CN114181134B - Norbornene-terminated imide small molecule compound and preparation method and application thereof - Google Patents
Norbornene-terminated imide small molecule compound and preparation method and application thereof Download PDFInfo
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- CN114181134B CN114181134B CN202010966690.1A CN202010966690A CN114181134B CN 114181134 B CN114181134 B CN 114181134B CN 202010966690 A CN202010966690 A CN 202010966690A CN 114181134 B CN114181134 B CN 114181134B
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- imide
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- -1 imide small molecule compound Chemical class 0.000 title claims description 20
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 25
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 150000004984 aromatic diamines Chemical class 0.000 claims description 11
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- CHWKGJOTGCSFNF-UHFFFAOYSA-N norbornene anhydride Chemical compound C1CC2C3C(=O)OC(=O)C3=C1C2 CHWKGJOTGCSFNF-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- UNZSJASIKFONPS-UHFFFAOYSA-N C(C)(=O)N(C)C.[N].[N] Chemical compound C(C)(=O)N(C)C.[N].[N] UNZSJASIKFONPS-UHFFFAOYSA-N 0.000 claims 1
- WRLVLKSWVLTFET-UHFFFAOYSA-N CN1C(CCC1)=O.[N].[N] Chemical compound CN1C(CCC1)=O.[N].[N] WRLVLKSWVLTFET-UHFFFAOYSA-N 0.000 claims 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 1
- BJMBNXMMZRCLFY-UHFFFAOYSA-N [N].[N].CN(C)C=O Chemical compound [N].[N].CN(C)C=O BJMBNXMMZRCLFY-UHFFFAOYSA-N 0.000 claims 1
- 229920001721 polyimide Polymers 0.000 abstract description 56
- 239000011347 resin Substances 0.000 abstract description 54
- 229920005989 resin Polymers 0.000 abstract description 54
- 239000009719 polyimide resin Substances 0.000 abstract description 33
- 150000003949 imides Chemical class 0.000 abstract description 23
- 239000000155 melt Substances 0.000 abstract description 6
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 6
- 238000004132 cross linking Methods 0.000 abstract description 4
- 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 abstract 2
- 239000004642 Polyimide Substances 0.000 description 23
- 230000009477 glass transition Effects 0.000 description 19
- 239000000243 solution Substances 0.000 description 18
- 238000002156 mixing Methods 0.000 description 15
- 239000000843 powder Substances 0.000 description 13
- 239000002243 precursor Substances 0.000 description 12
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 8
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 8
- 238000005303 weighing Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 150000003384 small molecules Chemical class 0.000 description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000004156 Azodicarbonamide Substances 0.000 description 2
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 2
- 235000019399 azodicarbonamide Nutrition 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000003181 co-melting Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/58—[b]- or [c]-condensed
- C07D209/72—4,7-Endo-alkylene-iso-indoles
- C07D209/76—4,7-Endo-alkylene-iso-indoles with oxygen atoms in positions 1 and 3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
- C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
Abstract
The invention provides a norbornene-terminated imide small molecular compound, a preparation method and application thereof, wherein the small molecular compound is norbornene-terminated bisphenol A type imide, and the imide small molecular compound is mixed with thermosetting polyimide resin, so that the melt viscosity of the thermosetting polyimide resin can be reduced, and the crosslinking density and the technological performance of the resin can be improved.
Description
Technical Field
The invention belongs to the technical field of blending of organic compounds and polymers, and particularly relates to a norbornene-terminated imide small molecule compound, a preparation method and application thereof.
Background
The thermosetting polyimide resin has outstanding heat resistance and excellent mechanical properties, and has important application in the aerospace field. However, the melt viscosity of the resin is high and the processing is difficult due to the strong interaction between polyimide molecular chains and the rigidity of the molecular chains themselves. Therefore, the melt viscosity of the polyimide resin is reduced, and the technological performance is improved, so that the difficulty of the polyimide in the application of the polyimide in the high-temperature resistant field is further expanded. The method for reducing the melt viscosity of polyimide resin is to introduce a flexible chain structure into a molecular main chain, and the method can reduce the melt viscosity of polyimide resin but obviously reduce the heat resistance of cured resin.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a norbornene-terminated imide small molecule compound, a preparation method and application thereof, so as to solve the technical problems in the modification of the existing polyimide resin.
The technical scheme of the invention is as follows:
according to a first aspect, there is provided a norbornene-terminated imide small molecule compound having the structural formula:
according to a second aspect, there is provided a method of preparing the above small molecule compound, the method comprising:
step 1, carrying out a chemical reaction on norbornene anhydride and ethanol under reflux to obtain norbornene monoester monoacid;
step 2, carrying out two-step chemical reaction and post-treatment on the norbornene monoester monoacid to obtain the small molecular compound, wherein the two-step chemical reaction is as follows:
1) Dissolving the norbornene monoester monoacid in an organic solvent and then carrying out chemical reaction with aromatic diamine BAPP;
2) The product obtained in 1) is further subjected to chemical reaction with acetic anhydride and pyridine.
Further, in the step 1, the amount of the substance of the ethanol is 10 to 20 times that of the norbornene anhydride; and/or, in the step 2, the mass ratio of the norbornene monoester monoacid to the aromatic diamine BAPP is 1.2:1 to 3:1, a step of; the mass ratio of the acetic anhydride to the norbornene monoester monoacid is 2:1 to 4:1, a step of; the mass ratio of acetic anhydride to pyridine is 1.5:1 to 3:1.
further, in the step 2, the organic solvent is any one of azodicarbonamide (DMF), azodicarbonamide (DMAc) and azomethicone (NMP), or a mixed solvent of any several of them in any proportion.
Further, in the step 2, the mass of the organic solvent is 2 to 4 times of the mass of the solid matter used.
Further, the reaction conditions in 1) are: after norbornene monoester monoacid is dissolved in an organic solvent, adding aromatic diamine BAPP under the protection of nitrogen, and stirring at room temperature for reaction for 1-3 hours; and/or, the reaction conditions in 2) are: 1) After the completion, adding acetic anhydride and pyridine, heating to 120-180 ℃ and reacting for 2-6 hours; and/or, the post-treatment is as follows: cooling the reaction solution obtained in the step 2) to room temperature, pouring the reaction solution into deionized water, precipitating white powdery solid, filtering, and drying a filter cake in a vacuum oven, wherein the drying temperature of the vacuum oven is 80-120 ℃ and the drying time is 10-24 hours.
Further, the volume of the deionized water is 5-15 times of the total volume of the reaction liquid.
According to a third aspect of the present invention, there is also provided the use of the norbornene-terminated imide small molecule compound described above as a diluent for modifying a norbornene-terminated polyimide resin.
Further, when the small molecule compound is used as a diluent for modifying the norbornene-terminated polyimide resin, the norbornene-terminated polyimide resin may be modified by the following method:
the small molecular compound is directly mixed with norbornene polyimide powder, and the preparation method comprises the following steps: and uniformly mixing a certain amount of norbornene-terminated polyimide and a small molecular compound by using powder mixing equipment, wherein the mass ratio of the small molecular compound to polyimide resin is (1:9) - (9:1).
Further, the powder mixing device comprises a stirring mixer, a conical mixer, a high-speed pulverizer or a mortar.
Further, when the small molecule compound is used as a diluent for modifying the norbornene-terminated polyimide resin, the norbornene-terminated polyimide resin may be modified by the following method:
the small molecular compound is directly added into a norbornene-terminated polyimide precursor solution to realize mixing, and the preparation method comprises the following steps: adding a certain amount of small molecular compound into polyimide precursor solution, stirring and mixing uniformly, and then placing the resin powder into an oven to dry for 1-8 hours at 150-250 ℃ to obtain mixed resin powder, wherein the mass ratio of the small molecular compound to polyimide resin is (1:9) - (9:1).
Compared with the prior art, the invention has the beneficial effects that:
the small molecule has very low melting temperature and melt viscosity, can obviously reduce the melt viscosity of polyimide through the co-melting effect and improve the technological performance of polyimide by taking the small molecule as a diluent of thermosetting polyimide resin, and meanwhile, the small molecule of the imide contains a thermally crosslinkable end group, can participate in the crosslinking solidification of norbornene-terminated polyimide resin and improve the crosslinking density (heat resistance) of the resin. The imide micromolecule prepared by the method has a thermally-crosslinkable end group structure and a compliant molecular structure, can be used for diluting high-viscosity thermosetting polyimide resin, can obviously improve the technological properties of the thermosetting polyimide resin, and has great application value in the fields of aerospace, carrier-borne ships, microelectronic packaging and the like.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of norbornene monoester monoacid obtained in example 1;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the norbornene-terminated imide small molecule compound obtained in example 1;
FIG. 3 is a DSC curve of the norbornene-terminated imide small molecule compound obtained in example 1;
FIG. 4 is a temperature-rising rheology curve of the norbornene-terminated imide small molecule compound obtained in example 1.
Detailed Description
Specific embodiments of the present invention are described in detail below. In the following description, for purposes of explanation and not limitation, specific details are set forth in order to provide a thorough understanding of the present invention. It will be apparent, however, to one skilled in the art that the present invention may be practiced in other embodiments that depart from these specific details. It should be noted here that, in order to avoid obscuring the present invention due to unnecessary details, only the device structures and/or processing steps closely related to the scheme according to the present invention are shown, while other details not greatly related to the present invention are omitted. The method is a conventional method unless otherwise specified. The starting materials are available from published commercial sources unless otherwise specified. The solid content in the invention is mass percent unless specified otherwise.
Example 1
Preparation of norbornene-terminated imide small molecule Compounds
1) 10.00g (0.06092 mol) of norbornene anhydride and 28.06g (0.6092 mol) of ethanol are added into a single-neck round-bottom flask, a reflux condensing device is connected to the flask, then the flask is added into an oil bath, the mixture is heated and subjected to reflux reaction for 4 hours, and then unreacted ethanol is removed by a rotary evaporator to obtain norbornene monoester monoacid;
2) 12.50g (0.03046 mol) of BAPP was weighed into the norbornene monoester monoacid, 70g of DMF was added thereto, and the mixture was stirred and mixed for 2 hours; 18.66g (0.18726 mol) acetic anhydride and 7.41g (0.09363 mol) pyridine were weighed into the above reaction system, heated to 160℃and reacted at that temperature for 4 hours; after cooling to room temperature, pouring the reaction solution into 800ml of deionized water, precipitating white powder, filtering, washing a filter cake with deionized water for three times, and then putting into a vacuum oven for drying at 100 ℃ for 10 hours to obtain the target compound imide micromolecule.
FIG. 1 is a nuclear magnetic resonance spectrum of norbornene monoester monoacid; FIG. 2 is a nuclear magnetic resonance spectrum of an imide small molecular compound, FIG. 3 is a DSC spectrum of the imide small molecular compound, and FIG. 4 is a heating rheogram of the imide small molecular compound, wherein the rheogram can show that the imide small molecules have melt viscosity lower than 1 Pa.s at 200-300 ℃ and have very good technological properties.
Example 2
The small imide molecule obtained in example 1 and the norbornene-terminated polyimide resin were mixed by a powder mixing method.
The polyimide used in this example was prepared from aromatic tetracarboxylic dianhydride sBPDA, metaphenylene diamine mPDA and end-capping agent NA, the molecular weight of the resin was 2500, and the resin number was BP-2500. The preparation method of the mixed resin comprises the steps of weighing 2gBP-2500 polyimide resin and 18g of the imide micromolecule prepared in the example 1, putting the polyimide resin and the imide micromolecule into a mortar, and grinding for 10 minutes to obtain the mixed resin. The viscosity profile of the mixed resin was measured using a high temperature rheometer (AR-2000) at a temperature rise rate of 4℃per minute, and the glass transition temperature of the mixed resin was measured using a parallax scanning calorimeter (DSC) at a temperature rise rate of 5℃per minute, and the lowest melt viscosity and glass transition temperature of the resin are shown in Table 1.
Example 3
The small imide molecule obtained in example 1 and the norbornene-terminated polyimide resin were mixed by a powder mixing method.
The polyimide used in this example was prepared from aromatic tetracarboxylic dianhydride sBPDA, metaphenylene diamine mPDA and end-capping agent NA, the molecular weight of the resin was 2500, and the resin number was BP-2500. The preparation method of the mixed resin comprises the steps of weighing 10gBP-2500 polyimide resin and 10g of the imide micromolecule prepared in the example 1, putting the polyimide resin and the imide micromolecule into a mortar, and grinding for 10 minutes to obtain the mixed resin. The viscosity profile of the mixed resin was measured using a high temperature rheometer (AR-2000) at a temperature rise rate of 4℃per minute, and the glass transition temperature of the mixed resin was measured using a parallax scanning calorimeter (DSC) at a temperature rise rate of 5℃per minute, and the lowest melt viscosity and glass transition temperature of the resin are shown in Table 1.
Example 4
The small imide molecule obtained in example 1 and the norbornene-terminated polyimide resin were mixed by a powder mixing method.
The polyimide used in this example was prepared from aromatic tetracarboxylic dianhydride sBPDA, metaphenylene diamine mPDA and end-capping agent NA, the molecular weight of the resin was 2500, and the resin number was BP-2500. The preparation method of the mixed resin comprises the steps of weighing 18-gBP-2500 polyimide resin and 2g of the imide micromolecule prepared in the example 1, putting the polyimide resin and the imide micromolecule into a mortar, and grinding for 10 minutes to obtain the mixed resin. The viscosity profile of the mixed resin was measured using a high temperature rheometer (AR-2000) at a temperature rise rate of 4℃per minute, and the glass transition temperature of the mixed resin was measured using a parallax scanning calorimeter (DSC) at a temperature rise rate of 5℃per minute, and the lowest melt viscosity and glass transition temperature of the resin are shown in Table 1.
Comparative example 1
The properties of the polyimide resin matrix without small molecules mixed are characterized.
The polyimide used in this example was prepared from aromatic tetracarboxylic dianhydride sBPDA, metaphenylene diamine mPDA and end-capping agent NA, the molecular weight of the resin was 2500, and the resin number was BP-2500. The polyimide resin 20-gBP-2500 is weighed and put into a mortar for grinding for 10 minutes. The viscosity profile of the resin was measured using a high temperature rheometer (AR-2000) at a temperature rise rate of 4℃per minute, and the glass transition temperature of the resin was measured using a parallax scanning calorimeter (DSC) at a temperature rise rate of 5℃per minute, and the lowest melt viscosity and glass transition temperature of the resin are shown in Table 1.
Example 5
The imide small molecule obtained in example 1 and the norbornene-terminated polyimide resin were mixed by a solution mixing method.
The polyimide precursor solution used in this example consisted of an alcohol esterified aromatic tetracarboxylic dianhydride aBPDA, an alcohol esterified NA and an aromatic diamine 3,4ODA, the solvent was ethanol, the designed molecular weight was 2500g/mol, and BO-2500. The preparation method of the mixed resin comprises the steps of weighing 18g of the imide micromolecule, adding the imide micromolecule into 4g of polyimide precursor solution with the solid content of 50%, mixing and stirring for 1 hour, then placing the mixed solution into a blast oven, and drying the mixed solution at 100 ℃/1h,150 ℃/1h and 200 ℃/1h to obtain mixed resin powder. The viscosity profile of the resin was measured using a high temperature rheometer (AR-2000) at a temperature rise rate of 4℃per minute, and the glass transition temperature of the resin was measured using a parallax scanning calorimeter (DSC) at a temperature rise rate of 5℃per minute, and the lowest melt viscosity and glass transition temperature of the resin are shown in Table 1.
Example 6
The imide small molecule obtained in example 1 and the norbornene-terminated polyimide resin were mixed by a solution mixing method.
The polyimide precursor solution used in this example consisted of an alcohol esterified aromatic tetracarboxylic dianhydride aBPDA, an alcohol esterified NA and an aromatic diamine 3,4ODA, the solvent was ethanol, the designed molecular weight was 2500g/mol, and BO-2500. The preparation method of the mixed resin comprises the steps of weighing 10g of the imide micromolecule, adding the imide micromolecule into 20g of polyimide precursor solution with the solid content of 50%, mixing and stirring for 1 hour, then placing the mixed solution into a blast oven, and drying the mixed solution at 100 ℃/1h,150 ℃/1h and 200 ℃/1h to obtain mixed resin powder. The viscosity profile of the resin was measured using a high temperature rheometer (AR-2000) at a temperature rise rate of 4℃per minute, and the glass transition temperature of the resin was measured using a parallax scanning calorimeter (DSC) at a temperature rise rate of 5℃per minute, and the lowest melt viscosity and glass transition temperature of the resin are shown in Table 1.
Example 7
The imide small molecule obtained in example 1 and the norbornene-terminated polyimide resin were mixed by a solution mixing method.
The polyimide precursor solution used in this example consisted of an alcohol esterified aromatic tetracarboxylic dianhydride aBPDA, an alcohol esterified NA and an aromatic diamine 3,4ODA, the solvent was ethanol, the designed molecular weight was 2500g/mol, and BO-2500. The preparation method of the mixed resin comprises the steps of weighing 2g of the imide micromolecule, adding the imide micromolecule into 36g of polyimide precursor solution with the solid content of 50%, mixing and stirring for 1 hour, then placing the mixed solution into a blast oven, and drying the mixed solution at 100 ℃/1h,150 ℃/1h and 200 ℃/1h to obtain mixed resin powder. The viscosity profile of the resin was measured using a high temperature rheometer (AR-2000) at a temperature rise rate of 4℃per minute, and the glass transition temperature of the resin was measured using a parallax scanning calorimeter (DSC) at a temperature rise rate of 5℃per minute, and the lowest melt viscosity and glass transition temperature of the resin are shown in Table 1.
Comparative example 2
The properties of the polyimide resin matrix without small molecules mixed are characterized.
The polyimide precursor solution used in this example consisted of an alcohol esterified aromatic tetracarboxylic dianhydride aBPDA, an alcohol esterified NA and an aromatic diamine 3,4ODA, the solvent was ethanol, the designed molecular weight was 2500g/mol, and BO-2500. The drying method of the resin comprises the steps of weighing 40g of polyimide precursor solution with the solid content of 50%, putting the polyimide precursor solution into a blast oven, and drying the polyimide precursor solution at 100 ℃/1h,150 ℃/1h and 200 ℃/1h to obtain resin powder. The viscosity profile of the resin was measured using a high temperature rheometer (AR-2000) at a temperature rise rate of 4℃per minute, and the glass transition temperature of the resin was measured using a parallax scanning calorimeter (DSC) at a temperature rise rate of 5℃per minute, and the lowest melt viscosity and glass transition temperature of the resin are shown in Table 1.
Table 1: viscosity Properties and glass transition temperature of the resin System
In Table 1, "-" indicates that the glass transition temperature of comparative example 1 was not measured, because the resin was a crystalline system, the melting point was high, the crosslinking reaction between molecular chains could not be achieved during heating, and the cured product had no glass transition temperature.
Features that are described and/or illustrated above with respect to one embodiment may be used in the same way or in a similar way in one or more other embodiments and/or in combination with or instead of the features of the other embodiments.
It should be emphasized that the term "comprises/comprising" when used herein is taken to specify the presence of stated features, integers, steps or components but does not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof.
The many features and advantages of the embodiments are apparent from the detailed specification, and thus, it is intended by the appended claims to cover all such features and advantages of the embodiments which fall within the true spirit and scope thereof. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the embodiments of the invention to the exact construction and operation illustrated and described, and accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope thereof.
The invention is not described in detail in a manner known to those skilled in the art.
Claims (1)
1. A method for preparing a norbornene-terminated imide small molecule compound, the method comprising:
step 1, carrying out a chemical reaction on norbornene anhydride and ethanol under reflux to obtain norbornene monoester monoacid;
step 2, carrying out two-step chemical reaction and post-treatment on the norbornene monoester monoacid to obtain the small molecular compound, wherein the two-step chemical reaction is as follows:
1) Dissolving the norbornene monoester monoacid in an organic solvent and then carrying out chemical reaction with aromatic diamine BAPP;
2) Carrying out further chemical reaction on the product obtained in the step 1) with acetic anhydride and pyridine;
in the step 2, the mass ratio of the norbornene monoester monoacid to the aromatic diamine BAPP is 1.2:1 to 3:1, a step of;
in the step 1, the amount of the ethanol is 10-20 times of that of norbornene anhydride; and/or the mass ratio of the acetic anhydride to the norbornene monoester monoacid is 2:1 to 4:1, a step of; the mass ratio of acetic anhydride to pyridine is 1.5:1 to 3:1, a step of;
in the step 2, the organic solvent is any one of nitrogen-nitrogen Dimethylformamide (DMF), nitrogen-nitrogen dimethylacetamide (DMAc) and nitrogen-Nitrogen Methylpyrrolidone (NMP), or a mixed solvent of any several of them according to any proportion;
in the step 2, the mass of the organic solvent is 2-4 times of the sum of the mass of the norbornene monoester monoacid and the mass of the aromatic diamine BAPP;
the reaction conditions in 1) are as follows: after norbornene monoester monoacid is dissolved in an organic solvent, adding aromatic diamine BAPP under the protection of nitrogen, and stirring at room temperature for reaction for 1-3 hours; and/or, the reaction conditions in 2) are: 1) After the completion, adding acetic anhydride and pyridine, heating to 120-180 ℃ and reacting for 2-6 hours;
and/or, the post-treatment is as follows: cooling the reaction solution obtained in the step 2) to room temperature, pouring the reaction solution into deionized water, precipitating white powdery solid, filtering, and drying a filter cake in a vacuum oven, wherein the drying temperature of the vacuum oven is 80-120 ℃ and the drying time is 10-24 hours;
the volume of the deionized water is 5-15 times of the total volume of the reaction solution;
the structural formula of the small molecule compound is as follows:
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004331596A (en) * | 2003-05-09 | 2004-11-25 | Shin Etsu Chem Co Ltd | Reactive silyl group-containing bisimide compound and method for producing the same |
| JP2004331856A (en) * | 2003-05-09 | 2004-11-25 | Shin Etsu Chem Co Ltd | Curable resin composition with reactive silyl group-containing bisimide compound therein |
| CN101454378A (en) * | 2006-07-07 | 2009-06-10 | 三菱瓦斯化学株式会社 | Polyimide resin |
| CN101717613A (en) * | 2009-12-07 | 2010-06-02 | 东华大学 | High-temperature resistant copper foil glue and preparation and application thereof |
| CN102433129A (en) * | 2010-09-14 | 2012-05-02 | 住友化学株式会社 | Polymerizable liquid crystal composition |
| CN105524546A (en) * | 2015-12-17 | 2016-04-27 | 南京理工大学 | Polyimide paint for enameled wire with high heat resistant grade |
| WO2020009016A1 (en) * | 2018-07-05 | 2020-01-09 | ユニチカ株式会社 | Method for producing organic compound |
-
2020
- 2020-09-15 CN CN202010966690.1A patent/CN114181134B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004331596A (en) * | 2003-05-09 | 2004-11-25 | Shin Etsu Chem Co Ltd | Reactive silyl group-containing bisimide compound and method for producing the same |
| JP2004331856A (en) * | 2003-05-09 | 2004-11-25 | Shin Etsu Chem Co Ltd | Curable resin composition with reactive silyl group-containing bisimide compound therein |
| CN101454378A (en) * | 2006-07-07 | 2009-06-10 | 三菱瓦斯化学株式会社 | Polyimide resin |
| CN101717613A (en) * | 2009-12-07 | 2010-06-02 | 东华大学 | High-temperature resistant copper foil glue and preparation and application thereof |
| CN102433129A (en) * | 2010-09-14 | 2012-05-02 | 住友化学株式会社 | Polymerizable liquid crystal composition |
| CN105524546A (en) * | 2015-12-17 | 2016-04-27 | 南京理工大学 | Polyimide paint for enameled wire with high heat resistant grade |
| WO2020009016A1 (en) * | 2018-07-05 | 2020-01-09 | ユニチカ株式会社 | Method for producing organic compound |
Non-Patent Citations (3)
| Title |
|---|
| I. K. VARMA，et al.Studies on Metathetical and Thermal Polymerization of 5- Norbornene 2,3-dicarboximide End-Capped Resins Pt-II.Journal of Polymer Science: Part A: Polymer Chemistry.1997,第35卷第 2323–2331页. * |
| Studies on Metathetical and Thermal Polymerization of 5- Norbornene 2,3-dicarboximide End-Capped Resins Pt-II;I. K. VARMA，et al;Journal of Polymer Science: Part A: Polymer Chemistry;第35卷;第 2323–2331页 * |
| 基于降冰片烯酸酐的酰亚胺封端剂 的研究进展;丁永红，等;应 用 化 工;第42卷(第7期);第1291-1295页 * |
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