CN1771219A - Novel phenol compound and novel epoxy resin derivable from such phenol compound - Google Patents
Novel phenol compound and novel epoxy resin derivable from such phenol compound Download PDFInfo
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- CN1771219A CN1771219A CN 200580000166 CN200580000166A CN1771219A CN 1771219 A CN1771219 A CN 1771219A CN 200580000166 CN200580000166 CN 200580000166 CN 200580000166 A CN200580000166 A CN 200580000166A CN 1771219 A CN1771219 A CN 1771219A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/17—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings containing other rings in addition to the six-membered aromatic rings, e.g. cyclohexylphenol
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/28—Ethers with hydroxy compounds containing oxirane rings
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- Chemical Kinetics & Catalysis (AREA)
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- Epoxy Resins (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Compounds (AREA)
Abstract
Disclosed is a phenol compound represented by the general formula (I) below which is preferably used as a raw material for synthetic resins and the like. Also disclosed is an epoxy resin represented by the general formula (II) below which is useful as a material for coating compositions, adhesives, moldings and the like. (In the formula, Cy represents a cycloalkyl group having 3-10 carbon atoms; X represents a hydrogen atom, a phenyl group which may be substituted with an alkyl group having 1-10 carbon atoms or a cycloalkyl group having 3-10 carbon atoms; Y and Z independently represent an alkyl group having 1-10 carbon atoms; p represents a number of 0-5; and r represents a number of 0-4.) (In the formula, Cy, X, Y, Z, p and r are as defined above for the formula (I); and n represents a number of 0-10.
Description
Technical field
The neo-epoxy resin that the present invention relates to novel phenolic compound and can derive and obtain from this phenolic compound, the Resins, epoxy that specifically relates to be suitable for use as the phenolic compound of synthetic resins raw material etc. and can be used as used material such as coating, caking agent, moulding product, can derive and obtain from this phenolic compound.
Background technology
The synthetic resins that polyphenolic substance can be used as phenol resins, Resins, epoxy, polycarbonate resin, vibrin etc. also can be used as the additive of antioxidant, sterilant, fungi-proofing mould inhibitor etc. with raw material of raw material, epoxy hardener, the developer that is used for thermal sensitive recording or anti-fading agent, electronic material etc.
Resins, epoxy is widely used as used materials such as coating, caking agent, moulding product because of its good cementability, thermotolerance, resistance to chemical reagents, electrical characteristic, mechanical characteristics etc., also be widely used in electric and electronic fields such as IC sealing material, stacking material, electrically insulating materials.
In recent years, particularly in the electric and electronic field, be accompanied by microminiaturization, the high performance of machine, used resin is also not only required the raising of mechanical characteristics and thermal property, and also more and more stronger to the requirement of the raising of wet fastness, insulativity, low-dielectric etc., also seeking simultaneously to provide the novel bisphenol cpd that satisfies the resin that requires like this.
The exploitation of novel phenolic compound has been carried out much, for example proposes to propose in terpenes two phenolic compound, the patent documentation 2 4-substituted ring hexylidene bisphenols in patent documentation 1, but these compounds also fail to satisfy above-mentioned requirements.
In addition, for example in patent documentation 3, propose 4-[1, two (4-hydroxy phenyl) ethyls of 1-] propose by biphenyl alkylidene group-4 in the recording materials that form as the compatible compound of electronics of bisphenol cpd such as biphenyl, patent documentation 4,4 '-bisphenol cpd is derived and is proposed with cyclohexylmethylene-4 heat-sensitive recording material that 4 '-bisphenol cpd etc. form as the compatible compound of electronics in the thermal recording medium that proposes in the polycarbonate based copolymer, patent documentation 5 of gained methyl-phenyl-methyne bis-phenol is formed as developer, the patent documentation 6.But these also fail to satisfy above-mentioned requirements.
Patent documentation 1: the spy opens flat 8-198791 communique
Patent documentation 2: the spy opens the 2003-146926 communique
Patent documentation 3: the spy opens clear 62-122782 communique
Patent documentation 4: the spy opens clear 63-43923 communique
Patent documentation 5: the spy opens clear 63-247085 communique
Patent documentation 6: the spy opens flat 5-42769 communique
Summary of the invention
Therefore, the purpose of this invention is to provide phenolic compound that is suitable for use as synthetic resins raw material etc. and the Resins, epoxy that can be used as used material such as coating, caking agent, moulding product.
The inventor is through constantly research with keen determination, and the result can find novel phenolic compound and can satisfy above-mentioned purpose from this phenolic compound Resins, epoxy that obtains of deriving, obtain the present invention thus.
Promptly the invention provides with the represented phenolic compound of following general formula (I).
[Chemical formula 1]
(Cy represents that carbonatoms is 3～10 cycloalkyl in the formula, X represents hydrogen atom, can be that 1～10 phenyl that alkyl replaced or carbonatoms are 3～10 cycloalkyl by carbonatoms, Y and Z represent independently that respectively carbonatoms is 1～10 alkyl, p represents 0～5 number, and r represents 0～4 number.)
The present invention also provides with the represented Resins, epoxy of following general formula (II).
[Chemical formula 2]
(in the formula Cy, X, Y, Z, p and r represent with above-mentioned general formula (I) in the same meaning, n represents 0～10 number.)
Embodiment
Be described in detail with regard to phenolic compound of the present invention and Resins, epoxy below.
In above-mentioned general formula (I),, can list groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, suberyl, ring octyl group, ring nonyl, ring decyl as the cycloalkyl that with the represented carbonatoms of Cy is 3～10.As the alkyl that with Y and the represented carbonatoms of Z is 1～10, can list straight chain, side chain and cyclic alkyls such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, hexyl, heptyl, octyl group, iso-octyl, uncle's octyl group, 2-ethylhexyl, nonyl, different nonyl, decyl, isodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl, ring decyl.As the cycloalkyl that with the represented carbonatoms of X is 3～10, can list with as the illustrated same group of Cy, as the carbonatoms with represented the replaced phenyl of X is 1～10 alkyl, can list with as Y and the illustrated same group of Z.
As phenolic compound of the present invention, can list for example following compound etc.
[chemical formula 3]
Compound P-1
[chemical formula 4]
[chemical formula 5]
Compound P-3
[chemical formula 6]
Compound P-4
[chemical formula 7]
[chemical formula 8]
[chemical formula 9]
[Chemical formula 1 0]
The manufacture method of phenolic compound of the present invention there is no special qualification, for example can easily make by ketone compound (1) and phenolic compound (2) are reacted in the presence of an acidic catalyst shown in following [Chemical formula 1 1].
[Chemical formula 1 1]
Employed an acidic catalyst in the above-mentioned reaction can list for example sulfonic acid classes such as methylsulfonic acid, Phenylsulfonic acid, m-xylene sulfonic acid, tosic acid, hydroxyl methylsulfonic acid, 2-ethylenehydrinsulfonic acid, hydroxy-propanesulfonic acid, trifluoromethanesulfonic acid, sulphosalicylic acid, sulfo group phthalic acid; Heteropolyacids such as sulfuric acid, sulphuric anhydride, oleum, chlorsulfonic acid, fluosulfonic acid, hydrochloric acid, hydrogen chloride gas, oxalic acid, formic acid, phosphoric acid, Tricholroacetic Acid, trifluoracetic acid, silicotungstic acid, phospho-wolframic acid, strong-acid ion exchange resin etc.
In addition, in above-mentioned reaction, can use the mercaptan catalyzer to promote reaction, as this mercaptan catalyzer, can list for example methyl mercaptan, ethanethio, propyl group mercaptan, butanethiol, octyl mercaptan, lauryl mercaptan, 1, alkyl sulfide alcohols such as 6-ethanthiol; Aromatic mercaptans such as thiophenol, tolylmercaptan class; Sulfydryl organic acids such as mercaptoacetic acid (thiol guanidine-acetic acid), 3-thiohydracrylic acid, sulfydryl undecanoic acid, sulfo-M-nitro benzoic acid; Heterocycle family thio-alcohols such as 2-mercaptobenzothiazole; Hydrogen sulfide etc.
In this reaction, phenolic compound (2) is with respect to (1) 1 mole of ketone compound, preferably 1 mole or above, use in particularly preferably in 2～10 molar range, an acidic catalyst is with respect to (1) 1 mole of ketone compound, 0.001～2.0 mole, preferred especially 0.01～1.5 mole of preferred use, the mercaptan catalyzer especially preferably uses 0.001～1.0 mole with respect to (1) 1 mole of ketone compound.
In above-mentioned reaction, also can use the solvent of normal application, can list for example aromatic hydrocarbons series solvents such as toluene, dimethylbenzene, isopropyl benzene as this solvent; Terpenic series hydrocarbon ils such as turps, D-limonene, firpene; Mineral turpentine, Swasol#310 (Cosmo Guia Hill oil (strain)), Solvesso#100 paraffinic hydrocarbons series solvents such as (Exxon chemistry (strains)); Pure series solvent such as methyl alcohol, ethanol; Ester solvents such as vinyl acetic monomer; Halo series solvents such as ethylene dichloride, tetracol phenixin, chloroform, trieline, methylene dichloride, chlorobenzene; Cyclic ether such as tetrahydrofuran (THF), dioxane series solvent; Aniline, triethylamine, pyridine, dioxane, acetic acid, acetonitrile, dithiocarbonic anhydride etc.
This reaction preferably 0～200 ℃, carry out in particularly preferably in 10～100 ℃ of scopes.As be lower than 0 ℃ and then react slack-off, need reaction for a long time, as surpass 200 ℃ then side reaction increase, so not preferred.When temperature of reaction was 0～200 ℃, the reaction times was selected in several minutes～tenss' hour scope usually.
Phenolic compound of the present invention can be used as synthetic resins raw materials such as phenol resins, Resins, epoxy, polycarbonate resin, vibrin, polysulfone resin, polyimide resin, polyamide-imide resin, polyetherimide resin, bismaleimide resins, polyarylate resin, polyacetal resin; Epoxy hardener; The heat-sensitive recording material of developer, anti-fading agent etc.; The electronic material raw material; The additive of antioxidant, uv-absorbing agent, fire retardant, sterilant, fungi-proofing mould inhibitor etc. and their raw material.
As with the represented Resins, epoxy of the present invention of above-mentioned general formula (II), can list for example following compound etc.
[Chemical formula 1 2]
[Chemical formula 1 3]
[Chemical formula 1 4]
[Chemical formula 1 5]
Compd E-4
[Chemical formula 1 6]
[Chemical formula 1 7]
Compd E-6
[Chemical formula 1 8]
Compd E-7
[Chemical formula 1 9]
Compd E-8
The manufacture method of Resins, epoxy of the present invention there is no special qualification, for example shown in following [Chemical formula 2 0], n is that 0 Resins, epoxy can the manufacturing easily by phenolic compound of the present invention (I) and epoxy chloropropane (3) reacts in the presence of alkali, Lewis acid and interlayer moving catalyst in the above-mentioned general formula (II).
[Chemical formula 2 0]
As employed alkali in the above-mentioned reaction, can list for example sodium hydroxide, potassium hydroxide, calcium hydroxide etc.As Lewis acid, can list and resemble above-mentioned illustrated an acidic catalyst, tin tetrachloride, boron trifluoride, titanium tetrachloride, atlapulgite, aluminum chloride, magnesium chloride, potassium permanganate, potassiumchromate etc.As the interlayer moving catalyst, can list for example tetramethyl-ammonia chloride, four butyl bromation amine, methyl trioctylphosphine ammonia chloride, methyl three decyl ammonia chlorides, the benzyl triethyl ammonium ammonia chloride, N, N-dimethyl pyrrolidine muriate, N-ethyl-N-crassitude iodide, N-butyl-N-crassitude bromide, N-benzyl-N-crassitude muriate, N-ethyl-N-crassitude bromide, N-butyl-N-methylmorpholine bromide, N-butyl-N-methylmorpholine iodide, N-allyl group-N-methylmorpholine bromide, N-methyl-N-benzyl piepridine muriate, N-methyl-N-benzyl piepridine bromide, N, N-lupetidine iodide, N-methyl-N-ethylpiperidine acetic ester, N-methyl-N-ethylpiperidine iodide etc., preferred tetramethyl-ammonia chloride, the benzyl triethyl ammonium ammonia chloride.
In above-mentioned reaction, epoxy chloropropane is with respect to hydroxyl 1 equivalent of phenolic compound of the present invention (I), preferably 1 equivalent or above, use in the weight range particularly preferably in 2～10, alkali is with respect to above-mentioned hydroxyl 1 equivalent, 0.1～2.0 mole, preferred especially 0.3～1.5 mole of preferred use, the interlayer moving catalyst preferably uses 0.01～10 mole of %, preferred especially 0.2～5 mole of % with respect to hydroxyl 1 equivalent of phenolic compound of the present invention (I).N is 1～10 Resins, epoxy in the above-mentioned general formula (II), can be that 0 o'clock above-mentioned reaction is made according to n also, at this moment suitably selects the usage quantity of epoxy chloropropane to get final product.In addition, n is that 1～10 Resins, epoxy also can be by to make n in the above-mentioned general formula (II) be 0 Resins, epoxy and make with the represented phenolic compound reaction of the present invention of above-mentioned general formula (I) in the above-mentioned general formula (II).
In the reaction of above-mentioned [Chemical formula 2 0] expression, can use with manufacturing as phenolic compound of the present invention (I) in the used illustrated same solvent of solvent, also can be used as solvent by excessive epoxy chloropropane.
This reaction is preferably at 20～100 ℃, particularly preferably in carrying out in 30～60 ℃ of scopes.As be lower than 20 ℃ and then react slack-off, need reaction for a long time, as surpass 100 ℃ then side reaction increase, so not preferred.When temperature of reaction was 20～100 ℃, the reaction times was usually by selecting in the several minutes～tens hour scope.
Resins, epoxy of the present invention usually is used in combination with hardener for epoxy resin, as this solidifying agent, can list following polyamines class, and for example Diethylenetriaminee (DETA), three ethylene triamines, tetrem support many alkyl polyamines classes such as pentamin; 1,2-diamino-cyclohexane, 1,4-diamino-3, ester ring type polyamines classes such as 6-diethyl cyclohexane, isophorone diamine; Between-aromatic polyamine class such as xylylene diamines, diaminodiphenyl-methane, diamino diphenyl sulfone etc.Can list in addition by make Racemic glycidol ethers such as these polyamines classes and phenyl glycidyl ether, butylglycidyl ether, dihydroxyphenyl propane-diglycidylether, bisphenol-f-diglycidylether or with various Resins, epoxy such as the glycidic ester class poly-epoxy addition modification thing that reaction is made according to usual method of carboxylic acid; By making carboxylic-acids such as these polyamines classes and phthalic acid, m-phthalic acid, the dimer acids amidation modifier that reaction is made according to usual method; By make aldehydes such as these polyamines classes and formaldehyde and with phenol, cresols, xylenol, tert.-butyl phenol, Resorcinol equimolecular in have the phenol Mannich modifier that reaction is made according to usual method etc. of an aldehyde reaction part at least.Also can use potentiality solidifying agent such as Dyhard RU 100, acid anhydrides, imidazoles in addition.
When using Resins, epoxy of the present invention, can add following additive commonly used as required: curing catalysts; Monoglycidyl ether class, dioctyl ester of phthalic acid, dibutyl ester of phthalic acid, benzyl ethyl alcohol, coal tar isoreactivity or non-reacted thinner (plasticizer); Weighting agent or pigment such as glass fibre, carbon fiber, Mierocrystalline cellulose, silica sand, cement, kaolin, clay, aluminium hydroxide, bentonite, talcum, silicon-dioxide, fine particle silica, titanium dioxide, carbon black, graphite, ferric oxide, asphaltic substances; γ-An Jibingjisanyiyangjiguiwan, N-β-(amino-ethyl)-γ-An Jibingjisanyiyangjiguiwan, N-β-(amino-ethyl)-N '-β-(amino-ethyl)-γ-An Jibingjisanyiyangjiguiwan, γ-anilino propyl-triethoxysilicane, γ-glycidoxy propyl-triethoxysilicane, β-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane, vinyltriethoxysilane, N-β-(N-vinyl benzyl amino-ethyl)-γ-An Jibingjisanyiyangjiguiwan, γ-methacryloxypropyl trimethoxy silane, γ-r-chloropropyl trimethoxyl silane, silane coupling agents such as γ-Qiu Jibingjisanjiayangjiguiwan; Lubricants such as gama wax, carnauba wax, haze tallow, Chinese wax, beeswax, hydrous wool, spermaceti, montanin wax, petroleum wax, fatty acid wax, fatty acid ester, lipid acid ether, aromatic ester, aromatic ether; Tackifier; Thixotropic agent; Antioxidant; Photostabilizer; Uv-absorbing agent; Fire retardant; Defoamer; Rust-preventive agent; Colloid silica, colloidal alumina etc. also can and be used adhesive resin classes such as xylene resin, petroleum resin.
In addition, Resins, epoxy of the present invention also can be used as the raw material of various modification product such as modification urethane, improved silica, modified phosphate, modified amine, modification (methyl) vinylformic acid.
Resins, epoxy of the present invention or its modification product can be used for following purposes widely: for example as the coating or the caking agent of concrete, cement plaster, various metal, leather, glass, rubber, plastics, wood, cloth, paper etc.; Packaging adhesive adhesive tape, adhesive label, frozen product label, remove label, POS label, bonding wallpaper, the tackiness agent of panel material adhesively; Converted papers such as art paper, lightweight enamelled paper, casting White Board, coated cardboard, carbon-free printer, impregnated paper; Astringent matters such as natural fiber, synthon, glass fibre, carbon fiber, steel fiber, the anti-fibre finishs such as line agent, machining agent that split; Material of construction such as sealing material, cement admixture, water-proof material; Electronics and electric machine are with sealing agent etc.
Embodiment
Below by embodiment etc. phenolic compound of the present invention and Resins, epoxy are described in further detail, but the present invention is not limited to these embodiment.
[reference example 1]
The manufacturing of cyclohexyl biphenyl hexyl ketone (ketone compound K-1)
Pack in having the 5L four-hole boiling flask of whipping appts, cooling tube, thermometer aluminum chloride 454.7g, chlorobenzene 2630g add biphenyl 438.3g while stirring, and make its dissolving under the ice bath.Afterwards chlorination hexahydrobenzoic acid 500.0g is dripped with 2.5 hours at 0～8 ℃, slowly be warming up to 20 ℃ then, make its reaction 2 hours again.Reaction solution is injected frozen water 4kg when stirring and noting heating, after the organic layer of oily water separation gained is washed with dilute hydrochloric acid 3kg again water 3kg divide 3 washings.Behind anhydrous sodium sulfate dehydration, heat up in a steamer and desolvate, get white crystals 563.5g (yield 75%) by the hexane recrystallize.
White crystals to gained carries out
1H-NMR and IR analyze, and the result shows following
1H-NMR chemical shift and IR absorb, and confirm as object ketone compound K-1 thus.The fusing point of this white crystals is 86.9 ℃ (differential thermal spike summits).
(
1The H-NMR chemical shift)
8.01(d：2H)、7.67(d：2H)、7.61(d：2H)、7.46(t：2H)、7.38(t：1H)、3.29(t：1H)、1.93～1.72(m：5H)、1.56～1.22(m：5H)
(IR absorption)
3330cm
-1、3090cm
-1、3058cm
-1、2928cm
-1、2849cm
-1、1670cm
-1、1603cm
-1、1582cm
-1、1559cm
-1、1520cm
-1、1486cm
-1、1462cm
-1、1448cm
-1、1404cm
-1、1377cm
-1、1339cm
-1、1315cm
-1、1295cm
-1、1254cm
-1、1201cm
-1、1173cm
-1、1159cm
-1、1135cm
-1、1122cm
-1、1075cm
-1、1057cm
-1、1028cm
-1、1005cm
-1、976cm
-1、824cm
-1、895cm
-1、842cm
-1、817cm
-1、767cm
-1、742cm
-1、729cm
-1、690cm
-1
[embodiment 1]
1, the manufacturing of two (4 '-hydroxy phenyl)-1-of 1-(1 "-xenyl)-1-cyclohexyl-methane (Compound P-1)
Ketone compound K-1, phenol 200.7g, the thioacetic acid 10.15g of gained in the 70.5g reference example 1 pack in having the 1L four-hole boiling flask of whipping appts, cooling tube, thermometer, with the following limit of stirring of water cooling trifluoromethanesulfonic acid 40.0g is being dripped with 20 minutes at 18 ℃, reaction is after 18 hours remain on 17～19 ℃ with water cooling under, keep adding entry 500g with water-cooled state, make the reaction chilling, with toluene 500g extraction.Organic layer is washed with water to pH3～4, and decompression is down heated up in a steamer toluene, water and excessive phenol, adds toluene again, and the leaching crystallization of separating out, and disperses washing with toluene, faint yellow crystallization 59.2g (yield 51.2%).
Faint yellow crystallization to gained is carried out
1H-NMR and IR analyze, and the result shows following
1H-NMR chemical shift and IR absorb, and confirm as object Compound P-1 thus.This faint yellow crystalline fusing point is 239.5 ℃ (differential thermal spike summits).
(
1The H-NMR chemical shift)
9.24(s：2H)、7.79(d：2H)、7.65(d：2H)、7.55(t：2H)、7.44(t：1H)、7.10(d：2H)、6.98(d：4H)、6.65(d：4H)、3.92(s：1H)、2.28～2.25(m：2H)、1.72～1.43(m：5H)、1.31～1.10(m：3H)
(IR absorption)
3324cm
-1、3033cm
-1、2933cm
-1、2854cm
-1、1610cm
-1、1597cm
-1、1558cm
-1、1510cm
-1、1488cm
-1、1446cm
-1、1380cm
-1、1232cm
-1、1175cm
-1、1117cm
-1、1080cm
-1、1039cm
-1、1007cm
-1、953cm
-1、909cm
-1、869cm
-1、845cm
-1、818cm
-1、777cm
-1、761cm
-1、741cm
-1、695cm
-1
[embodiment 2]
1, the manufacturing of two (4 '-epoxy propionyloxy phenyl)-1-of 1-(1 "-xenyl)-1-cyclohexyl-methane (compd E-1)
Phenolic compound (Compound P-1) 57.5g, the epoxy chloropropane 195.8g of gained among the embodiment 1 pack in having the 500mL four-hole boiling flask of whipping appts, cooling tube, thermometer, add benzyl triethyl ammonium ammonia chloride 0.602g, be warming up to 64 ℃ and stirred 18 hours, be cooled to 54 ℃ afterwards, drip 24 quality % aqueous sodium hydroxide solution 43.0g and stirred 30 minutes.Then, heat up in a steamer decyclization oxygen chloropropane and water by azeotropic, be warming up to 121 ℃ again to heat up in a steamer decyclization oxygen chloropropane fully, then add methyl iso-butyl ketone (MIBK) 216g and wash 3 times, 24 quality % sodium hydroxide 2.2g drip, stirred 2 hours at 80 ℃, be back to room temperature, with in the 3 quality % biphosphate sodium water solutions and after, wash 3 times, heat up in a steamer and desolvate, get yellow solid epoxy resin 57g (yield 78.8%).
Yellow solid epoxy resin to gained carries out
1H-NMR and IR analyze, and the result shows following
1H-NMR chemical shift and IR absorb, and confirm as object compd E-1 thus.The fusing point of this yellow solid epoxy resin is 64.2 ℃ (differential thermal spike summits).
(
1The H-NMR chemical shift)
7.67(d：2H)、7.50～7.44(m：4H)、7.34(t：1H)、6.98(d：6H)、6.72(d：4H)、4.15(t：1H)、4.13(t：1H)、3.93～3.87(m：3H)、3.34～3.30(m：2H)、2.88(t：2H)、2.74～2.72(m：2H)、2.24～2.10(m：2H)、1.67～1.40(m：5H)、1.35～1.11(m：3H)
(IR absorption)
3447cm
-1、3029cm
-1、3008cm
-1、2929cm
-1、2857cm
-1、1606cm
-1、1580cm
-1、1508cm
-1、1487cm
-1、1469cm
-1、1453cm
-1、1420cm
-1、1346cm
-1、1299cm
-1、1243cm
-1、1180cm
-1、1158cm
-1、1119cm
-1、1076cm
-1、1037cm
-1、1008cm
-1、969cm
-1、914cm
-1、862cm
-1、844cm
-1、762cm
-1、742cm
-1、698cm
-1、653cm
-1
[making use-case 1]
With 100g compd E-1, ア デ カ Ha one De Na one EH-3326 (Asahi Denka Kogyo K. K's system; The methyltetrahydro phthalate anhydride) 58.8g, triphenylphosphine 1.59g mix, and respectively 2 hours, 160 ℃ heating of 1 hour, 130 ℃ heating of 100 ℃ of heating 2 hours, thereby obtain cured article.
The second-order transition temperature (Tg) of measuring this cured article is 155 ℃.
[relatively making use-case 1]
With Epikote 834 (japan epoxy resin systems; Bisphenol A type epoxy resin) ア デ カ Ha one De Na one EH-3326, the triphenylphosphine 1.66g of 100g, 66.4g mix, and respectively 2 hours, 160 ℃ heating of 1 hour, 130 ℃ heating of 100 ℃ of heating 2 hours, thereby obtain cured article.
The second-order transition temperature (Tg) of measuring this cured article is 130 ℃.
[comparative example 1]
1, the manufacturing of two (4 '-epoxy propionyloxy phenyl)-1-of 1-(1 "-xenyl)-1-ethane (compound H E-1)
The 4-[1 that packs into, two (4-hydroxy phenyl) ethyls of 1-] biphenyl 21.9g and epoxy chloropropane 99.7g, and add benzyl triethyl ammonium ammonia chloride 0.272g, be warming up to 75 ℃ and make its reaction 15 hours.With water and epoxy chloropropane azeotropic, make its reflux dewatering, on one side Yi Bian drip 48 quality % aqueous sodium hydroxide solution 10.01g, carry out again being warming up to 130 ℃ behind the reflux dewatering, heat up in a steamer decyclization oxygen chloropropane, add toluene 59.9g and stirred 1 hour, add water 23g and wash at 80 ℃.
Add 48 quality % aqueous sodium hydroxide solution 0.72g, water 0.29g and benzyl triethyl ammonium ammonia chloride 0.273g then, make 3 hours after washings of its reaction at 80 ℃, then neutralize with 1 quality % biphosphate sodium water solution, filter after washing 3 times again, under 130 ℃ of decompressions, remove and desolvate, get yellow solid epoxy resin 23.9g (yield 83%).
Yellow solid epoxy resin to gained carries out
1H-NMR and IR analyze, and the result shows following
1H-NMR chemical shift and IR absorb, and confirm as the compound H E-1 as target compound thus.
(
1The H-NMR chemical shift)
6.81-7.59(m：17H)、4.18(dd：2H)、3.92(dd：2H)、3.33(m：2H)、2.88(dd：2H)、2.73(dd：2H)、2.15(s：3H)
(IR absorption)
1246cm
-1、1031cm
-1、913cm
-1
[comparative example 2]
1, the manufacturing of two (4 '-epoxy propionyloxy phenyl)-1-of 1-(1 "-xenyl)-1-propane (compound H E-2)
The 4-[1 that packs into, two (4-hydroxy phenyl) propyl group of 1-] biphenyl 13.5g and epoxy chloropropane 59.7g, and add benzyl triethyl ammonium ammonia chloride 0.163g, be warming up to 75 ℃ and stirred 14 hours.With water and epoxy chloropropane azeotropic, make its reflux dewatering, on one side Yi Bian drip 48 quality % aqueous sodium hydroxide solution 5.43g, carry out again being warming up to 130 ℃ behind the reflux dewatering, heat up in a steamer decyclization oxygen chloropropane, add toluene 32.6g and stirred 1 hour, add water 12.4g and wash at 80 ℃.
Add 48 quality % aqueous sodium hydroxide solution 0.72g, water 0.29g and benzyl triethyl ammonium ammonia chloride 0.152g then, make 3 hours after washings of its reaction at 80 ℃, then add the neutralization of 1 quality % biphosphate sodium water solution, filter after washing 3 times again, under 130 ℃ of decompressions, remove and desolvate, get orange solid epoxy resin 13.8g (yield 79%).
Orange solid epoxy resin to gained carries out
1H-NMR and IR analyze, and the result shows following
1H-NMR chemical shift and IR absorb, and confirm as the compound H E-2 as target compound thus.
(
1The H-NMR chemical shift)
6.82-7.59(m：17H)、4.18(dd：2H)、3.94(dd：2H)、3.34(m：2H)、2.89(dd：2H)、2.74(dd：2H)、2.59(q：2H)、0.79(t：3H)
(IR absorption)
1244cm
-1、1034cm
-1、914cm
-1
[make use-case 2 and relatively make use-case 2～4]
(four countries change into industry (strain) system with Resins, epoxy (seeing [table 1]) 3.5g, propylene glycol methyl ether acetate (PGM-Ac) 1.5g, ア デ カ Ha one De Na, one EH-3326 (combined amount is seen [table 1]) and キ ュ ア ゾ one Le 2E4MZ; 2-ethyl-4-methylimidazole) 0.06g mixes, and makes solidification compound.This solidification compound 3g is uniformly coated into diameter on sheet glass be 7cm, and 80 ℃ of heating 60 minutes, 150 ℃ of heating 120 minutes, make its curing, thereby obtain cured article again.The cured article of gained was flooded 60 minutes in 80 ℃ hot water bath, ask quality increment rate (%) [water-intake rate].Its result is as shown in table 1.
[table 1]
| Make use-case | Relatively make use-case | ||||
| 2 | 2 | 3 | 4 | ||
| Resins, epoxy | Compd E-1 | 3.5 | |||
| Epikote 834 | 3.5 | ||||
| Compound H E-1 | 3.5 | ||||
| Compound H E-2 | 3.5 | ||||
| PGM-Ac | 1.5 | 1.5 | 1.5 | 1.5 | |
| ア デ カ Ha one De Na one EH-3326 | 2.28 | 2.52 | 2.58 | 2.46 | |
| キ ュ ア ゾ one Le 2E4MZ | 0.06 | 0.06 | 0.06 | 0.06 | |
| Specific absorption (%) | 0.35 | 0.79 | 0.65 | 0.60 | |
Phenolic compound of the present invention can be used as used for epoxy resin raw material etc.Can provide the cured article that solidifies rerum natura and have excellent water-resistance by this phenolic compound deutero-Resins, epoxy.
Claims (12)
1. one kind with the represented phenolic compound of following general formula (I),
Cy represents that carbonatoms is 3～10 cycloalkyl in the formula, X represents hydrogen atom, can be that 1～10 phenyl that alkyl replaced or carbonatoms are 3～10 cycloalkyl by carbonatoms, Y and Z represent independently that respectively carbonatoms is 1～10 alkyl, p represents 0～5 number, and r represents 0～4 number.
2. phenolic compound according to claim 1, wherein in described general formula (I), Cy is a cyclohexyl.
3. phenolic compound according to claim 1 and 2, wherein in described general formula (I), r is 0.
4. phenolic compound according to claim 1 and 2, wherein in described general formula (I), r is 1, and Z is a methyl.
5. according to any described phenolic compound of claim 1～4, wherein in described general formula (I), p is 0, and X is phenyl, cyclohexyl or the 4-aminomethyl phenyl of the replacement of 4-position.
6. phenolic compound according to claim 1, wherein in described general formula (I), Cy is a cyclohexyl, X is a phenyl, and p and r are 0.
7. one kind with the represented Resins, epoxy of following general formula (II),
In the formula Cy, X, Y, Z, p and r represent with described general formula (I) in the same meaning, n represents 0～10 number.
8. Resins, epoxy according to claim 7, wherein in described general formula (II), Cy is a cyclohexyl.
9. according to claim 7 or 8 described Resins, epoxy, wherein in described general formula (II), r is 0.
10. according to claim 7 or 8 described Resins, epoxy, wherein in described general formula (II), r is 1, and Z is a methyl.
11. according to any described Resins, epoxy of claim 7～10, wherein in described general formula (II), p is 0, and X is phenyl, cyclohexyl or the 4-aminomethyl phenyl of the replacement of 4-position.
12. Resins, epoxy according to claim 7, wherein in described general formula (II), Cy is a cyclohexyl, and X is a phenyl, and p and r are 0.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP090129/2004 | 2004-03-25 | ||
| JP2004090129 | 2004-03-25 |
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|---|---|
| JP (1) | JP4698586B2 (en) |
| CN (1) | CN100386298C (en) |
| TW (1) | TW200609207A (en) |
| WO (1) | WO2005092826A1 (en) |
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| JP4198101B2 (en) * | 2004-09-17 | 2008-12-17 | 株式会社Ａｄｅｋａ | Alkali developable resin composition |
| JP4198173B2 (en) | 2004-09-17 | 2008-12-17 | 凸版印刷株式会社 | Colored alkali-developable photosensitive resin composition and color filter using the colored alkali-developable photosensitive resin composition |
| JP4916224B2 (en) * | 2005-06-20 | 2012-04-11 | 株式会社Ａｄｅｋａ | Alkali-developable photosensitive resin composition |
| KR101317223B1 (en) * | 2005-06-20 | 2013-10-15 | 가부시키가이샤 아데카 | Colored alkali-developable photosensitive resin composition and color filters made by using the same |
| JP4878845B2 (en) * | 2006-01-10 | 2012-02-15 | 凸版印刷株式会社 | SUBSTRATE WITH PROJECT FOR CONTROLLING LIQUID CRYSTAL ORIENTATION CONTROL FORMED USING ALKALINE DEVELOPING PHOTOSENSITIVE RESIN COMPOSITION |
| JP4667261B2 (en) * | 2006-02-01 | 2011-04-06 | 株式会社Ａｄｅｋａ | Alkali-developable photosensitive resin composition |
| JP4738190B2 (en) * | 2006-02-01 | 2011-08-03 | 株式会社Ａｄｅｋａ | Epoxy resin, alkali-developable resin composition, and alkali-developable photosensitive resin composition |
| JP4878876B2 (en) * | 2006-03-15 | 2012-02-15 | 株式会社Ａｄｅｋａ | Epoxy resin, alkali-developable resin composition, and alkali-developable photosensitive resin composition |
| JP5546093B2 (en) * | 2006-12-26 | 2014-07-09 | 株式会社Ａｄｅｋａ | Polymerizable compound and polymerizable composition |
| JP5311750B2 (en) * | 2007-02-28 | 2013-10-09 | 株式会社Ａｄｅｋａ | Phenol resin, epoxy resin, alkali-developable resin composition, and alkali-developable photosensitive resin composition |
| EP2507283B1 (en) | 2009-12-02 | 2013-10-23 | Dow Global Technologies LLC | Epoxy resin compositions |
| EP2507285A2 (en) * | 2009-12-02 | 2012-10-10 | Dow Global Technologies LLC | Composite compositions |
| EP2507325B1 (en) | 2009-12-02 | 2014-05-21 | Dow Global Technologies LLC | Coating compositions |
| JP7465673B2 (en) | 2020-02-25 | 2024-04-11 | 株式会社Adeka | Polymers, molded articles and optical materials |
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| EP0263129B1 (en) * | 1986-04-14 | 1993-02-03 | Hughes Aircraft Company | Structural epoxy paste adhesive curable at ambient temperature and process for preparation thereof |
| JP3200123B2 (en) * | 1991-11-27 | 2001-08-20 | 住友化学工業株式会社 | Epoxy resin composition for sealing electronic parts |
| JP3173629B2 (en) * | 1992-02-12 | 2001-06-04 | 日本化薬株式会社 | Epoxy resin composition and cured product thereof |
| JPH05295089A (en) * | 1992-04-21 | 1993-11-09 | Daihachi Chem Ind Co Ltd | Curable resin composition |
| TW343990B (en) * | 1996-02-09 | 1998-11-01 | Nippon Kayaku Kk | Epoxy resin, epoxy resin composition and hardened product thereof |
| JP2000239206A (en) * | 1998-12-25 | 2000-09-05 | Honshu Chem Ind Co Ltd | Asymmetric alkylidene polyhydric phenols and production thereof |
| JP2002316963A (en) * | 2001-02-15 | 2002-10-31 | Osaka Gas Co Ltd | Bisphenol with low activity as endocrine disruptor |
| JP2003064121A (en) * | 2001-08-23 | 2003-03-05 | Tosoh Corp | Method of producing polyolefin |
| JP4067974B2 (en) * | 2002-02-15 | 2008-03-26 | 本州化学工業株式会社 | 1,3,5-tris (4-hydroxyphenyl) adamantanes and process for producing the same |
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| JPWO2005092826A1 (en) | 2008-02-14 |
| TW200609207A (en) | 2006-03-16 |
| JP4698586B2 (en) | 2011-06-08 |
| CN100386298C (en) | 2008-05-07 |
| WO2005092826A1 (en) | 2005-10-06 |
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