CN109503520A - 5- aldehyde radical resorcinolformaldehyde resin and preparation method thereof - Google Patents
5- aldehyde radical resorcinolformaldehyde resin and preparation method thereof Download PDFInfo
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- CN109503520A CN109503520A CN201811635852.2A CN201811635852A CN109503520A CN 109503520 A CN109503520 A CN 109503520A CN 201811635852 A CN201811635852 A CN 201811635852A CN 109503520 A CN109503520 A CN 109503520A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
- C07D301/28—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms by reaction with hydroxyl radicals
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- 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
- C07D303/30—Ethers of oxirane-containing polyhydroxy compounds in which all hydroxyl radicals are etherified with oxirane-containing hydroxy compounds
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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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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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Abstract
5- aldehyde radical resorcinolformaldehyde resin and preparation method thereof is related to a kind of glycerin ether and preparation method thereof.It is that solve the problems, such as that existing tetraglycidel ether epoxy resin deposits adhesive strength at high temperature poor.3,5- 4-dihydroxy benzaldehyde, epoxy bromopropane and catalyst: one, being put into reaction kettle by the preparation method of 5- aldehyde radical resorcinolformaldehyde resin, and temperature reaction, decompression steams, and obtains concentrate；Two, after solution to be concentrated temperature is cooling, organic solvent and metal base solid particle, stirring is added；Three, to after reaction, be washed repeatedly with water, liquid separation removes water phase, is finally evaporated under reduced pressure organic phase and removes organic solvent, and recycling obtains 5- aldehyde radical resorcinolformaldehyde resin.5- aldehyde radical resorcinolformaldehyde resin is used to prepare thermostable epoxy resin adhesive.The epoxyn of 5- aldehyde radical resorcinolformaldehyde resin preparation of the invention has characteristic resistant to high temperature.The present invention is used for epoxyn field.
Description
Technical field
The present invention relates to a kind of glycerin ethers and preparation method thereof.
Background technique
Epoxy resin refers to compound in the molecular structure containing two or more epoxy groups.This resinoid tool
There are excellent physical mechanical property, chemical stability, corrosion resistance, heat-resisting and adhesive property, is widely used to aviation, boat
It, the fields such as chemical industry, machinery, electronics, automobile, play an important role to the national economic development.
Traditional tetraglycidel ether epoxy resin has excellent mechanical property and processing performance, and be widely used aerospace
Equal fields.Bis-phenol A glycidyl ether is the based epoxy resin that current dosage is maximum, application range is most wide, in practical applications
Temperature resistant grade shows slightly insufficient, is also easy to produce with the solidification of other resin alloys and mutually separates, to influence the comprehensive performance of material.Cause
This existing tetraglycidel ether epoxy resin deposits the poor problem of adhesive strength at high temperature.
Summary of the invention
The present invention is to solve existing tetraglycidel ether epoxy resins to deposit the poor problem of adhesive strength at high temperature, provides
5- aldehyde radical resorcinolformaldehyde resin and preparation method thereof.
The molecular structural formula of 5- aldehyde radical resorcinolformaldehyde resin of the present invention are as follows:
The preparation method of above-mentioned 5- aldehyde radical resorcinolformaldehyde resin, comprising the following steps:
One, 3,5- 4-dihydroxy benzaldehyde, epoxy bromopropane and catalyst are put into reaction kettle, are warming up to 80 DEG C~100
It is stirred to react 2h~8h after DEG C, then heats to reflux temperature and steams the decompression of excessive epoxy bromopropane, recycle,
Obtain concentrate；Wherein the molar ratio of 3,5- 4-dihydroxy benzaldehyde and epoxy bromopropane is 1:(6~20), 3,5- dihydroxy benzenes first
The mass ratio of aldehyde and catalyst is 100:(0.1~5)；
Two, after solution to be concentrated temperature is cooled to 40 DEG C~60 DEG C, organic solvent and metal base solid particle is added, continues to stir
Mix 2h~6h；Wherein the mass ratio of 3,5- 4-dihydroxy benzaldehyde and organic solvent is 1:(10~25), 3,5- 4-dihydroxy benzaldehydes
Molar ratio with metal base solid particle is 1:(1.5~5)；
Three, to after reaction, be washed repeatedly with water 3~5 times, liquid separation removes water phase, is finally evaporated under reduced pressure organic phase
Organic solvent is removed, recycling obtains 5- aldehyde radical resorcinolformaldehyde resin.
