CN107573470A - A kind of modified thermosetting phenolic resin and preparation method thereof - Google Patents
A kind of modified thermosetting phenolic resin and preparation method thereof Download PDFInfo
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- CN107573470A CN107573470A CN201710842775.7A CN201710842775A CN107573470A CN 107573470 A CN107573470 A CN 107573470A CN 201710842775 A CN201710842775 A CN 201710842775A CN 107573470 A CN107573470 A CN 107573470A
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Abstract
The present invention relates to 4, 5 7-oxa-bicyclo[4.1.0s 1, 2 dicarboxylic acid diglycidyl ester modified thermosetting phenolic resins and preparation method thereof, the phenolic resin is according to quality parts ratio, reactant includes 200~300 mass parts phenol, 200~300 mass parts formalins, 150~250 mass parts 4, 5 7-oxa-bicyclo[4.1.0s 1, 2 dicarboxylic acid diglycidyl esters, 10~50 mass parts o-phenyl phenols, the orthoresol of 10~50 mass parts, and add the catalysis of 2~20 mass parts ammonia spirits and be prepared, the present invention solves the problems, such as that Bakeland is porous to a certain extent, improve the mechanical property of phenolic resin.
Description
Technical field
The present invention relates to a kind of 4,5- 7-oxa-bicyclo[4.1.0s -1,2- dicarboxylic acid diglycidyl ester modified thermosetting phenolic resins
And preparation method thereof, belong to polymer matrix composites technical field.
Background technology
Phenolic resin be widely used in because of its excellent heat-resistant stability, processing performance, fire resistance Aeronautics and Astronautics,
The fields such as building, auto industry.But due to the curing mechanism of phenolic resin is between methylol, on methylol and phenyl ring it is living
The dehydration condensation between hydrogen atom is sprinkled, causes phenolic resin inevitably to produce a large amount of small molecules in the curing process
Water, cause product porous；In addition, agent structure, which is the mode that phenol ring-methylene is connected, make it that phenolic resin chemical constitution is in
Rigidity, steric hindrance is big, can reactive functionality it is limited, can not form larger sized corsslinking molecular in resin solidification hot stage
Structure, reached the resin mechanical property upper limit, caused the phenolic resin after solidification crisp and mechanical property is poor, it is impossible to meet with
Phenolic resin is the mechanical property requirements of high temperature resistant composite product made of matrix.
The content of the invention
The technology of the present invention solves problem：Overcome the deficiencies in the prior art, propose one kind 4,5- 7-oxa-bicyclo[4.1.0s -1,2-
Dicarboxylic acid diglycidyl ester modified thermosetting phenolic resin and preparation method thereof.
The present invention technical solution be：
One kind 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl ester modified thermosetting phenolic resins, modification heat
The raw material of solidity phenolic resin includes 200~300 mass parts phenol, 200~300 mass parts formalins, 150~250 mass
Part 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl ester, 10~50 mass parts o-phenyl phenols, 10~50 mass parts
Orthoresol and 2~20 mass parts ammonia spirits；
Preferred embodiment is：Raw material include 210~280 mass parts phenol, 210~280 mass parts formalins, 160~
240 mass parts 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters, 15~45 mass parts o-phenyl phenols, 15~45
The orthoresol of mass parts and 6~14 mass parts ammonia spirits；
Further preferred embodiment is：Raw material include 220~260 mass parts phenol, 220~260 mass parts formalins,
180~220 mass parts 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters, 20~40 mass parts o-phenyl phenols, 20
The orthoresol of~40 mass parts and 8~10 mass parts ammonia spirits；
The structural formula of described 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters is as follows：
Described ammonia concn is 25%~28%.
A kind of preparation side of 4,5- 7-oxa-bicyclo[4.1.0s -1,2- dicarboxylic acid diglycidyl ester modified thermosetting phenolic resins
Method, comprise the following steps：
(1) phenol is dissolved in formalin by quality parts ratio, and sequentially adds o-phenyl phenol, orthoresol, 40-
Under the conditions of 45 DEG C of stirring in water bath, after o-phenyl phenol and orthoresol are completely dissolved, ammoniacal liquor of the mass fraction than 1/2 is added, slowly
65~75 DEG C are warming up to, carries out isothermal reaction；
(2) solution obtained in step (1) is further continued for after being warming up to 85~95 DEG C, adds remaining mass fraction than 1/2
Ammoniacal liquor, carry out isothermal reaction；
(3) 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters are added in the solution that step (2) obtains, and
It is stirred, 85~95 DEG C of stirring dehydrations of water-bath under vacuum condition afterwards, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dioctyl phthalate is prepared
2-glycidyl ester modified thermosetting phenolic resin.
In described step (1), the isothermal reaction time is 1~3h；
In described step (2), the isothermal reaction time is 1~3h；
In described step (3), after stirring 10~20min first, 85~95 DEG C of stirring dehydrations 0.5 of water-bath under vacuum condition
~1.5h.
The present invention has the advantages that compared with prior art：
(1) present invention prepares 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters by the method for in-situ polymerization
Modified thermosetting phenolic resin, by phenol, o-phenyl phenol, orthoresol and formaldehyde, generation addition is anti-under ammonia-catalyzed effect
The oligomer containing a large amount of methylols should be generated, the methylol on phenol ring continues to occur dehydration condensation to reach chain increasing
It is long, after chain increases to a certain extent, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters are added, utilize phenolic hydroxyl group
Ring-opening reaction occurs with epoxy-functional 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters are incorporated into phenolic resin
In backbone structure, reduce the release of Analysis on Curing Process of Phenolic small molecular water, by accessing 4,5- 7-oxa-bicyclo[4.1.0s -1,2-
The flexible molecule of dicarboxylic acid diglycidyl ester polyfunctionality, solve the problems, such as that product is porous, improves phenol to a certain extent
The mechanical property of urea formaldehyde, improve the stretch modulus of phenolic resin.
(2) present invention uses situ aggregation method by more officials of 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters
The flexible chain structure of energy degree is introduced in the skeleton structure of phenolic resin, anti-by epoxy-reactive group and phenolic hydroxyl group generation open loop
It should realize, its advantage is the polyfunctionality flexible structure of 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters,
Molecule cross-link degree is improved while reducing molecule space steric hindrance to a certain extent, improves phenolic resin mechanical property,
Such as improve the stretch modulus of phenolic resin.
(3) 4,5- of present invention 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl ester modified thermosetting phenolic resins, solid
Content is more than 75%, the phenolic resin methanol solution rotary viscosity according to solids content configuration 50wt% in 10~150mPas,
Stretch modulus is 3.96~5.22GPa.
(4) 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl ester modified heat convertible phenolic aldehyde trees prepared by the present invention
Fat has more excellent performance；
(5) prepared by 4,5- 7-oxa-bicyclo[4.1.0s -1,2- dicarboxylic acid diglycidyl esters modified thermosetting phenolic resin of the present invention
Method technique is simple, operation is simple, equipment requirement performance is low, application easy to spread.
(6) the present invention relates to 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl ester modified thermosetting phenolic resins
And preparation method thereof, for the phenolic resin according to quality parts ratio, reactant includes 200~300 mass parts phenol, 200~300
Mass parts formalin, 150~250 mass parts 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters, 10~50 mass
Part o-phenyl phenol, the orthoresol of 10~50 mass parts, and add the catalysis of 2~20 mass parts ammonia spirits and be prepared, this hair
It is bright to solve the problems, such as that Bakeland is porous, improve the mechanical property of phenolic resin.
(7) preparation method of the invention, reduces the release of Analysis on Curing Process of Phenolic small molecular water, to a certain extent
Solve the problems, such as that product is porous, improve the mechanical property of phenolic resin, improve the stretch modulus of phenolic resin.
(8) present invention can solve the problem that using phenolic resin as the product of matrix is porous, poor mechanical property the problems such as, by reasonable
Phenolic resin chemical constitution is designed, optimizes phenolic resin curing reaction mechanism, so that the defects of reducing product to a certain extent
Hole.Meanwhile the polyfunctionality molecule with certain flexibility is introduced, make it relatively violent in the warm-up movement of hot setting multi-stage molecular
And possess less steric hindrance relatively, so as to improve resin crosslinks degree to a certain extent, while and can ensures resin
Excellent in mechanical performance.The present invention using 4,5- 7-oxa-bicyclo[4.1.0s -1,2- dicarboxylic acid diglycidyl ester as strand modifying agent,
Utilize the phenolic hydroxyl group and 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters of the phenolic resin with certain chain length
In epoxy-functional occur ring-opening reaction, be grafted in phenol-formaldehyde resin matrix structure, 4,5- 7-oxa-bicyclo[4.1.0s -1,2- bis-
The modified phenolic resin curing mechanism of formic acid 2-glycidyl ester is by can originally produce the dehydration condensations of a large amount of small molecules
The curing reaction of epoxide ring and the mechanism of dehydration condensation collaboration solidification are converted to, the release of small molecule is reduced, reduces
Product hole, while improve the mechanical property of resin.
Brief description of the drawings
Fig. 1 closes for 4,5- 7-oxa-bicyclo[4.1.0s -1,2- dicarboxylic acid diglycidyl esters modified thermosetting phenolic resin of the present invention
Into mechanism schematic diagram；
Fig. 2 be 4,5- 7-oxa-bicyclo[4.1.0s -1,2- dicarboxylic acid diglycidyl esters modified thermosetting phenolic resin of the present invention, 4,
5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl ester infrared spectrum comparison diagrams, wherein curve (a) are 4,5- epoxy hexamethylenes
Alkane -1,2- dicarboxylic acid diglycidyl ester, curve (b) are modified for 4,5- 7-oxa-bicyclo[4.1.0s -1,2- dicarboxylic acid diglycidyl ester
Thermosetting phenolic resin.
Embodiment
4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl ester modified thermosetting phenolic resins, in the reactant
Including 200~300 mass parts phenol, 200~300 mass parts formalins, 150~250 mass parts 4,5- 7-oxa-bicyclo[4.1.0-1,
2- dicarboxylic acid diglycidyl esters, 10~50 mass parts o-phenyl phenols, the orthoresol of 10~50 mass parts, and add 2~20
The catalysis of mass parts ammonia spirit is prepared.
The reactant includes 210~280 mass parts phenol, 210~280 mass parts formalins, 160~240 matter
Measure part 4,5- 7-oxa-bicyclo[4.1.0s -1,2- dicarboxylic acid diglycidyl ester, 15~45 mass parts o-phenyl phenols, 15~45 mass parts
Orthoresol, and add 6~14 mass parts ammonia spirits catalysis be prepared；
The reactant includes 220~260 mass parts phenol, 220~260 mass parts formalins, 180~220 matter
Measure part 4,5- 7-oxa-bicyclo[4.1.0s -1,2- dicarboxylic acid diglycidyl ester, 20~40 mass parts o-phenyl phenols, 20~40 mass parts
Orthoresol, and add 8~10 mass parts ammonia spirits catalysis be prepared.
The ammonia concn is 10%~50%.
The preparation method of 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl ester modified thermosetting phenolic resins, bag
Include following steps：
(1) phenol is dissolved in formalin by quality parts ratio, and sequentially adds o-phenyl phenol, orthoresol, 40
Under the conditions of DEG C stirring in water bath, after o-phenyl phenol and orthoresol are completely dissolved, ammoniacal liquor of the mass fraction than 1/2 is added, is slowly risen
Temperature carries out isothermal reaction to 65~75 DEG C；
(2) after the solution obtained in step (1) being to slowly warm up into 85~95 DEG C by 65~75 DEG C, remaining quality point is added
Ammoniacal liquor of the number than 1/2, carries out isothermal reaction；
(3) 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters are added, and are stirred, afterwards vacuum condition
Lower 85~95 DEG C of stirring dehydrations of water-bath, are prepared 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl ester modified thermosets
Property phenolic resin.
1~3h of isothermal reaction in the step (1).
1~3h of isothermal reaction in the step (2).
After 10~20min being stirred in the step (3) first, 85~95 DEG C of water-bath stirring dehydration 0.5 under vacuum condition~
1.5h。
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings：
4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl ester modified thermosetting phenolic resins, by 200~300 matter
Amount part phenol, 200~300 mass parts formalins, 150~250 mass parts 4,5- 7-oxa-bicyclo[4.1.0-1,2- dioctyl phthalate two shrink
Glyceride, 10~50 mass parts o-phenyl phenols, the orthoresol of 10~50 mass parts, and add 2~20 mass parts ammonia spirits
Catalysis is prepared.
Reactant is preferred：Including 210~280 mass parts phenol, 210~280 mass parts formalins, 160~240 mass
Part 4,5- 7-oxa-bicyclo[4.1.0s -1,2- dicarboxylic acid diglycidyl ester, 15~45 mass parts o-phenyl phenols, 15~45 mass parts
Orthoresol, and add the catalysis of 6~14 mass parts ammonia spirits and be prepared.
Further preferably：Including 220~260 mass parts phenol, 220~260 mass parts formalins, 180~220 mass
Part 4,5- 7-oxa-bicyclo[4.1.0s -1,2- dicarboxylic acid diglycidyl ester, 20~40 mass parts o-phenyl phenols, 20~40 mass parts
Orthoresol, and add the catalysis of 8~10 mass parts ammonia spirits and be prepared.
Most preferably：Including 230~250 mass parts phenol, 230~250 mass parts formalins, 190~200 mass parts 4,
5- 7-oxa-bicyclo[4.1.0s -1,2- dicarboxylic acid diglycidyl ester, 25~35 mass parts o-phenyl phenols, the adjacent first of 25~35 mass parts
Phenol, and add the catalysis of 8.5~9.5 mass parts ammonia spirits and be prepared.
Wherein ammonia concn is 25%~28%.
The preparation side of 4,5- 7-oxa-bicyclo[4.1.0s -1,2- dicarboxylic acid diglycidyl ester modified thermosetting phenolic resins of the present invention
Method, comprise the following steps：
(1) 200~300 parts of phenol are dissolved in 200~300 parts of formalins by quality parts ratio, and sequentially added
10~50 parts of o-phenyl phenols, 10~50 parts of orthoresols, under the conditions of 40 DEG C of stirring in water bath, o-phenyl phenol and orthoresol are completely molten
Xie Hou, 1~7.5 part of ammoniacal liquor is added, is to slowly warm up to 65~75 DEG C, 1~3h of isothermal reaction；
(2) after the solution obtained in step (1) being to slowly warm up into 85~95 DEG C by 65~75 DEG C, remainder 1~7.5 is added
The ammoniacal liquor of part, 1~3h of isothermal reaction；
(3) 150~250 parts of 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters are added, stir 10~20min,
85~95 DEG C of stirring 0.5~1.5h of dehydration of water-bath under vacuum condition afterwards, are cooled to room temperature, 4,5- epoxy hexamethylenes are prepared
Alkane -1,2- dicarboxylic acid diglycidyl ester modified thermosetting phenolic resins.
It is 4,5- 7-oxa-bicyclo[4.1.0s -1,2- dicarboxylic acid diglycidyl ester modified heat convertible phenolic aldehyde of the present invention as shown in Figure 1
The schematic diagram of resins synthesis mechanism.
4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters the modified thermosetting phenolic resin of the present invention is yellowish
Color thick liquid, solids content are more than 75%, the phenolic resin methanol solution rotary viscosity according to solids content configuration 50wt%
10~150mPas, stretch modulus average value are 3.96~5.22GPa (being higher than common 3~4GPa of phenolic aldehyde).
Embodiment 1
240 parts of phenol are dissolved in 240 parts of formalins by quality parts ratio, and sequentially add 30 parts of adjacent phenyl benzene
Phenol, 30 parts of orthoresols, under the conditions of 40 DEG C of stirring in water bath, after o-phenyl phenol and orthoresol are completely dissolved, add 4.5 parts of ammonia
Water, 70 DEG C are to slowly warm up to, isothermal reaction 1.5h；
After obtained solution is to slowly warm up into 90 DEG C by 70 DEG C afterwards, remaining 4.5 parts ammoniacal liquor, isothermal reaction are added
2h；
200 parts of 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters are added afterwards, stir 20min, Zhi Houzhen
90 DEG C of stirring dehydration 1h of water-bath, are cooled to room temperature, 4,5- 7-oxa-bicyclo[4.1.0s -1,2- dioctyl phthalate two are prepared and shrinks under empty condition
Glyceride modified thermosetting phenolic resin.Ammonia concn is 26%.
4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl ester the modified thermosetting phenolic resins that the present embodiment obtains
For light yellow viscous liquid, solids content 81%；Phenolic resin methanol solution rotation according to solids content configuration 50wt%
Viscosity is 96mPas, and the stretch modulus of thermosetting phenolic resin solidfied material is 5.22GPa.
It is illustrated in figure 2 the 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl ester modified heat convertible phenolic aldehyde of preparation
Resin and 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl ester infrared spectrum comparison diagram, as seen from the figure, in 1735cm-1、
910cm-1It is nearby epoxy-functional characteristic absorption peak, 1020cm-1、1180cm-1Nearby occur for phenolic hydroxyl group and epoxy-functional
The ehter bond absworption peak generated after reaction, it was demonstrated that by situ aggregation method successfully by 4,5- 7-oxa-bicyclo[4.1.0s -1,2- dioctyl phthalate two
The flexible structure of ethylene oxidic ester is introduced in phenol-formaldehyde resin matrix structure, and other characteristic absorption peaks are shown in Table 1：
4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl ester modified thermosetting phenolic resins the infrared spectrum point of table 1
Analysis
Embodiment 2
200 parts of phenol are dissolved in 200 parts of formalins by quality parts ratio, and sequentially add 10 parts of adjacent phenyl benzene
Phenol, 10 parts of orthoresols, under the conditions of 40 DEG C of stirring in water bath, after o-phenyl phenol and orthoresol are completely dissolved, 1 part of ammoniacal liquor is added,
65 DEG C are to slowly warm up to, isothermal reaction 1h；
After obtained solution is to slowly warm up into 85 DEG C by 65 DEG C afterwards, remaining 1 part ammoniacal liquor, isothermal reaction 1h are added；
150 parts of 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters are added, stir 10min, afterwards vacuum condition
Lower 85 DEG C of stirring dehydration 0.5h of water-bath, are cooled to room temperature, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dioctyl phthalate 2-glycidyls are prepared
Ester modified thermosetting phenolic resin.Ammonia mass concentration is 25% in ammonia spirit.
4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl ester the modified thermosetting phenolic resins that the present embodiment obtains
For pale yellow viscous liquid, solids content 75%；Phenolic resin methanol solution rotation according to solids content configuration 50wt%
Viscosity is 18mPas；The stretch modulus of thermosetting phenolic resin solidfied material is 4.03GPa.
Embodiment 3
300 parts of phenol are dissolved in 300 parts of formalins by quality parts ratio, and sequentially add 50 parts of adjacent phenyl benzene
Phenol, 50 parts of orthoresols, under the conditions of 40 DEG C of stirring in water bath, after o-phenyl phenol and orthoresol are completely dissolved, add 7.5 parts of ammonia
Water, 75 DEG C are to slowly warm up to, isothermal reaction 3h；
After obtained solution is to slowly warm up into 95 DEG C by 75 DEG C afterwards, remaining 7.5 parts ammoniacal liquor, isothermal reaction are added
3h；
250 parts of 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters are added, stir 20min, afterwards vacuum condition
Lower 95 DEG C of stirring dehydration 1.5h of water-bath, are cooled to room temperature, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dioctyl phthalate 2-glycidyls are prepared
Ester modified thermosetting phenolic resin.Ammonia mass concentration is 28% in ammonia spirit.
4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl ester the modified thermosetting phenolic resins that the present embodiment obtains
It is solid for the very viscous thick liquid of yellow, under normal temperature, solids content 83%；Phenolic resin according to solids content configuration 50wt%
Methanol solution rotary viscosity is 120mPas；The stretch modulus of thermosetting phenolic resin solidfied material is 4.87GPa.
Embodiment 4
220 parts of phenol are dissolved in 280 parts of formalins by quality parts ratio, and sequentially add 20 parts of adjacent phenyl benzene
Phenol, 20 parts of orthoresols, under the conditions of 40 DEG C of stirring in water bath, after o-phenyl phenol and orthoresol are completely dissolved, 6 parts of ammoniacal liquor is added,
70 DEG C are to slowly warm up to, isothermal reaction 2.5h；
After obtained solution is to slowly warm up into 90 DEG C by 70 DEG C afterwards, remaining 6 parts ammoniacal liquor, isothermal reaction 1h are added；
180 parts of 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters are added, stir 15min, afterwards vacuum condition
Lower 90 DEG C of stirring dehydration 1h of water-bath, are cooled to room temperature, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters are prepared
Modified thermosetting phenolic resin.Ammonia mass concentration is 26% in ammonia spirit.
4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl ester the modified thermosetting phenolic resins that the present embodiment obtains
For yellow viscous liquid, solids content 78%；Phenolic resin methanol solution rotation according to solids content configuration 50wt% is viscous
Spend for 103mPas；The stretch modulus of thermosetting phenolic resin solidfied material is 4.51GPa.
Embodiment 5
280 parts of phenol are dissolved in 220 parts of formalins by quality parts ratio, and sequentially add 40 parts of adjacent phenyl benzene
Phenol, 40 parts of orthoresols, under the conditions of 40 DEG C of stirring in water bath, after o-phenyl phenol and orthoresol are completely dissolved, 4 parts of ammoniacal liquor is added,
70 DEG C are to slowly warm up to, isothermal reaction 2.5h；
After obtained solution is to slowly warm up into 90 DEG C by 70 DEG C afterwards, remaining 4 parts ammoniacal liquor, isothermal reaction 1h are added；
220 parts of 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters are added, stir 15min, afterwards vacuum condition
Lower 90 DEG C of stirring dehydration 1h of water-bath, are cooled to room temperature, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters are prepared
Modified thermosetting phenolic resin.Ammonia mass concentration is 26% in ammonia spirit.
4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl ester the modified thermosetting phenolic resins that the present embodiment obtains
For yellow viscous liquid, solids content 79%；Phenolic resin methanol solution rotation according to solids content configuration 50wt% is viscous
Spend for 62mPas；The stretch modulus of thermosetting phenolic resin solidfied material is 3.96GPa.
It is described above, it is only the optimal embodiment of the present invention, but protection scope of the present invention is not limited thereto,
Any one skilled in the art the invention discloses technical scope in, the change or replacement that can readily occur in,
It should all be included within the scope of the present invention.
The content not being described in detail in description of the invention belongs to the known technology of professional and technical personnel in the field.
Claims (10)
1. one kind 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl ester modified thermosetting phenolic resins, it is characterised in that：
The raw material of the modified thermosetting phenolic resin include 200~300 mass parts phenol, 200~300 mass parts formalins, 150~
250 mass parts 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters, 10~50 mass parts o-phenyl phenols, 10~50
The orthoresol of mass parts and 2~20 mass parts ammonia spirits.
A kind of 2. 4,5- 7-oxa-bicyclo[4.1.0s -1,2- dicarboxylic acid diglycidyl ester modified heat convertibles according to claim 1
Phenolic resin, it is characterised in that：The raw material of the modified thermosetting phenolic resin includes 210~280 mass parts phenol, 210~280
Mass parts formalin, 160~240 mass parts 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters, 15~45 mass
Part o-phenyl phenol, the orthoresol and 6~14 mass parts ammonia spirits of 15~45 mass parts.
A kind of 3. 4,5- 7-oxa-bicyclo[4.1.0s -1,2- dicarboxylic acid diglycidyl ester modified heat convertibles according to claim 1
Phenolic resin, it is characterised in that：The raw material of the modified thermosetting phenolic resin includes 220~260 mass parts phenol, 220~260
Mass parts formalin, 180~220 mass parts 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters, 20~40 mass
Part o-phenyl phenol, the orthoresol and 8~10 mass parts ammonia spirits of 20~40 mass parts.
4. it is modified according to a kind of any described 4,5- 7-oxa-bicyclo[4.1.0s -1,2- dicarboxylic acid diglycidyl esters of claim 1-3
Thermosetting phenolic resin, it is characterised in that：
The structural formula of described 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters is as follows：
5. it is modified according to a kind of any described 4,5- 7-oxa-bicyclo[4.1.0s -1,2- dicarboxylic acid diglycidyl esters of claim 1-3
Thermosetting phenolic resin, it is characterised in that：Described ammonia concn is 25%~28%.
6. one kind 4, the preparation method of 5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl ester modified thermosetting phenolic resins,
It is characterized in that comprise the following steps：
(1) phenol is dissolved in formalin by quality parts ratio, and sequentially adds o-phenyl phenol, orthoresol, 40-45 DEG C
Under the conditions of stirring in water bath, after o-phenyl phenol and orthoresol are completely dissolved, ammoniacal liquor of the mass fraction than 1/2 is added, slowly heating
To 65~75 DEG C, isothermal reaction is carried out；
(2) solution obtained in step (1) is further continued for after being warming up to 85~95 DEG C, adds ammonia of the remaining mass fraction than 1/2
Water, carry out isothermal reaction；
(3) 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters are added in the solution that step (2) obtains, and are carried out
Stirring, afterwards 85~95 DEG C of stirring dehydrations of water-bath under vacuum condition, is prepared 4,5- 7-oxa-bicyclo[4.1.0s -1,2- dioctyl phthalate two and contracts
Water glyceride modified thermosetting phenolic resin.
A kind of 7. 4,5- 7-oxa-bicyclo[4.1.0s -1,2- dicarboxylic acid diglycidyl ester modified heat convertibles according to claim 6
The preparation method of phenolic resin, it is characterised in that：In described step (1), the isothermal reaction time is 1~3h.
A kind of 8. 4,5- 7-oxa-bicyclo[4.1.0s -1,2- dicarboxylic acid diglycidyl ester modified heat convertibles according to claim 6
The preparation method of phenolic resin, it is characterised in that：In described step (2), the isothermal reaction time is 1~3h.
A kind of 9. 4,5- 7-oxa-bicyclo[4.1.0s -1,2- dicarboxylic acid diglycidyl ester modified heat convertibles according to claim 6
The preparation method of phenolic resin, it is characterised in that：In described step (3), mixing time is 10~20min first.
A kind of 10. 4,5- 7-oxa-bicyclo[4.1.0s -1,2- dicarboxylic acid diglycidyl ester modified heat convertibles according to claim 6
The preparation method of phenolic resin, it is characterised in that：In described step (3), 85~95 DEG C of stirring dehydrations of water-bath under vacuum condition
0.5~1.5h.
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