CN111440336B - Surface modified polyimide particles, and preparation method and application thereof - Google Patents
Surface modified polyimide particles, and preparation method and application thereof Download PDFInfo
- Publication number
- CN111440336B CN111440336B CN202010157541.0A CN202010157541A CN111440336B CN 111440336 B CN111440336 B CN 111440336B CN 202010157541 A CN202010157541 A CN 202010157541A CN 111440336 B CN111440336 B CN 111440336B
- Authority
- CN
- China
- Prior art keywords
- polystyrene
- polyimide
- bis
- amino
- acid solution
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a surface modified polyimide particle and a preparation method thereof, belonging to the technical field of high polymer materials. According to the invention, the surface modification of the particles is finished simultaneously in the preparation process of polyimide particles, the surface modification process of post-treatment is omitted, and the surfaces of the particles are not polluted; meanwhile, the surface modified polyimide particles provided by the invention have good toughening effect on thermosetting resin.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a surface modified polyimide particle and a preparation method thereof.
Technical Field
High-performance resins such as multifunctional epoxy resins, bismaleimide resins, cyanate resins, or hybrid resins thereof, etc., have excellent properties and have been widely used. However, most of these high-performance resins are thermosetting, and the cured products thereof have remarkable brittleness and must be toughened and modified. Among the existing toughening modifiers such as rubber, nylon, polyetherimide, polysulfone and the like, polyimide particles are being widely focused and studied because they have a lower/higher use temperature, excellent mechanical properties, flame retardance, dimensional stability, radiation resistance, good chemical stability, wet heat resistance and the like, not only can realize toughening modification, but also can improve mechanical properties, heat resistance and the like. However, polyimide materials have a surface energy too low to be interface-bonded with other thermosetting resin materials, and must be surface-treated.
In the existing surface treatment technology, the surface plasma treatment technology is used for surface modification of polyimide films, fibers or profiles, and is not suitable for surface modification of polyimide particles; the alkali treatment technology is easy to pollute the polyimide surface and influence the surface performance of the material.
The patent provides a preparation method of surface modified polyimide particles, and the surface modified polyimide particles are prepared, and good expected effects are obtained in toughening high-performance resin.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of polyimide particles with modified surfaces, which aims to solve the problems of poor surface treatment effect, pollution and the like of polyimide particles in the prior art.
The invention also solves the technical problem of providing application of the surface modified polyimide particles.
In order to solve the technical problems, the invention provides the following technical scheme:
a mixed copolymer having a structure represented by the general formula (I),
wherein k is a natural number representing the number of repeating structural units;
rx is a tetravalent functional group, and the structural formula of the functional group is any one or a mixture of a plurality of the following structures in any proportion:
ry is a divalent functional group, and the structural formula of the Ry is any one or a mixture of a plurality of the following structures in any proportion:
in the formula (I), the end-capped chain segment of the polyimide macromolecular chain segment is a polystyrene-maleimide random alternating copolymer; the polystyrene-maleimide random alternating copolymer has a structure shown in a formula (II), wherein h, m, n and q are natural numbers, and PI represents a polyimide macromolecular chain segment in the formula (I);
in the formula (II), rz is a monovalent functional group, and the structural formula of the Rz is one or a mixture of a plurality of the following structures in any proportion;
wherein j is a natural number between 1 and 4, and R is a linear alkane group; w is a natural number between 4 and 16.
Wherein the aromatic dianhydride having an Rx structure comprises: 1,2,4, 5-pyromellitic dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, 3', 4' -diphenyl ether tetracarboxylic dianhydride, 3',4,4' -benzophenone tetracarboxylic dianhydride, 4' - (4, 4' -isopropylidenediphenoxy) bis (phthalic anhydride), 4' - (4, 4' -hexafluoroisopropylidenediphenoxy) bis (phthalic anhydride), and 4,4' -isopropylidenediphenyl-bis-trimellitate dianhydride.
Wherein the aromatic diamine having an Ry structure comprises: 4,4' -diaminodiphenyl ether, 4' -diaminodiphenyl methane, 2' -bis [4- (4-aminophenoxyphenyl) ] propane, 2, 4-diaminotoluene, 2, 6-diaminotoluene, 5 (6) -amino-1- (4-aminophenyl) -1, 3-trimethylindan 4,4' -bis (4-aminophenoxy) diphenylsulfone, 4' -bis (3-aminophenoxy) diphenylsulfone, 9-bis (4-aminophenyl) fluorene, 9-bis (4-amino-3-methylphenyl) fluorene, 9-bis (3-fluoro-4-aminophenyl) fluorene.
Wherein, the compound with Rz structure is: para-aminophenol, meta-aminophenol, 1-amino-5-naphthol, 1-amino-7-naphthol, 4-amino-1-naphthol, 6-amino-2-naphthol; an amidoamine comprising: n-tall oil fatty amido diethylenetriamine, N-tall oil fatty amido triethylenetetramine and N-tall oil fatty amido tetraethylenepentamine; a linear alkyl fatty amine comprising: 1-aminohexane, 1-aminoheptane, 1-aminooctane, 1-aminononane, 1-aminodecane, 1-aminoundecane, 1-aminododecane, 1-aminooctadecane.
The preparation method of the surface modified polyimide particles comprises the following steps:
(1) Adding 100.00 mol parts of aromatic diamine with Ry structure into polar aprotic solvents (such as N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide), stirring and dissolving completely, adding 95.00-99.60 mol parts of aromatic monomer dianhydride with Rx structure, and stirring and polymerizing to form amino-terminated polyamide acid solution;
(2) Adding 0.10-10.00 mol parts of polystyrene-maleic anhydride random alternating copolymer into the amido end-capped polyamic acid solution to generate polystyrene-maleic anhydride end-capped polyamic acid solution; polystyrene-maleic anhydride random alternating copolymer, abbreviated as polystyrene-maleic anhydride (hereinafter); as polystyrene-maleic anhydride, commercial products such as SMA-1000, SMA-2000, SMA-3000, EF-30, EF-40, EF-60 and EF-80 of CRAY VALLEY are used.
(3) Adding 0.20-10.00 mol parts of one or a mixture of more of aminophenol, amino naphthol, amido amine or linear alkyl fatty amine into the polystyrene-maleic anhydride end-capped polyamic acid solution to generate polystyrene-maleic anhydride end-capped polyamic acid solution;
(4) 400.00 mol parts of dehydrating agent (such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride and the like) and 200-250 mol parts of tertiary amine catalyst (such as pyridine, triethylamine, 3-methylpyridine, isoquinoline and the like) are added into the polystyrene-maleamic acid end-capped polyamide acid solution to generate polystyrene-maleimide end-capped polyimide solution;
(5) A poor solvent (such as methanol, ethanol, acetone, water or a mixture thereof in any ratio) is gradually added to the high-speed shearing dispersion polystyrene-maleimide-terminated polyimide solution to produce a cloudy solution of surface-modified polyimide particles. The shearing dispersion speed is 2000-8000 rpm, the volume of the poor solvent is 0.5-4.0 times of that of the polyimide solution capped by polystyrene-maleimide, and the solution temperature in the high-speed shearing dispersion process is controlled to be between 10 and 25 ℃;
(6) Separating the turbid liquid to obtain wet powder of polyimide particles with modified surfaces; soaking-separating wet powder with poor solvent, and repeating for 3 times; the wet powder after soaking-separation is subjected to stepped vacuum drying and then impact crushing to obtain a sample passing through a 120-mesh screen, and the sample is marked as a surface modified polyimide particle sample, SFPI.
The beneficial effects are that:
the invention discloses a polyimide particle surface modification method, which is used for eliminating the traditional method of directly carrying out post-treatment surface modification on a polyimide particle finished product, directly completing the particle surface modification in the polyimide particle preparation process, omitting the post-treatment surface modification process and avoiding the pollution of the particle surface; meanwhile, the surface modified polyimide particles provided by the invention have good toughening effect on thermosetting resin
Detailed Description
The particle size and distribution of the surface modified polyimide particle sample in the invention are detected according to the wet method in the detection standard GB/T19077.1-2003.
The test and detection process of the surface modified polyimide particles-SFPI toughened high-performance resin are as follows:
1. preparing SFPI toughened high-performance resin:
(1) TGMDA: n, N-tetraglycidyl ether-4, 4' -diaminodiphenylmethane, 75.8 g;
(2) DDS:4,4' -diaminodiphenyl sulfone, 19.2 grams;
(3) Diuron: 4.8 g of 3- (3, 4-dichlorophenyl) -1, 1-dimethylurea;
(4) DDA: dicyandiamide, 0.2 g;
(5) SFPI: surface-modified polyimide particles (hereinafter, referred to as "16 g").
(6) The components are fully sheared and uniformly mixed at 45-50 ℃, and then vacuum defoamed for 12 hours, and then casting test sample bars are carried out; the test bars had dimensions of 100mm (length) 10mm (width) 4mm (thickness).
2. Curing of cast test bars:
the phase heat preservation and solidification program of the cast test sample strip is as follows: 110 ℃/60min, 120 ℃/60min, 130 ℃/60min, 140 ℃/60min, 150 ℃/60min, 180 ℃/120min and room temperature. The temperature rise and fall rate is as follows: 2 ℃/min.
Solidifying and casting the test sample bar according to the above procedure, cooling to room temperature, and taking out the test sample bar.
3. The test sample bar detects the unnotched impact strength of the simply supported beam according to GB/T1043.1-2008, and characterizes the effect of the surface modified polyimide particles SFPI toughening high-performance resin.
Example 1:
(1) To a 15L stainless steel reaction vessel, 7046 g of N, N-dimethylacetamide was added, 378.900 g (1.422 mol) of 5 (6) -amino-1- (4-aminophenyl) -1, 3-trimethylindan and 70.515 g (0.356 mol) of 4,4' -diaminodiphenylmethane were added and completely dissolved, 561.449 g (1.742 mol) of 3,3', 4' -benzophenone tetracarboxylic dianhydride was added, and the mixture was stirred and polymerized at 20℃and 30rpm for 12 hours to produce an amino-terminated polyamic acid solution.
(2) SMA-1000.113 g (about 0.004 mol) was added to the amine-terminated polyamic acid solution, and the polymerization was stirred at 20℃and 30rpm for 4 hours to produce a polystyrene-maleic anhydride-terminated polyamic acid solution.
(3) To the polystyrene-maleic anhydride-terminated polyamic acid solution were added 1.600 g (0.015 mol), 4.058 g (about 0.011 mol) of N-tall oil fatty amido diethylenetriamine and 5.031 g (0.019 mol) of 1-amino octadecane, and the polymerization was stirred at 20℃and 30rpm for 4 hours to produce a polystyrene-maleic acid-terminated polyamic acid solution.
(4) To the polystyrene-maleamic acid-terminated polyamic acid solution were added 726.064 g (7.112 mol) of acetic anhydride and 413.963 g (4.445 mol) of 3-methylpyridine in this order, and the mixture was stirred at 60℃and 30rpm for chemical imidization for 5 hours to produce a polystyrene-maleimide-terminated polyimide solution.
(5) The polystyrene-maleimide terminated polyimide solution was transferred to a 30L stainless steel high-speed shear dispersing kettle, and 10 liters of poor solvent acetone (about 1.0 times the volume of the polystyrene-maleimide terminated polyimide solution) was gradually added under shear dispersion at 5000rpm, resulting in a cloudy solution of surface-modified polyimide particles.
(6) Separating the turbid liquid to obtain polyimide microparticle wet powder with modified surface; soaking and separating the wet powder by using 10 liters of poor solvent acetone each time, and repeating for 3 times to obtain cleaned surface-modified polyimide particle wet powder; the wet powder after soaking-separation was vacuum dried at 70 deg.C/4 hr, 150 deg.C/4 hr, 200 deg.C/4 hr, 250 deg.C/4 hr, and then impact crushed to obtain a sample passing through a 120 mesh sieve, designated SFPI-1.
(7) The particle size and distribution of the samples were measured according to the wet method in the test standard GB/T19077.1-2003.
(8) According to the test and detection process of the surface modified polyimide particle toughened high-performance resin, SFPI-1 toughened high-performance resin is used and the notch-free impact strength detection of the simple beam is carried out on the sample strip.
Example 2:
(1) To a 15L stainless steel reaction vessel was added 8212 g of N, N-dimethylacetamide, 535.519 g (1.422 mol) of 9, 9-bis (4-amino-3-methylphenyl) fluorene and 43.444 g (0.356 mol) of 2, 6-diaminotoluene and completely dissolved, and 540.530 g (1.742 mol) of 3,3', 4' -diphenylether tetracarboxylic dianhydride was further added, and the mixture was stirred and polymerized at 20℃and 30rpm for 12 hours to produce an amino-terminated polyamic acid solution.
(2) SMA-1000.113 g (about 0.004 mol) was added to the amine-terminated polyamic acid solution, and the polymerization was stirred at 20℃and 30rpm for 4 hours to produce a polystyrene-maleic anhydride-terminated polyamic acid solution.
