WO2011099517A1 - 5-ノルボルネン-2-スピロ-α-シクロアルカノン-α'-スピロ-2''-5''-ノルボルネン類、及び、その製造方法 - Google Patents
5-ノルボルネン-2-スピロ-α-シクロアルカノン-α'-スピロ-2''-5''-ノルボルネン類、及び、その製造方法 Download PDFInfo
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- 0 CC(CN(*)*)C(C(C)CN(*)*)=O Chemical compound CC(CN(*)*)C(C(C)CN(*)*)=O 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/613—Unsaturated compounds containing a keto groups being part of a ring polycyclic
- C07C49/617—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system
- C07C49/643—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system having three rings
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/613—Unsaturated compounds containing a keto groups being part of a ring polycyclic
- C07C49/617—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C2603/93—Spiro compounds
Definitions
- the present invention relates to 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornenes and a method for producing the same.
- wholly aromatic polyimide (trade name “Kapton”) is known as an indispensable material for advanced industries such as space and aviation.
- Such a wholly aromatic polyimide has the following reaction formula (I):
- Examples of such alicyclic polyimide include a combination of alicyclic tetracarboxylic dianhydride and alicyclic diamine, a combination of alicyclic tetracarboxylic dianhydride and aromatic diamine, aromatic 3 types of a combination of a group tetracarboxylic dianhydride and an alicyclic diamine.
- those using alicyclic diamines are 10 5 to 10 6 times as basic as aromatic diamines and have completely different polymerization behavior from aromatic diamines. For this reason, salts were precipitated during the polymerization, and it was difficult to increase the molecular weight.
- an alicyclic polyimide obtained by combining an alicyclic tetracarboxylic dianhydride and an aromatic diamine can be applied to a general synthetic method of a wholly aromatic polyimide as it is and can easily be made high in molecular weight. Therefore, in recent years, alicyclic polyimides obtained by combining alicyclic tetracarboxylic dianhydrides and aromatic diamines among alicyclic polyimides have attracted attention.
- alicyclic tetracarboxylic dianhydride used for the production of such alicyclic polyimide, monocyclic, bicyclocyclic, tricyclocyclic, tetracyclocyclic, spirocyclic and the like are known, for example
- an alicyclic polyimide using a tetracycloalicyclic alicyclic tetracarboxylic dianhydride the following reaction formula (II):
- An alicyclic polyimide obtained from a dimethanonaphthalene-type tetracarboxylic dianhydride is known using a reaction represented by the formula (see Macromolecules, 27, 1994, p1117 (non-patent document 2)). . And in the alicyclic polyimide obtained from such a dimethana naphthalene type
- JP-A-55-36406 Patent Document 1
- 5- (2,5-dioxotetrahydro-3-furanyl)- 3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride is disclosed.
- JP-A-63-57589 Patent Document 2 discloses bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydrides.
- JP-A-7-304868 Patent Document 3 discloses bicyclo [2.2.2] octanetetracarboxylic dianhydrides as raw materials for polyimide resins. Further, in JP-A No.
- Patent Document 4 1,2-bis (4′-oxa-3 ′, 5′-dioxotri Cyclo [5.2.1.0 2,6 ] decan-8′-yloxy) ethane is disclosed. Further, in JP-A-10-310640 (Patent Document 6), bicyclo [2.2.1] heptane-2,3,5-tricarboxyl-5-acetic 2,3: 5,5-acid diacid is disclosed. Anhydrides are disclosed. However, when such an alicyclic tetracarboxylic dianhydride is used to produce an alicyclic polyimide, it has not been possible to produce a polyimide having a sufficiently high heat resistance.
- This invention is made
- 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornenes and 5-norbornene that can be suitably used as a dianhydride raw material compound -2-Spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornenes can be efficiently produced in a sufficiently high yield and 5-norbornene-2-spiro
- the object is to provide a process for producing - ⁇ -cycloalkanone- ⁇ '-spiro-2 ''-5 ''-norbornenes.
- the 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornene of the present invention is represented by the following general formula (1):
- R 1 , R 2 and R 3 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and n is 0 Indicates an integer of ⁇ 12. ] It is represented by
- tetracarboxylic dianhydride is converted from 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornenes represented by the general formula (1).
- the reason why an alicyclic polyimide having sufficiently high heat resistance is obtained is not always clear when an alicyclic polyimide is produced using this, but the heat resistance of the polyimide is not necessarily determined in its structure. It has a ketone group that is a polar group that can be improved and does not inhibit the polymerization reaction, and active ⁇ -hydrogen remains on the carbon atom adjacent to the ketone of the ketone group-containing norbornene due to its structure.
- the 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornene represented by the general formula (1) has a chemically sufficiently stable structure.
- the process for producing 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornenes of the present invention contains a formaldehyde derivative and has the formula HX (formula Wherein X is F, Cl, Br, I, CH 3 COO, CF 3 COO, CH 3 SO 3 , CF 3 SO 3 , C 6 H 5 SO 3 , CH 3 C 6 H 4 SO 3 , HOSO 3 and . indicating the one selected from the group consisting of H 2 PO 4 acidic solvent containing more than 0.01 mol / L of an acid represented by), the following general formula (2):
- R 2 and R 3 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and n is 0 to 12 Indicates an integer.
- each R 4 independently represents a linear saturated hydrocarbon group having 1 to 20 carbon atoms, a branched saturated hydrocarbon group having 3 to 20 carbon atoms, or the number of carbon atoms.
- 3 ⁇ represents one selected from the group consisting of saturated hydrocarbon group having 1 to 10 carbon atoms having a saturated cyclic hydrocarbon group and the hydroxyl group of 20, the two R 4 pyrrolidine ring linked to each other, a piperidine ring
- X ⁇ represents F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , CH 3 COO ⁇ , CF 3 COO ⁇ , which may form one ring selected from the group consisting of a piperazine ring and a morpholine ring.
- R 1 represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom.
- the diene compound represented by formula (1) is added and heated to react the Mannich base with the diene compound, and the following general formula (1):
- the acidic solvent contains an acid of 0.01 to 2 It is preferable to contain 0.0 mol / L.
- the base is preferably at least one selected from the group consisting of amines, alkali metal hydroxides and alkaline earth metal hydroxides. Further, the amount of the base added to the reaction solution is preferably 1.0 to 20.0 times equivalent, more preferably 1.0 to 10.0 times equivalent to the acid. preferable. Furthermore, the heating temperature in the second step is preferably 30 to 180 ° C.
- an organic solvent added to the reaction solution is used.
- 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornenes can be directly converted from the reaction solution with saturated hydrocarbons having 5 to 30 carbon atoms. Liquid-liquid extraction can be performed, and the process can be simplified.
- the organic solvent added to the reaction solution is an organic solvent that is not miscible with the saturated hydrocarbon having 5 to 30 carbon atoms, and after the reaction, 5-norbornene-2 is directly added from the reaction solution. It is preferable to liquid-liquid extract spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornenes with saturated hydrocarbons having 5 to 30 carbon atoms.
- the organic solvent has 5 to 5 carbon atoms. It is also possible to use an organic solvent that is miscible with 30 saturated hydrocarbons.
- the second step after forming the 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornenes,
- the organic solvent miscible with 30 saturated hydrocarbons is removed and used as it is or after adding water, and the 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ is obtained by using a saturated hydrocarbon having 5 to 30 carbon atoms.
- the resulting mixture is used as it is, or water is appropriately added to the mixture, and the mixture is saturated with a hydrocarbon having 5 to 30 carbon atoms. It is preferable to extract and separate 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornenes. Further, after the extraction / separation step (including the liquid-liquid extraction step), the 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro is added with the saturated hydrocarbon having 5 to 30 carbon atoms.
- the method further includes a step of washing the extract containing saturated hydrocarbons with an aqueous alkali solution and an aqueous acid solution.
- FIG. 2 is a graph showing an IR spectrum of 5-norbornene-2-spiro-2′-cyclopentanone-5′-spiro-2 ′′ -5 ′′ -norbornene obtained in Example 1.
- FIG. 2 is a graph showing a 1 H-NMR (CDCl 3 ) spectrum of 5-norbornene-2-spiro-2′-cyclopentanone-5′-spiro-2 ′′ -5 ′′ -norbornene obtained in Example 1.
- FIG. is there. 6 is a graph showing a 13 C-NMR (CDCl 3 ) spectrum of 5-norbornene-2-spiro-2′-cyclopentanone-5′-spiro-2 ′′ -5 ′′ -norbornene obtained in Example 1.
- FIG. 4 is a graph showing an IR spectrum of 5-norbornene-2-spiro-2′-cyclohexanone-6′-spiro-2 ′′ -5 ′′ -norbornene obtained in Example 2.
- FIG. 2 is a graph showing a 1 H-NMR (CDCl 3 ) spectrum of 5-norbornene-2-spiro-2′-cyclohexanone-6′-spiro-2 ′′ -5 ′′ -norbornene obtained in Example 2.
- FIG. 4 is a graph showing an IR spectrum of 5-norbornene-2-spiro-2′-cyclohexanone-6′-spiro-2 ′′ -5 ′′ -norbornene obtained in Example 2.
- FIG. 2 is a graph showing a 1 H-NMR (CDCl 3 ) spectrum of 5-norbornene-2-spiro-2′-cyclohexanone-6′-spiro-2 ′′ -5 ′′ -norbornene obtained in Example 2.
- FIG. 2 is a graph showing a 13 C-NMR (CDCl 3 ) spectrum of 5-norbornene-2-spiro-2′-cyclohexanone-6′-spiro-2 ′′ -5 ′′ -norbornene obtained in Example 2.
- FIG. 2 is a graph showing a 13 C-NMR (CDCl 3 ) spectrum of 5-norbornene-2-spiro-2′-cyclohexanone-6′-spiro-2 ′′ -5 ′′ -norbornene obtained in Example 2.
- the 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornenes of the present invention will be described. That is, the 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornenes of the present invention are represented by the following general formula (1):
- R 1 , R 2 and R 3 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and n is 0 Indicates an integer of ⁇ 12.
- n is 0 Indicates an integer of ⁇ 12.
- 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornenes represented by the general formula (1) are optionally represented as follows. This is simply called “bis (spironorbornene)”.
- the alkyl group that can be selected as R 1 in the general formula (1) is an alkyl group having 1 to 10 carbon atoms. When carbon number of such an alkyl group exceeds 10, when it uses as a monomer of a polyimide, the heat resistance of the polyimide obtained will fall.
- the number of carbon atoms of the alkyl group that can be selected as R 1 is preferably 1 to 5, and preferably 1 to 3, from the viewpoint that higher heat resistance can be obtained when a polyimide is produced. It is more preferable.
- Such an alkyl group that can be selected as R 1 may be linear or branched.
- R 1 in the general formula (1) is more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, from the viewpoint that higher heat resistance can be obtained when a polyimide is produced.
- a hydrogen atom or a methyl group is particularly preferable.
- it is especially preferable that several R ⁇ 1 > in such a formula is the same from viewpoints, such as easiness of refinement
- n represents an integer of 0 to 12.
- the upper limit of the numerical range of n in the general formula (1) is more preferably 5 and more preferably 3 from the viewpoint of facilitating the purification of bis (spironorbornene) s. Is particularly preferred.
- the lower limit of the numerical range of n in the general formula (1) is more preferably 1 and particularly preferably 2 from the viewpoint of the stability of the raw material.
- n in the general formula (1) is particularly preferably an integer of 2 to 3.
- the alkyl group having 1 to 10 carbon atoms that can be selected as R 2 and R 3 in the general formula (1) is the same as the alkyl group having 1 to 10 carbon atoms that can be selected as R 1. is there.
- substituents that can be selected as R 2 and R 3 from the viewpoint of ease of purification, among the above-mentioned substituents, among the above substituents, a hydrogen atom, a carbon number of 1 to 10 (more preferably 1 to 5, more preferably).
- the alkyl group of 1 to 3) is preferable, and a hydrogen atom or a methyl group is particularly preferable.
- bis (spironorbornene) represented by the general formula (1) include 5-norbornene-2-spiro- ⁇ -cyclopentanone- ⁇ ′-spiro-2 ′′ -5.
- '' -Norbornene also known as “5-norbornene-2-spiro-2'-cyclopentanone-5'-spiro-2" -5 "-norbornene”
- 5-norbornene-2-spiro- ⁇ -cyclohexanone- ⁇ '-spiro-2 ''-5 ''-norbornene Also known as “5-norbornene-2-spiro-2′-cyclohexanone-6′-spiro-2 ′′ -5 ′′ -norbornene”
- the process for producing 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornenes of the present invention comprises a formaldehyde derivative and has the formula HX (wherein X represents F, Cl, Br, I, CH 3 COO, CF 3 COO, CH 3 SO 3 , CF 3 SO 3 , C 6 H 5 SO 3 , CH 3 C 6 H 4 SO 3 , HOSO 3 and H 2. . indicating the one selected from the group consisting of PO 4 acidic solvent containing more than 0.01 mol / L of an acid represented by), the following general formula (2):
- R 2 and R 3 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and n is 0 to 12 Indicates an integer.
- each R 4 independently represents a linear saturated hydrocarbon group having 1 to 20 carbon atoms, a branched saturated hydrocarbon group having 3 to 20 carbon atoms, or the number of carbon atoms.
- 3 ⁇ represents one selected from the group consisting of saturated hydrocarbon group having 1 to 10 carbon atoms having a saturated cyclic hydrocarbon group and the hydroxyl group of 20, the two R 4 pyrrolidine ring linked to each other, a piperidine ring
- X ⁇ represents F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , CH 3 COO ⁇ , CF 3 COO ⁇ , and may form one ring selected from the group consisting of a piperazine ring and a morpholine ring.
- R 1 represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom.
- the diene compound represented by formula (1) is added and heated to react the Mannich base with the diene compound, and the 5-norbornene-2-spiro- ⁇ -cycloalkanone represented by the above general formula (1)
- the first process and the second process will be described separately.
- the first step is represented by the general formula (4) by reacting the carbonyl compound represented by the general formula (2) with the amine compound represented by the general formula (3) in the acidic solvent. Forming a Mannich base to obtain a reaction solution containing the Mannich base in the acidic solvent.
- the acidic solvent used in such a first step contains a formaldehyde derivative.