Further, the catalyst is benzyltriethylammoinium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, four fourths
Base ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, 18- hat
The mixture of one or more of ether -6,15- crown ether -5.
Further, the organic solvent is the mixture of one or more of benzene,toluene,xylene, chlorobenzene.
Further, the metal base solid particle is one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide
Mixture.
Further, the partial size of the metal base solid particle is 80~100.
The present invention also provides 5- aldehyde radical resorcinolformaldehyde resins in preparing thermostable epoxy resin adhesive
Application.
The 5- aldehyde radical resorcinolformaldehyde resin prepares thermostable epoxy resin adhesive method particularly includes:
By mass fraction weigh 100 parts 5- aldehyde radical resorcinolformaldehyde resin, CTBN and 0.3 of 5 parts part recessed
Convex stick stone；
CTBN and attapulgite are added in 5- aldehyde radical resorcinolformaldehyde resin, is added further according to stoichiometric ratio
4,4 '-diaminodiphenylmethane curing agent simultaneously stir evenly, and thermostable epoxy resin adhesive is prepared.
Further, the solidification temperature of the thermostable epoxy resin adhesive is 120 DEG C, curing time 3h.
Beneficial effects of the present invention:
Reaction condition of the present invention is mild, easy to operate, a large amount of organic solvent is not necessarily to, without thin-layer chromatography and column chromatography
Further refined product, so that it may obtain the relatively narrow product of molecular weight distribution.The molecular weight distribution of product is 1.03~1.13.
Two epoxy groups in material molecular structure of the invention are symmetrically distributed in the meta position of aldehyde radical, not by aldehyde radical steric hindrance
Effects have higher reactivity, and the resin network compact structure after solidify, with better heat resistance.
By cured dose of 5- aldehyde radical resorcinolformaldehyde resin solidification of the invention, cured product is obtained, then carry out air and nitrogen
Thermogravimetric analysis under atmosphere is enclosed is tested, and 5% mass-heat weightless temperature of the cured product under air and nitrogen is respectively 293.2 DEG C
It is respectively 0.86% and 56.7% with the carbon yield at 295.4 DEG C, corresponding 800 DEG C, there is preferable heat resistance.
Have with epoxyn prepared by 5- aldehyde radical resorcinolformaldehyde resin of the invention resistant to high temperature
Characteristic, the epoxyn are bonded 2024-T3 aluminium alloy plates after 120 DEG C, 3h solidification, after tested, room temperature
Lower shear strength is 27.2MPa, and shear strength is 21.4MPa at 120 DEG C, and shear strength is 6.2MPa, 90 DEG C of removings at 200 DEG C
Intensity is 3.8KN/m；The epoxyn is 23.5MPa to the adhesive shear strength room temperature of 45# steel plate, and 200 DEG C of whens are
5.4MPa。
Contain aldehyde radical in material molecular structure of the invention, can occur with the groups such as amino, alcohol, phenol chemical reaction or
Self-condensation.More crosslinking points can be formed by using as epoxy resin, so that temperature resistant grade and glass transition temperature are improved, and
Resin itself also has preferable mobility and processing performance.Substance of the invention can be also used for reaction intermediate, prepare it
Its high-performance polymer.
5- aldehyde radical resorcinolformaldehyde resin appearance of the present invention is mobility liquid, is used as epoxy resin-base
When can be solidified with fatty amine, aromatic amine, imidazoles and acid anhydrides, can also be with other heat containing groups such as amino, alcohol, phenol
Thermosetting resin, thermoplastic resin and rubber are blended to use, and can be also used for preparing high-temperature resistance adhesive.
Detailed description of the invention
Fig. 1 is the infrared spectrum of 5- aldehyde radical resorcinolformaldehyde resin.
Specific embodiment
The technical solution of the present invention is not limited to the following list, further includes between each specific embodiment
Any combination.
Specific embodiment 1: the molecular structural formula of present embodiment 5- aldehyde radical resorcinolformaldehyde resin are as follows:
Specific embodiment 2: the preparation method of present embodiment 5- aldehyde radical resorcinolformaldehyde resin, including with
Lower step:
One, 3,5- 4-dihydroxy benzaldehyde, epoxy bromopropane and catalyst are put into reaction kettle, are warming up to 80 DEG C~100
It is stirred to react 2h~8h after DEG C, then heats to reflux temperature and steams the decompression of excessive epoxy bromopropane, recycle,
Obtain concentrate；Wherein the molar ratio of 3,5- 4-dihydroxy benzaldehyde and epoxy bromopropane is 1:(6~20), 3,5- dihydroxy benzenes first
The mass ratio of aldehyde and catalyst is 100:(0.1~5)；
Two, after solution to be concentrated temperature is cooled to 40 DEG C~60 DEG C, organic solvent and metal base solid particle is added, continues to stir
Mix 2h~6h；Wherein the mass ratio of 3,5- 4-dihydroxy benzaldehyde and organic solvent is 1:(10~25), 3,5- 4-dihydroxy benzaldehydes
Molar ratio with metal base solid particle is 1:(1.5~5)；
Three, to after reaction, be washed repeatedly with water 3~5 times, liquid separation removes water phase, is finally evaporated under reduced pressure organic phase
Organic solvent is removed, recycling obtains 5- aldehyde radical resorcinolformaldehyde resin.
Specific embodiment 3: the present embodiment is different from the first embodiment in that: the catalyst is benzyl three
Ethyl ammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, dodecyl
The mixture of one or more of trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, 18- crown ether -6,15- crown ether -5.
It is other same as the specific embodiment one.
Specific embodiment 4: the present embodiment is different from the first embodiment in that: the organic solvent is benzene, first
The mixture of one or more of benzene, dimethylbenzene, chlorobenzene.It is other same as the specific embodiment one.
Specific embodiment 5: the present embodiment is different from the first embodiment in that: the metal base solid particle
For the mixture of one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide.It is other same as the specific embodiment one.
Specific embodiment 6: the present embodiment is different from the first embodiment in that: the metal base solid particle
Partial size be 80~100.It is other same as the specific embodiment one.
Specific embodiment 7: the present embodiment is different from the first embodiment in that: 3,5- dihydroxy in step 1
The molar ratio of benzaldehyde and epoxy bromopropane is 1:(10~15).It is other same as the specific embodiment one.
Specific embodiment 8: the present embodiment is different from the first embodiment in that: 3,5- dihydroxy in step 1
The mass ratio of benzaldehyde and catalyst is 100:(0.5~4).It is other same as the specific embodiment one.
Specific embodiment 9: the present embodiment is different from the first embodiment in that: 3,5- dihydroxy in step 1
The mass ratio of benzaldehyde and catalyst is 100:(1~3).It is other same as the specific embodiment one.
Specific embodiment 10: the present embodiment is different from the first embodiment in that: 3,5- dihydroxy in step 2
The mass ratio of benzaldehyde and organic solvent is 1:(15~20).It is other same as the specific embodiment one.
Specific embodiment 11: the present embodiment is different from the first embodiment in that: 3,5- dihydroxy in step 2
The molar ratio of benzaldehyde and metal base solid particle is 1:(2~4).It is other same as the specific embodiment one.
Specific embodiment 12: present embodiment 5- aldehyde radical resorcinolformaldehyde resin is preparing fire resistant epoxy
Application in resin adhesive.
Specific embodiment 13: present embodiment is unlike specific embodiment 12: the 5- aldehyde radical isophthalic
Diphenol diglycidyl ether prepares thermostable epoxy resin adhesive method particularly includes:
By mass fraction weigh 100 parts 5- aldehyde radical resorcinolformaldehyde resin, CTBN and 0.3 of 5 parts part recessed
Convex stick stone；
CTBN and attapulgite are added in 5- aldehyde radical resorcinolformaldehyde resin, is added further according to stoichiometric ratio
4,4 '-diaminodiphenylmethane curing agent simultaneously stir evenly, and thermostable epoxy resin adhesive is prepared.Other and specific reality
It is identical to apply mode 12.
Specific embodiment 14: present embodiment is unlike specific embodiment 12 or 13: the resistance to height
The solidification temperature of temperature epoxy resin adhesive is 120 DEG C, curing time 3h.Other and specific embodiment 12 or ten three-phases
Together.
Elaborate below to the embodiment of the present invention, following embodiment under the premise of the technical scheme of the present invention into
Row is implemented, and gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following realities
Apply example.