(3) To the polystyrene-maleic anhydride-terminated polyamic acid solution were added 1.600 g (0.015 mol), 4.058 g (about 0.011 mol) of N-tall oil fatty amido diethylenetriamine and 5.031 g (0.019 mol) of 1-amino octadecane, and the polymerization was stirred at 20℃and 30rpm for 4 hours to produce a polystyrene-maleic acid-terminated polyamic acid solution.
(4) To the polystyrene-maleamic acid-terminated polyamic acid solution were added 726.064 g (7.112 mol) of acetic anhydride and 413.963 g (4.445 mol) of 3-methylpyridine in this order, and the mixture was stirred at 60℃and 30rpm for chemical imidization for 5 hours to produce a polystyrene-maleimide-terminated polyimide solution.
(5) The polystyrene-maleimide terminated polyimide solution was transferred to a 30L stainless steel high-speed shear dispersing kettle, and 10.5 liters of poor solvent acetone (about 1.0 times the volume of the polystyrene-maleimide terminated polyimide solution) was gradually added under shear dispersion at 5000rpm, resulting in a cloudy solution of surface-modified hybrid polyimide particles.
(6) Separating the turbid liquid to obtain polyimide microparticle wet powder with modified surface; 10.5 liters of poor solvent acetone is used for soaking and separating wet powder each time, and the process is repeated for 3 times to obtain cleaned surface modified polyimide particle wet powder; the wet powder after soaking-separation was vacuum dried at 70 deg.C/4 hr, 150 deg.C/4 hr, 200 deg.C/4 hr, 250 deg.C/4 hr, and then impact crushed to obtain a sample passing through a 120 mesh sieve, designated SFPI-2.
(7) The particle size and distribution of the samples were measured according to the wet method in the test standard GB/T19077.1-2003.
(8) According to the test and detection process of the surface modified polyimide particle toughened high-performance resin, SFPI-2 toughened high-performance resin is used and the notch-free impact strength detection of the simple beam is carried out on the sample strip.
Example 3:
(1) To a 30L stainless steel reaction vessel was added 11969 g of N, N-dimethylacetamide, 615.174 g (1.422 mol) of 4,4' -bis (4-aminophenoxy) diphenylsulfone and 71.205 g (0.356 mol) of 4,4' -diaminodiphenyl ether and completely dissolved, 1004.527 g (1.742 mol) of 4,4' -isopropylidenediphenyl-bis-trimellitate dianhydride was further added and polymerized under stirring at 20℃and 30rpm for 12 hours to produce an amine-terminated polyamic acid solution.
(2) SMA-1000.113 g (about 0.004 mol) was added to the amine-terminated polyamic acid solution, and the polymerization was stirred at 20℃and 30rpm for 4 hours to produce a polystyrene-maleic anhydride-terminated polyamic acid solution.
(3) To the polystyrene-maleic anhydride-terminated polyamic acid solution were added 1.600 g (0.015 mol), 4.058 g (about 0.011 mol) of N-tall oil fatty amido diethylenetriamine and 5.031 g (0.019 mol) of 1-amino octadecane, and the polymerization was stirred at 20℃and 30rpm for 4 hours to produce a polystyrene-maleic acid-terminated polyamic acid solution.
(4) To the polystyrene-maleamic acid-terminated polyamic acid solution were added 726.064 g (7.112 mol) of acetic anhydride and 413.963 g (4.445 mol) of 3-methylpyridine in this order, and the mixture was stirred at 60℃and 30rpm for chemical imidization for 5 hours to produce a polystyrene-maleimide-terminated polyimide solution.
(5) The polystyrene-maleimide terminated polyimide solution was transferred to a 50L stainless steel high-speed shear dispersing kettle, and 15 liters of poor solvent acetone (about 1.0 times the volume of the polystyrene-maleimide terminated polyimide solution) was gradually added under shear dispersion at 5000rpm, resulting in a cloudy solution of surface-modified hybrid polyimide particles.
(6) Separating the turbid liquid to obtain polyimide microparticle wet powder with modified surface; soaking and separating wet powder by using 15 liters of poor solvent acetone each time, and repeating for 3 times to obtain cleaned surface modified polyimide particle wet powder; the wet powder after soaking-separation was vacuum dried at 70 deg.C/4 hr, 150 deg.C/4 hr, 200 deg.C/4 hr, 250 deg.C/4 hr, and then impact crushed to obtain a sample passing through a 120 mesh screen, designated SFPI-3.
(7) The particle size and distribution of the samples were measured according to the wet method in the test standard GB/T19077.1-2003.
(8) According to the test and detection process of the surface modified polyimide particle toughened high-performance resin, SFPI-3 toughened high-performance resin is used and the notch-free impact strength detection of the simple beam is carried out on the sample strip.
Comparative example 1
(1) To a 15L stainless steel reaction vessel, 7046 g of N, N-dimethylacetamide was added, 378.900 g (1.422 mol) of 5 (6) -amino-1- (4-aminophenyl) -1, 3-trimethylindan and 70.515 g (0.356 mol) of 4,4' -diaminodiphenylmethane were added and completely dissolved, 572.907 g (1.778 mol) of 3,3', 4' -benzophenone tetracarboxylic dianhydride was added, and the mixture was stirred and polymerized at 20℃and 30rpm for 12 hours to obtain a polyamic acid solution.
(2) To the polyamic acid solution, 726.064 g (7.112 mol) of acetic anhydride and 413.963 g (4.445 mol) of 3-methylpyridine were added in this order, and the solution was subjected to chemical imidization at 60℃and 30rpm for 5 hours with stirring, to produce a polyimide solution.
(3) The polyimide solution was transferred to a 30L stainless steel high-speed shearing dispersing kettle, and 10 liters of poor solvent acetone (about 1.0 times the volume of the polyimide solution) was gradually added under shearing dispersion at 5000rpm, to produce a cloudy solution of polyimide particles.
(4) Separating the turbid liquid to obtain polyimide microparticle wet powder; soaking and separating the wet powder by using 10 liters of poor solvent acetone each time, and repeating for 3 times to obtain cleaned polyimide particle wet powder; the wet powder after soaking-separation was dried in vacuo at 70℃4hr, 150℃4hr, 200℃4hr, 250℃4hr, and then impact-crushed to obtain a sample passing through a 120 mesh sieve, which was designated PI-1.
(5) The particle size and distribution of the samples were measured according to the wet method in the test standard GB/T19077.1-2003.
(6) According to the test and detection process of the surface modified polyimide particle toughened high-performance resin, PI-1 toughened high-performance resin is used and the detection of the notch-free impact strength of the simply supported beam is carried out on the sample strip.
Comparative example 2
(1) To a 15L stainless steel reaction vessel, 8212 g of N, N-dimethylacetamide was added, 535.519 g (1.422 mol) of 9, 9-bis (4-amino-3-methylphenyl) fluorene and 43.444 g (0.356 mol) of 2, 6-diaminotoluene were added and completely dissolved, 551.562 g (1.778 mol) of 3,3', 4' -diphenylether tetracarboxylic dianhydride was added, and the mixture was stirred and polymerized at 20℃and 30rpm for 12 hours to produce a polyamic acid solution.
(2) To the polyamic acid solution were sequentially added 726.064 g (7.112 mol) of acetic anhydride and 413.963 g (4.445 mol) of 3-methylpyridine, and the mixture was stirred at 60℃and 30rpm for chemical imidization for 5 hours to produce a polyimide solution.
(3) The polyimide solution was transferred to a 30L stainless steel high-speed shearing dispersing kettle, and 10.5 liters of poor solvent acetone (about 1.0 times the volume of the polyimide solution) was gradually added under shearing dispersion at 5000rpm, to produce a cloudy solution of polyimide particles.
(4) Separating the turbid liquid to obtain polyimide microparticle wet powder; 10.5 liters of poor solvent acetone is used for soaking and separating wet powder each time, and the process is repeated for 3 times to obtain cleaned polyimide particle wet powder; vacuum drying wet powder after soaking-separation at 70 deg.C/4 hr, 150 deg.C/4 hr, 200 deg.C/4 hr, 250 deg.C/4 hr, and impact pulverizing to obtain sample passing through 120 mesh sieve, which is named PI-2.
(5) The particle size and distribution of the samples were measured according to the wet method in the test standard GB/T19077.1-2003.
(6) According to the test and detection process of the surface modified polyimide particle toughened high-performance resin, PI-2 toughened high-performance resin is used and the detection of the notch-free impact strength of the simply supported beam is carried out on the sample strip.
Comparative example 3
(1) To a 30L stainless steel reaction vessel was added 11969 g of N, N-dimethylacetamide, 615.174 g (1.422 mol) of 4,4' -bis (4-aminophenoxy) diphenylsulfone and 71.205 g (0.356 mol) of 4,4' -diaminodiphenyl ether and completely dissolved, 1025.028 g (1.778 mol) of 4,4' -isopropylidenediphenyl-bis-trimellitate dianhydride was further added, and the mixture was stirred and polymerized at 20℃and 30rpm for 12 hours to produce a polyamic acid solution.
(2) To the polyamic acid solution were sequentially added 726.064 g (7.112 mol) of acetic anhydride and 413.963 g (4.445 mol) of 3-methylpyridine, and the mixture was stirred at 60℃and 30rpm for chemical imidization for 5 hours to produce a polyimide solution.
(3) The polyimide solution was transferred to a 50L stainless steel high-speed shearing dispersing kettle, and 15 liters of poor solvent acetone (about 1.0 times the volume of the polyimide solution) was gradually added under shearing dispersion at 5000rpm, to produce a cloudy solution of polyimide particles.
(4) Separating the turbid liquid to obtain polyimide microparticle wet powder; soaking and separating the wet powder by using 15 liters of poor solvent acetone each time, and repeating for 3 times to obtain cleaned polyimide particle wet powder; vacuum drying wet powder after soaking-separation at 70 deg.C/4 hr, 150 deg.C/4 hr, 200 deg.C/4 hr, 250 deg.C/4 hr, and impact pulverizing to obtain sample passing through 120 mesh sieve, which is named PI-3.
(5) The particle size and distribution of the samples were measured according to the wet method in the test standard GB/T19077.1-2003.
(6) According to the test and detection process of the surface modified polyimide particle toughened high-performance resin, PI-3 toughened high-performance resin is used and the detection of the notch-free impact strength of the simply supported beam is carried out on the sample strip.
Comparative example 4
According to the test and detection process of the surface modified polyimide particle toughened high-performance resin, no toughening component is used for toughening the high-performance resin and the detection of the notch-free impact strength of the simply supported beam is carried out on the sample strip.
The detection results of the surface modified polyimide particle sample, SFPI toughened high performance resin, are shown in Table 1. As can be seen from Table 1, the use of the non-surface-modified polyimide particles to toughen the high-performance resin improved the notched impact strength of the simply supported beams by 40% or less, while the use of the surface-modified polyimide particles to toughen the high-performance resin improved the notched impact strength of the simply supported beams by 120% or more, and the toughening effect was more remarkable.
TABLE 1 detection results of SFPI toughened high Performance resins
Claims (8)
1. A mixed copolymer with a structure shown as a general formula (I),
wherein k is a natural number representing the number of repeating structural units;
rx is a tetravalent functional group, and the structural formula of the functional group is any one or a mixture of a plurality of the following structures in any proportion:
ry is a divalent functional group, and the structural formula of the Ry is any one or a mixture of a plurality of the following structures in any proportion:
in the formula (I), the end-capped chain segment of the polyimide macromolecular chain segment is a polystyrene-maleimide random alternating copolymer; the polystyrene-maleimide random alternating copolymer has a structure shown in a formula (II), wherein in the formula (II), h, m, n and q are natural numbers which are not zero, and PI represents a polyimide macromolecular chain segment in the formula (I);
in the formula (II), rz is a monovalent functional group, and the structural formula of the Rz is one or a mixture of a plurality of the following structures in any proportion;
wherein j is a natural number between 1 and 4, and R is a linear alkane group; w is a natural number between 4 and 16.
2. The hybrid copolymer according to claim 1, wherein the aromatic dianhydride having an Rx structure comprises: 1,2,4, 5-pyromellitic dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, 3', 4' -diphenyl ether tetracarboxylic dianhydride, 3',4,4' -benzophenone tetracarboxylic dianhydride, 4' - (4, 4' -isopropylidenediphenoxy) bis (phthalic anhydride), 4' - (4, 4' -hexafluoroisopropylidenediphenoxy) bis (phthalic anhydride), and 4,4' -isopropylidenediphenyl-bis-trimellitate dianhydride.
3. The hybrid copolymer according to claim 1, wherein the aromatic diamine having an Ry structure comprises: 4,4' -diaminodiphenyl ether, 4' -diaminodiphenyl methane, 2' -bis [4- (4-aminophenoxyphenyl) ] propane, 2, 4-diaminotoluene, 2, 6-diaminotoluene, 5 (6) -amino-1- (4-aminophenyl) -1, 3-trimethylindan 4,4' -bis (4-aminophenoxy) diphenylsulfone, 4' -bis (3-aminophenoxy) diphenylsulfone, 9-bis (4-aminophenyl) fluorene, 9-bis (4-amino-3-methylphenyl) fluorene, 9-bis (3-fluoro-4-aminophenyl) fluorene.
4. The hybrid copolymer of claim 1, wherein the compound having an Rz structure is: para-aminophenol, meta-aminophenol, 1-amino-5-naphthol, 1-amino-7-naphthol, 4-amino-1-naphthol, 6-amino-2-naphthol; an amidoamine comprising: n-tall oil fatty amido diethylenetriamine, N-tall oil fatty amido triethylenetetramine and N-tall oil fatty amido tetraethylenepentamine; a linear alkyl fatty amine comprising: 1-aminohexane, 1-aminoheptane, 1-aminooctane, 1-aminononane, 1-aminodecane, 1-aminoundecane, 1-aminododecane, 1-aminooctadecane.
5. The process for producing a mixed copolymer according to any one of claims 1 to 4, comprising the steps of:
(1) Adding 100.00 mol parts of aromatic diamine with Ry structure into polar aprotic solvent, stirring and dissolving completely, adding 95.00-99.60 mol parts of aromatic monomer dianhydride with Rx structure, stirring and polymerizing to form amino-terminated polyamide acid solution;
(2) Adding 0.10-10.00 mol parts of polystyrene-maleic anhydride random alternating copolymer into the amido end-capped polyamic acid solution to generate polystyrene-maleic anhydride end-capped polyamic acid solution; polystyrene-maleic anhydride random alternating copolymer, polystyrene-maleic anhydride for short;
(3) Adding 0.20-10.00 mol parts of one or a mixture of more of aminophenol, amino naphthol, amido amine or linear alkyl fatty amine into the polystyrene-maleic anhydride end-capped polyamic acid solution to generate polystyrene-maleic anhydride end-capped polyamic acid solution;
(4) 400.00 mol parts of dehydrating agent and 200-250 mol parts of tertiary amine catalyst are added into the polystyrene-maleamic acid end-capped polyamide acid solution to generate polystyrene-maleimide end-capped polyimide solution;
(5) Gradually adding a poor solvent into the high-speed shearing dispersion polystyrene-maleimide terminated polyimide solution to generate turbid liquid of surface modified polyimide particles, wherein the shearing dispersion speed is 2000-8000 rpm, the volume of the poor solvent is 0.5-4.0 times that of the polystyrene-maleimide terminated polyimide solution, and the solution temperature is controlled to be 10-25 ℃ in the high-speed shearing dispersion process;
(6) Separating the turbid liquid to obtain wet powder of polyimide particles with modified surfaces; soaking-separating wet powder with poor solvent, and repeating for 3 times; the wet powder after soaking-separation is subjected to stepped vacuum drying and then impact crushing to obtain a sample passing through a 120-mesh screen, and the sample is marked as surface modified polyimide particles.
6. The method for producing a hybrid copolymer according to claim 5, wherein in the step (1), the polar aprotic solvent comprises: n, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethylsulfoxide.
7. The method for producing a mixed copolymer according to claim 5, wherein in the step (4), the dehydrating agent is acetic anhydride, propionic anhydride or trifluoroacetic anhydride, and the tertiary amine catalyst is pyridine, triethylamine, 3-methylpyridine or isoquinoline.
8. The method for producing a mixed copolymer according to claim 5, wherein in the step (5), the poor solvent comprises one or a mixture of several of methanol, ethanol, acetone and water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010157541.0A CN111440336B (en) | 2020-03-09 | 2020-03-09 | Surface modified polyimide particles, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010157541.0A CN111440336B (en) | 2020-03-09 | 2020-03-09 | Surface modified polyimide particles, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111440336A CN111440336A (en) | 2020-07-24 |
| CN111440336B true CN111440336B (en) | 2023-08-18 |
Family
ID=71650556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010157541.0A Active CN111440336B (en) | 2020-03-09 | 2020-03-09 | Surface modified polyimide particles, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111440336B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112795011B (en) * | 2020-12-31 | 2022-08-09 | 常州市尚科新材料有限公司 | Soluble thermoplastic polyimide superfine powder and preparation method thereof |
| CN113185653A (en) * | 2021-06-17 | 2021-07-30 | 江西金石三维智能制造科技有限公司 | High-strength high-toughness three-dimensional photo-molding resin and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101392056A (en) * | 2008-10-17 | 2009-03-25 | 吉林大学 | High performance and low cost polyimide preformed polymer and preparation method thereof |
| CN101608019A (en) * | 2007-09-06 | 2009-12-23 | 湖北省化学研究院 | A kind of preparation method of maleimide end-sealed type polyimide resin |
| CN103102796A (en) * | 2013-01-10 | 2013-05-15 | 东华大学 | Benzimidazole polyimide wire enamel and preparation method thereof |
| CN109679095A (en) * | 2018-12-18 | 2019-04-26 | 苏州予信天材新材料应用技术有限公司 | A kind of high temperature resistant type polyamide-polyether acid imide toughening polymer and preparation method thereof |
-
2020
- 2020-03-09 CN CN202010157541.0A patent/CN111440336B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101608019A (en) * | 2007-09-06 | 2009-12-23 | 湖北省化学研究院 | A kind of preparation method of maleimide end-sealed type polyimide resin |
| CN101392056A (en) * | 2008-10-17 | 2009-03-25 | 吉林大学 | High performance and low cost polyimide preformed polymer and preparation method thereof |
| CN103102796A (en) * | 2013-01-10 | 2013-05-15 | 东华大学 | Benzimidazole polyimide wire enamel and preparation method thereof |
| CN109679095A (en) * | 2018-12-18 | 2019-04-26 | 苏州予信天材新材料应用技术有限公司 | A kind of high temperature resistant type polyamide-polyether acid imide toughening polymer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111440336A (en) | 2020-07-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111440336B (en) | Surface modified polyimide particles, and preparation method and application thereof | |
| CN108219133A (en) | A kind of polyimide resin containing furan nucleus and preparation method thereof | |
| CN113861421B (en) | Polyimide type epoxy resin toughening agent and preparation method thereof | |
| JP5495464B2 (en) | Fusible polyimide molding compound and method for preparing the same | |
| CN108373542B (en) | Cage-like silsesquioxane/polyimide-containing nano hybrid membrane and preparation method thereof | |
| CN105461926B (en) | A kind of environment-friendly type stability polyamic acid solution and preparation method thereof | |
| CN111019129A (en) | Low-thermal expansion coefficient soluble polyimide resin powder and preparation method thereof | |
| WO2014181670A1 (en) | Polyimide resin composition comprising terminal-modified imide oligomer prepared using 2-phenyl-4,4'-diaminodiphenyl ether and aromatic thermoplastic polyimide prepared using oxydiphthalic acid, varnish, polyimide resin composition molded article having excellent heat resistance and mechanical properties, prepreg, and fiber-reinforced composite material containing said prepreg | |
| CN114621440A (en) | High-temperature-resistant polyamide-polyetherimide toughened polymer and preparation method thereof | |
| CN113185693A (en) | Polyamide acid solution and preparation method thereof, polyimide and polyimide film | |
| CN115418079B (en) | Tough epoxy resin system and preparation method and application thereof | |
| CN109666170A (en) | The preparation method of uniform high-performance polyimide film | |
| CN109054018B (en) | Polyamide acid solution and preparation method thereof | |
| CN114456381B (en) | Method for preparing polyimide film by unidirectional stretching | |
| CN110079884A (en) | A kind of preparation method of high-specific surface area polyimides fibrid | |
| CN114230791B (en) | Intrinsic low-dielectric fluorine-containing polyimide film and preparation method thereof | |
| CN113402709B (en) | High-temperature-resistant polyimide soluble in o-diallyl bisphenol A and preparation method thereof | |
| CN1428360A (en) | Method for preparing polyimide molding powder | |
| CN101973147B (en) | Preparation method of high-temperature resistant polyimide glass fabric laminated board | |
| CN114621439A (en) | Preparation method of polyimide film | |
| CN112795186A (en) | Modified polyimide resin and preparation method thereof | |
| CN114015044A (en) | Colorless transparent polyimide resin film and preparation method thereof | |
| JP7250593B2 (en) | Particulate imide oligomer and method for producing the same | |
| CN113336940A (en) | Method for preparing polyamic acid solution by reacting dianhydride with low reactivity with diamine | |
| JP2631926B2 (en) | Thermosetting resin composition |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |