CN110483763B - Branched phthalonitrile resin containing benzoyl structure and preparation method thereof - Google Patents

Branched phthalonitrile resin containing benzoyl structure and preparation method thereof Download PDF

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CN110483763B
CN110483763B CN201910780801.7A CN201910780801A CN110483763B CN 110483763 B CN110483763 B CN 110483763B CN 201910780801 A CN201910780801 A CN 201910780801A CN 110483763 B CN110483763 B CN 110483763B
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branched
phthalonitrile
benzoyl
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CN110483763A (en
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蹇锡高
王锦艳
宗立率
刘程
李楠
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Dalian University of Technology
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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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment

Abstract

The invention belongs to the field of preparation of novel low-melting-point high-temperature-resistant high polymer materials, and provides a branched phthalonitrile resin containing a benzoyl structure and a preparation method thereof. The invention creatively introduces the benzoyl structure with rigidity and flexibility to obtain a novel branched phthalonitrile structure. The benzoyl group-containing branched phthalonitrile resin contains an aryl group and phthalonitrile group having excellent heat resistance, and the flexibility of the acyl structure imparts good solubility to the resin. The branched structure is used for increasing the crosslinking density, so that the heat resistance is improved, and the thermal stability is excellent. Glass transition temperature TgGreater than 500 deg.C, thermal decomposition temperature Td5％Can reach 553 ℃, is used as a novel branched phthalonitrile, expands the application range of phthalonitrile resin, and can be applied to high-tech fields such as microelectronics, aerospace and the like.

Description

Branched phthalonitrile resin containing benzoyl structure and preparation method thereof
Technical Field
The invention belongs to the technical field of preparation of novel low-melting-point high-temperature-resistant high polymer materials, and relates to novel low-melting-point high-temperature-resistant phthalonitrile resin containing a branched structure and a preparation method thereof.
Background
The phthalonitrile resin containing the benzoyl branched structure is a high-performance thermosetting resin, has excellent solubility, thermal stability, thermal oxidation stability, moisture resistance, flame retardance, chemical stability and mechanical performance, has wide application in the fields of aerospace, electronics, ships, machinery and the like, and has wide application prospect.
The branched phthalonitrile resin containing the benzoyl structure is high-temperature-resistant dissoluble high-performance thermosetting resin formed by polymerizing phthalonitrile structural units. The research of the resin is pioneering in the research laboratory of the American navy, and the phthalonitrile resin with various typical structures is prepared in the long-term research process.
The following documents list Phthalonitrile monomers which have been prepared synthetically in some recent years, Low melting point (Y.Han, D.Tang, G.Wang, Y.Guo, H.ZHou, W.Qiu, T.ZHao, Low melting polymeric resins and/or acrylic Polymers: Synthesis, curing behavor, thermal and mechanical Polymers, Eur.Polymer.J. 111(2019)104-113, H.Wang, J.Wang, H.Guo, X.Chen, X.Yu, Y.set, P.Ji, K.Naito, Z.Zhang, Q.Zhang, additive high molecular cellulose-butyl-phenolic resins, K.N.P.N.P.N.P.N.P.N.P.N.P.N.P.N.P.J.P.M.P.N.P.N.P.J.P.P.P.P.N.P.P.P.N.N.P.N.J.P.P.P.P.N.M.J.P.M.P.M.P.J.P.P.J.P.P.P.M.S., Z.J.P.P.P.P.P.P.P.P.J.P.P.P.P.J.P.P.P.P.P.P.P.P.P.M.S.P.P.P.N.M.M.M.M.M.M.M.C.C.P.M.M.J.P.M.M.M.M.P.P.M.M.M.P.C.P.M.M.J.P.P.C.P.P.C.P.P.C.P.P.M.M.M.M.P.P.M.C.M.P.P.P.P.C.P.M.C.C.M.C.C.C.M.P.P.C.C.C.C.C.C.C.M.C.P.P.C.C.P.M.P.P.C.C.C.C.C.C.C.C.C.P.C.C.C.M.C.P.P.P.P.P.P.P.P.C.P.P.P.C.C.C.C.P.P.P.C.C.P.M.P.C.C.C.C.C.C.C.C.C.C.C.C.P.P.J.C.P.P.P.P.P.P.C.P.P.P.C.C.C.C.P.P.P.C.C.P.P.P.P.P.P.P.P.P.P.P.P.P.C.C.C.C.C.C.C.C.C.C.C.C.C.P.C.C.C.P.P.P.C.C.P.P.P.C.C.C.C.C.C.C.C.C.C.C.C.C.C.P.C.C.P.C.C.C.C.C.C.C.C.C.C.C.C.P.P.C.C.P.C.C.P.P.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.D.C.D.C.C.C.C.C.C.C.C.C.C.D.C.C.C.C.C, appl.therm.eng.115(2017) 630-; still other studies have focused on functional and optical extensions (Y.Han, D.Tang, G.Wang, Y.Zhang, Y.Guo, H.ZHou, W.Qiu, T.ZHao, Crosslinkable hyperbranched poly (arylene ether nitrile) modifier for thermoplastic resins Synthesis, chain-end functionalization and Properties, Polymer 173(2019)88-102, W.ZHong, Y.ZHao, W.H.ZHuang, J.J.Wu, F.Z.Wang, C.H.Li, J.L.Zuo, Phosphorins: Fused-bed Synthesized chemical chemistry, chemical Synthesis 130, and chemical reaction 1568 (1568).
