CN114181134A - Norbornene-terminated imide micromolecule compound and preparation method and application thereof - Google Patents
Norbornene-terminated imide micromolecule compound and preparation method and application thereof Download PDFInfo
- Publication number
- CN114181134A CN114181134A CN202010966690.1A CN202010966690A CN114181134A CN 114181134 A CN114181134 A CN 114181134A CN 202010966690 A CN202010966690 A CN 202010966690A CN 114181134 A CN114181134 A CN 114181134A
- Authority
- CN
- China
- Prior art keywords
- norbornene
- resin
- compound
- terminated
- nitrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 150000003949 imides Chemical class 0.000 title abstract description 29
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims abstract description 17
- 229920001721 polyimide Polymers 0.000 claims description 59
- 239000011347 resin Substances 0.000 claims description 53
- 229920005989 resin Polymers 0.000 claims description 53
- 239000009719 polyimide resin Substances 0.000 claims description 36
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 27
- 239000004642 Polyimide Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- -1 imide small molecule compound Chemical class 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 15
- 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 14
- 239000002243 precursor Substances 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 150000004984 aromatic diamines Chemical class 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- 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 7
- 239000003085 diluting agent Substances 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 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
- 239000002904 solvent Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 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 description 3
- WRLVLKSWVLTFET-UHFFFAOYSA-N CN1C(CCC1)=O.[N].[N] Chemical compound CN1C(CCC1)=O.[N].[N] WRLVLKSWVLTFET-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- BJMBNXMMZRCLFY-UHFFFAOYSA-N [N].[N].CN(C)C=O Chemical compound [N].[N].CN(C)C=O BJMBNXMMZRCLFY-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 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
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 230000009477 glass transition Effects 0.000 description 19
- 239000000243 solution Substances 0.000 description 16
- 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
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 8
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 239000000155 melt Substances 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229940018564 m-phenylenediamine Drugs 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 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
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting 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
- 239000007858 starting material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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 end-capped imide micromolecule compound, a preparation method and application thereof.
Description
Technical Field
The invention belongs to the technical field of organic compound and polymer blending, and particularly relates to a norbornene-terminated imide micromolecule compound, and a preparation method and application thereof.
Background
The thermosetting polyimide resin has outstanding heat resistance and excellent mechanical property, and has important application in the field of aerospace. 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 difficulty of further expanding the application of polyimide in the high temperature resistant field is to reduce the melt viscosity of the polyimide resin and improve the process performance. The method for reducing the melt viscosity of the polyimide resin is to introduce a flexible chain structure into a molecular main chain, and although the method can reduce the melt viscosity of the polyimide resin, the heat resistance of the cured resin is obviously reduced.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a norbornene-terminated imide micromolecule compound, a preparation method and application thereof, so as to solve the technical problems in the modification of the existing polyimide resin.
The technical solution of the invention is as follows:
according to a first aspect, there is provided a norbornene-terminated imide small molecule compound having the following structural formula:
according to a second aspect, there is provided a method for preparing the above small molecule compound, the method comprising:
step 1, refluxing norbornene anhydride and ethanol to perform chemical reaction to obtain norbornene monoester monoacid;
1) dissolving the norbornene monoester monoacid in an organic solvent, and then carrying out chemical reaction with aromatic diamine BAPP;
2) and further carrying out chemical reaction on the product obtained in the step 1) with acetic anhydride and pyridine.
Further, in the step 1, the amount of the ethanol is 10-20 times of that of the norbornene anhydride; and/or, in step 2, the material quantity ratio of the norbornene monoester monoacid to the aromatic diamine BAPP is 1.2: 1-3: 1; the mass ratio of acetic anhydride to norbornene monoester monoacid is 2: 1-4: 1; the mass ratio of acetic anhydride to pyridine is 1.5: 1-3: 1.
further, in the step 2, the organic solvent is any one of nitrogen-nitrogen Dimethylformamide (DMF), nitrogen-nitrogen dimethylacetamide (DMAc) and nitrogen-Nitrogen Methyl Pyrrolidone (NMP), or a mixed solvent of any several of nitrogen-nitrogen dimethyl formamide (DMF), nitrogen-nitrogen dimethyl acetamide (DMAc) and nitrogen-Nitrogen Methyl Pyrrolidone (NMP) in any proportion.
Further, in the step 2, the mass of the organic solvent is 2-4 times of that of the solid matters.
Further, the reaction conditions in 1) are as follows: dissolving norbornene monoester monoacid 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 reaction is finished, adding acetic anhydride and pyridine, heating to 120-180 ℃, and reacting for 2-6 hours; and/or the post-treatment comprises the following steps: and (3) cooling the reaction liquid obtained in the step (2) to room temperature, pouring the reaction liquid into deionized water, separating out 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 a use of the above norbornene-terminated imide small molecule compound 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 preparation method of the mixture comprises the following steps: 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 the 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 micromolecule compound is directly added into the norbornene-terminated polyimide precursor solution to realize mixing, and the preparation method comprises the following steps: adding a certain amount of micromolecular compound into the polyimide precursor solution, stirring and mixing uniformly, then placing the resin powder into an oven, and drying for 1-8 hours at 150-250 ℃ to obtain mixed resin powder, wherein the mass ratio of the micromolecular compound to the polyimide resin is (1: 9) - (9: 1).
Compared with the prior art, the invention has the beneficial effects that:
the small molecule is used as a diluent of thermosetting polyimide resin, the melt viscosity of the polyimide can be obviously reduced through the co-melting effect, the technological performance of the polyimide is improved, meanwhile, the small molecule of the imide contains a terminal group capable of being crosslinked by heat, the terminal group can participate in crosslinking and curing of the norbornene-terminated polyimide resin, and the crosslinking density (heat resistance) of the resin is improved. The imide micromolecules prepared by the method have a thermally crosslinkable end group structure and a soft molecular structure, can be used for diluting high-viscosity thermosetting polyimide resin, can also obviously improve the process performance of the thermosetting polyimide resin, and has great application value in the fields of aerospace, ship-based ships, microelectronic packaging and the like.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of norbornene monoester monoacid obtained in example 1;
FIG. 2 is a nuclear magnetic hydrogen spectrum of a norbornene-terminated imide small molecule compound obtained in example 1;
FIG. 3 is a DSC curve of a norbornene-terminated imide small molecule compound obtained in example 1;
FIG. 4 is a temperature-rising rheological curve of the norbornene-terminated imide small molecule compound obtained in example 1.
Detailed Description
The following provides a detailed description of specific embodiments of the present invention. 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. However, it will be apparent 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 that, in order to avoid obscuring the present invention by unnecessary details, only the device structure and/or the processing steps closely related to the scheme according to the present invention are shown, and other details not closely related to the present invention are omitted. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified. In the present invention, the solid content is the mass% unless otherwise specified.
Example 1
Preparation of norbornene-terminated imide Small molecule Compound
1) Adding 10.00g (0.06092 mol) of norbornene anhydride and 28.06g (0.6092mol) of ethanol into a single-neck round-bottom flask, connecting the flask with a reflux condensing device, adding the mixture into an oil bath, heating and refluxing for reaction for 4 hours, and removing unreacted ethanol by using a rotary evaporator to obtain norbornene monoester monoacid;
2) weighing 12.50g (0.03046mol) of BAPP, adding to the above norbornene monoester monoacid, adding 70g of DMF, and mixing under stirring for 2 hours; 18.66g (0.18726mol) of acetic anhydride and 7.41g (0.09363mol) of pyridine are weighed and added into the reaction system, heated to 160 ℃ and reacted for 4 hours at the temperature; and cooling to room temperature, pouring the reaction solution into 800ml of deionized water, separating out white powder, filtering, washing a filter cake for three times by using the deionized water, and then drying in a vacuum oven at 100 ℃ for 10 hours to obtain the target compound, namely the imide micromolecule.
FIG. 1 is a nuclear magnetic hydrogen spectrum of norbornene monoester monoacid; FIG. 2 is a nuclear magnetic hydrogen spectrum of an imide small molecular compound, FIG. 3 is a DSC spectrogram of the imide small molecular compound, FIG. 4 is a heating rheological spectrum of the imide small molecular compound, and rheological curves show that the melt viscosity of the imide small molecular compound is lower than 1 Pa.s at 200-300 ℃, and the imide small molecular compound has very good process performance.
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, m-phenylenediamine mPDMS, and end-capping agent NA, the molecular weight of the resin was 2500, and the resin was numbered BP-2500. The preparation method of the mixed resin comprises the steps of weighing 2gBP-2500 parts of polyimide resin and 18g of the imide micromolecules prepared in the example 1, putting the polyimide resin and the imide micromolecules into a mortar, and grinding the mixture for 10 minutes to obtain the mixed resin. The viscosity curve of the mixed resin was measured using a high temperature rheometer (AR-2000) at a temperature rise rate of 4 deg.C/min, the glass transition temperature of the mixed resin was measured using a parallax scanning calorimeter (DSC) at a temperature rise rate of 5 deg.C/min, 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, m-phenylenediamine mPDMS, and end-capping agent NA, the molecular weight of the resin was 2500, and the resin was numbered BP-2500. The mixed resin was prepared by weighing 10gBP-2500 parts of polyimide resin and 10g of the small imide molecule prepared in example 1 into a mortar and grinding for 10 minutes. The viscosity curve of the mixed resin was measured using a high temperature rheometer (AR-2000) at a temperature rise rate of 4 deg.C/min, the glass transition temperature of the mixed resin was measured using a parallax scanning calorimeter (DSC) at a temperature rise rate of 5 deg.C/min, 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, m-phenylenediamine mPDMS, and end-capping agent NA, the molecular weight of the resin was 2500, and the resin was numbered BP-2500. The mixed resin was prepared by weighing 18gBP-2500 parts of polyimide resin and 2g of the small imide molecule prepared in example 1 into a mortar and grinding for 10 minutes. The viscosity curve of the mixed resin was measured using a high temperature rheometer (AR-2000) at a temperature rise rate of 4 deg.C/min, the glass transition temperature of the mixed resin was measured using a parallax scanning calorimeter (DSC) at a temperature rise rate of 5 deg.C/min, 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 mixed molecules are characterized.
The polyimide used in this example was prepared from aromatic tetracarboxylic dianhydride sBPDA, m-phenylenediamine mPDMS, and end-capping agent NA, the molecular weight of the resin was 2500, and the resin was numbered BP-2500. Polyimide resin 20gBP-2500 was weighed into a mortar and ground for 10 minutes. The viscosity curve of the resin was measured using a high temperature rheometer (AR-2000) at a temperature rise rate of 4 deg.C/min, the glass transition temperature of the resin was measured using a parallax scanning calorimeter (DSC) at a temperature rise rate of 5 deg.C/min, and the lowest melt viscosity and glass transition temperature of the resin are shown in Table 1.
Example 5
The small imide molecule obtained in example 1 and a norbornene-terminated polyimide resin were mixed by a solution mixing method.
The polyimide precursor solution used in this example was composed of an ethanolate aromatic tetracarboxylic dianhydride bpda, an ethanolate NA, and an aromatic diamine 3,4ODA, the solvent was ethanol, the design molecular weight was 2500g/mol, and the number BO-2500. The preparation method of the mixed resin comprises the steps of weighing 18g of the imide micromolecules, adding the imide micromolecules into 4g of polyimide precursor solution with the solid content of 50%, mixing and stirring for 1 hour, then putting the mixed solution into a forced air oven, and drying at 100 ℃/1 hour, 150 ℃/1 hour and 200 ℃/1 hour to obtain the mixed resin powder. The viscosity curve of the resin was measured using a high temperature rheometer (AR-2000) at a temperature rise rate of 4 deg.C/min, the glass transition temperature of the resin was measured using a parallax scanning calorimeter (DSC) at a temperature rise rate of 5 deg.C/min, and the lowest melt viscosity and glass transition temperature of the resin are shown in Table 1.
Example 6
The small imide molecule obtained in example 1 and a norbornene-terminated polyimide resin were mixed by a solution mixing method.
The polyimide precursor solution used in this example was composed of an ethanolate aromatic tetracarboxylic dianhydride bpda, an ethanolate NA, and an aromatic diamine 3,4ODA, the solvent was ethanol, the design molecular weight was 2500g/mol, and the number BO-2500. The preparation method of the mixed resin comprises the steps of weighing 10g of the imide micromolecules, adding the imide micromolecules into 20g of polyimide precursor solution with the solid content of 50%, mixing and stirring for 1 hour, then putting the mixed solution into a forced air oven, and drying at 100 ℃/1 hour, 150 ℃/1 hour and 200 ℃/1 hour to obtain the mixed resin powder. The viscosity curve of the resin was measured using a high temperature rheometer (AR-2000) at a temperature rise rate of 4 deg.C/min, the glass transition temperature of the resin was measured using a parallax scanning calorimeter (DSC) at a temperature rise rate of 5 deg.C/min, and the lowest melt viscosity and glass transition temperature of the resin are shown in Table 1.
Example 7
The small imide molecule obtained in example 1 and a norbornene-terminated polyimide resin were mixed by a solution mixing method.