Embodiment 1:
The preparation method of the present embodiment 5- aldehyde radical resorcinolformaldehyde resin, comprising the following steps:
One, 134 grams of 3,5- 4-dihydroxy benzaldehydes, 822 grams of epoxy bromopropanes and 0.69 gram of benzyltriethylammoinium chloride are put
Enter in 3L reaction kettle, stirs 4.5h after being warming up to 85 DEG C.It is warming up to reflux temperature to steam the decompression of excessive epoxy bromopropane, return
Receipts recycle, and obtain concentrate.
Two, after then concentrate being made to be cooled to 40 DEG C, 1760 grams of toluene and 112 grams of potassium hydroxide solid particles are added, after
Continuous stirring 2h.
Three, water phase is removed to after reaction, wash 3 liquid separations repeatedly with water, finally organic phase is evaporated under reduced pressure and is removed
Organic solvent, recycling, obtains brown liquid 5- aldehyde radical resorcinolformaldehyde resin, according to hydrochloric acid-acetone method
Measuring epoxide number is 0.72.Number-average molecular weight is 246, molecular weight distribution 1.08.
Infrared spectrum such as Fig. 1 of 5- aldehyde radical resorcinolformaldehyde resin manufactured in the present embodiment.2930cm-1Characteristic peak
Belong to methylene (- CH2) stretching vibration.1701cm-1Belong to aldehyde radical (C=O) characteristic peak.1055cm-1And 1172cm-1Place
Characteristic peak belongs to C-O-C group.910cm-1Illustrate the presence of epoxy group.
4,4 '-diaminodiphenylmethane curing agent are added according to stoichiometric ratio in the product of the present embodiment, through 120 DEG C,
3h solidifies to obtain cured product.The thermogravimetric analysis test under air and nitrogen atmosphere is carried out respectively, and heating rate is 10 DEG C/min.It surveys
Test result shows that the 5% mass-heat weightless temperature under air and nitrogen is respectively 293.2 DEG C and 295.4 DEG C, corresponds to 800 DEG C
Under carbon yield be respectively 0.86% and 56.7%, it is preferable to illustrate that 5- aldehyde radical resorcinolformaldehyde resin of the invention has
Heat resistance.
The molecular structural formula of 5- aldehyde radical resorcinolformaldehyde resin manufactured in the present embodiment are as follows:
Embodiment 2:
The preparation method of the present embodiment 5- aldehyde radical resorcinolformaldehyde resin, comprising the following steps:
One, 168 grams of 3,5- 4-dihydroxy benzaldehydes, 1337 grams of epoxy bromopropanes and 2.06 grams of tetrabutylammonium bromide are put into 3L
In reaction kettle, 3h is stirred after being warming up to 90 DEG C.It is warming up to reflux temperature to steam the decompression of excessive epoxy bromopropane, recycling circulation
It utilizes, obtains concentrate.
Two, after then concentrate being made to be cooled to 45 DEG C, 980 grams of toluene, 1200 grams of dimethylbenzene and 148 grams of sodium hydroxides are added
Solid particle continues to stir 4h.
Three, water phase is removed to after reaction, wash 3 liquid separations repeatedly with water, finally organic phase is evaporated under reduced pressure and is removed
Organic solvent, recycling, obtains brown liquid 5- aldehyde radical resorcinolformaldehyde resin, according to hydrochloric acid-acetone method
Measuring epoxide number is 0.68.Number-average molecular weight is 269, molecular weight distribution 1.13.
The molecular structural formula of 5- aldehyde radical resorcinolformaldehyde resin manufactured in the present embodiment are as follows:
Embodiment 3:
The preparation method of the present embodiment 5- aldehyde radical resorcinolformaldehyde resin, comprising the following steps:
By 121 grams of 3,5- 4-dihydroxy benzaldehydes, 2040 grams of epoxy bromopropanes, 1.62 grams of 4-butyl ammonium hydrogen sulfates and 1.39 grams
Tetradecyl trimethyl ammonium chloride is put into 3L reaction kettle, stirs 6h after being warming up to 82 DEG C.Being warming up to reflux temperature will be excessive
Epoxy bromopropane decompression steams, and recycles, obtains concentrate.
Two, after then concentrate being made to be cooled to 55 DEG C, 760 grams of benzene, 1350 grams of dimethylbenzene, 470 gram chlorobenzenes and 182 grams are added
Potassium hydroxide solid particle continues to stir 3.5h.
Three, water phase is removed to after reaction, wash 3 liquid separations repeatedly with water, finally organic phase is evaporated under reduced pressure and is removed
Organic solvent, recycling, obtains brown liquid 5- aldehyde radical resorcinolformaldehyde resin, according to hydrochloric acid-acetone method
Measuring epoxide number is 0.75.Number-average molecular weight is 248, molecular weight distribution 1.03.
The molecular structural formula of 5- aldehyde radical resorcinolformaldehyde resin manufactured in the present embodiment are as follows:
Embodiment 4:
The preparation method of the present embodiment 5- aldehyde radical resorcinolformaldehyde resin, comprising the following steps:
One, by 185 grams of 3,5- 4-dihydroxy benzaldehydes, 1641 grams of epoxy bromopropanes, 3.44 grams of tetrabutylammonium chlorides and 1.29
Gram tri-n-octyl methyl ammonium chloride is put into 3L reaction kettle, stirs 2h after being warming up to 95 DEG C.Reflux temperature is warming up to by excessive ring
The decompression of oxygen N-Propyl Bromide steams, and recycles, obtains concentrate.
Two, after then concentrate being made to be cooled to 53 DEG C, 2540 grams of dimethylbenzene, 24 grams of lithium hydroxides and 79 grams of hydroxides are added
Sodium solid particle continues to stir 5.5h.
Three, water phase is removed to after reaction, wash 3 liquid separations repeatedly with water, finally organic phase is evaporated under reduced pressure and is removed
Organic solvent, recycling, obtains brown liquid 5- aldehyde radical resorcinolformaldehyde resin, according to hydrochloric acid-acetone method
Measuring epoxide number is 0.71.Number-average molecular weight is 255, molecular weight distribution 1.09.
The molecular structural formula of 5- aldehyde radical resorcinolformaldehyde resin manufactured in the present embodiment are as follows:
Embodiment 5:
The preparation method of the present embodiment 5- aldehyde radical resorcinolformaldehyde resin, comprising the following steps:
One, by 185 grams of 3,5- 4-dihydroxy benzaldehydes, 1641 grams of epoxy bromopropanes, 3.44 grams of trimethyl chlorinations
Ammonium and 2.02 grams of 15- crown ethers -5 are put into 3L reaction kettle, stir 2h after being warming up to 100 DEG C.Being warming up to reflux temperature will be excessive
Epoxy bromopropane decompression steams, and recycles, obtains concentrate.
Two, after being subsequently cooled to 53 DEG C, 2540 grams of dimethylbenzene and 64 grams of lithium hydroxide solid particles is added, continue to stir
6h。
Three, water phase is removed to after reaction, wash 3 liquid separations repeatedly with water, finally organic phase is evaporated under reduced pressure and is removed
Organic solvent, recycling, obtains brown liquid 5- aldehyde radical resorcinolformaldehyde resin, according to hydrochloric acid-acetone method
Measuring epoxide number is 0.69.Number-average molecular weight is 265, molecular weight distribution 1.12.
The molecular structural formula of 5- aldehyde radical resorcinolformaldehyde resin manufactured in the present embodiment are as follows:
Embodiment 6:
The preparation method of the present embodiment 5- aldehyde radical resorcinolformaldehyde resin, comprising the following steps:
One, 167 grams of 3,5- 4-dihydroxy benzaldehydes, 1855 grams of epoxy bromopropanes, 5.72 grams of 18- crown ethers -6 are put into 3L reaction
In kettle, 8h is stirred after being warming up to 80 DEG C.It is warming up to reflux temperature to steam the decompression of excessive epoxy bromopropane, recycling circulation benefit
With obtaining concentrate.
Two, after being subsequently cooled to 45 DEG C, 1120 grams of toluene, 2540 grams of dimethylbenzene and 174 grams of sodium hydrate solids are added
Grain continues to stir 5h.
Three, water phase is removed to after reaction, wash 3 liquid separations repeatedly with water, finally organic phase is evaporated under reduced pressure and is removed
Organic solvent, recycling, obtains brown liquid 5- aldehyde radical resorcinolformaldehyde resin, according to hydrochloric acid-acetone method
Measuring epoxide number is 0.74.Number-average molecular weight is 250, molecular weight distribution 1.05.
The molecular structural formula of 5- aldehyde radical resorcinolformaldehyde resin manufactured in the present embodiment are as follows:
Comparative experiments:
In order to compare from architectural difference, this comparative example has synthesized 4- aldehyde radical resorcinolformaldehyde resin, tool
Steps are as follows for body:
By 121 grams of 2,4- 4-dihydroxy benzaldehydes, 2040 grams of epoxy bromopropanes, 1.62 grams of 4-butyl ammonium hydrogen sulfates and 1.39 grams
Tetradecyl trimethyl ammonium chloride is put into 3L reaction kettle, stirs 6h after being warming up to 82 DEG C.Being warming up to reflux temperature will be excessive
Epoxy bromopropane decompression steams, and recycles, obtains concentrate.After being subsequently cooled to 55 DEG C, 760 grams of benzene, 1350 are added
Gram dimethylbenzene, 470 gram chlorobenzenes and 182 grams of potassium hydroxide solid particles continue to stir 3.5h.To after reaction, repeatedly with water
It washs 3 liquid separations and removes water phase, finally organic phase is evaporated under reduced pressure and removes organic solvent, recycling obtains brown liquid
Body 4- aldehyde radical resorcinolformaldehyde resin, measuring epoxide number according to hydrochloric acid-acetone method is 0.76, number-average molecular weight 251,
Molecular weight distribution is 1.02, and molecular formula is as follows.
The product property of product and embodiment 3 that comparative experiments obtains is compared.Respectively according to stoichiometric ratio
4,4 '-diaminodiphenylmethane curing agent are added, through 120 DEG C, 3h solidifies to obtain cured product.Air and nitrogen atmosphere are carried out respectively
Under thermogravimetric analysis test, heating rate be 10 DEG C/min.
5% mass-heat weightless temperature of the cured product of comparative experiments under air and nitrogen be respectively 285.3 DEG C and
285.1 DEG C, the carbon yield corresponded at 800 DEG C is respectively 0.12% and 50.7%.
And 5% mass-heat weightless temperature of 3 cured product of embodiment under air and nitrogen be respectively 293.2 DEG C and
295.4 DEG C, the carbon yield corresponded at 800 DEG C is respectively 0.86% and 56.7%, illustrates 5- aldehyde radical resorcinol two of the invention
Glycidol ether has better heat resistance.
Embodiment 7:
Thermostable epoxy resin adhesive is prepared with 5- aldehyde radical resorcinolformaldehyde resin prepared by embodiment 2.
The 5- aldehyde radical resorcinolformaldehyde resin prepares thermostable epoxy resin adhesive method particularly includes:
By mass fraction weigh 100 parts 5- aldehyde radical resorcinolformaldehyde resin, CTBN and 0.3 of 5 parts part recessed
Convex stick stone；
CTBN and attapulgite are added in 5- aldehyde radical resorcinolformaldehyde resin, is added further according to stoichiometric ratio
4,4 '-diaminodiphenylmethane curing agent simultaneously stir evenly, and thermostable epoxy resin adhesive is prepared.
By thermostable epoxy resin adhesive in 120 DEG C of solidification 3h, bonding test is carried out to 2024-T3 aluminium alloy plates.
As a result are as follows: shear strength is 27.2MPa under room temperature, and shear strength is 21.4MPa at 120 DEG C, and shearing is strong at 200 DEG C
Degree is 6.2MPa, and 90 DEG C of peel strengths are 3.8KN/m；Adhesive shear strength room temperature of the epoxyn to 45# steel plate
For 23.5MPa, 200 DEG C of whens are 5.4MPa.
Claims (10)
1.5- aldehyde radical resorcinolformaldehyde resin, it is characterised in that the molecule knot of 5- aldehyde radical resorcinolformaldehyde resin
Structure formula are as follows:
2. the preparation method of 5- aldehyde radical resorcinolformaldehyde resin described in claim 1, it is characterised in that this method includes
Following steps:
One, 3,5- 4-dihydroxy benzaldehyde, epoxy bromopropane and catalyst are put into reaction kettle, after being warming up to 80 DEG C~100 DEG C
It is stirred to react 2h~8h, reflux temperature is then heated to and steams the decompression of excessive epoxy bromopropane, recycle, obtain
Concentrate；Wherein the molar ratio of 3,5- 4-dihydroxy benzaldehyde and epoxy bromopropane be 1:(6~20), 3,5- 4-dihydroxy benzaldehydes and
The mass ratio of catalyst is 100:(0.1~5)；
Two, after solution to be concentrated temperature is cooled to 40 DEG C~60 DEG C, organic solvent and metal base solid particle is added, continues to stir 2h
~6h；Wherein the mass ratio of 3,5- 4-dihydroxy benzaldehyde and organic solvent is 1:(10~25), 3,5- 4-dihydroxy benzaldehydes and gold
The molar ratio for belonging to alkali solid particle is 1:(1.5~5)；
Three, to after reaction, be washed repeatedly with water 3~5 times, liquid separation removes water phase, is finally evaporated under reduced pressure organic phase and removes
Organic solvent, recycling, obtains 5- aldehyde radical resorcinolformaldehyde resin.
3. the preparation method of 5- aldehyde radical resorcinolformaldehyde resin according to claim 2, it is characterised in that described
Catalyst is benzyltriethylammoinium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tricaprylmethyl
One of ammonium chloride, dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, 18- crown ether -6,15- crown ether -5
Or several mixture.
4. the preparation method of 5- aldehyde radical resorcinolformaldehyde resin according to claim 2, it is characterised in that described
Organic solvent is the mixture of one or more of benzene,toluene,xylene, chlorobenzene.
5. the preparation method of 5- aldehyde radical resorcinolformaldehyde resin according to claim 2, it is characterised in that described
Metal base solid particle is the mixture of one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide.
6. the preparation method of 5- aldehyde radical resorcinolformaldehyde resin according to claim 2, it is characterised in that step
The molar ratio of 3,5- 4-dihydroxy benzaldehyde and epoxy bromopropane is 1:(10~15 in one).
7. the preparation method of 5- aldehyde radical resorcinolformaldehyde resin according to claim 2, it is characterised in that step
The mass ratio of 3,5- 4-dihydroxy benzaldehyde and catalyst is 100:(0.5~4 in one).
8. 5- aldehyde radical resorcinolformaldehyde resin described in claim 1 is in preparing thermostable epoxy resin adhesive
Using.
9. application according to claim 8, it is characterised in that the thermostable epoxy resin adhesive the preparation method comprises the following steps:
100 parts of 5- aldehyde radical resorcinolformaldehyde resin, CTBN and 0.3 of 5 parts part of concave convex rod are weighed by mass fraction
Stone；
CTBN and attapulgite are added in 5- aldehyde radical resorcinolformaldehyde resin, is added 4 further according to stoichiometric ratio,
4 '-diaminodiphenylmethane curing agent simultaneously stir evenly, and thermostable epoxy resin adhesive is prepared.
10. application according to claim 9, it is characterised in that the solidification temperature of the thermostable epoxy resin adhesive is
120 DEG C, curing time 3h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113024487A (en) * | 2021-03-12 | 2021-06-25 | 哈尔滨商业大学 | Barley malt base glycidyl ether and preparation method and application thereof |
| CN115466372A (en) * | 2022-09-27 | 2022-12-13 | 华南理工大学 | Epoxy resin prepolymer containing aldehyde group, preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3925315A (en) * | 1974-09-20 | 1975-12-09 | Us Army | Diglycidyl ether of 4-methylol resorcinol |
-
2018
- 2018-12-29 CN CN201811635852.2A patent/CN109503520B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3925315A (en) * | 1974-09-20 | 1975-12-09 | Us Army | Diglycidyl ether of 4-methylol resorcinol |
Non-Patent Citations (2)
| Title |
|---|
| 彭小平: "间苯二酚二缩水甘油醚的制备", 《中国环氧树脂应用技术学会"第十五次全国环氧树脂应用技术学术交流会"论文集》 * |
| 袁慧五等: "间苯二酚二缩水甘油醚的制备及其应用", 《热固性树脂》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113024487A (en) * | 2021-03-12 | 2021-06-25 | 哈尔滨商业大学 | Barley malt base glycidyl ether and preparation method and application thereof |
| CN113024487B (en) * | 2021-03-12 | 2023-01-17 | 哈尔滨商业大学 | Barley malt base glycidyl ether and preparation method and application thereof |
| CN115466372A (en) * | 2022-09-27 | 2022-12-13 | 华南理工大学 | Epoxy resin prepolymer containing aldehyde group, preparation method and application thereof |
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