The phthalonitrile monomer mostly takes a benzene ring as a basic skeleton and is mostly in a linear structure, and the polymer and the composite material thereof show excellent heat resistance and mechanical property.
Disclosure of Invention
In order to expand the structural diversity, aiming at exploring a novel low-melting-point high-temperature-resistant phthalonitrile structure, a benzoyl structure and a branched structure which have rigidity and flexibility are introduced into a main chain of a polymer to prepare a branched novel low-melting-point high-temperature-resistant phthalonitrile resin, so that the application range and the application prospect of the branched novel low-melting-point high-temperature-resistant phthalonitrile resin are expanded, the obtained novel resin can have good solubility in various low-boiling-point solvents, and the cured resin also has excellent thermal stability.
The technical scheme of the invention is as follows:
a branched phthalonitrile resin containing a benzoyl structure has the following chemical structure:
Figure BDA0002176517700000021
wherein m is more than or equal to 1, n is more than or equal to 1, and Z is more than or equal to 1;
Figure BDA0002176517700000022
the structure of (1) is as follows:
Figure BDA0002176517700000023
Figure BDA0002176517700000024
the structure of (1) is as follows:
Figure BDA0002176517700000025
Figure BDA0002176517700000031
Figure BDA0002176517700000041
one or a combination of two or more of them; wherein, R, R1、R2、R3、R4、R5、R6、R7、R8Structure of (1)Comprises the following steps: H. f, Cl, Br, I, CN, NH2、Cr+1H2r+2、CrH2r+1、CrH2r+1COOH、CrH2r+1COOCrH2r+1、CF3、
Figure BDA0002176517700000042
Figure BDA0002176517700000043
One or more than two of the (a) and r is more than or equal to 1; r, R1、R2、R3、R4、R5、R6、R7And R8The same or different.
A preparation method of branched phthalonitrile resin containing a benzoyl structure comprises the following polymerization reaction formula:
Figure BDA0002176517700000044
wherein m is more than or equal to 1, n is more than or equal to 1, Z is more than or equal to 1, and X is F, Cl, Br or I;
the preparation method comprises the following specific steps:
under the protection of inert gas, the compound containing benzoyl structure
Figure BDA0002176517700000045
Trihalomonomer of (a) or (b) and (c) containing
Figure BDA0002176517700000046
Mixing structural diphenol monomer and alkali, adding strong polar aprotic solvent and azeotropic solvent, carrying out water treatment on the reaction system at the temperature of 90-140 ℃, removing the azeotropic solvent after reacting for 2-3 hours, and heating to 150-220 ℃ for reacting for 8-12 hours; when the temperature is reduced to 60-90 ℃, 4-nitrophthalonitrile is added for reaction for 10-12 hours; then pouring the product into excessive 0.1-0.2mol/L diluted hydrochloric acid, washing the filtrate to be neutral by using distilled water, and carrying out vacuum drying at 80-120 ℃ for 24-48 hours to obtain the benzoyl structure-containing branched phthalonitrile prepolymerAnd is ready for use; wherein
Figure BDA0002176517700000051
And containing benzoyl structure
Figure BDA0002176517700000052
The molar ratio of (A) to (B) is 3 to 4.2; comprises
Figure BDA0002176517700000053
The mol ratio of structural diphenol monomer to alkali is 1.2-1.6:1, and the volume mL of the strong polar aprotic solvent is 5-20 times
Figure BDA0002176517700000054
Structural bisphenols and
Figure BDA0002176517700000055
the sum of the mass g, the volume of the azeotropic solvent is 0.5 to 2 times of the volume of the strong polar aprotic solvent, the molar weight of the 4-nitrophthalonitrile is 1.2 to 1.4 times of the excess hydroxyl, wherein the excess hydroxyl is
Figure BDA0002176517700000056
With benzoyl structure
Figure BDA0002176517700000057
The residual hydroxyl after the reaction of the trihalo monomer;
and (3) curing: mixing the benzoyl structure-containing branched phthalonitrile prepolymer with aromatic diamine, fully mixing and stirring, compounding with glass fiber to obtain a laminated board, placing the laminated board in a muffle furnace at 250-375 ℃ for temperature programming and curing for 16 hours to finally obtain the cured benzoyl structure-containing branched phthalonitrile resin; wherein the mass ratio of the benzoyl structure-containing branched phthalonitrile prepolymer to the aromatic diamine is 1: 0.05.
The structure containing benzoyl
Figure BDA0002176517700000058
The trihalomonomer of (a) having the formula:
Figure BDA0002176517700000059
wherein, X structure is: x is one of F, Cl, Br and I;
Figure BDA00021765177000000510
the specific synthesis steps are as follows:
when the temperature is below zero ℃, adding fluorobenzene into a reactor, then gradually adding anhydrous aluminum trichloride by using a feeder, uniformly stirring, adding 1,3, 5-benzene trimethyl acyl chloride, stirring, removing the reactor from a constant temperature tank, reacting at room temperature for 10-24 hours, and heating to 90 ℃ for 2 hours; after cooling to room temperature, pouring the product into a glacial acid bath, washing a filter cake with distilled water, and performing vacuum drying at 80-120 ℃ for 24-48 hours to obtain a monomer 1,3, 5-tris (4-fluorobenzoyl) benzene (TB) for later use; wherein the molar ratio of the 1,3, 5-benzene trimethyl chloride to the fluorobenzene is 1:1.9, and the molar ratio of the 1,3, 5-benzene trimethyl chloride to the aluminum trichloride is 1: 2.4;
Figure BDA0002176517700000061
the specific synthesis steps are as follows:
when the temperature is below zero ℃, chlorobenzene is firstly added into a reactor, then anhydrous aluminum trichloride is gradually stirred by a feeder uniformly, 1,3, 5-benzene trimethyl acyl chloride is added, the mixture is stirred, the reactor is moved out of a constant temperature tank, and after the mixture reacts for 10 to 24 hours at room temperature, the temperature is raised to 90 ℃ for reaction for 2 hours; after cooling to room temperature, pouring the product into a glacial acid bath, washing a filter cake with distilled water, and performing vacuum drying at 80-120 ℃ for 24-48 hours to obtain a monomer 1,3, 5-tri (4-chlorophenyl) benzene (TB) for later use; wherein the molar ratio of the 1,3, 5-benzene trimethyl acyl chloride to the chlorobenzene is 1:2.1, and the molar ratio of the 1,3, 5-benzene trimethyl acyl chloride to the aluminum trichloride is 1: 2.6;
Figure BDA0002176517700000062
the specific synthesis steps are as follows:
when the temperature is below zero, bromobenzene is firstly added into a reactor, then anhydrous aluminum trichloride is gradually stirred uniformly by a feeder, 1,3, 5-benzene trimethyl acyl chloride is added, the mixture is stirred, the reactor is moved out of a constant temperature tank, the temperature is increased to 90 ℃ for reaction for 2 hours after the reaction is carried out for 10 to 24 hours at room temperature; after cooling to room temperature, pouring the product into a glacial acid bath, washing a filter cake with distilled water, and carrying out vacuum drying at 80-120 ℃ for 24-48 hours to obtain a monomer 1,3, 5-tris (4-bromobenzoyl) benzene (TB) for later use; wherein the molar ratio of the 1,3, 5-benzene trimethyl acyl chloride to the bromobenzene is 1:2.3, and the molar ratio of the 1,3, 5-benzene trimethyl acyl chloride to the aluminum trichloride is 1: 2.8;
the inert gas is one of nitrogen, argon and helium.
The alkali is one or more of potassium carbonate, cesium carbonate, sodium hydroxide and potassium hydroxide.
The strong polar aprotic solvent is one or a mixture of more than two of N, N-methylformamide, N-methylacetamide, dimethyl sulfoxide and N-methylpyrrolidone.
The azeotropic solvent is one or more of toluene, xylene and chlorobenzene.
The aromatic diamine is one or the mixture of more than two of 4,4 '-diaminodiphenyl sulfone, 4' -diaminodiphenyl ether, 4 '-diaminodiphenyl methane, 1, 3-di (4-aminophenoxy) benzene, 4' -bis (4-aminophenoxy) diphenyl sulfone, 2, 6-di (4-aminophenoxy) benzonitrile and 2, 4-di [4- (4-aminophenoxy) phenyl ] -6-phenyl-1, 3, 5-triazine.
The invention has the beneficial effects that: introducing benzoyl and combining with a branched structure to obtain a novel branched phthalonitrile resin structure. The trifunctional monomer containing the benzoyl structure has the characteristic of compatibility between rigidity and flexibility, and is introduced into the main chain of phthalonitrile resin to show good processability, and the branched structure is added to increase the crosslinking density, so that the thermal property of the resin is excellent, and the thermal decomposition temperature (T) is highd5％) A glass transition temperature (T) of 553 ℃ at the maximumg) Over 500 ℃, as a novel branched phthalonitrile, the application range of phthalonitrile resin is expanded and the method can be appliedThe method is used in high-tech fields such as ships, aerospace and the like.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of hydroquinone branched phthalonitrile (TBHQPh);
FIG. 2 is an infrared spectrum of hydroquinone branched phthalonitrile (TBHQPh).
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Example 1
Monomer synthesis: when the temperature is below zero ℃, 4.8 g (0.095mol) of fluorobenzene is firstly added into a reactor, then 16 g (0.12mol) of anhydrous aluminum trichloride is gradually added into the reactor by a feeder, after uniform stirring, 13.25 g (0.05mol) of 1,3, 5-benzene tricarboxychloride is added, after stirring for a period of time, the reactor is removed from a constant temperature tank, and after 10-24 hours of reaction at room temperature, the temperature is increased to 90 ℃ for 2 hours of reaction. After cooling to room temperature, pouring the product into a glacial acid bath, washing a filter cake with distilled water, and performing vacuum drying at 80-120 ℃ for 24-48 hours to obtain a monomer 1,3, 5-tris (4-fluorobenzoyl) benzene (TB) for later use;
prepolymer synthesis: adding 0.025 mol of TB, 0.09 mol of hydroquinone, 0.108 mol of catalyst anhydrous potassium carbonate into a reactor, adding 210.2ml of solvent NMP, adding 106ml of toluene with the volume of the solvent, adding water into the toluene at 130 ℃ for 2 hours, evaporating the toluene at 150 ℃, and reacting for 8 hours; adding 0.126 mol of 4-nitrophthalonitrile for end capping and 20ml of solvent NMP; the reaction is carried out for 10 to 12 hours at the temperature of 80 ℃; then pouring the product into 500ml of 0.1 mol/L diluted hydrochloric acid, washing the filtrate to be neutral by using distilled water, and carrying out vacuum drying for 24 hours at 80 ℃ to obtain a branched phthalonitrile prepolymer for later use;
and (3) curing: weighing 10 g of the branched phthalonitrile prepolymer obtained above, mixing with 0.5 g of aromatic diamine, fully mixing and stirring, compounding with quartz fiber to obtain a laminated board, and placing in a muffle furnace for heating and curing by adopting a program of 250 ℃/3 h, 325 ℃/3 h, 350 ℃/2 h and 375 ℃/8 h to finally obtain the branched phthalonitrile resin.
FIG. 1 is a nuclear magnetic hydrogen spectrum of hydroquinone branched phthalonitrile (TBHQPh), and it can be seen from the figure that the baseline of the spectrum is flat and the peak shape is clear. Through calculation, each hydrogen in the monomer structure is proved in a nuclear magnetic hydrogen spectrum, and the synthesized structure is proved to be hydroquinone branched phthalonitrile.
FIG. 2 shows an infrared spectrum of hydroquinone-branched phthalonitrile (TBHQPh) at 2231cm-1An extensional vibration absorption peak of 1658cm which is-CN-11240cm, which is the stretching vibration absorption peak of carbonyl group-1Is the absorption peak of the stretching vibration of the aromatic ether. And (4) combining the infrared spectrogram and the nuclear magnetic hydrogen spectrum to show that the obtained structure is consistent with the designed structure.
Figure BDA0002176517700000081
The thermal decomposition temperature of the branched phthalonitrile prepared according to the method under the conditions of air and nitrogen is as follows:
(1) air: t isid(initial thermal decomposition temperature) 481 ℃ C, T5％(5% temperature of thermal weight loss) 527 ℃ and the carbon residue rate (800 ℃) 11.3%;
(2) nitrogen gas: t isid(initial thermal decomposition temperature) 496 ℃ C. T5％The heat loss 5% temperature was 536 ℃ and the char yield (800 ℃) was 79.3%, showing excellent heat resistance.
Example 2
The monomer synthesis procedure was the same as in example 1.
Prepolymer synthesis: adding 0.025 mol of TB, 0.09 mol of resorcinol and 0.108 mol of catalyst anhydrous potassium carbonate into a reactor, adding 210.2ml of solvent NMP, adding 106ml of toluene with the volume of the solvent, adding water into the toluene at 130 ℃ for 2 hours, evaporating the toluene at 150 ℃, and reacting for 8 hours; adding 0.126 mol of 4-nitrophthalonitrile for end capping and 20ml of solvent NMP; the reaction is carried out for 10 to 12 hours at the temperature of 80 ℃; then, the product was poured into 500ml of 0.1 mol/L diluted hydrochloric acid, and after the filtrate was washed with distilled water to neutrality, it was vacuum-dried at 80 ℃ for 24 hours to obtain a branched phthalonitrile prepolymer. The structural formula is as follows:
Figure BDA0002176517700000082
the curing procedure was the same as in example 1.
The thermal decomposition temperature of the branched phthalonitrile prepared according to the method under the conditions of air and nitrogen is as follows:
(1) air: t isid(initial pyrolysis temperature) 475 ℃, T5％(5% of thermal weight loss temperature) 524 ℃, and carbon residue rate (800 ℃) 4%;
(2) nitrogen gas: t isid(initial thermal decomposition temperature) 498 ℃ C, T5％The heat loss 5% temperature was 540 ℃ and the char yield (800 ℃) was 77.8%, showing excellent heat resistance.
Example 3
The monomer synthesis procedure was the same as in example 1.
Prepolymer synthesis: 0.025 mol of TB and 0.09 mol of 4- (4-hydroxy) phenyl-2, 3-naphthyridin-1-one (DHPZ), 0.108 mol of anhydrous potassium carbonate as a catalyst, 210.2ml of NMP as a solvent, 106ml of toluene as a solvent volume, water-carrying toluene at 130 ℃ for 2 hours, and reacting at 150 ℃ for 8 hours after evaporating toluene; adding 0.126 mol of 4-nitrophthalonitrile for end capping and 20ml of solvent NMP; the reaction is carried out for 10 to 12 hours at the temperature of 80 ℃; then, the product was poured into 500ml of 0.1 mol/L diluted hydrochloric acid, and after the filtrate was washed with distilled water to neutrality, it was vacuum-dried at 80 ℃ for 24 hours to obtain a branched phthalonitrile prepolymer. The structural formula is as follows:
Figure BDA0002176517700000091
the curing procedure was the same as in example 1.
The thermal decomposition temperature of the DHPZ-type phthalonitrile prepared by the method under the conditions of air and nitrogen is as follows:
(1) air: t isid(initial thermal decomposition temperature) 590 ℃ C., T5％(Heat loss)Weight 5%) 540 ℃, and carbon residue (800 ℃), 12%;
(2) nitrogen gas: t isid(initial pyrolysis temperature) 508 ℃ C, T5％The heat loss 5% temperature was 550 ℃ and the char yield (800 ℃) was 78.1%, showing excellent heat resistance.

Claims (10)

1. The benzoyl structure-containing branched phthalonitrile resin is characterized by having the following chemical structure:
Figure FDA0003396295160000011
wherein m is more than or equal to 1, n is more than or equal to 1, and Z is more than or equal to 1;
Figure FDA0003396295160000012
the structure of (1) is as follows:
Figure FDA0003396295160000013
Figure FDA0003396295160000014
the structure of (1) is as follows:
Figure FDA0003396295160000015
Figure FDA0003396295160000021
one or a combination of two or more of them; wherein, R, R1、R2、R3、R4、R5、R6、R7、R8The structure of (1) is as follows: H. f, Cl, Br, I, CN, NH2、CrH2r+1、CF3、
Figure FDA0003396295160000031
One or more than two of the (a) and r is more than or equal to 1; r, R1、R2、R3、R4、R5、R6、R7And R8The same or different.
2. The method for preparing the branched phthalonitrile resin containing the benzoyl structure according to claim 1, wherein the polymerization reaction formula is as follows:
Figure FDA0003396295160000032
wherein m is more than or equal to 1, n is more than or equal to 1, Z is more than or equal to 1, and X is F, Cl, Br or I;
the preparation method comprises the following specific steps: under the protection of inert gas, the compound containing benzoyl structure
Figure FDA0003396295160000033
Trihalomonomer of (a) or (b) and (c) containing
Figure FDA0003396295160000034
Mixing structural diphenol monomer and alkali, adding strong polar aprotic solvent and azeotropic solvent, carrying out water treatment on the reaction system at the temperature of 90-140 ℃, removing the azeotropic solvent after reacting for 2-3 hours, and heating to 150-220 ℃ for reacting for 8-12 hours; when the temperature is reduced to 60-90 ℃, 4-nitrophthalonitrile is added for reaction for 10-12 hours; then pouring the product into excessive 0.1-0.2mol/L diluted hydrochloric acid, washing the filtrate to be neutral by using distilled water, and carrying out vacuum drying for 24-48 hours at the temperature of 80-120 ℃ to obtain a branched phthalonitrile prepolymer containing a benzoyl structure for later use; wherein
Figure FDA0003396295160000035
And containing benzoyl structure
Figure FDA0003396295160000036
The molar ratio of (A) to (B) is 3 to 4.2; comprises
Figure FDA0003396295160000037
The mol ratio of structural diphenol monomer to alkali is 1.2-1.6:1, and the volume mL of the strong polar aprotic solvent is 5-20 times
Figure FDA0003396295160000038
Structural bisphenols and
Figure FDA0003396295160000039
the sum of the mass g, the volume of the azeotropic solvent is 0.5 to 2 times of the volume of the strong polar aprotic solvent, the molar weight of the 4-nitrophthalonitrile is 1.2 to 1.4 times of the excess hydroxyl, wherein the excess hydroxyl is
Figure FDA00033962951600000310
With benzoyl structure
Figure FDA00033962951600000311
The residual hydroxyl after the reaction of the trihalo monomer;
and (3) curing: mixing the benzoyl structure-containing branched phthalonitrile prepolymer with aromatic diamine, fully mixing and stirring, compounding with glass fiber to obtain a laminated board, placing the laminated board in a muffle furnace at 250-375 ℃ for temperature programming and curing for 16 hours to finally obtain the cured benzoyl structure-containing branched phthalonitrile resin; wherein the mass ratio of the branched phthalonitrile prepolymer containing the benzoyl structure to the aromatic diamine is 1: 0.05;
the structure containing benzoyl
Figure FDA00033962951600000312
The trihalomonomer of (a) having the formula:
Figure FDA0003396295160000041
wherein, X structure is: x is one of F, Cl, Br and I.
3. The production method according to claim 2,
Figure FDA0003396295160000042
the specific synthesis steps are as follows:
when the temperature is below zero, adding fluorobenzene into a reactor, then gradually adding anhydrous aluminum trichloride by using a feeder, uniformly stirring, adding 1,3, 5-benzenetricarboxychloride, stirring, removing the reactor from a constant temperature tank, reacting at room temperature for 10-24 hours, and heating to 90 ℃ for reacting for 2 hours; after cooling to room temperature, pouring the product into a glacial acid bath, washing a filter cake with distilled water, and performing vacuum drying at 80-120 ℃ for 24-48 hours to obtain monomer 1,3, 5-tri (4-fluorobenzoyl) benzene for later use; wherein the molar ratio of the 1,3, 5-benzene trimethyl chloride to the fluorobenzene is 1:1.9, and the molar ratio of the 1,3, 5-benzene trimethyl chloride to the aluminum trichloride is 1: 2.4;
Figure FDA0003396295160000043
the specific synthesis steps are as follows:
when the temperature is below zero ℃, chlorobenzene is firstly added into a reactor, then anhydrous aluminum trichloride is gradually added by a feeder, after the mixture is uniformly stirred, 1,3, 5-benzene trimethyl acyl chloride is added, the mixture is stirred, the reactor is moved out of a constant temperature tank, after the mixture reacts for 10 to 24 hours at room temperature, the temperature is raised to 90 ℃ for reaction for 2 hours; after cooling to room temperature, pouring the product into a glacial acid bath, washing a filter cake with distilled water, and carrying out vacuum drying at 80-120 ℃ for 24-48 hours to obtain a monomer 1,3, 5-tri (4-chlorophenyl) benzene for later use; wherein the molar ratio of the 1,3, 5-benzene trimethyl acyl chloride to the chlorobenzene is 1:2.1, and the molar ratio of the 1,3, 5-benzene trimethyl acyl chloride to the aluminum trichloride is 1: 2.6;
Figure FDA0003396295160000044
specific combinationsThe method comprises the following steps:
when the temperature is below zero, bromobenzene is firstly added into a reactor, then anhydrous aluminum trichloride is gradually added by a feeder, after the mixture is uniformly stirred, 1,3, 5-benzene trimethyl acyl chloride is added, the mixture is stirred, the reactor is moved out of a constant temperature tank, after the mixture reacts for 10 to 24 hours at room temperature, the temperature is raised to 90 ℃ for reaction for 2 hours; after cooling to room temperature, pouring the product into a glacial acid bath, washing a filter cake with distilled water, and carrying out vacuum drying at 80-120 ℃ for 24-48 hours to obtain monomer 1,3, 5-tri (4-bromobenzoyl) benzene for later use; wherein the molar ratio of the 1,3, 5-benzene trimethyl chloride to the bromobenzene is 1:2.3, and the molar ratio of the 1,3, 5-benzene trimethyl chloride to the aluminum trichloride is 1: 2.8.
4. The production method according to claim 2 or 3,
the strong polar aprotic solvent is one or a mixture of more than two of N, N-methylformamide, N-methylacetamide, dimethyl sulfoxide and N-methylpyrrolidone;
the azeotropic solvent is one or more of toluene, xylene and chlorobenzene.
5. The production method according to claim 4,
the aromatic diamine is one or the mixture of more than two of 4,4 '-diaminodiphenyl sulfone, 4' -diaminodiphenyl ether, 4 '-diaminodiphenyl methane, 1, 3-di (4-aminophenoxy) benzene, 4' -bis (4-aminophenoxy) diphenyl sulfone, 2, 6-di (4-aminophenoxy) benzonitrile and 2, 4-di [4- (4-aminophenoxy) phenyl ] -6-phenyl-1, 3, 5-triazine.
6. The production method according to claim 2,3 or 5,
the inert gas is one of nitrogen, argon and helium.
7. The production method according to claim 4,
the inert gas is one of nitrogen, argon and helium.
8. The production method according to claim 2,3, 5 or 7,
the alkali is one or more of potassium carbonate, cesium carbonate, sodium hydroxide and potassium hydroxide.
9. The production method according to claim 4,
the alkali is one or more of potassium carbonate, cesium carbonate, sodium hydroxide and potassium hydroxide.
10. The production method according to claim 6,
the alkali is one or more of potassium carbonate, cesium carbonate, sodium hydroxide and potassium hydroxide.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103214638A (en) * 2013-04-27 2013-07-24 大连理工大学 Preparation method of branching unit-containing polyether-ether-ketone terpolymer
CN107151320A (en) * 2017-05-22 2017-09-12 大连理工大学 A kind of method for preparing branching type aryl s-triazine structure o-phthalonitrile resin
CN108997544A (en) * 2018-08-13 2018-12-14 宁波高新区诠宝绶新材料科技有限公司 A kind of preparation method of the polyether-ether-ketone new material containing branched structure

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103214638A (en) * 2013-04-27 2013-07-24 大连理工大学 Preparation method of branching unit-containing polyether-ether-ketone terpolymer
CN107151320A (en) * 2017-05-22 2017-09-12 大连理工大学 A kind of method for preparing branching type aryl s-triazine structure o-phthalonitrile resin
CN108997544A (en) * 2018-08-13 2018-12-14 宁波高新区诠宝绶新材料科技有限公司 A kind of preparation method of the polyether-ether-ketone new material containing branched structure

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"含有支化单元聚醚醚酮三元共聚物的合成研究";李继琛;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20130915;摘要、正文第37、47页 *

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