- a formaldehyde derivative is not particularly limited as long as it can be used in producing a so-called Mannich base, and examples thereof include formalin, paraformaldehyde, trioxane, 1,3-dioxolane, 1,3.
- formaldehyde derivatives formalin, paraformaldehyde, trioxane, and 1,3-dioxolane are preferable from the viewpoint of availability, and formalin and paraformaldehyde are more preferable.
- Such formaldehyde derivatives may be used singly or in combination of two or more, but it is preferable to use one alone from the viewpoint of purification.
- the content of such a formaldehyde derivative is preferably 2.0 to 50.0% by mass in the acidic solvent, and more preferably 4.0 to 25.0% by mass.
- the content of the formaldehyde derivative is less than the lower limit, the yield of the Mannich base represented by the general formula (4) tends to decrease.
- the upper limit is exceeded, the yield decreases. Tends to be difficult to purify.
- the acidic solvent used in the first step, together with the formaldehyde derivative is represented by the formula: HX (where X is F, Cl, Br, I, CH 3 COO, CF 3 COO, CH 3 SO 3 , CF 3
- the type of the acid (HX) is not particularly limited as long as it is represented by the above formula: HX, but the Mannich base represented by the above general formula (4) in an acidic solvent. From the viewpoint of stability, an acid in which X in the formula is F, Cl, Br, CH 3 COO, or CF 3 COO is more preferable, and an acid in which X in the formula is Cl or CH 3 COO is more preferable. .
- the acid (HX) content is 0.01 mol / L or more (more preferably 0.01 to 2.0 mol / L, still more preferably 0.02 to 2.0 mol / L, Particularly preferably, it should be 0.04 to 1.0 mol / L).
- the acid content is less than the lower limit, the yield of the Mannich base prepared in the first step is not sufficient, and the bis (spironorbornene) represented by the general formula (1) is sufficient. Cannot be prepared efficiently.
- content of the said acid (HX) exceeds the said upper limit, it exists in the tendency for a yield to fall or for refinement
- such an acidic solvent may contain a solvent in addition to the formaldehyde derivative and the acid.
- a solvent include water, alcohol, glycol, glycerin, ether, cellosolve, nitrile, amide and the like.
- the content of such a solvent is preferably 20 to 60% by mass in the acidic solvent, and more preferably 30 to 50% by mass. If the content of such a solvent is less than the lower limit, mixing tends to be uneven, and the yield of Mannich base tends to decrease.On the other hand, if the upper limit is exceeded, the reaction rate decreases and the yield decreases. It tends to end up.
- the acid is excessively contained by using the acidic solvent containing the formaldehyde derivative and containing the acid (formula: acid represented by HX) in an amount of 0.01 mol / L or more. It becomes possible to react the carbonyl compound and the amino compound under the existing acidic conditions, whereby the Mannich represented by the above general formula (4), which is a reaction intermediate used for the preparation of bis (spironorbornene) s It becomes possible to produce a base efficiently.
- the carbonyl compound used in the first step is represented by the following general formula (2):
- R 2 and R 3 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and n is 0 to 12 Indicates an integer.
- It is a carbonyl compound represented by these.
- R 2 substituents which can be selected as R 3 in the general formula (2) is of the general formula (1) similar to the substituents that R 2, may be selected as R 3 in.
- substituents that can be selected as R 2 and R 3 from the viewpoint of ease of purification, among the above-mentioned substituents, among the above substituents, among the above substituents, a hydrogen atom, a carbon number of 1 to 10 (more preferably 1 to 5, more preferably).
- the alkyl group of 1 to 3) is preferable, and a hydrogen atom or a methyl group is particularly preferable.
- n in the general formula (2) is an integer similar to n in the general formula (1), and a suitable value thereof is also the same as n in the general formula (1).
- Examples of the carbonyl compound represented by the general formula (2) include cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclononanone, cyclodecanone, cycloundecanone, and cyclododecanone.
- the method for preparing the carbonyl compound represented by the general formula (2) is not particularly limited, and a known method can be appropriately employed. Moreover, you may use a commercially available compound represented by such General formula (2).
- the amine compound used in the first step is represented by the following general formula (3):
- each R 4 independently represents a linear saturated hydrocarbon group having 1 to 20 carbon atoms, a branched saturated hydrocarbon group having 3 to 20 carbon atoms, or the number of carbon atoms.
- 3 ⁇ indicates any one selected from the group consisting of saturated hydrocarbon group having 1 to 10 carbon atoms having a saturated cyclic hydrocarbon group and the hydroxyl group of 20, a pyrrolidine ring linked two R 4 with each other, One ring selected from the group consisting of a piperidine ring, a piperazine ring and a morpholine ring may be formed, and X ⁇ represents F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , CH 3 COO ⁇ , CF 3.
- the linear saturated hydrocarbon group that can be selected as R 4 in the general formula (3) has 1 to 20 carbon atoms. Such a linear saturated hydrocarbon group preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. If the number of carbon atoms of such a linear saturated hydrocarbon group exceeds the upper limit, purification tends to be difficult.
- the linear saturated hydrocarbon group that can be selected as R 4 is more preferably a methyl group or an ethyl group from the viewpoint of ease of purification.
- such a branched saturated hydrocarbon group that can be selected as R 4 has 3 to 20 carbon atoms.
- Such a branched saturated hydrocarbon group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5. If the number of carbon atoms of such a branched chain saturated hydrocarbon group exceeds the upper limit, purification tends to be difficult.
- the branched saturated hydrocarbon group that can be selected as R 4 is more preferably an isopropyl group from the viewpoint of ease of purification.
- the saturated cyclic hydrocarbon group that can be selected as R 4 is one having 3 to 20 carbon atoms. Such a saturated cyclic hydrocarbon group preferably has 3 to 10 carbon atoms, and more preferably 5 to 6. If the number of carbon atoms of such a saturated cyclic hydrocarbon group exceeds the upper limit, purification becomes difficult. On the other hand, if the number is less than the lower limit, chemical stability tends to decrease.
- the saturated cyclic hydrocarbon group that can be selected as R 4 is more preferably a cyclopentyl group or a cyclohexyl group from the viewpoint of ease of purification and chemical stability.
- the saturated hydrocarbon group having a hydroxyl group that can be selected as R 4 is a hydrocarbon group having 1 to 10 carbon atoms.
- the number of carbon atoms is more preferably 2 to 10, and further preferably 2 to 5. If the number of carbon atoms of the saturated hydrocarbon group having such a hydroxyl group exceeds the upper limit, purification becomes difficult. On the other hand, if it is less than the lower limit, the chemical stability tends to be inferior.
- the saturated hydrocarbon group having a hydroxyl group that can be selected as R 4 is more preferably a 2-hydroxyethyl group from the viewpoint of ease of purification and chemical stability.
- R ⁇ 4 > in General formula (3) these may couple
- the general formula (3) two R 4 in combines R 4 together with each other, together with the nitrogen atom in the formula (3) (N), pyrrolidine ring, piperidine ring, piperazine ring, Or you may form the morpholine ring.
- R 4 in the general formula (3) is more preferably a methyl group, an ethyl group, a 2-hydroxyethyl group, or morpholine from the viewpoint of ease of purification.
- X ⁇ in the general formula (3) is a so-called counter anion.
- Such X ⁇ is F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , CH 3 COO ⁇ , CF 3 COO ⁇ , CH 3 SO 3 ⁇ , CF 3 SO 3 ⁇ , C 6 H 5 SO 3 ⁇ , CH Any one selected from the group consisting of 3 C 6 H 4 SO 3 ⁇ , HOSO 3 — and H 2 PO 4 — .
- Such X - include, from the viewpoint of stability of the Mannich base represented by the resulting Formula (4), F -, Cl -, Br -, CH 3 COO -, CF 3 COO - are preferred, Cl -, CH 3 COO - is more preferable.
- Examples of the amine compound represented by the general formula (3) include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, and di-sec-butylamine.
- Di-t-butylamine dipentylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, di (2-ethylhexyl) amine, dinonylamine, didecylamine, diundecylamine, didodecylamine, ditridecylamine , Ditetradecylamine, dipentadecylamine, dihexadecylamine, diheptadecylamine, dioctadecylamine, dinonadecylamine, morpholine, diethanolamine, aziridine, azetidine, pyridine Lysine, piperidine, indoline, secondary amine salts, such as isoindoline (above wherein X - salt of secondary amine as a counter anion) and the like.
- the method for producing such an amine compound is not particularly limited, and a known method can be appropriately used.
- the carbonyl compound represented by the general formula (2) is reacted with the amine compound represented by the general formula (3) in the acidic solvent.
- the amount of the carbonyl compound used in such a reaction is preferably 0.01 to 5.0 mol / L, more preferably 0.1 to 2.0 mol / L in the acidic solvent.
- the amount of the carbonyl compound is less than the lower limit, the production efficiency of the Mannich base represented by the general formula (4) tends to be reduced.
- the upper limit is exceeded, a by-product reactant due to a side reaction is present. It tends to increase.
- the amount of the amine compound used is preferably 2 equivalents or more, more preferably 2 to 10 equivalents, relative to the carbonyl compound. If the amount used is less than the lower limit, the yield of Mannich base tends to decrease. On the other hand, if the amount exceeds the upper limit, by-product reactants due to side reactions tend to increase.
- the reaction conditions for reacting the carbonyl compound and the amine compound in the acidic solvent are not particularly limited, and the conditions can be appropriately changed according to the type of the solvent used.
- the atmosphere in contact with the acidic solvent is preferably an inert gas atmosphere such as nitrogen gas.
- heating conditions it is preferable to adopt a condition of heating at a temperature of 30 to 180 ° C. (more preferably 80 to 120 ° C.) for 0.5 to 10 hours (more preferably 1 to 5 hours).
- the yield of the Mannich base represented by the general formula (4) tends to decrease.
- the upper limit is exceeded, bis (vinyl ketone) or vinyl ketone By-products such as dimer increase, and the yield of Mannich base represented by the general formula (4) tends to decrease.
- the Mannich base represented by the general formula (4) can be formed in a sufficiently high yield.
- the production efficiency and yield of the reaction intermediate (Mannich base) are sufficiently improved.
- the Mannich base can be used efficiently. The rate is estimated to improve.
- the reaction solution obtained in the first step is used.
- the Mannich base since the Mannich base is not isolated from the reaction solution in the second step, the Mannich base, which is a reaction intermediate existing in the reaction solution, is used with high efficiency.
- the process can be simplified, and bis (spironorbornene) can be produced sufficiently efficiently.
- an organic solvent is added to the reaction solution.
- an organic solvent is not particularly limited, and an organic solvent that can be used for the so-called Diels-Alder reaction can be appropriately used. Examples include alcohol solvents (including glycol solvents, glycerol solvents, and other polyhydric alcohol solvents), cellosolve solvents, ether solvents, amide solvents, and nitrile solvents.
- a suitable organic solvent can be appropriately selected and used depending on the type of norbornene).
- an organic solvent that is immiscible with a saturated hydrocarbon having 5 to 30 carbon atoms is preferable from the viewpoint of simplifying the extraction step after the reaction.
- the organic solvent immiscible with the saturated hydrocarbon having 5 to 30 carbon atoms include methanol, methyl cellosolve, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, propylene glycol, 1,3-propanediol, glycerin, propylene glycol monomethyl.
- Ether, ethyl cellosolve, dimethylformamide, acetonitrile and the like are preferable, and methanol and methyl cellosolve are more preferable from the viewpoint of simplicity of extraction operation.
- the amount of the organic solvent added to the reaction solution is not particularly limited, but is 10 to 80% by mass (more preferably 20 to 60% by mass) with respect to the total amount of the reaction solution and the organic solvent to be added. It is preferable to do. If the addition amount of the organic solvent is less than the lower limit, the reaction rate tends to decrease and the yield tends to decrease.On the other hand, if the upper limit is exceeded, by-products such as vinyl ketone dimer increase, and the yield of the target product Tend to decrease.
- a base is added to the reaction solution.
- amine alkali metal hydroxide, and alkaline earth metal hydroxide can be preferably used from the viewpoint of basicity.
- dimethylamine, diethylamine, dipropylamine, and dibutylamine are preferable from the viewpoint of purification, and dimethylamine is particularly preferable.
- the amount of such base added is 1.0 to 20.0 equivalents (more preferably 1.0 to 10.0 equivalents, and still more preferably 1.30 times equivalents to the acid contained in the reaction solution). 0 to 5.0 times equivalent).
- amount of the base added is less than the lower limit, decomposition of the Mannich base is suppressed, and a bis (vinyl ketone) intermediate serving as a raw material of the target product is not generated.
- the upper limit is exceeded, a large amount of neutralizing agent is used during purification. Is necessary and extraction becomes difficult.
- the reaction solution is neutral or basic, and the Mannich base and the diene compound are reacted to produce a by-product (for example, the Mannich base to the amino compound).
- a by-product for example, the Mannich base to the amino compound.
- Bis (vinylketone) formed by elimination of bismuth sufficiently suppresses the formation of dimerization product (dimer) dimerized by hetero-Diels-Alder reaction, and the desired bis (spironorbornene) is sufficiently It is possible to manufacture with high selectivity.
- reaction solution contains the following general formula (5):
- R 1 represents at least one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom.
- a diene compound represented by the formula is added.
- the general formula (5) substituents may be selected as R 1 in the are of the general formula (1) similar to the substituents which can be selected as R 1, the same applies as what its preferred .
- the amount of such a diene compound added is preferably 2 equivalents or more, more preferably 2 to 10 equivalents relative to the Mannich base represented by the general formula (4). If the addition amount of such a diene compound is less than the lower limit, the yield of bis (spironorbornene) tends to decrease. On the other hand, if it exceeds the upper limit, the by-products due to side reactions tend to increase.
- the organic solvent, the base, and the diene compound are added to the reaction solution, and then the resulting mixture is heated to produce the Mannich base and the diene compound. And react.
- Such heating is performed by reacting the Mannich base with the diene compound in the mixed solution to produce the bis (spironorbornene) represented by the general formula (1). Any condition is possible.
- the heating temperature for reacting such a Mannich base with the diene compound is preferably 30 to 180 ° C. (more preferably 80 to 140 ° C.). If the heating temperature is less than the lower limit, the decomposition rate of Mannich base tends to decrease and the yield of the target product tends to decrease.On the other hand, if the upper limit is exceeded, vinyl ketone dimer or diene is already present in the target product. By-products such as tetracyclododecene added with single-molecule Diels-Alder increase, and the selectivity of the target product tends to decrease.
- the heating time for reacting the Mannich base with the diene compound is preferably 0.01 to 5.0 hours, more preferably 0.1 to 1.5 hours.
- the atmosphere in the case of this heating is inert gas atmosphere, such as nitrogen gas, from a viewpoint of coloring prevention or safety
- a heating method a method in which a mixed liquid of the Mannich base, the diene compound, the base, and the organic solvent is dropped into a reaction vessel that is heated in advance to the heating temperature may be employed.
- a part of the organic solvent may be put in a reaction vessel in advance. This also makes it possible to proceed the reaction more safely.
- a pressurized container such as an autoclave may be adopted.
- heating may be started at normal pressure, or heating may be started from a certain predetermined pressure.
- various types of organic solvents can be used, and the thermal energy during solvent recycling can be reduced.
- the abundance of the compound having the bis (vinyl ketone) structure in the mixed solution after the reaction is bis (spirononorbornene) ( It is preferable that it is 2 mol% or less with respect to the target object. If the abundance of the compound having the bis (vinyl ketone) structure exceeds the upper limit, the target product tends to be colored, or the product tends to become viscous due to dimerization. From the viewpoint of ensuring that the abundance of the compound having the bis (vinyl ketone) structure is 2 mol% or less, the content of the base is changed to the acid contained in the reaction solution in the second step. It is preferable that the equivalent is 2.0 to 5.0 times, the heating temperature is 50 to 125 ° C., and the heating time is 0.5 to 10 hours.
- a dimerization product in which the compound having the bis (vinyl ketone) structure is dimerized in the mixed solution after the reaction.
- a dimerization product Is preferably 2 mol% or less with respect to the bis (spironorbornene) (target product). If the abundance ratio of such a dimer exceeds the upper limit, the product tends to become viscous. From the viewpoint of more surely making the abundance of the dimer 2 mol% or less, in the second step, the content of the base is 2.0 to 5 with respect to the acid contained in the reaction solution.
- the equivalent is 0.0 times
- the heating temperature is 50 to 125 ° C.
- the heating time is 0.5 to 10 hours.
- the presence rate of the compound and dimer which have a bis (vinyl ketone) structure in such a liquid mixture can be measured by what is called HPLC analysis. A well-known thing can be utilized suitably for the apparatus etc. which are used for such HPLC analysis.
- the method for extracting bis (spirononorbornene) from the mixed solution after the reaction is not particularly limited, and a known method is appropriately adopted. May be.
- the resulting mixture is used as it is, or water is added as appropriate, and carbon atoms are used. It is preferable to employ a method of extracting and separating the bis (spironorbornene) with a saturated hydrocarbon of several 5 to 30 (more preferably 5 to 10).
- the amount of water added is not particularly limited, and the amount can be appropriately changed according to the amount of the resulting mixture and the apparatus used for extraction. Good.
- the solvent to be removed from the mixed solution is an organic solvent added to the reaction solution, for example, an organic solvent miscible with a saturated hydrocarbon having 5 to 30 carbon atoms. It may be.
- the organic solvent added to the reaction solution is not miscible with a saturated hydrocarbon having 5 to 30 carbon atoms.
- the bis (spironorbornene) s are formed using an organic solvent, and then, in the mixed solution after the reaction, the number of carbon atoms is 5 to 30 (more preferably 5 to 20, more preferably 5 to 10). It is preferable to employ a method of liquid-liquid extraction and separation of the bis (spironorbornene) using saturated hydrocarbons.
- the method for isolating and purifying the bis (spirononorbornene) after extracting and separating the bis (spirononorbornene) in this way is not particularly limited. It can be adopted as appropriate.
- the bis (spirononorbornene) obtained by extracting and separating the bis (spirononorbornene) with the saturated hydrocarbon having 5 to 30 carbon atoms and the saturated carbonization are obtained. It is preferable to further include a step of washing the extract containing hydrogen with an aqueous alkali solution and an aqueous acid solution. In such washing treatment, the extract is washed with an alkaline aqueous solution containing an amine, an alkali metal hydroxide, an alkaline earth metal hydroxide or the like, and then an acid aqueous solution containing an inorganic acid or an organic acid. It is desirable to wash, then neutralize with weakly alkaline or weakly acidic water and dehydrate with a dehydrating agent such as saturated saline.
- an alkaline aqueous solution ammonia water, sodium hydroxide water, potassium hydroxide water, calcium hydroxide water and the like are preferable, and sodium hydroxide water is particularly preferable.
- the concentration of the alkali component in such an aqueous alkali solution is preferably about 1 to 20% by mass.
- hydrochloric acid water sulfuric acid water, phosphoric acid water, nitric acid water, acetic acid water and the like are preferable, and hydrochloric acid water is particularly preferable.
- the acid concentration in the acid aqueous solution is preferably about 1 to 20% by mass.
- washing with an aqueous acid solution may be performed before washing with an alkaline aqueous solution.
- weak alkali water used for the said neutralization in such a washing process sodium carbonate water, sodium hydrogencarbonate water, potassium carbonate water, sodium acetate water, etc. are preferable, and sodium hydrogencarbonate water is especially preferable.
- the weakly acidic water used for the neutralization in such washing treatment ammonium chloride water, ammonium sulfate water, ammonium nitrate water, ammonium phosphate water, and the like are preferable, and ammonium chloride water is particularly preferable.
- the pH of the liquid can be made near neutral in a short time, and decomposition during subsequent distillation purification can be suppressed.
- saturated saline, anhydrous magnesium sulfate, anhydrous sodium sulfate, silica gel, calcium oxide, diphosphorus pentoxide and the like are preferable, and in particular, saturated saline, anhydrous magnesium sulfate. Is preferred.
- azeotropic dehydration by adding benzene, toluene or the like is also possible.
- the Mannich base is decomposed in the second step, and at the same time, the Diels-Alder reaction is caused to produce bis (spironorbornene).
- the heating temperature (reaction temperature) in the second step is preferably the above-described preferred one. If the temperature is within such a range (for example, 30 to 180 ° C.), the variable endo / exo ratio naturally falls within the above range.
- the bis (spironorbornene) of the present invention has a ketone group, and since the ketone group is given priority in naming, it becomes an endo adduct in the reaction, but the bis (spironorbornene) obtained by the reaction. Is an exo body for naming purposes.
- the bis (spirononorbornene) represented by the general formula (1) thus obtained is suitable as a raw material for acid dianhydride monomers for polyimide, and such bis (spirononorbornene) s.
- the colorless and transparent polyimide starting from the following materials: flexible wiring board films, heat-resistant insulating tapes, wire enamels, semiconductor protective coatings, liquid crystal alignment films, transparent conductive films for organic EL, flexible substrate films, flexible transparent conductive films It is particularly useful as a material for producing a transparent conductive film for organic thin film solar cells, a transparent conductive film for dye-sensitized solar cells, a flexible gas barrier film, a touch panel film, and the like.
- such bis (spironorbornene) s can be made into a desired polymer or cross-linked product by metathesis reaction, addition polymerization, radical polymerization, cationic polymerization, anionic polymerization, etc. alone. Accordingly, it is also possible to obtain a copolymer or a crosslinked copolymer by copolymerizing with any copolymerizable compound. Further, acid dianhydrides obtained from such bis (spironorbornenes) are useful as epoxy curing agents and maleimide raw materials in addition to polyimide monomers.
- a method for producing an acid dianhydride suitable as a raw material compound for polyimide using such bis (spironorbornene) is not particularly limited, and a known method can be appropriately used.
- a known method can be appropriately used.
- 1994 The method described on page 1117 of Macromolecules (Vol. 27) published in the year may be used.
- the molecular structure of the compound obtained in each example is identified by an IR measuring instrument (manufactured by JASCO Corporation, trade names: FT / IR-460, FT / IR-4100) and an NMR measuring instrument ( The measurement was carried out by measuring IR and NMR spectra using VARIAN, trade name: UNITY INOVA-600 and JEOL Ltd. JNM-Lambda500). Moreover, the glass transition temperature (Tg) shown in the test example was measured using a DSC 7020 differential scanning calorimeter manufactured by SII Nano Technology.
- Example 1 First, 6.83 g (dimethylamine: 75.9 mmol) of a 50 mass% dimethylamine aqueous solution was added to a 100 ml two-necked flask. Next, 8.19 g (hydrogen chloride: 78.9 mmol) of 35 mass% hydrochloric acid aqueous solution was added to a 100 ml dropping funnel. Next, the dropping funnel was set in the two-necked flask, and the aqueous hydrochloric acid solution was dropped into the dimethylamine aqueous solution under ice cooling to prepare dimethylamine hydrochloride in the two-necked flask.
- ⁇ Second step> After cooling the reaction solution in the two-necked flask to 50 ° C., methyl cellosolve (50 ml) and 1.12 g (12%) of a 50% by mass aqueous dimethylamine solution were added to the reaction solution in the two-necked flask. .4 mmol) and 7.13 g (108 mmol) of cyclopentadiene were added to obtain a mixed solution.
- the inside of the two-necked flask was purged with nitrogen, the two-necked flask was submerged in an oil bath at 120 ° C., and the mixture was heated for 90 minutes.
- the n-heptane extract was washed once with 5% by mass NaOH aqueous solution (25 ml) and then once with 5% by mass hydrochloric acid water (25 ml).
- the n-heptane extract after washing with hydrochloric acid was washed once with 5% aqueous sodium bicarbonate (25 ml) and then once with saturated saline (25 ml).
- the n-heptane extract thus washed was dried over anhydrous magnesium sulfate, and the anhydrous magnesium sulfate was filtered to obtain a filtrate.
- FIG. 1 shows the IR spectrum of the compound thus obtained
- FIG. 2 shows the 1 H-NMR (CDCl 3 ) spectrum
- FIG. 3 shows the 13 C-NMR (CDCl 3 ) spectrum. From the results shown in FIGS. 1 to 3, the obtained compound has the following general formula (7):
- 5-norbornene-2-spiro-2'-cyclopentanone-5'-spiro-2 "-5" -norbornene represented by Further, from the results shown in FIGS. 1 to 3, in such 5-norbornene-2-spiro-2′-cyclopentanone-5′-spiro-2 ′′ -5 ′′ -norbornene, the endo isomer and exo It was also found that the body ratio (endo / exo) was 10/90.
- Example 2 (Example 2) ⁇ First step> First, 6.83 g (dimethylamine: 75.9 mmol) of a 50 mass% dimethylamine aqueous solution was added to a 100 ml two-necked flask. Next, 8.19 g (hydrogen chloride: 78.9 mmol) of 35 mass% hydrochloric acid aqueous solution was added to a 100 ml dropping funnel. Subsequently, the dropping funnel was set in the two-necked flask, and the hydrochloric acid aqueous solution was dropped into the dimethylamine aqueous solution under ice-cooling to prepare dimethylamine hydrochloride in the two-necked flask.
- ⁇ Second step> After cooling the reaction solution in the two-necked flask to 50 ° C., methyl cellosolve (50 ml), 1.12 g (12.4 mmol) of 50 mass% dimethylamine aqueous solution, 7.13 g (108 mmol) of pentadiene was added to obtain a mixed solution. Next, after the inside of the two-necked flask was purged with nitrogen, the two-necked flask was submerged in an oil bath at 120 ° C., and the mixture was heated for 90 minutes.
- the n-heptane extract was washed once with 5% by mass NaOH aqueous solution (25 ml) and then once with 5% by mass hydrochloric acid water (25 ml).
- the n-heptane extract after washing with hydrochloric acid was washed once with 5% aqueous sodium bicarbonate (25 ml) and then once with saturated saline (25 ml).
- the n-heptane extract thus washed was dried over anhydrous magnesium sulfate, and the anhydrous magnesium sulfate was filtered to obtain a filtrate.
- FIG. 4 shows the IR spectrum of the compound thus obtained
- FIG. 5 shows the 1 H-NMR (CDCl 3 ) spectrum
- FIG. 6 shows the 13 C-NMR (CDCl 3 ) spectrum. From the results shown in FIGS. 4 to 6, the obtained compound has the following general formula (8):
- 5-norbornene-2-spiro-2'-cyclohexanone-6'-spiro-2 "-5" -norbornene represented by
- the cis and trans isomers of the spiro-fused ring are the endo and exo respectively. From the number of olefins, it was found to be a mixture of 6 isomers.
- the glass plate on which the coating film has been formed is put into a vacuum oven, and at 80 ° C. under a pressure of 1 mmHg.
- the coating was cured by sequentially heating for 1 hour at 170 ° C. for 1 hour and 250 ° C. for 1 hour to form a film on the glass plate.
- the glass plate in which the said film was formed was taken out from the vacuum oven, and it immersed in the hot water of 70 degreeC, and collect
- the glass transition temperature Tg was not observed from room temperature to 420 ° C., and the glass transition temperature Tg of the obtained polyimide was 420 ° C. It was found that the temperature was higher than. From the results of such thermal analysis, it was confirmed that the polyimide produced from the bis (spironorbornene) obtained in Example 1 has a sufficiently high heat resistance. Moreover, it was found that such a film is colorless and transparent and exhibits a sufficiently high light transmittance.
- Tetracarboxylic dianhydride was prepared according to the method described. As a result of producing tetracarboxylic dianhydride in this way, the total yield was 87%, norbornane-2-spiro- ⁇ -cyclohexanone- ⁇ '-spiro-2 ′′ -norbornane-5,5 ′′, 6 , 6 ′′ -tetracarboxylic dianhydride was obtained.
- the glass plate on which the coating film has been formed is put into a vacuum oven, and at 80 ° C. under a pressure of 1 mmHg.
- the coating was cured by sequentially heating for 1 hour at 170 ° C. for 1 hour and 250 ° C. for 1 hour to form a film on the glass plate.
- the glass plate in which the said film was formed was taken out from the vacuum oven, and it immersed in the hot water of 70 degreeC, and collect
- the glass transition temperature Tg was not observed from room temperature to 420 ° C., and the glass transition temperature Tg of the obtained polyimide was 420 ° C. It was found that the temperature was higher than. From the result of such thermal analysis, it was confirmed that the polyimide derived from bis (spirorbornone) obtained in Example 2 has sufficiently high heat resistance. Moreover, it was found that such a film is colorless and transparent and exhibits a sufficiently high light transmittance.
- Such a 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornene of the present invention is obtained by converting a polyimide obtained therefrom into an alicyclic ring.
- a polyimide it is possible to have sufficiently high heat resistance that exhibits a glass transition temperature comparable to wholly aromatic polyimide (trade name “Kapton”: glass transition temperature 410 ° C.).
- polyimide for flexible wiring boards that require extremely high heat resistance
- polyimide for heat-resistant insulating tape polyimide for wire enamel
- polyimide for semiconductor protective coating polyimide for liquid crystal alignment film
- organic EL Polyimide for transparent electrode substrates polyimide for transparent electrode substrates for solar cells
- polyimide for transparent electrode substrates for electronic paper It is particularly useful as a raw material compound (raw material monomer) or the like for producing a subbarrier film substrate material or the like.
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Abstract
Description
で表されるものである。
で表されるカルボニル化合物と、下記一般式(3):
で表されるアミン化合物とを反応させて、下記一般式(4):
で表されるマンニッヒ塩基を形成せしめ、前記酸性溶媒中に前記マンニッヒ塩基を含有する反応液を得る第一工程と、
前記反応液中に、有機溶媒と、前記酸に対して1.0~20.0倍当量の塩基と、下記一般式(5):
で表されるジエン化合物とを添加し、加熱して、前記マンニッヒ塩基と前記ジエン化合物とを反応せしめ、下記一般式(1):
で表される5-ノルボルネン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-5’’-ノルボルネン類を形成せしめる第二工程と、
を含む方法である。
で表されるものである。なお、以下において、このような一般式(1)で表される5-ノルボルネン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-5’’-ノルボルネン類を、場合により、単に「ビス(スピロノルボルネン)類」という。
で表されるカルボニル化合物と、下記一般式(3):
で表されるアミン化合物とを反応させて、下記一般式(4):
で表されるマンニッヒ塩基を形成せしめ、前記酸性溶媒中に前記マンニッヒ塩基を含有する反応液を得る第一工程と、
前記反応液中に、有機溶媒と、前記酸に対して1.0~20.0倍当量の塩基と、下記一般式(5):
で表されるジエン化合物とを添加し、加熱して、前記マンニッヒ塩基と前記ジエン化合物とを反応せしめ、上記一般式(1)で表される5-ノルボルネン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-5’’-ノルボルネン類を形成せしめる第二工程と、
を含む方法である。以下、第一工程と第二工程とに分けて説明する。
第一工程は、前記酸性溶媒中、上記一般式(2)で表されるカルボニル化合物と上記一般式(3)で表されるアミン化合物とを反応させて、上記一般式(4)で表されるマンニッヒ塩基を形成せしめ、前記酸性溶媒中に前記マンニッヒ塩基を含有する反応液を得る工程である。
で表されるカルボニル化合物である。
で表されるアミン化合物である。
で表されるマンニッヒ塩基を形成することができ、これにより、前記酸性溶媒中に前記マンニッヒ塩基を含有する反応液を得ることができる。
第二工程は、前記反応液中に、有機溶媒と、前記酸に対して1.0~20.0倍当量の塩基と、上記一般式(5)で表されるジエン化合物とを添加し、加熱して、前記マンニッヒ塩基と前記ジエン化合物とを反応せしめ、上記一般式(1)で表されるビス(スピロノルボルネン)類を形成せしめる工程である。
で表されるジエン化合物を添加する。
で表されるビス(ビニルケトン)構造を有する化合物が形成され、次いで、そのビス(ビニルケトン)構造を有する化合物と、上記一般式(5)で表されるジエン化合物とが、いわゆるディールス・アルダー反応により反応し、上記一般式(1)で表されるビス(スピロノルボルネン)類が形成される。本発明においては、このように中性又は塩基性条件下において反応を進行させるため、副生成物の生成がより高度な水準で抑制され、より効率よくビス(スピロノルボルネン)類が製造される。
<第一工程>
先ず、100mlの二口フラスコに50質量%ジメチルアミン水溶液を6.83g(ジメチルアミン:75.9mmol)添加した。次に、100mlの滴下ロートに35質量%塩酸水溶液を8.19g(塩化水素:78.9mmol)添加した。次いで、前記二口フラスコに前記滴下ロートをセットし、氷冷下において前記ジメチルアミン水溶液中に前記塩酸水溶液を滴下し、前記二口フラスコ中でジメチルアミン塩酸塩を調製した。次に、前記二口フラスコ中に、パラホルムアルデヒド2.78g(92.4mmol)と、シクロペンタノン2.59g(30.8mmol)とを更に添加した。次いで、前記二口フラスコに玉付きコンデンサーをセットした後、前記二口フラスコの内部を窒素で置換した。その後、前記二口フラスコを90℃のオイルバスに沈め、3時間加熱攪拌を行なって、上記一般式(4)で表される化合物であって式中のnが2であり、R2及びR3がいずれも水素原子であり且つR4がいずれもメチル基であるマンニッヒ塩基を含有する反応液を得た。なお、このようにして得られた反応液に対してガスクロマトグラフィー分析(GC分析:検出器としてAgilent Technologies社製の商品名「6890N」を使用)を行った結果、シクロペンタノンの転化率は99%であることが確認された。
次に、前記二口フラスコ中の前記反応液を50℃に冷却した後、前記二口フラスコ中の前記反応液に対してメチルセロソルブ(50ml)と、50質量%ジメチルアミン水溶液1.12g(12.4mmol)と、シクロペンタジエン7.13g(108mmol)とを添加し、混合液を得た。次いで、前記二口フラスコの内部を窒素置換し、前記二口フラスコを120℃のオイルバスに沈め、前記混合液を90分間加熱した。
前記加熱後の混合液を室温(25℃)まで冷却した後、200mlの分液ロートに移し変え、n-ヘプタン(80ml)を添加した後、n-ヘプタン層を回収して1回目の抽出操作を行った。次に、残ったメチルセロソルブ層に対して、n-ヘプタン(40ml)を添加し、n-ヘプタン層を回収して2回目の抽出操作を行った。そして、1回目及び2回目の抽出操作により得られたn-ヘプタン層を混合してn-ヘプタン抽出液を得た。
<第一工程>
先ず、100mlの二口フラスコに50質量%ジメチルアミン水溶液を6.83g(ジメチルアミン:75.9mmol)添加した。次に、100mlの滴下ロートに35質量%塩酸水溶液を8.19g(塩化水素:78.9mmol)添加した。次いで、前記二口フラスコに前記滴下ロートをセットし、氷冷下において前記ジメチルアミン水溶液中に前記塩酸水溶液を滴下し、前記二口フラスコ中でジメチルアミン塩酸塩を調製した。次に、前記二口フラスコ中に、パラホルムアルデヒド2.78g(92.4mmol)と、シクロヘキサノン3.02g(30.8mmol)とを更に添加した。次いで、前記二口フラスコに玉付きコンデンサーをセットした後、前記二口フラスコの内部を窒素で置換した。その後、前記二口フラスコを90℃のオイルバスに沈め、4時間加熱攪拌を行なって、上記一般式(4)で表される化合物であって式中のnが2であり、R2及びR3がいずれも水素原子であり且つR4がいずれもメチル基であるマンニッヒ塩基を含有する反応液を得た。なお、このようにして得られた反応液に対して、実施例1と同様にGC分析を行った結果、シクロヘキサノンの転化率は99%であることが確認された。
次に、前記二口フラスコ中の前記反応液を50℃に冷却した後、前記反応液に対してメチルセロソルブ(50ml)と、50質量%ジメチルアミン水溶液1.12g(12.4mmol)と、シクロペンタジエン7.13g(108mmol)とを添加して混合液を得た。次いで、前記二口フラスコの内部を窒素置換した後、前記二口フラスコを120℃のオイルバスに沈め、前記混合液を90分間加熱した。
前記加熱後の混合液を室温(25℃)まで冷却した後、200mlの分液ロートに移し変え、n-ヘプタン(80ml)を添加した後、n-ヘプタン層を回収して1回目の抽出操作を行った。次に、残ったメチルセロソルブ層に対して、n-ヘプタン(40ml)を添加し、n-ヘプタン層を回収して2回目の抽出操作を行った。そして、1回目及び2回目の抽出操作により得られたn-ヘプタン層を混合してn-ヘプタン抽出液を得た。
実施例1で得られた5-ノルボルネン-2-スピロ-2’-シクロペンタノン-5’-スピロ-2’’-5’’-ノルボルネンを用い、1994年に発行されたMacromolecules(27巻)の1117頁に記載の方法に従って、テトラカルボン酸二無水物を製造した。このようにしてテトラカルボン酸二無水物を製造した結果、全収率88%で、ノルボルナン-2-スピロ-α-シクロペンタノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸二無水物を得た。
実施例2で得られた5-ノルボルネン-2-スピロ-2’-シクロヘキサノン-6’-スピロ-2’’-5’’-ノルボルネンを用い、1994年発行のMacromolecules(27巻)の1117頁に記載の方法に従って、テトラカルボン酸二無水物を製造した。このようにしてテトラカルボン酸二無水物を製造した結果、全収率87%で、ノルボルナン-2-スピロ-α-シクロヘキサノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸二無水物を得た。
Claims (9)
- ホルムアルデヒド誘導体を含有し且つ式:HX(式中、Xは、F、Cl、Br、I、CH3COO、CF3COO、CH3SO3、CF3SO3、C6H5SO3、CH3C6H4SO3、HOSO3及びH2PO4からなる群から選択される1種を示す。)で表される酸を0.01mol/L以上含有している酸性溶媒中、下記一般式(2):
で表されるカルボニル化合物と、下記一般式(3):
で表されるアミン化合物とを反応させて、下記一般式(4):
で表されるマンニッヒ塩基を形成せしめ、前記酸性溶媒中に前記マンニッヒ塩基を含有する反応液を得る第一工程と、
前記反応液中に、有機溶媒と、前記酸に対して1.0~20.0倍当量の塩基と、下記一般式(5):
で表されるジエン化合物とを添加し、加熱して、前記マンニッヒ塩基と前記ジエン化合物とを反応せしめ、下記一般式(1):
で表される5-ノルボルネン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-5’’-ノルボルネン類を形成せしめる第二工程と、
を含む5-ノルボルネン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-5’’-ノルボルネン類の製造方法。 - 前記酸性溶媒が酸を0.01~2.0mol/L含有している請求項2に記載の5-ノルボルネン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-5’’-ノルボルネン類の製造方法。
- 前記塩基がアミン、アルカリ金属水酸化物及びアルカリ土類金属水酸化物からなる群から選択される少なくとも1種である請求項2又は3に記載の5-ノルボルネン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-5’’-ノルボルネン類の製造方法。
- 前記反応液中に添加する前記塩基の量が、前記酸に対して1.0~10.0倍当量である請求項2~4のうちのいずれか一項に記載の5-ノルボルネン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-5’’-ノルボルネン類の製造方法。
- 前記第二工程における加熱温度が30~180℃である請求項2~5のうちのいずれか一項に記載の5-ノルボルネン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-5’’-ノルボルネン類の製造方法。
- 前記反応液中に添加する有機溶媒が炭素原子数5~30の飽和炭化水素と混和しない有機溶媒であり、反応後、反応液中から直接5-ノルボルネン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-5’’-ノルボルネン類を、炭素原子数5~30の飽和炭化水素で液液抽出する請求項2~6のうちのいずれか一項に記載の5-ノルボルネン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-5’’-ノルボルネン類の製造方法。
- 前記第二工程において、炭素原子数5~30の飽和炭化水素と混和する有機溶媒を用いて前記5-ノルボルネン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-5’’-ノルボルネン類を形成せしめた後、炭素原子数5~30の飽和炭化水素と混和する有機溶媒を除去し、そのままあるいは水を添加して用い、炭素原子数5~30の飽和炭化水素により前記5-ノルボルネン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-5’’-ノルボルネン類を抽出分離する工程を含む請求項2~7のうちのいずれか一項に記載の5-ノルボルネン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-5’’-ノルボルネン類の製造方法。
- 前記抽出分離工程後に、前記炭素原子数5~30の飽和炭化水素を用いて前記5-ノルボルネン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-5’’-ノルボルネン類を抽出分離して得られる前記5-ノルボルネン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-5’’-ノルボルネン類と前記飽和炭化水素とを含有する抽出液とを、アルカリ水溶液及び酸水溶液で洗浄する工程を更に含む請求項7又は8に記載の5-ノルボルネン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-5’’-ノルボルネン類の製造方法。
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WO2015107987A1 (ja) * | 2014-01-20 | 2015-07-23 | Jx日鉱日石エネルギー株式会社 | 5-ノルボルネン-2-スピロ-α-シクロアルカノン-α'-スピロ-2''-5''-ノルボルネン類の製造方法 |
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KR20160110966A (ko) | 2014-01-20 | 2016-09-23 | 제이엑스 에네루기 가부시키가이샤 | 5-노르보르넨-2-스피로-α-시클로알카논-α'-스피로-2"-5"-노르보르넨류의 제조 방법 |
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JP2015218160A (ja) * | 2014-05-21 | 2015-12-07 | Jx日鉱日石エネルギー株式会社 | カルボン酸無水物の製造方法 |
KR20170007768A (ko) * | 2014-05-21 | 2017-01-20 | 제이엑스 에네루기 가부시키가이샤 | 카르복실산 무수물의 제조 방법 |
KR102370253B1 (ko) | 2014-05-21 | 2022-03-04 | 에네오스 가부시키가이샤 | 카르복실산 무수물의 제조 방법 |
US11525037B2 (en) | 2017-04-28 | 2022-12-13 | Eneos Corporation | Tetracarboxylic dianhydride, polyimide precursor resin and solution thereof, and polyimide and solution thereof |
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JP5562062B2 (ja) | 2014-07-30 |
EP2535324A1 (en) | 2012-12-19 |
CN102791669B (zh) | 2014-08-06 |
JP2011162479A (ja) | 2011-08-25 |
US20120310013A1 (en) | 2012-12-06 |
CN102791669A (zh) | 2012-11-21 |
EP2535324A4 (en) | 2016-01-20 |
KR20120131176A (ko) | 2012-12-04 |
EP2535324B1 (en) | 2018-11-14 |
US8629303B2 (en) | 2014-01-14 |
KR101795092B1 (ko) | 2017-11-07 |
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