIG. 4: comparative example 1 IR spectrum of conventional polyimide resin prepared by solvent Synthesis
Detailed Description
The present invention is further illustrated by the following examples, which are only illustrative of the technical solutions of the present invention and are not intended to limit the scope of the present invention.
And (3) IR testing: model IR Tracer-100, test method: 0.2 g of resin powder is pressed into a sheet shape and put into an ATR accessory of Fourier IR for testing, and the testing wavelength range is 450-4000cm-1。
Unnotched impact strength test: the test temperature is 23 ℃ with reference to GB/T1043.1-2008 or ASTM D256-2010.
The main raw material information is as follows:
raw materials Manufacturer of the product Rank of Purity%
Biphenyl dianhydride SHANGHAI GUCHUANG NEW CHEMICAL MATERIALS Co.,Ltd. Industrial grade ＞98.5
Diphenyl ether dianhydride Shanghai resin institute Industrial grade ＞98.5
Diaminodiphenyl ether Shandong Wanda group Industrial grade ＞99
P-phenylenediamine Aladdin reagent Industrial grade ＞99
Bisphenol A diether dianhydride SHANGHAI GUCHUANG NEW CHEMICAL MATERIALS Co.,Ltd. Industrial grade ＞98.5
Bisphenol S diether diamine NANJING YUEZI CHEMICLA Co.,Ltd. Industrial grade ＞99
Pyromellitic dianhydride SHANGHAI GUCHUANG NEW CHEMICAL MATERIALS Co.,Ltd. Industrial grade ＞99
Benzophenone dianhydride Aladdin reagent Industrial grade ＞99
Diaminodiphenylmethane Wanhua Chemical Group Co., Ltd. Industrial grade ＞99
Biphenol diether dianhydride Self-made —— ＞98.5
Linalyl maleate Self-made —— ＞98
Citraconic anhydride nerol ester Self-made —— ＞98
Citraconic anhydride eaglewood alcohol ester Self-made —— ＞98
Farnesol ester with maleic anhydride Self-made —— ＞98
Geraniol maleic anhydride ester Self-made —— ＞98
The preparation of the diphenol diether dianhydride of the above table is described in US 4417044; the preparation method of the alcohol ester comprises the following steps: a1000 ml three-neck flask was charged with 0.1mol of a butenedioic anhydride compound, 0.10mol of a terpene alcohol compound, 300ml of dried DMAC, and 200ml of toluene or o-xylene, and a water separator and a condenser were disposed on the three-neck flask. Stirring and heating reflux are started (the temperature is between about 135 ℃ and 150 ℃), when no water drops appear in the water separator, the water separator is opened, the water layer is discharged, most of the benzene series and the solvent in the three-mouth bottle are distilled out to 350ml, and then heating is stopped. Adding the residual viscous substance in the three-necked bottle into 100ml ethanol, stirring, adding 200ml water into the mixture, stirring, layering, adding the liquid into a separating funnel, adding 200ml dichloroethane, extracting, discharging water, discharging the organic phase, extracting ethanol in the organic phase with 200ml water, and discharging the water layer. Evaporating the organic layer, and cooling to below 10 ℃ to obtain the maleic anhydride terpene alcohol ester solid.
Example 1
Respectively crushing the biphenyl dianhydride, the diphenyl ether dianhydride, the diaminodiphenyl ether and the maleic anhydride geraniol ester, and uniformly mixing the biphenyl dianhydride, the diphenyl ether dianhydride and the diaminodiphenyl ether main material according to the molar ratio of 8:2:10 and the mass ratio of the main material to the maleic anhydride geraniol ester of 100:0.5 by using a high-speed mixer for later use. Heating a double-screw extruder with the screw diameter of 26mm, wherein the temperature of a feeding section is 50 ℃, cooling water is introduced for constant temperature, the temperature of a 1 st section is 180 ℃, the temperature of a 2 nd section is 250 ℃, the temperature of a 3 rd section is 330 ℃, and the temperature of a 4 th section to an 8 th section is 370 ℃. The length-diameter ratio of the screw is 42: 1. The 1 st section and the 2 nd section are respectively provided with an air exhaust hole, and the vacuum degree is kept at-0.06 MPa. Continuously feeding the uniformly mixed material from the 1 st section at a feeding speed of 18g/min, simultaneously starting a screw, continuously extruding material particles from the tail end of the reactor after the screw rotates at 70rpm for about 5 minutes, and collecting and crushing the material.
After the prepared molding powder was compression molded, unnotched impact strength was measured, and the results are shown in Table 1.
Example 2
After the biphenyl diphenol diether dianhydride, the diaminodiphenyl ether and the linalool maleate are respectively crushed, the biphenyl diphenol diether dianhydride and the diaminodiphenyl ether main material are respectively crushed according to the molar ratio of 1:1 and the mass ratio of the total main material to the linalool maleate of 100:0.1, and then are uniformly mixed by a high-speed mixer for later use. Heating a double-screw extruder with the screw diameter of 20mm, wherein the temperature of a feeding section is 70 ℃, cooling water is introduced for constant temperature, the temperature of a 1 st section is 160 ℃, the temperature of a 2 nd section is 230 ℃, the temperature of a 3 rd section is 270 ℃, and the temperature of a 4 th section to a 10 th section is 340 ℃. The length-diameter ratio of the screw is 50: 1. The feed rate was set at 19.8g/min and the screw speed was 60 rpm. The 2 nd section and the 3 rd section are respectively provided with an air exhaust hole, and the vacuum degree is kept at-0.07 MPa. Continuously feeding the uniformly mixed materials from the 1 st section, simultaneously starting a screw, continuously extruding the material particles from the tail end of the reactor after the retention time is about 4.2 minutes, and crushing the materials after the materials are collected.
After the prepared molding powder was compression molded, unnotched impact strength was measured, and the results are shown in Table 1.
Example 3
Respectively crushing bisphenol A diether dianhydride, p-phenylenediamine and citraconic anhydride nerol ester, respectively crushing the bisphenol A diether dianhydride and the p-phenylenediamine main material according to the molar ratio of 1:1 and the mass ratio of the total main material to the citraconic anhydride nerol ester of 100:4.7, and uniformly mixing the materials by using a high-speed mixer for later use. Heating a single-screw extruder with the diameter of 35mm, wherein the temperature of a feeding section is 90 ℃, cooling water is introduced for constant temperature, the temperature of a 1 st section is 170 ℃, the temperature of a 2 nd section is 250 ℃, the temperature of a 3 rd section is 270 ℃, and the temperature of a 4 th section to a 10 th section is 330 ℃. The length-diameter ratio of the screw is 56: 1. The feed rate was set at 60g/min and the screw speed was 100 rpm. And the 2 nd section and the 3 rd section are provided with air exhaust holes, and the vacuum degree is kept at-0.055 MPa. Continuously feeding the uniformly mixed materials from the 1 st section, simultaneously starting a screw, continuously extruding the material particles from the tail end of the reactor after the retention time is about 6 minutes, and crushing the materials after the materials are collected.
After the prepared molding powder was compression molded, unnotched impact strength was measured, and the results are shown in Table 1.
Example 4
Respectively crushing the pyromellitic dianhydride, the bisphenol S diether diamine and the citraconic anhydride linalool ester, respectively crushing the main materials of the pyromellitic dianhydride and the bisphenol A diether diamine according to the molar ratio of 1:1 and the mass ratio of the total main materials to the citraconic anhydride linalool ester of 100:2.5, and uniformly mixing the crushed materials by using a high-speed mixer for later use. And (3) heating the continuous double-blade dryer, wherein the temperature of the feeding section is 55 ℃, cooling water is introduced for constant temperature, the temperature of the 1 st section is 190 ℃, the temperature of the 2 nd section is 230 ℃, the temperature of the 3 rd section is 265 ℃, the temperature of the 4 th section is 300 ℃, the temperature of the 5 th section is 310 ℃, and the temperature of the 6 th section to the 11 th section is 340 ℃. The length-diameter ratio of the screw is 60: 1. The feed rate was set at 35g/min and the screw speed was set at 120 rpm. And the second section is provided with an exhaust hole for normal pressure reaction. Continuously feeding the uniformly mixed materials from the 1 st section, simultaneously starting a screw, continuously extruding the material particles from the tail end of the reactor after the retention time is about 15 minutes, and crushing the materials after the materials are collected.
After the prepared molding powder was compression molded, unnotched impact strength was measured, and the results are shown in Table 1.
Example 5
After benzophenone dianhydride, diaminodiphenylmethane and maleic anhydride farnesol ester are respectively crushed, the main materials of benzophenone dianhydride and diaminodiphenylmethane are respectively crushed according to the molar ratio of 1:1 and the mass ratio of the total main materials to the maleic anhydride farnesol ester of 100:4, and then are uniformly mixed by a high-speed mixer for later use. Heating a double-screw extruder with the diameter of 26mm, wherein the temperature of a feeding section is 40 ℃, cooling water is introduced for constant temperature, the temperature of the 1 st section is 250 ℃, the temperature of the 2 nd section is 270 ℃, the temperature of the 3 rd to 5 th sections is 300 ℃, the temperature of the 6 th to 8 th sections is 330 ℃, and the temperature of the 9 th to 12 th sections is 380 ℃. The length-diameter ratio of the screw is 66: 1. The feed rate was set at 48g/min and the screw speed was 150 rpm. And the 2 nd section and the 3 rd section are provided with air exhaust holes, and the vacuum degree is kept at-0.07 MPa. Continuously feeding the uniformly mixed materials from the 1 st section, simultaneously starting a screw, continuously extruding the material particles from the tail end of the reactor after the retention time is about 9 minutes, and crushing the materials after the materials are collected.
After the prepared molding powder was compression molded, unnotched impact strength was measured, and the results are shown in Table 1.
Comparative examples 1 to 5
Referring to patent US3179631, polyimide was synthesized using a conventional aprotic polar solvent method. When the synthesis is carried out by a solvent method:
comparative example 1 the starting material of example 1 was used, but the maleic anhydride geraniol ester was absent;
comparative example 2 the starting material of example 2 was used, but without linalyl maleate;
comparative example 3 the feed of example 3 was used, but the neryl citraconate anhydride was absent;
comparative example 4 the feed of example 4 was used, but without the linalool citraconate anhydride;
comparative example 5 the feed of example 5 was used, but without maleic anhydride farnesol ester.
After the prepared solid resin was compression molded, unnotched impact strength was measured, and the results are shown in table 1.
TABLE 1 test spline notch impact Strength test results (KJ/Square Meter)
Numbering 1 2 3 4 5
Examples 135 192 230 103 155
Comparative example 60-80 155 175 75 115
As is apparent from the above table, the polyimide solids prepared by the process of the present invention have higher impact resistance.

Claims (19)

1. A method for preparing polyimide molding powder by solid-phase polymerization comprises the following steps:
a) respectively crushing aromatic binary primary amine, aromatic binary anhydride and toughening plasticizer maleic anhydride ester, and uniformly mixing in a high-speed mixer;
b) continuously feeding the mixed materials in a continuous rotary screw type conveying device, and reacting to generate polyimide;
c) the generated polyimide is rotated and extruded by equipment to form polyimide particles, and the polyimide particles are crushed to obtain polyimide molding powder;
wherein, the maleic anhydride ester in the step a) is maleic anhydride terpene alcohol ester, and the structural general formula is as follows:
Figure FDA0003330729520000011
the substance is a compound containing R1And a compound containing R2The terpene alcohol is generated through esterification reaction; the terpene alcohol ester of the butenedioic anhydride in the step a) is
Figure FDA0003330729520000012
Figure FDA0003330729520000013
One or more of (a) or (b),
wherein R is1Is H or-CH3Containing R2The terpene alcohol has at least 2 unsaturated bonds, and is one or more of geraniol, nerol, linalool, farnesol and linalool.
2. The method according to claim 1, wherein the primary aromatic diamine in step a) has 6 to 27 carbon atoms.
3. The method according to claim 1, wherein the aromatic diprimary amine in step a) is one or more selected from the group consisting of diaminodiphenyl ether, diaminodiphenyl sulfone, diaminodiphenylmethane, dimethyldiaminodiphenylmethane, bisphenol a diether diamine, bisphenol S diether diamine, p-phenylenediamine, and m-phenylenediamine.
4. The method according to claim 1, wherein the aromatic diprimary amine in step a) is one or more of p-phenylenediamine, m-phenylenediamine, diaminodiphenyl ether, diaminodiphenyl sulfone, bisphenol A diether diamine.
5. The method according to claim 1, wherein the aromatic dicarboxylic anhydride in step a) is an aromatic dicarboxylic anhydride having 10 to 31 carbon atoms.
6. The method according to claim 1, wherein the aromatic dicarboxylic anhydride in step a) is one or more selected from the group consisting of pyromellitic dianhydride, benzophenone dianhydride, biphenyl dianhydride, diphenyl ether dianhydride, diphenyl sulfide dianhydride, triphenyl diether dianhydride, bisphenol a diether dianhydride, bisphenol S diether dianhydride, biphenyl diphenol diether dianhydride, and diphenyl sulfone dianhydride.
7. The method according to claim 1, wherein the aromatic dicarboxylic anhydride in step a) is one or more of pyromellitic dianhydride, biphenyl dianhydride, diphenyl ether dianhydride, triphenyl diether dianhydride, biphenyl diphenol diether dianhydride, bisphenol a diether dianhydride, and bisphenol S diether dianhydride.
8. The method according to claim 1, wherein the aromatic diprimary amine and the aromatic diprimary anhydride are present in an equimolar ratio in step a); the butene diacid anhydride ester is 0.01-5 wt% of the sum of the mass of the aromatic binary primary amine and the mass of the aromatic binary anhydride.
9. The method according to claim 1, wherein the butene diacid anhydride ester in the step a) is 0.5 to 4 weight percent of the mass sum of the aromatic diamine primary amine and the aromatic diamine anhydride.
10. The method as claimed in claim 1, wherein the continuous rotary screw type conveying device in step b) is a continuous extrusion reaction device with internal rotation and conveyance.
11. The method of claim 1, wherein the continuous rotary screw type conveying apparatus in step b) is one or more of a single screw extruder, a twin screw extruder, a continuous twin paddle dryer, and a rake dryer.
12. The method according to claim 1 or 10, wherein the screw length-diameter ratio of step b) is (42-66):1 when a screw extruder is used.
13. The method according to claim 1 or 10, wherein the screw length-diameter ratio in step b) is (50-60):1, when a screw extruder is used.
14. The preparation method according to claim 10, wherein the process temperatures of the continuous extrusion reaction equipment in the step b) are respectively as follows: the feeding section is between room temperature and 100 ℃, the temperature of the first section is 160-250 ℃, and the temperature of the second section and the subsequent sections thereof is 230-380 ℃; step b) needs normal pressure or vacuum pumping, the vacuum degree is 0 to-0.095 MPa, and the number of vacuum pumping holes is 0-4.
15. The preparation method according to claim 10, wherein the process temperatures of the continuous extrusion reaction equipment in the step b) are respectively as follows: the temperature of the first section is 170-190 ℃, and the temperature of the second section and the subsequent sections thereof is 265-330 ℃.
16. The process of claim 1, wherein the feed rate of step b) is from 18 to 60 g/min; the rotating speed of the screw is 60-150 rpm; the retention time is 4.2-15 min.
17. The process of claim 1, wherein the feed rate of step b) is 19.8 to 48 g/min; the screw speed is 70-120 rpm.
18. Use of a polyimide molding powder prepared by the process according to any one of claims 1 to 17 for preparing a polyimide.
19. Use according to claim 18, for the preparation of polyetherimides, polyesterimides, polyamideimides.
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