CN105860030B - Glycidyl amine type epoxy resin of structure containing Cardo and preparation method thereof - Google Patents

Glycidyl amine type epoxy resin of structure containing Cardo and preparation method thereof Download PDF

Info

Publication number
CN105860030B
CN105860030B CN201610266115.4A CN201610266115A CN105860030B CN 105860030 B CN105860030 B CN 105860030B CN 201610266115 A CN201610266115 A CN 201610266115A CN 105860030 B CN105860030 B CN 105860030B
Authority
CN
China
Prior art keywords
glycidyl amine
structure containing
cardo
amine type
type epoxy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610266115.4A
Other languages
Chinese (zh)
Other versions
CN105860030A (en
Inventor
熊需海
任荣
陈平
卢少微
王�琦
贾彩霞
王静
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenyang Aerospace University
Original Assignee
Shenyang Aerospace University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenyang Aerospace University filed Critical Shenyang Aerospace University
Priority to CN201610266115.4A priority Critical patent/CN105860030B/en
Publication of CN105860030A publication Critical patent/CN105860030A/en
Application granted granted Critical
Publication of CN105860030B publication Critical patent/CN105860030B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3236—Heterocylic compounds
    • 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
    • C07D303/36—Compounds containing oxirane rings with hydrocarbon radicals, substituted by nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing three or more hetero rings
    • 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
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3227—Compounds containing acyclic nitrogen atoms

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Epoxy Resins (AREA)

Abstract

The present invention relates to a kind of glycidyl amine type epoxy resin of structure containing Cardo, there is the structural formula that Formulas I represents：X is in formulaOrR1And R2Respectively hydrogen atom, methyl or isopropyl；Its preparation method comprises the following steps：The aromatic diamine of structure containing Cardo reacts a period of time in the solution with epoxychloropropane；Add alkali metal hydroxide aqueous solution and carry out ring-closure reaction；Reaction added after terminating extractant extracted, washed, the operation such as liquid separation；Finally extractant decompression is steamed to obtain the glycidyl amine type epoxy resin of water white transparency.The glycidyl amine type epoxy resin of structure containing Cardo of the present invention has excellent heat resistance, is expected to the base-material of matrix resin, high-temperature insulating paint and adhesive as advanced polymer matrix composite etc., and tool has been widely used.

Description

Glycidyl amine type epoxy resin of structure containing Cardo and preparation method thereof
Technical field
The invention belongs to technical field of polymer materials, more particularly to a kind of glycidyl amine type ring of structure containing Cardo Oxygen tree fat and preparation method thereof.
Background technology
Glycidyl amine type epoxy resin is a kind of high-performance multiple functionality epoxide resin, with the solidification shape such as arylamine, acid anhydrides Into three-dimensional network there is good heat endurance, electrical insulation capability, chemicals-resistant burn into radiation hardness and excellent mechanical performance, It is widely used in the fields such as Aero-Space, mechano-electronic, communications and transportation as coating, adhesive, composite matrix resin.
The glycidyl amine (abbreviation TGDDM) of 4,4 ' MDA four is the most frequently used glycidyl amine epoxy tree Fat, its have viscosity it is low, it is active it is high, cementability is strong, cured product crosslink density is big, shrinkage factor is low, excellent in mechanical performance etc. is excellent Point.Ciba-Geigy companies of the U.S., Japanese Dongdu chemical conversion and China Shanghai resin research institute be proposed respectively in succession MY720 and The glycidic amine type resin of the trade mark such as MY721, YH-434 and YH434L and Ag-80.The resinoid and 4,4 '-diaminourea two The solidfied material stretch modulus of benzene sulfone is 3.7GPa, and about 246 DEG C of glass transition temperature, long-term heat resistance is up to 177 DEG C.Therefore its Carbon fibre reinforced composite is widely used in substituting aluminium alloy manufacture high temperature resistant aviation structural member.But this kind of resin there is also The problems such as hydroscopicity is big, and humidity resistance performance is bad.
Two phenyl ring planes are formed in distorted shape and with Cardo side base planes subvertical in phthalein (fluorenes) Cardo structures Plane included angle, this structure, which is introduced into thermosetting resin molecular structure, can make strand be difficult to take the non-linear configuration stretched, drop The low crystallinity of resin, substantially improves the solubility property of resin.Multiple heteroaromatics, which introduce, simultaneously can both improve strand Rigidity, improves the glass transition temperature of resin；The nonpolar increase of molecule can be made again, the water imbibition of resin is reduced, carry Its high wet-hot aging performance.Based on above-mentioned advantage, the thermosetting resin of all multiple types structures containing Cardo is designed and synthesized. B.F.Zhang et al. exists【Polymer(2009)50:817–824】Disclose the synthetic technology of one kind cyanates of Cardo containing phthalein. X.H.Xiong et al. exists【Polym.Int.(2010)59:1665】Disclose chain extension type BMI in Cardo containing phthalein (BMI) synthetic technology of resin.Zhai Chun and Zhang Wei et al. exist respectively【Using chemical industry (2003) 32:47】With【Composite journal (2003)20:81】Disclose the synthetic technology of phenolphthalein type and bisphenol fluorene type diglycidyl ether type epoxy resin.
Neo-epoxy resin-contain phthalein (fluorenes) Cardo structure glycidyl amine type epoxy resins, because its molecule segment length increases Add and heteroaromatic content is further improved, cause the crosslink density of its solidfied material to decline and toughness increase, hydroscopicity reduction And wet-hot aging performance increase, while keep good resistance to elevated temperatures.Therefore, the fibre reinforced composites being made from it have More superior combination property, can be widely used for aerospace field.Containing phthalein (fluorenes) Cardo structure glycidyl amine epoxy trees Fat and preparation method thereof is at home and abroad not yet seen in about scientific and technological patent and public publication.
The content of the invention
It is sweet that the technical problems to be solved by the invention are to provide a kind of more excellent shrink of structure containing Cardo of combination property Oleyl amine type epoxy resin and preparation method thereof, overcomes the shortcomings of the prior art and defect, meets the demands of production and living.
The adopted technical solution is that：A kind of glycidyl amine type epoxy resin of structure containing Cardo, Cardo structure glycidyl amine type epoxy resins have following molecular structural formula：
X is in formulaR1And R2Respectively hydrogen atom, methyl or isopropyl.
A kind of method of the glycidyl amine type epoxy resin of structure containing Cardo prepared described in claim 1, comprising as follows Step：
Step 1：It is 1 by mol ratio:The aromatic diamine of structure containing Cardo and epoxychloropropane of (4~30), in water and Alcoholic solvent volume ratio is 1:The in the mixed solvent of (3~10) is reacted 4~9 hours at a temperature of 40~90 DEG C, wherein being tied containing Cardo Structure aromatic diamine and mixed solvent amount ratio are 1mol:(2~6) L；
Step 2：Reaction is cooled to 30~40 DEG C, adds the alkali metal hydroxide water that mass percentage concentration is 15~30% Solution, wherein the mol ratio of the aromatic diamine of structure containing Cardo and alkali metal hydroxide is 1:(4~10)；Then rise again Warm to 70~90 DEG C are reacted 3~6 hours；
Step 3：Reaction adds extractant after terminating, and is extracted, washed, liquid separation, removes aqueous phase and retains organic phase mother liquor； Mother liquor heating, vacuum devolatilization, obtain the glycidyl amine type epoxy resin of structure containing Cardo of water white transparency.
The aromatic diamine of structure containing Cardo of the step 1 and step 2 be with phenolphthalein, o-cresolphthalein, thymolphthalein, Bisphenol fluorene, double orthoresol fluorenes are that phenol source and parachloronitrobenzene pass through dinitro compound that Williamson etherification reactions synthesize again The product obtained through nitro-reduction reaction.
Alcoholic solvent described in step 1 is the mixture of one or both of methanol, ethanol, isopropanol, n-butanol.
Alkali metal hydroxide described in step 2 is sodium hydroxide, potassium hydroxide or lithium hydroxide.
Extractant described in step 3 is toluene, dimethylbenzene, dichloromethane or chloroform.
The glycidyl amine type epoxy resin of structure containing Cardo synthetic route of the present invention is as follows：
X is in formulaR1And R2Respectively hydrogen atom, methyl or isopropyl.
Compared with prior art, the advantageous effect of present invention is that：
1) combination property containing phthalein (fluorenes) Cardo structure glycidyl amine type epoxy resins is more superior：Its molecular structure The increase of middle heteroaromatic content can keep its solidfied material to have good heat resistance, while reduce polarity of chain so that resistance to Hygrothermal Properties are improved；The increase of other molecule segment length reduces the crosslink density of solidfied material, is beneficial to changing for toughness It is kind；
2) preparation method containing phthalein (fluorenes) Cardo structure glycidyl amine type epoxy resins uses commercial run, step letter List, cost is low, reaction condition is gentle, yield is high；Excessive raw material and solvent can reclaim cycling and reutilization, three in course of reaction Give up less, be environment-friendly.
Brief description of the drawings
Fig. 1 is the infrared spectrum of the glycidyl amine epoxy of skeleton containing phenolphthalein (TGPP) resin；
Fig. 2 is the hydrogen nuclear magnetic resonance spectrum of the glycidyl amine epoxy of skeleton containing phenolphthalein (TGPP) resin；
Fig. 3 be the glycidyl amine epoxy of skeleton containing phenolphthalein (TGPP) resin (etc. stoichiometric proportion 4,4 '-diaminourea hexichol Methane is curing agent) the DMA time spectrums of prepreg solidification process；
Fig. 4 be etc. stoichiometric proportion skeleton containing phenolphthalein glycidyl amine epoxy (TGPP) resin (etc. stoichiometric proportion 4, 4 '-MDA is curing agent) the DMA TEMPERATURE SPECTROSCOPYs of composite；
Fig. 5 be stoichiometric proportion skeleton containing phenolphthalein glycidyl amine epoxy (TGPP) resin cured matter (etc. stoichiometry Be curing agent than 4,4 '-MDA) hot weightless picture.
Embodiment
The synthesis of embodiment 1 glycidyl amine epoxy of skeleton containing phenolphthalein (TGPP) resin
By 0.05mol 3,3- bis- [4- (4- amino-benzene oxygens) phenyl] -3H- isobenzofuranones, 0.4mol epoxy chloropropionates Alkane, 50ml deionized waters and 150ml ethanol add reactor, are reacted 6 hours under the conditions of 70 DEG C；40 DEG C are cooled to after reaction, The sodium hydrate aqueous solution that 60g mass percentage concentrations are 20% is added dropwise；Then reaction 4 hours is continued after being warming up to 70 DEG C again；Instead After should terminating, reaction solution is poured into stirring and dissolving in 500ml toluene, filtration from sodium chloride, then through washing, standing, liquid separation, remove Aqueous phase is gone to retain organic phase mother liquor；Mother liquor heating, vacuum devolatilization, volatile matter are collected and recycled, and residue is cooled to room temperature in saturating Bright colorless solid is the glycidyl amine epoxy of skeleton containing phenolphthalein (TGPP) resin.Yield 85%.
3,3- bis- [4- (4- amino-benzene oxygens) the phenyl] -3H- isobenzofuranones are as phenol source and to chlorine using phenolphthalein The product that dinitro compound of the nitrobenzene by the synthesis of Williamson etherification reactions obtains through nitro-reduction reaction again.
The infrared structure of the glycidyl amine epoxy of skeleton containing phenolphthalein (TGPP) resin characterizes (as shown in Figure 1) data For：FT-IR (KBr, cm-1)：2980-2965(-CH2,-CH)；1762 (cyclic lactone C=O)；1511,1493(Ar)1247(Ar- O)；920 (epoxide groups).
Nuclear-magnetism structural characterization data are (as shown in Figure 2)：1H NMR (400MHz, DMSO-d6)：7.95 (1H, ArH), 7.70 (2H, ArH), 7.63 (1H, ArH), 7.29 (4H, ArH), 6.94 (12H, ArH), 3.69 (4H ,-CH-H), 3.43 (4H ,-CH- H), 3.41 (4H ,-CH), 2.75 (4H ,-CH-H), 2.56 (4H ,-CH-H).
TGPP resins have good dissolubility energy (table 1) in conventional organic solvent；With etc. stoichiometric proportion 4,4 '-two The resin system that diaminodiphenylmethane is mixed with 100 DEG C can fast reaction, continue at 150 DEG C react 90min it is basic Reaction is completely (as shown in Figure 3)；The glass transition temperature of solidfied material is up to 290 DEG C (Fig. 4)；Initial pyrolyzation temperature is up to 401 DEG C (as shown in Figure 5).This is a kind of epoxy-resin systems with good process performance and heat resistance as can be seen here.
The synthesis of embodiment 2 glycidyl amine epoxy of skeleton containing o-cresolphthalein (TGMP) resin
3 implemented in 1 are replaced with 3,3- bis- [3- methyl -4- (4- amino-benzene oxygens) phenyl] -3H- isobenzofuranones, 3- bis- [4- (4- amino-benzene oxygens) phenyl] -3H- isobenzofuranones, other raw materials and its proportioning, reaction condition, synthesis step It is same as Example 1.It is clear, colorless solid to react obtained product, yield 90%.
3,3- bis- [3- methyl -4- (4- amino-benzene oxygens) the phenyl] -3H- isobenzofuranones be using o-cresolphthalein as The dinitro compound that phenol source synthesizes with parachloronitrobenzene by Williamson etherification reactions, then obtained through nitro-reduction reaction Product.
The infrared structure characterize data of the glycidyl amine epoxy of skeleton containing o-cresolphthalein (TGMP) resin is：FT- IR (KBr, cm-1)：2980-2965(-CH3,-CH2,-CH)；1762 (cyclic lactone C=O)；1510(Ar)；1248(Ar-O)；923 (epoxide group).
Nuclear-magnetism structural characterization data are：1H NMR (400MHz, DMSO-d6)：7.92 (1H, ArH), 7.67 (2H, ArH), 7.56 (1H, ArH), 7.19 (2H, ArH), 7.02 (2H, ArH), 6.72 (10H, ArH), 3.69 (4H ,-CH-H), 3.43 (4H ,- CH-H), 3.41 (4H ,-CH), 2.75 (4H ,-CH-H), 2.56 (4H ,-CH-H), 2.23 (6H, Ar-CH3)。
The solubility property and heat resistance of TGMP resins are shown in Tables 1 and 2 respectively.
The synthesis of the glycidyl amine type epoxy resin of skeleton containing thymolphthalein (TGIP) of embodiment 3
Replaced with 3,3- bis- [the 2- methyl -5- tert-butyl groups -4- (4- amino-benzene oxygens) phenyl] -3H- isobenzofuranones real Apply 3,3- bis- [4- (4- amino-benzene oxygens) phenyl] -3H- isobenzofuranones in 1, other raw materials and its proportioning, reaction bar Part, synthesis step are same as Example 1.It is clear, colorless solid to react obtained product, yield 92%.
3,3- bis- [the 2- methyl -5- tert-butyl groups -4- (4- amino-benzene oxygens) the phenyl] -3H- isobenzofuranones be with Thymolphthalein is the dinitro compound that phenol source synthesizes with parachloronitrobenzene by Williamson etherification reactions, then through nitro also The product that original reaction obtains.
The infrared structure characterize data of the glycidyl amine type epoxy resin of skeleton containing thymolphthalein (TGIP) is：FT- IR (KBr, cm-1)：2980-2965(-CH3,-CH2,-CH)；1765 (cyclic lactone C=O)；1512(Ar)；1251(Ar-O)；921 (epoxide group).
Nuclear-magnetism structural characterization data are：1H NMR (400MHz, DMSO-d6)：7.94 (1H, ArH), 7.70 (1H, ArH), 7.62 (1H, ArH), 7.45 (1H, ArH), 7.00 (2H, ArH), 6.64 (10H, ArH), 3.69 (4H, Ar-CH-H), 3.43 (4H, Ar-CH-H), 3.41 (4H ,-CH), 3.25 (m, 2H, Ar-CH (CH3)2), 2.78 (4H ,-CH-H), 2.61 (4H ,-CH- H), 2.17 (6H, Ar-CH3), 1.25 (12H, Ar-CH (CH3)2)。
The solubility property and heat resistance of TGIP resins are shown in Tables 1 and 2 respectively.
The synthesis of embodiment 4 glycidyl amine epoxy of fluorene skeleton containing bis-phenol (TGPF) resin
3,3- bis- [4- (4- amino-benzene oxygens) phenyl] -3H- is replaced with 9,9- bis- [4- (4- amino-benzene oxygens) phenyl] fluorenes Isobenzofuranone, other raw materials and its proportioning, reaction condition, synthesis step are same as Example 1.Reacting obtained product is Clear, colorless solid, yield 86%.
9,9- bis- [4- (4- amino-benzene oxygens) phenyl] fluorenes is passed through by phenol source and parachloronitrobenzene of bisphenol fluorene The dinitro compound of Williamson etherification reactions synthesis, then the product obtained through nitro-reduction reaction.
The infrared structure characterize data of the glycidyl amine epoxy of fluorene skeleton containing bis-phenol (TGPF) resin is：FT-IR (KBr, cm-1)：2980-2965(-CH2,-CH), 1243 (Ar-O)；924 (epoxide groups).
Nuclear-magnetism structural characterization data are：1H NMR (400MHz, DMSO-d6)：7.78 (2H, ArH), 7.42 (2H, ArH), 7.38 (2H, Ar H), 7.32 (2H, ArH), 7.29 (4H, ArH), 7.20 (4H, ArH), 7.06 (4H, ArH), 6.90 (4H, ArH), 3.65 (4H ,-CH-H), 3.40 (4H ,-CH-H), 3.35 (4H ,-CH), 2.72 (4H ,-CH-H), 2.54 (4H ,-CH- H)。
The solubility property and heat resistance of TGPF resins are shown in Tables 1 and 2 respectively.
Embodiment 5 contains the synthesis of double orthoresol fluorene skeleton glycidyl amine epoxy (TGMF) resins
[4- (the 4- aminobenzenes of 3,3- bis- implemented in 1 are replaced with 9,9- bis- [3- methyl-(4- amino-benzene oxygens) phenyl] fluorenes Epoxide) phenyl] -3H- isobenzofuranones, other raw materials and its proportioning, reaction condition, synthesis step are same as Example 1.Instead The product that should be obtained is clear, colorless solid, yield 89%.
9,9- bis- [3- methyl-(4- amino-benzene oxygens) phenyl] fluorenes is as phenol source and to chlorine nitro using double orthoresol fluorenes Benzene passes through the dinitro compound of Williamson etherification reactions synthesis, then the product obtained through nitro-reduction reaction.
The infrared structure characterize data containing double orthoresol fluorene skeleton glycidyl amine epoxy (TGMF) resins is： FT-IR (KBr, cm-1)：2980-2965(-CH3,-CH2,-CH) and 1245 (Ar-O)；925 (epoxide groups).
Nuclear-magnetism structural characterization data are：1H NMR (400MHz, DMSO-d6)：7.79 (2H, ArH), 7.43 (2H, ArH), 7.36 (2H, Ar H), 7.30 (2H, ArH), 7.24 (4H, ArH), 7.05 (4H, ArH), 6.96 (4H, ArH), 6.78 (2H, ArH), 3.67 (4H ,-CH-H), 3.41 (4H ,-CH-H), 3.33 (4H ,-CH), 2.70 (4H ,-CH-H), 2.52 (4H ,-CH- H), 2.13 (6H, Ar-CH3).
The solubility property and heat resistance of TGMF resins are shown in Tables 1 and 2 respectively.
The dissolubility of the present invention is shown in Table 1：
Table 1 contains the dissolubility of phthalein (fluorenes) Cardo structure glycidyl amine type epoxy resins
"-" is insoluble；"+- " dissolves by heating；" ++ " room-temperature dissolution.
The hot property table 2 of the solidfied material of the present invention：
The hot property of solidfied material of the table 2 containing phthalein (fluorenes) Cardo structure glycidyl amine type epoxy resins
The synthesis of embodiment 6 glycidyl amine epoxy of skeleton containing phenolphthalein (TGPP) resin
By 0.05mol 3,3- bis- [4- (4- amino-benzene oxygens) phenyl] -3H- isobenzofuranones, 1.5mol epoxy chloropropionates Alkane, 20ml deionized waters and 80ml isopropanols add reactor, are reacted 4 hours under the conditions of 90 DEG C；35 DEG C are cooled to after reaction, The lithium hydroxide aqueous solution that 67g mass percentage concentrations are 30% is added dropwise；Then reaction 6 hours is continued after being warming up to 90 DEG C again；Instead After should terminating, reaction solution is poured into stirring and dissolving in 500ml dichloromethane, refilters removing lithium chloride, then pass through and wash, be quiet Put, liquid separation, remove aqueous phase and retain organic phase mother liquor；Mother liquor heating, vacuum devolatilization, volatile matter are collected and recycled, residue cooling It is the glycidyl amine epoxy of skeleton containing phenolphthalein (TGPP) resin to the transparent colorless solid of room temperature.Yield 80%.
3,3- bis- [4- (4- amino-benzene oxygens) the phenyl] -3H- isobenzofuranones are as phenol source and to chlorine using phenolphthalein Nitrobenzene passes through the dinitro compound of Williamson etherification reactions synthesis, then the product obtained through nitro-reduction reaction.
The synthesis of embodiment 7 glycidyl amine epoxy of skeleton containing phenolphthalein (TGPP) resin
By 0.05mol 3,3- bis- [4- (4- amino-benzene oxygens) phenyl] -3H- isobenzofuranones, 1.5mol epoxy chloropropionates Alkane, 50ml deionized waters and 250ml methanol add reactor, are reacted 9 hours under the conditions of 40 DEG C；30 DEG C are cooled to after reaction, The potassium hydroxide aqueous solution that 53g mass percentage concentrations are 15% is added dropwise；Then reaction 3 hours is continued after being warming up to 80 DEG C again；Instead After should terminating, reaction solution is poured into stirring and dissolving in 500ml dimethylbenzene, refilters removing potassium chloride, then pass through and wash, stand, Liquid separation, remove aqueous phase and retain organic phase mother liquor；Mother liquor heating, vacuum devolatilization, volatile matter are collected and recycled, and residue is cooled to The transparent colorless solid of room temperature is the glycidyl amine epoxy of skeleton containing phenolphthalein (TGPP) resin.Yield 82%.
3,3- bis- [4- (4- amino-benzene oxygens) the phenyl] -3H- isobenzofuranones are as phenol source and to chlorine using phenolphthalein Nitrobenzene passes through the dinitro compound of Williamson etherification reactions synthesis, then the product obtained through nitro-reduction reaction.
The synthesis of embodiment 8 glycidyl amine epoxy of skeleton containing phenolphthalein (TGPP) resin
By 0.05mol 3,3- bis- [4- (4- amino-benzene oxygens) phenyl] -3H- isobenzofuranones, 0.4mol epoxy chloropropionates Alkane, 50ml deionized waters and 150ml n-butanols add reactor, are reacted 6 hours under the conditions of 70 DEG C；40 are cooled to after reaction DEG C, the aqueous solution of the 60g mass percentage concentrations for 20% sodium hydroxide is added dropwise；Then it is small to continue reaction 4 after being warming up to 70 DEG C again When；After reaction terminates, reaction solution is poured into stirring and dissolving in 500ml chloroforms, refilters removing sodium chloride, then pass through and wash, be quiet Put, liquid separation, remove aqueous phase and retain organic phase mother liquor；Mother liquor heating, vacuum devolatilization, volatile matter are collected and recycled, residue cooling It is the glycidyl amine epoxy of skeleton containing phenolphthalein (TGPP) resin to the transparent colorless solid of room temperature.Yield 84%.
3,3- bis- [4- (4- amino-benzene oxygens) the phenyl] -3H- isobenzofuranones are as phenol source and to chlorine using phenolphthalein Nitrobenzene passes through the dinitro compound of Williamson etherification reactions synthesis, then the product obtained through nitro-reduction reaction.
The synthesis of embodiment 9 glycidyl amine epoxy of skeleton containing o-cresolphthalein (TGMP) resin
By 0.05mol 3,3- bis- [3- methyl -4- (4- amino-benzene oxygens) phenyl] -3H- isobenzofuranones, 0.4mol Epoxychloropropane, 50ml deionized waters and 150ml n-butanols and methanol add reactor, are reacted 6 hours under the conditions of 70 DEG C；Instead Should after be cooled to 40 DEG C, the aqueous solution for the sodium hydroxide that 60g mass percentage concentrations are 20% is added dropwise；Then after being warming up to 70 DEG C again Continue reaction 4 hours；After reaction terminates, reaction solution is poured into stirring and dissolving in 500ml toluene, refilters removing sodium chloride, then By washing, standing, liquid separation, remove aqueous phase and retain organic phase mother liquor；Mother liquor heating, vacuum devolatilization, volatile matter collect circulation profit With it is the glycidyl amine epoxy of skeleton containing o-cresolphthalein (TGMP) tree that residue, which is cooled to the transparent colorless solid of room temperature, Fat.Yield 85%.
3,3- bis- [3- methyl -4- (4- amino-benzene oxygens) the phenyl] -3H- isobenzofuranones are using phenolphthalein as phenol source The dinitro compound synthesized with parachloronitrobenzene by Williamson etherification reactions, then the production obtained through nitro-reduction reaction Thing.
The synthesis of embodiment 10 glycidyl amine epoxy of skeleton containing phenolphthalein (TGPP) resin
By 0.05mol 3,3- bis- [4- (4- amino-benzene oxygens) phenyl] -3H- isobenzofuranones, 0.4mol epoxy chloropropionates Alkane, 50ml deionized waters and the mixture of 150ml n-butanols and isopropanol add reactor, are reacted 6 hours under the conditions of 70 DEG C； 40 DEG C are cooled to after reaction, the aqueous solution for the potassium hydroxide that 60g mass percentage concentrations are 20% is added dropwise；Then 70 DEG C are warming up to again After continue reaction 4 hours；After reaction terminates, reaction solution is poured into stirring and dissolving in 500ml dimethylbenzene, refilters removing chlorination Potassium, then by washing, standing, liquid separation, remove aqueous phase and retain organic phase mother liquor；Mother liquor heating, vacuum devolatilization, volatile matter are collected and followed Ring utilizes, and it is the glycidyl amine epoxy of skeleton containing phenolphthalein (TGPP) tree that residue, which is cooled to the transparent colorless solid of room temperature, Fat.Yield 81%.
3,3- bis- [4- (4- amino-benzene oxygens) the phenyl] -3H- isobenzofuranones are as phenol source and to chlorine using phenolphthalein Nitrobenzene passes through the dinitro compound of Williamson etherification reactions synthesis, then the product obtained through nitro-reduction reaction.
The synthesis of embodiment 11 glycidyl amine epoxy of skeleton containing phenolphthalein (TGPP) resin
By 0.05mol 3,3- bis- [4- (4- amino-benzene oxygens) phenyl] -3H- isobenzofuranones, 0.4mol epoxy chloropropionates Alkane, 50ml deionized waters and the mixture of 150ml n-butanols and ethanol add reactor, are reacted 6 hours under the conditions of 70 DEG C；Instead Should after be cooled to 40 DEG C, the aqueous solution for the potassium hydroxide mixture that 60g mass percentage concentrations are 20% is added dropwise；Then it is warming up to again Continue reaction 4 hours after 70 DEG C；After reaction terminates, reaction solution is poured into stirring and dissolving in 500ml chloroforms, refilters removing chlorination Potassium, then by washing, standing, liquid separation, remove aqueous phase and retain organic phase mother liquor；Mother liquor heating, vacuum devolatilization, volatile matter are collected and followed Ring utilizes, and it is the glycidyl amine epoxy of skeleton containing phenolphthalein (TGPP) tree that residue, which is cooled to the transparent colorless solid of room temperature, Fat.Yield 82%.
3,3- bis- [4- (4- amino-benzene oxygens) the phenyl] -3H- isobenzofuranones are as phenol source and to chlorine using phenolphthalein Nitrobenzene passes through the dinitro compound of Williamson etherification reactions synthesis, then the product obtained through nitro-reduction reaction.
The synthesis of embodiment 12 glycidyl amine epoxy of skeleton containing phenolphthalein (TGPP) resin
By 0.05mol 3,3- bis- [4- (4- amino-benzene oxygens) phenyl] -3H- isobenzofuranones, 0.4mol epoxy chloropropionates Alkane, 50ml deionized waters and the mixture of 150ml ethanol and isopropanol add reactor, are reacted 6 hours under the conditions of 70 DEG C；Instead Should after be cooled to 40 DEG C, the aqueous solution for the potassium hydroxide that 60g mass percentage concentrations are 20% is added dropwise；Then after being warming up to 70 DEG C again Continue reaction 4 hours；After reaction terminates, reaction solution is poured into stirring and dissolving in 500ml dichloromethane, refilters removing chlorination Potassium, then by washing, standing, liquid separation, remove aqueous phase and retain organic phase mother liquor；Mother liquor heating, vacuum devolatilization, volatile matter are collected and followed Ring utilizes, and it is the glycidyl amine epoxy of skeleton containing phenolphthalein (TGPP) tree that residue, which is cooled to the transparent colorless solid of room temperature, Fat.Yield 84%.
3,3- bis- [4- (4- amino-benzene oxygens) the phenyl] -3H- isobenzofuranones are as phenol source and to chlorine using phenolphthalein Nitrobenzene passes through the dinitro compound of Williamson etherification reactions synthesis, then the product obtained through nitro-reduction reaction.
The synthesis of embodiment 13 glycidyl amine epoxy of skeleton containing phenolphthalein (TGPP) resin
By 0.05mol 3,3- bis- [4- (4- amino-benzene oxygens) phenyl] -3H- isobenzofuranones, 0.4mol epoxy chloropropionates Alkane, 50ml deionized waters and the mixture of 150ml methanol and isopropanol add reactor, are reacted 6 hours under the conditions of 70 DEG C；Instead Should after be cooled to 40 DEG C, the aqueous solution for the potassium hydroxide that 60g mass percentage concentrations are 20% is added dropwise；Then after being warming up to 70 DEG C again Continue reaction 4 hours；After reaction terminates, reaction solution is poured into stirring and dissolving in 500ml chloroforms, refilters removing potassium chloride, then By washing, standing, liquid separation, remove aqueous phase and retain organic phase mother liquor；Mother liquor heating, vacuum devolatilization, volatile matter collect circulation profit With it is the glycidyl amine epoxy of skeleton containing phenolphthalein (TGPP) resin that residue, which is cooled to the transparent colorless solid of room temperature,.Production Rate 80%.
3,3- bis- [4- (4- amino-benzene oxygens) the phenyl] -3H- isobenzofuranones are as phenol source and to chlorine using phenolphthalein Nitrobenzene passes through the dinitro compound of Williamson etherification reactions synthesis, then the product obtained through nitro-reduction reaction.
The synthesis of embodiment 14 glycidyl amine epoxy of skeleton containing phenolphthalein (TGPP) resin
By 0.05mol 3,3- bis- [4- (4- amino-benzene oxygens) phenyl] -3H- isobenzofuranones, 0.4mol epoxy chloropropionates Alkane, 50ml deionized waters and the mixture of 150ml methanol and ethanol add reactor, are reacted 6 hours under the conditions of 70 DEG C；Reaction After be cooled to 40 DEG C, the aqueous solution for the potassium hydroxide that 60g mass percentage concentrations are 20% is added dropwise；Then be warming up to again 70 DEG C it is follow-up Continuous reaction 4 hours；After reaction terminates, reaction solution is poured into stirring and dissolving in 500ml dichloromethane, refilters removing potassium chloride, Again by washing, standing, liquid separation, remove aqueous phase and retain organic phase mother liquor；Mother liquor heating, vacuum devolatilization, volatile matter collect circulation profit With it is the glycidyl amine epoxy of skeleton containing phenolphthalein (TGPP) resin that residue, which is cooled to the transparent colorless solid of room temperature,.Production Rate 82%.
3,3- bis- [4- (4- amino-benzene oxygens) the phenyl] -3H- isobenzofuranones are as phenol source and to chlorine using phenolphthalein Nitrobenzene passes through the dinitro compound of Williamson etherification reactions synthesis, then the product obtained through nitro-reduction reaction.
General principle, principal character and the advantages of the present invention of the present invention has been shown and described above.The technology of the industry Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the simply explanation described in above-described embodiment and specification is originally The principle of invention, various changes and modifications of the present invention are possible without departing from the spirit and scope of the present invention, these changes Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its Equivalent defines.

Claims (6)

  1. A kind of 1. glycidyl amine type epoxy resin of structure containing Cardo, it is characterised in that：The glycidic amine type of structure containing Cardo Epoxy resin has following molecular structural formula：
    X is in formulaR1And R2Respectively hydrogen atom, methyl or isopropyl.
  2. A kind of 2. method of the glycidyl amine type epoxy resin of structure containing Cardo prepared described in claim 1, it is characterised in that Comprise the following steps：
    Step 1：It is 1 by mol ratio：The aromatic diamine of structure containing Cardo and epoxychloropropane of (4~30), it is molten in water and alcohol Agent volume ratio is 1：The in the mixed solvent of (3~10) is reacted 4~9 hours at a temperature of 40~90 DEG C, wherein structure containing Cardo is fragrant Fragrant race's diamine and mixed solvent amount ratio are 1mol：(2~6) L；
    Step 2：Reaction is cooled to 30~40 DEG C, and it is water-soluble to add the alkali metal hydroxide that mass percentage concentration is 15~30% Liquid, wherein the mol ratio of the aromatic diamine of structure containing Cardo and alkali metal hydroxide is 1：(4~10)；Then heat up again Reacted 3~6 hours to 70~90 DEG C；
    Step 3：Reaction adds extractant after terminating, and is extracted, washed, liquid separation, removes aqueous phase and retains organic phase mother liquor；Mother liquor Heating, vacuum devolatilization, obtain the Cardo structure glycidyl amine type epoxy resins of water white transparency.
  3. 3. preparation method according to claim 2, it is characterised in that the fragrance of structure containing Cardo described in step 1 and step 2 Race's diamine be the dinitro compound synthesized by Williamson etherification reactions with phenolphthalein, bisphenol fluorene and parachloronitrobenzene again The product obtained through nitro-reduction reaction.
  4. 4. preparation method according to claim 2, it is characterised in that the alcoholic solvent described in step 1 is methanol, ethanol, isopropyl Mixture more than one or both of alcohol, n-butanol.
  5. 5. preparation method according to claim 2, it is characterised in that the alkali metal hydroxide described in step 2 is hydroxide Sodium, potassium hydroxide, lithium hydroxide.
  6. 6. preparation method according to claim 2, it is characterised in that the extractant described in step 3 is toluene, dimethylbenzene, two Chloromethanes, chloroform.
CN201610266115.4A 2016-04-26 2016-04-26 Glycidyl amine type epoxy resin of structure containing Cardo and preparation method thereof Active CN105860030B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610266115.4A CN105860030B (en) 2016-04-26 2016-04-26 Glycidyl amine type epoxy resin of structure containing Cardo and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610266115.4A CN105860030B (en) 2016-04-26 2016-04-26 Glycidyl amine type epoxy resin of structure containing Cardo and preparation method thereof

Publications (2)

Publication Number Publication Date
CN105860030A CN105860030A (en) 2016-08-17
CN105860030B true CN105860030B (en) 2018-03-16

Family

ID=56628451

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610266115.4A Active CN105860030B (en) 2016-04-26 2016-04-26 Glycidyl amine type epoxy resin of structure containing Cardo and preparation method thereof

Country Status (1)

Country Link
CN (1) CN105860030B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106905529A (en) * 2017-03-17 2017-06-30 大连理工大学 Cyano-containing and fluorenyl bimaleimide resin and preparation method thereof
EP3563927A1 (en) * 2018-04-30 2019-11-06 Hexion Research Belgium SA Purification of high performance epoxy resins via membrane filtration technology
CN110845704A (en) * 2019-11-07 2020-02-28 江苏泰特尔新材料科技有限公司 Preparation process of high-temperature-resistant glycidylamine epoxy resin
CN112694714B (en) * 2020-12-18 2023-01-06 广东盈骅新材料科技有限公司 Epoxy resin composition, prepreg, laminate, and printed wiring board
CN113045516B (en) * 2021-05-18 2023-03-24 湖南大学 Preparation method of tetra-functional epoxy resin containing fluorene structure
CN115448898A (en) * 2022-09-26 2022-12-09 常州大学 Aromatic diamine monomer simultaneously containing phenolphthalein Cardo and alkyl structure and preparation method and application of polyimide thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1900135A (en) * 2006-07-06 2007-01-24 东华大学 Process for preparing glycidic amine type polyfunctional epoxy resin
CN104877109A (en) * 2015-05-08 2015-09-02 华东理工大学 Tetra-(3-ethynylaniline)-based silane-modified TGDDM/DDS (tetraglycidyl 4,4'-diaminodiphenyl methane/4,4'-diaminodiphenyl sulfone) system and preparation method thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0241312A (en) * 1988-07-29 1990-02-09 Dainippon Ink & Chem Inc Epoxy resin composition
JP5857844B2 (en) * 2012-03-29 2016-02-10 ナガセケムテックス株式会社 Epoxy compound

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1900135A (en) * 2006-07-06 2007-01-24 东华大学 Process for preparing glycidic amine type polyfunctional epoxy resin
CN104877109A (en) * 2015-05-08 2015-09-02 华东理工大学 Tetra-(3-ethynylaniline)-based silane-modified TGDDM/DDS (tetraglycidyl 4,4'-diaminodiphenyl methane/4,4'-diaminodiphenyl sulfone) system and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"芴基环氧树脂的合成及扩链改性研究";李国兵;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20130615;第B016-155页 *

Also Published As

Publication number Publication date
CN105860030A (en) 2016-08-17

Similar Documents

Publication Publication Date Title
CN105860030B (en) Glycidyl amine type epoxy resin of structure containing Cardo and preparation method thereof
CN101348560B (en) Epoxide resin containing furan group and preparation thereof
CN103724575B (en) A kind of preparation method of phosphorous bisphenol A phenolic resin
CN105254528B (en) Synthesis of diamine monomer with azo and polyimide prepared from diamine monomer
CN104016870B (en) One contains meta-terphenyl structure diamine compound and synthetic method thereof and application
CN104212394A (en) Room-temperature curing epoxy resin adhesive and preparation method thereof
CN109734684A (en) A kind of biology base fire retarding epoxide resin presoma and its preparation method and application based on natural phenolic monomer
CN102250318B (en) Full-rosinyl epoxy resin composite and condensate thereof
CN110028652A (en) A kind of high purity epoxy resins and preparation method thereof containing biphenyl structural
CN103435504B (en) A kind of preparation method of degradable primary amine curing agent
CN104530387B (en) Liquid crystal epoxy resin as well as preparation method and application thereof
CN110240692B (en) Bio-based flame-retardant furan epoxy resin and preparation method thereof
CN104672431B (en) A kind of tetra functional epoxy resin and preparation method and application
US4861810A (en) Resin materials based on amines
CN108863988B (en) Sulfone group-containing four-functional epoxy, and preparation method and application thereof
CN101962372A (en) Biphenyl-containing compound liquid crystal epoxy resin and preparation method thereof
EP4148047A1 (en) Epoxy resin
CN102585210A (en) Phenolphthalein polyaryletherketone and preparation method thereof
CN104497270B (en) Side base substituted biphenyl type shape memory epoxy resin by using liquid crystal and preparation method thereof and application
CN104163912B (en) A kind of dual-network cross-linking type epoxy resin and preparation method thereof
CN115160540A (en) High-modulus high-activity epoxy resin and synthesis method and application thereof
CN110078715A (en) A kind of flame-resistant high-temperature-resistant contains two degree of functionality epoxy resin of Phthalazinone and synthetic method
CN105153407B (en) A kind of thermosetting rosin resin compositions and preparation method thereof
Li et al. Synthesis, characterization, and properties of a polyhedral oligomeric octadiphenylsulfonylsilsesquioxane
CN106008917A (en) Method for preparation of heat-resistant epoxy resin with lignin

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant