CN115745856B - Cyclohexyl-containing phthalonitrile monomer and preparation method and application thereof - Google Patents
Cyclohexyl-containing phthalonitrile monomer and preparation method and application thereof Download PDFInfo
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- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229920006391 phthalonitrile polymer Polymers 0.000 title claims abstract description 62
- 239000000178 monomer Substances 0.000 title claims abstract description 61
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000011347 resin Substances 0.000 claims abstract description 37
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 30
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- FTVOPKROFUTOKY-UHFFFAOYSA-N 4-hydroxybenzene-1,2-dicarbonitrile Chemical compound OC1=CC=C(C#N)C(C#N)=C1 FTVOPKROFUTOKY-UHFFFAOYSA-N 0.000 claims description 8
- FSDSKERRNURGGO-UHFFFAOYSA-N cyclohexane-1,3,5-triol Chemical compound OC1CC(O)CC(O)C1 FSDSKERRNURGGO-UHFFFAOYSA-N 0.000 claims description 8
- FKXXEYDHWDUXLD-UHFFFAOYSA-N 3-cyclohexylbenzene-1,2-dicarbonitrile Chemical compound C1(CCCCC1)C1=C(C(C#N)=CC=C1)C#N FKXXEYDHWDUXLD-UHFFFAOYSA-N 0.000 claims description 7
- 239000013067 intermediate product Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000010 aprotic solvent Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 6
- MJEPOVIWHVRBIT-UHFFFAOYSA-N 1-chloro-4-(4-chlorophenyl)sulfanylbenzene Chemical compound C1=CC(Cl)=CC=C1SC1=CC=C(Cl)C=C1 MJEPOVIWHVRBIT-UHFFFAOYSA-N 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000004982 aromatic amines Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 claims description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 3
- -1 4-aminophenoxy Chemical group 0.000 claims description 3
- 239000003929 acidic solution Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000012264 purified product Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 230000035484 reaction time Effects 0.000 claims 1
- 238000002844 melting Methods 0.000 abstract description 13
- 230000008018 melting Effects 0.000 abstract description 13
- 238000004132 cross linking Methods 0.000 abstract description 10
- 238000012545 processing Methods 0.000 abstract description 10
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 12
- 238000001816 cooling Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical class [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000012295 chemical reaction liquid Substances 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- NTZMSBAAHBICLE-UHFFFAOYSA-N 4-nitrobenzene-1,2-dicarbonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)C(C#N)=C1 NTZMSBAAHBICLE-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a cyclohexyl-containing phthalonitrile monomer and a preparation method and application thereof, wherein the cyclohexyl-containing phthalonitrile monomer has the following molecular structural expression, the monomer has a remarkably reduced melting point, the processing window is wider, the monomer is applied to the preparation of phthalonitrile resin, the degree of crosslinking of the resin can be ensured, and the non-coplanar structure brought by cis-trans isomerism taking cyclohexyl as the center is more beneficial to the movement of a molecular chain in space, so that the sufficient curing and crosslinking at a lower temperature can be realized.
Description
Technical Field
The invention relates to a phthalonitrile monomer, in particular to a cyclohexyl-containing phthalonitrile monomer, a preparation method and application thereof.
Background
The phthalonitrile resin is a high-performance thermosetting resin and is prepared by addition polymerization of phthalonitrile monomer and curing agent. The resin has excellent heat stability and mechanical performance, and the glass transition temperature can reach 350 deg.c, which is higher than most of known polymer materials. Meanwhile, phthalonitrile resin has no small molecule generation in polymerization, and compact matrix resin can be prepared. Based on the advantages, the phthalonitrile resin has good application prospect in the fields of aerospace, microelectronics, ships, machining and the like.
The research of phthalonitrile resin has been reported for forty years, and the research of the American naval research laboratory reports that a series of phthalonitrile resin (Keller T M.Phthalonitrile-based high-temperature resin.J Polym Sci,Part A:Polym Chem,1988,26:3199-3212). prepared from phenols with different structures is developed, and traditional phthalonitrile resin monomers are mostly linear monomers capped by bisphthalonitrile (such as CN111819221A, CN 109705072B), but the melting point of the monomers is higher, the processing window is too narrow (the difference between the melting point of the monomers and the curing temperature of the resin is too small), and in order to enrich the structural diversity of the monomers and improve the processability of the resin, researchers develop monomers with branched structures (such as CN107151320B, CN 110483763B), and the branched monomers increase the crosslinking density of polymers, so that the thermal and mechanical properties of the resin are more excellent.
However, the skeleton of the branched structure monomer is a fully rigid aromatic heterocycle, on one hand, the melting point of the monomer is higher, which is unfavorable for processing, and on the other hand, the crosslinking difficulty is increased, and the fully cured crosslinking of the resin can be realized by heating to more than 350 ℃ through a programmed temperature.
Disclosure of Invention
In order to solve the technical problems, the invention firstly provides the cyclohexyl-containing phthalonitrile monomer, which introduces flexible thioether bonds into a branched structure from the aspect of molecular structure design, and simultaneously takes cyclohexyl as the center of three branched chains, thereby not only ensuring the crosslinking degree of resin, but also obviously reducing the melting point of the monomer, and the non-coplanar structure brought by cis-trans isomerism taking cyclohexyl as the center is more beneficial to the movement of the molecular chains in space, so that the full curing crosslinking can be realized at a lower temperature.
Based on the second aspect of the invention, the invention also provides a preparation method of the monomer containing cyclohexyl phthalonitrile, which takes 1,3, 5-cyclohexanetriol as a molecular design center and simultaneously reacts with 4,4' -dichloro diphenyl sulfide and 4-hydroxy phthalonitrile to prepare the phthalonitrile monomer, and has the advantages of simple operation flow, low process difficulty and strong industrial applicability.
Based on the third aspect of the invention, a phthalonitrile resin is also provided, which is obtained by polymerizing the phthalonitrile monomer and the curing agent, can realize full curing and crosslinking at a lower curing temperature, and has obviously reduced processing difficulty.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a cyclohexyl-containing phthalonitrile monomer having a molecular structural expression as shown below:
a preparation method of a monomer containing cyclohexyl phthalonitrile comprises the following steps:
1) Mixing 4,4' -dichloro diphenyl sulfide and 4-hydroxy phthalonitrile in an aprotic solvent, adding anhydrous potassium carbonate, heating to 80-120 ℃, reacting for 2-5h, and purifying to obtain an intermediate product;
2) Mixing the intermediate product and 1,3, 5-cyclohexanetriol in an aprotic solvent, adding anhydrous potassium carbonate, heating to 90-140 ℃, reacting for 3-6h, and purifying to obtain the phthalonitrile monomer.
As a preferred embodiment, in step 1), the molar ratio of 4,4' -dichlorodiphenyl sulfide, 4-hydroxyphthalonitrile and anhydrous potassium carbonate is 1 (1-1.05): 1.2-1.5.
As a preferred embodiment, in step 2), the molar ratio of 1,3, 5-cyclohexanetriol, intermediate, anhydrous potassium carbonate is 1 (3-3.1): 3.5-4.5.
As a preferred embodiment, the aprotic solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone.
As a preferred embodiment, after the reaction in the steps 1) and 2), the reaction solution is poured into an acid solution to precipitate solids, and the purified product is obtained by filtration, washing and drying.
As a preferred embodiment, the acidic solution is dilute hydrochloric acid with a mass concentration of 0.1-0.5 mol/L; the dosage of the dilute hydrochloric acid is 3-5 times of the volume of the reaction solution.
A phthalonitrile resin obtained by polymerizing the above-described phthalonitrile monomer or the above-described phthalonitrile monomer obtained by the above-described method and an aromatic amine curing agent.
As a preferred embodiment, the polymerization temperature is 230 to 250℃and is, for example, 230℃235 ℃, 240 ℃, 245 ℃, 250℃and the like. The polymerization time is 5 to 8 hours, for example, 5 hours, 6 hours, 7 hours, 8 hours, etc.
As a preferred embodiment, the aromatic amine curative is one or more of 4,4 '-diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 4 '-bis (4-aminophenoxy) diphenyl sulfone, 4' -diaminodiphenyl methane.
Preferably, the curing agent is used in an amount of 5 to 10% by mass, for example 5%, 6%, 7%, 8%, 9%, 10% by mass, etc., of the phthalonitrile monomer.
The invention has the beneficial effects that:
the melting point of the phthalonitrile monomer is as low as 104 ℃, the processing window of the resin is wider, and meanwhile, the phthalonitrile monomer can be fully solidified at a lower temperature (230-250 ℃), so that the processing technology difficulty is remarkably reduced.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
Unless otherwise indicated, the starting materials and reagents used in the examples below were purchased from commercial sources.
The main analysis and test method related by the invention is as follows:
<1> resin curing temperature: analyzing the curing exothermic temperature of the phthalonitrile monomer, namely the curing temperature of the resin by adopting a Differential Scanning Calorimeter (DSC);
<2> processing window: processing window (°c) =resin cure temperature-monomer melting point;
<3> degree of resin crosslinking: dissolving the resin sample in N-methylpyrrolidone under reflux for 48h with N-methylpyrrolidone as solvent, wherein the residue is a crosslinked gel component, and the degree of crosslinking (%) = residue mass remaining/initial sample mass
<4> Thermal initial decomposition temperature: adopting a Thermal Gravimetric Analysis (TGA) method;
<5> glass transition temperature: dynamic Mechanical Analysis (DMA) method is adopted;
<6> impact Strength: the test was performed according to standard ASTM D256 (23 ℃).
The following examples 1-3, comparative examples 1-2, respectively, provide methods for the preparation of different phthalonitrile monomers:
[ example 1]
(1) To the reactor were added 0.1mol of 4,4' -dichlorophenyl sulfide, 0.1mol of 4-hydroxyphthalonitrile, 0.15mol of anhydrous potassium carbonate, 250ml of dehydrated dimethyl sulfoxide, stirring was started under nitrogen protection, and the mixture was heated to 80℃to react for 3 hours. Cooling to room temperature after stopping heating, pouring the mixture into 0.1mol/L dilute hydrochloric acid with the volume of 3 times of the reaction liquid to precipitate, carrying out suction filtration, repeatedly washing to neutrality by deionized water, and carrying out vacuum drying at 70 ℃ for 12 hours to obtain a pale yellow powdery intermediate product. After the powder was recrystallized from acetonitrile, the nuclear magnetic structure analysis was performed, and the analytical data were as follows:
1 H NMR (deuterated DMSO,400MHz,TMS): delta 8.16 (d, 1H), 7.94 (s, 1H), 7.57 (d, 2H), 7.47 (d, 2H), 7.43 (s, 1H), 7.37 (d, 4H).
(2) To the reactor were added 0.3mol of the intermediate, 0.1mol of 1,3, 5-cyclohexanetriol, 0.4mol of anhydrous potassium carbonate, 150ml of dehydrated N, N-dimethylformamide were added, and the mixture was stirred under nitrogen atmosphere, heated to 90℃and reacted for 3 hours. Cooling to room temperature after stopping heating, pouring the mixture into 0.1mol/L dilute hydrochloric acid with the volume of 3 times of the reaction liquid to precipitate, filtering, repeatedly washing to neutrality, and vacuum drying at 70 ℃ for 12 hours to obtain white powder, namely phthalonitrile monomer, wherein the product yield is 97%, and the melting point is 104 ℃. The analysis data of the nuclear magnetic characterization of the product are as follows:
1 H NMR (deuterated DMSO,400MHz,TMS):δ8.16(d,3H),7.94(s,3H),7.51(d,3H),7.40(d,12H),7.31(d,6H),6.96(d,6H),3.64(m,3H),2.33(m,3H),2.08(d,3H).)
[ Example 2]
(1) To the reactor were added 0.1mol of 4,4' -dichlorophenyl sulfide, 0.103mol of 4-hydroxyphthalonitrile, 0.13mol of anhydrous potassium carbonate, 250ml of dehydrated N, N-dimethylformamide, stirring was started under nitrogen protection, and the mixture was heated to 110℃to react for 5 hours. Cooling to room temperature after stopping heating, pouring the mixture into 0.5mol/L dilute hydrochloric acid with the volume of 3 times of the reaction liquid to precipitate, carrying out suction filtration, repeatedly washing to neutrality by deionized water, and carrying out vacuum drying at 70 ℃ for 12 hours to obtain a pale yellow powdery intermediate product.
(2) To the reactor were added 0.305mol of the intermediate, 0.1mol of 1,3, 5-cyclohexanetriol, 0.45mol of anhydrous potassium carbonate, and 150ml of dehydrated dimethyl sulfoxide, followed by stirring under nitrogen atmosphere, heating to 140℃and reacting for 3 hours. Cooling to room temperature after stopping heating, pouring the mixture into 0.5mol/L dilute hydrochloric acid with the volume of 3 times of the reaction liquid to precipitate, filtering, repeatedly washing to neutrality, and vacuum drying at 70 ℃ for 12 hours to obtain white powder, namely phthalonitrile monomer, wherein the product yield is 95%, and the melting point is 104 ℃.
[ Example 3]
(1) To the reactor were added 0.1mol of 4,4' -dichlorophenyl sulfide, 0.105mol of 4-hydroxyphthalonitrile, 0.12mol of anhydrous potassium carbonate, 250ml of dehydrated N-methylpyrrolidone, stirring under nitrogen protection, heating to 100℃and reacting for 4 hours. Cooling to room temperature after stopping heating, pouring the mixture into 0.3mol/L dilute hydrochloric acid with the volume of 4 times of the reaction liquid to precipitate, carrying out suction filtration, repeatedly washing to neutrality by deionized water, and carrying out vacuum drying at 70 ℃ for 12 hours to obtain a pale yellow powdery intermediate product.
(2) To the reactor were added 0.31mol of the intermediate, 0.1mol of 1,3, 5-cyclohexanetriol, 0.35mol of anhydrous potassium carbonate, 150ml of dehydrated N-methylpyrrolidone, and the mixture was stirred under nitrogen atmosphere, heated to 125℃and reacted for 5 hours. Cooling to room temperature after stopping heating, pouring the mixture into 0.3mol/L dilute hydrochloric acid with the volume of 4 times of the reaction liquid to precipitate, filtering, repeatedly washing to neutrality, and vacuum drying at 70 ℃ for 12 hours to obtain white powder, namely the phthalonitrile monomer, wherein the product yield is 98%, and the melting point is 104 ℃.
Comparative example 1
To the reactor were added 0.1mol of bisphenol A, 0.2mol of 4-nitrophthalonitrile, 0.25mol of anhydrous potassium carbonate, 250ml of dehydrated N, N-dimethylformamide were added, stirring was started under nitrogen protection, and the mixture was heated to 85℃to react for 5 hours. Cooling to room temperature after stopping heating, pouring the mixture into 0.1mol/L dilute hydrochloric acid with the volume of 3 times of the reaction liquid to precipitate, filtering, repeatedly washing the precipitate to neutrality, and vacuum drying at 70 ℃ for 12 hours to obtain pale yellow powder, namely bisphenol A type phthalonitrile monomer, wherein the product yield is 98%, and the melting point is 192 ℃. The analysis data of the nuclear magnetic characterization of the product are as follows:
1 H NMR (deuterated DMSO,400MHz,TMS): delta 8.16 (d, 2H), 7.94 (s, 2H), 7.44 (dd, 2H), 7.32 (d, 4H), 7.26 (dd, 4H), 1.72 (s, 6H).
Comparative example 2
The branched phthalonitrile prepolymer prepared in example 1 of patent CN107151320 has a melting point of 204 ℃.
The following examples 4-8, comparative examples 3-5 were used to prepare different phthalonitrile resins:
[ example 4]
10G of the phthalonitrile monomer prepared in example 1 and 1g of 4,4' -diaminodiphenyl ether were weighed, mixed, sufficiently ground, poured into a reaction vessel with stirring, heated to 150℃and stirred for 2 minutes to obtain a prepolymer. Cooling the prepolymer, crushing the prepolymer by a crusher, pouring the crushed prepolymer into a square mold, pumping residual micromolecules in the material in a vacuum oven at 160 ℃, then placing the dried prepolymer into a muffle furnace while the dried prepolymer is hot, and preserving the heat for 5 hours at 250 ℃ to obtain the cured phthalonitrile resin.
[ Example 5]
10G of the phthalonitrile monomer prepared in example 1 and 0.5g of 4,4' -bis (4-aminophenoxy) diphenylsulfone were weighed, mixed, sufficiently ground, poured into a reaction vessel with stirring, heated to 150℃and stirred for 2 minutes to obtain a prepolymer. Cooling the prepolymer, crushing the prepolymer by a crusher, pouring the crushed prepolymer into a square mold, pumping residual micromolecules in the material in a vacuum oven at 160 ℃, then placing the dried prepolymer into a muffle furnace while the dried prepolymer is hot, and preserving the heat for 6 hours at 240 ℃ to obtain the cured phthalonitrile resin.
[ Example 6]
10G of the phthalonitrile monomer prepared in example 1 and 0.8g of 4,4' -diaminodiphenyl sulfone were weighed and mixed, and after sufficient grinding, poured into a reaction vessel with stirring, heated to 150℃and stirred for 2 minutes to obtain a prepolymer. Cooling the prepolymer, crushing the prepolymer by a crusher, pouring the crushed prepolymer into a square mold, pumping residual micromolecules in the material in a vacuum oven at 160 ℃, then placing the dried prepolymer into a muffle furnace while the dried prepolymer is hot, and preserving the heat for 8 hours at 230 ℃ to obtain the cured phthalonitrile resin.
[ Example 7]
10G of the phthalonitrile monomer prepared in example 2 and 0.7g of 4,4' -diaminodiphenyl methane were weighed and mixed, and after sufficient grinding, poured into a reaction vessel with stirring, heated to 150℃and stirred for 2 minutes to obtain a prepolymer. Cooling the prepolymer, crushing the prepolymer by a crusher, pouring the crushed prepolymer into a square mold, pumping residual micromolecules in the material in a vacuum oven at 160 ℃, then placing the dried prepolymer into a muffle furnace while the dried prepolymer is hot, and preserving the heat for 6 hours at 245 ℃ to obtain the cured phthalonitrile resin.
[ Example 8]
10G of the phthalonitrile monomer prepared in example 3 and 0.9g of 3,4' -diaminodiphenyl ether were weighed, mixed, sufficiently ground, poured into a reaction vessel with stirring, heated to 150℃and stirred for 2 minutes to obtain a prepolymer. Cooling the prepolymer, crushing the prepolymer by a crusher, pouring the crushed prepolymer into a square mold, pumping residual micromolecules in the material in a vacuum oven at 160 ℃, then placing the dried prepolymer into a muffle furnace while the dried prepolymer is hot, and preserving the heat for 7 hours at 235 ℃ to obtain the cured phthalonitrile resin.
[ Comparative example 3]
A phthalonitrile resin was prepared in substantially the same manner as in example 4, except that the phthalonitrile monomer prepared in example 1 was replaced with the bisphenol A type phthalonitrile monomer prepared in comparative example 1.
[ Comparative example 4]
A phthalonitrile resin was prepared in substantially the same manner as in example 4, except that the phthalonitrile monomer prepared in example 1 was replaced with the branched phthalonitrile prepolymer prepared in comparative example 2.
Comparative example 5
A phthalonitrile resin was prepared in substantially the same manner as in comparative example 4, except that the curing temperature in the muffle furnace was modified to be 230℃at 250℃for 3 hours, 325℃for 3 hours, 350℃for 2 hours, and 375℃for 8 hours, and the temperature was raised for curing.
The performance test in Table 1 was conducted on the phthalonitrile resins prepared in examples 4 to 8 and comparative examples 3 to 5, respectively, and the results were as follows:
TABLE 1 Performance test results
As can be seen from the table, the phthalonitrile monomer in the comparative example can be fully crosslinked only after being cured at a temperature of more than 350 ℃, so that better performance is achieved, but the phthalonitrile monomer containing cyclohexyl designed by the invention can be fully crosslinked only by being cured at a lower temperature (230-250 ℃) for a few hours, and has excellent high temperature resistance, and meanwhile, the impact strength is improved to a certain extent due to the flexible center and chain segment in the monomer molecule. In addition, the monomer of the invention has lower melting point, wide processing window and is very beneficial to the processing of resin.
Claims (8)
1. A cyclohexyl-containing phthalonitrile monomer, characterized in that the phthalonitrile monomer has a molecular structural expression as shown below:
2. The preparation method of the cyclohexyl-containing phthalonitrile monomer is characterized by comprising the following steps:
1) Mixing 4,4' -dichloro diphenyl sulfide and 4-hydroxy phthalonitrile in an aprotic solvent, adding anhydrous potassium carbonate, heating to 80-120 ℃, reacting for 2-5h, and purifying to obtain an intermediate product;
2) Mixing the intermediate product and 1,3, 5-cyclohexanetriol in an aprotic solvent, adding anhydrous potassium carbonate, heating to 90-140 ℃, reacting for 3-6h, and purifying to obtain the phthalonitrile monomer.
3. The method for producing a cyclohexylphthalonitrile-containing monomer according to claim 2, wherein in step 1), the molar ratio of 4,4' -dichlorodiphenyl sulfide, 4-hydroxyphthalonitrile, and anhydrous potassium carbonate is 1 (1-1.05): 1.2-1.5.
4. The method for producing a cyclohexylphthalonitrile-containing monomer according to claim 3, wherein in step 2), the molar ratio of 1,3, 5-cyclohexanetriol, intermediate, and anhydrous potassium carbonate is 1 (3-3.1): 3.5-4.5.
5. The method for producing a cyclohexylphthalonitrile-containing monomer according to any one of claims 2 to 4, wherein the aprotic solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone.
6. The process for producing a cyclohexylphthalonitrile-containing monomer as claimed in any one of claims 2 to 4, wherein after the completion of the reaction in steps 1) and 2), the reaction solution is poured into an acidic solution to precipitate a solid, and the solid is filtered, washed and dried to obtain a purified product.
7. The method for producing a cyclohexylphthalonitrile-containing monomer according to claim 6, wherein the acidic solution is dilute hydrochloric acid having a mass concentration of 0.1 to 0.5 mol/L; the dosage of the dilute hydrochloric acid is 3-5 times of the volume of the reaction solution.
8. A phthalonitrile resin, characterized in that it is polymerized from the phthalonitrile monomer of claim 1 or the phthalonitrile monomer produced by the method of any one of claims 2 to 7 and an aromatic amine curing agent;
the polymerization reaction temperature is 230-250 ℃ and the reaction time is 5-8h;
The aromatic amine curing agent is one or more of 4,4' -diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 4' -bis (4-aminophenoxy) diphenyl sulfone, 4' -diaminodiphenyl sulfone and 4,4' -diaminodiphenyl methane.
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