The polyimide precursor solution used in this example was composed of an ethanolate aromatic tetracarboxylic dianhydride bpda, an ethanolate NA, and an aromatic diamine 3,4ODA, the solvent was ethanol, the design molecular weight was 2500g/mol, and the number BO-2500. The preparation method of the mixed resin comprises the steps of weighing 2g of the imide micromolecules, adding the imide micromolecules into 36g of polyimide precursor solution with the solid content of 50%, mixing and stirring for 1 hour, then putting the mixed solution into a forced air oven, and drying at 100 ℃/1 hour, 150 ℃/1 hour and 200 ℃/1 hour to obtain the mixed resin powder. The viscosity curve of the resin was measured using a high temperature rheometer (AR-2000) at a temperature rise rate of 4 deg.C/min, the glass transition temperature of the resin was measured using a parallax scanning calorimeter (DSC) at a temperature rise rate of 5 deg.C/min, 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 mixed molecules are characterized.
The polyimide precursor solution used in this example was composed of an ethanolate aromatic tetracarboxylic dianhydride bpda, an ethanolate NA, and an aromatic diamine 3,4ODA, the solvent was ethanol, the design molecular weight was 2500g/mol, and the number 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 at 100 ℃/1h, 150 ℃/1h and 200 ℃/1h to obtain resin powder. The viscosity curve of the resin was measured using a high temperature rheometer (AR-2000) at a temperature rise rate of 4 deg.C/min, the glass transition temperature of the resin was measured using a parallax scanning calorimeter (DSC) at a temperature rise rate of 5 deg.C/min, and the lowest melt viscosity and glass transition temperature of the resin are shown in Table 1.
Table 1: viscosity behavior and glass transition temperature of the resin System
In Table 1, "-" indicates that the glass transition temperature of comparative example 1 could not be measured because the resin was a crystalline system, the melting point was high, the crosslinking reaction between the 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 these embodiments are apparent from the detailed specification, and thus, it is intended by the appended claims to cover all such features and advantages of these 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 has not been described in detail and is in part known to those of skill in the art.
Claims (10)
1. A norbornene-terminated imide small molecule compound, wherein the structural formula of the small molecule compound is as follows:
2. the method for preparing norbornene-terminated imide small molecule compounds as claimed in claim 1, wherein said method comprises:
step 1, refluxing norbornene anhydride and ethanol to perform chemical reaction to obtain norbornene monoester monoacid;
step 2, carrying out two-step chemical reaction and post-treatment on the norbornene monoester monoacid to obtain the micromolecule compound, wherein the two-step chemical reaction comprises the following steps:
1) dissolving the norbornene monoester monoacid in an organic solvent, and then carrying out chemical reaction with aromatic diamine BAPP;
2) and further carrying out chemical reaction on the product obtained in the step 1) with acetic anhydride and pyridine.
3. The method according to claim 2, wherein in step 1, the amount 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: 1-3: 1; the mass ratio of the acetic anhydride to the norbornene monoester monoacid is 2: 1-4: 1; the mass ratio of acetic anhydride to pyridine is 1.5: 1-3: 1.
4. The preparation method according to claim 2, wherein in the step 2, the organic solvent is any one of nitrogen-nitrogen Dimethylformamide (DMF), nitrogen-nitrogen dimethylacetamide (DMAc) and nitrogen-Nitrogen Methyl Pyrrolidone (NMP), or a mixed solvent of any several of the above solvents in any ratio.
5. The method according to any one of claims 2 to 4, wherein in the step 2, the mass of the organic solvent is 2 to 4 times that of the solid substance used.
6. The production method according to any one of claims 2 to 5, wherein the reaction conditions in 1) are: dissolving norbornene monoester monoacid 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 reaction is finished, adding acetic anhydride and pyridine, heating to 120-180 ℃, and reacting for 2-6 hours; and/or the post-treatment comprises the following steps: and (3) cooling the reaction liquid obtained in the step (2) to room temperature, pouring the reaction liquid into deionized water, separating out 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.
7. The preparation method according to claim 6, wherein the volume of the deionized water is 5 to 15 times of the total volume of the reaction solution.
8. Use of a norbornene-terminated imide small molecule compound as claimed in claim 1 wherein said small molecule compound is utilized as a diluent for modified norbornene-terminated polyimide resin.
9. The use according to claim 8, wherein the small molecule compound is used as a diluent for modifying a norbornene-terminated polyimide resin, the norbornene-terminated polyimide resin is modified by the following method:
the preparation method of the mixture comprises the following steps: 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 the polyimide resin is (1: 9) - (9: 1).
10. The use according to claim 8, wherein the small molecule compound is used as a diluent for modifying a norbornene-terminated polyimide resin, the norbornene-terminated polyimide resin is modified by the following method:
the micromolecule compound is directly added into the norbornene-terminated polyimide precursor solution to realize mixing, and the preparation method comprises the following steps: adding a certain amount of micromolecular compound into the polyimide precursor solution, stirring and mixing uniformly, then placing the resin powder into an oven, and drying for 1-8 hours at 150-250 ℃ to obtain mixed resin powder, wherein the mass ratio of the micromolecular compound to the polyimide resin is (1: 9) - (9: 1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010966690.1A CN114181134B (en) | 2020-09-15 | 2020-09-15 | Norbornene-terminated imide small molecule compound and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010966690.1A CN114181134B (en) | 2020-09-15 | 2020-09-15 | Norbornene-terminated imide small molecule compound and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114181134A true CN114181134A (en) | 2022-03-15 |
| CN114181134B CN114181134B (en) | 2024-01-05 |
Family
ID=80601186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010966690.1A Active CN114181134B (en) | 2020-09-15 | 2020-09-15 | Norbornene-terminated imide small molecule compound and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114181134B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004331856A (en) * | 2003-05-09 | 2004-11-25 | Shin Etsu Chem Co Ltd | Curable resin composition with reactive silyl group-containing bisimide compound therein |
| 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 |
| 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 |
|---|---|---|---|---|
| JP2004331856A (en) * | 2003-05-09 | 2004-11-25 | Shin Etsu Chem Co Ltd | Curable resin composition with reactive silyl group-containing bisimide compound therein |
| 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 |
| 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 (2)
| 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 * |
| 丁永红，等: "基于降冰片烯酸酐的酰亚胺封端剂 的研究进展", 应 用 化 工 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114181134B (en) | 2024-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111117241B (en) | High-transparency low-expansion polyimide film and preparation method thereof | |
| CN107759478B (en) | Thermosetting polyimide material containing dicarboborane, preparation method and application | |
| CN107722314B (en) | Preparation method of thermoplastic polyimide composite material | |
| Wang et al. | Preparation of self-promoted hydroxy-containing phthalonitrile resins by an in situ reaction | |
| CN105461922B (en) | A kind of low viscosity thermoset polyimide resin and its preparation method and application | |
| EP2520606B1 (en) | Method for manufacturing a wholly aromatic polyimide resin having improved heat resistance and elongation properties in a high temperature range | |
| CN113667120B (en) | Polyimide and preparation method thereof | |
| CN108641082A (en) | A kind of Thermocurable polyimide performed polymer and its preparation method and application | |
| JP5985977B2 (en) | Polyimide resin solution | |
| CN112029099B (en) | Preparation method of polyamide acid solution and polyimide film | |
| CN111019129A (en) | Low-thermal expansion coefficient soluble polyimide resin powder and preparation method thereof | |
| CN114805802A (en) | Benzoxazine-terminated imide, preparation method thereof and polybenzoxazine-terminated imide film | |
| CN113527683B (en) | Polyimide and polyimide film using the same | |
| US4613637A (en) | Copolymers utilizing isoimides and method of preparing same | |
| CN108395534A (en) | A kind of solubility height and the good bismaleimide performed polymer and its preparation method and application of temperature tolerance | |
| CN109928907B (en) | Reactive diluent with excellent processability and high temperature resistance and preparation method thereof | |
| CN114181134A (en) | Norbornene-terminated imide micromolecule compound and preparation method and application thereof | |
| CN112708133A (en) | Low-viscosity thermosetting polyimide resin and preparation method and application thereof | |
| JP5435207B2 (en) | Terminal-modified imide oligomer | |
| CN114276544A (en) | High-temperature-resistant polyimide composite material and preparation method and application thereof | |
| CN108659527B (en) | High-strength glass fiber composite material and preparation method thereof | |
| Chen et al. | Synthesis and properties of novel meltable fluorinated aromatic oligoimides endcapped with 4-phenylethynylphthalic anhydride | |
| CN108997579A (en) | A kind of aromatic series super-branched polyimide of the structure containing anthracene and its preparation method and application | |
| CN114854011B (en) | Polyamide acid solution, polyimide film and preparation method thereof | |
| KR100700749B1 (en) | Imide oligomer, method for preparing the same and polyimide thin layer prepared from crosslinking reaction of the imide oligomer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |