CN110105905A - A kind of modified by cardanol itrile group phenolic resin adhesive and preparation method thereof - Google Patents
A kind of modified by cardanol itrile group phenolic resin adhesive and preparation method thereof Download PDFInfo
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- CN110105905A CN110105905A CN201910501143.3A CN201910501143A CN110105905A CN 110105905 A CN110105905 A CN 110105905A CN 201910501143 A CN201910501143 A CN 201910501143A CN 110105905 A CN110105905 A CN 110105905A
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- phenolic resin
- itrile group
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- anacardol
- cardanol
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09J161/14—Modified phenol-aldehyde condensates
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- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The present invention relates to a kind of modified by cardanol itrile group phenolic resin adhesives and preparation method thereof, belong to adhesive technology field.For the existing phenolic resin brittleness of solution is big, glue-joint strength is low and viscosity is big, the problem of processing performance difference, the present invention provides a kind of modified by cardanol itrile group phenolic resin adhesive, component includes itrile group phenolic resin and anacardol cyano resin；Preparation method includes preparing anacardol cyano resin, preparing phenolic resin, prepare itrile group phenolic resin and obtain adhesive using the modified itrile group phenolic resin of anacardol cyano resin.The present invention utilizes anacardol cyano resin low viscosity, the active characteristic of high temperature resistant, the viscosity of itrile group phenolic resin can be significantly reduced while improving adhesive flexibility and bonding property by being used for modified itrile group phenolic resin, so as to improve the process industrial art performance of high-temperature Resistance Adhesives, the usage amount for reducing solvent is a kind of environment-friendly material.
Description
Technical field
The invention belongs to adhesive technology field more particularly to a kind of modified by cardanol itrile group phenolic resin adhesive and its
Preparation method.
Background technique
Cashew nut shell oil is processed and is made through multiple working procedure using the shell of natural products cashew nut as raw material, and main component is waist
Tartaric acid and cardol, to get anacardol after handling its further decarboxylation, vacuum distillation.Brand-new anacardol is faint yellow micro-
Bright oily liquids has minimal irritation taste, and 25 DEG C of viscosity are about 94mPas.Anacardol structural formula such as (I) is shown, structural unit
In contain phenolic hydroxy group and long alkyl chain structure, the rigidity of existing phenyl ring, and have Long carbon chain bring flexible, and due to it
For renewable resource, abundance is cheap, so application field is extensive, there is highly important application value.Such as it is used for
Synthesis cashew pnenolic aldehyde resinoid partially substitutes phenol-modified phenol formaldehyde (PF) resinoid, improves the performances such as its toughness；For friction material
Frictional behaviour modifying agent of material etc..
Wherein, R=C15H32-n。
Phenolic resin is a kind of cheap, high comprehensive performance macromolecule resin kind, is had good mechanical strong
Degree and heat resistance especially have instantaneous high temperature resistant ablation property outstanding, can be used for manufacturing adhesive, coating and composite wood
Material etc..But when operating temperature is more than 300 DEG C, there is the problems such as vigorous oxidation decomposition in phenolic resin, limits application range.It is adjacent
Phthalonitrile resin is a kind of novel fire resistant resin, and solidfied material glass transition temperature is greater than 450 DEG C, and has excellent mechanical property
Its structure can be introduced into phenolic structure, phenolic resin height can be significantly improved with brilliant moisture-proof and resistance to chemical corrosion etc.
Warm nature energy, but solidfied material there are brittleness it is larger, glue-joint strength is lower the problems such as.The method of traditional tough-increased phenolic is to introduce high temperature resistant
Toughener, such as heat-resisting thermoplastic resin, heat-resisting modification by copolymerization resin, nanofiller, although phenolic resin toughness can be improved
And glue-joint strength, but there are the increase of modified resin process viscosity, use processing performance compromises.
Summary of the invention
To solve, existing phenolic resin brittleness is big, glue-joint strength is low and viscosity is big, the problem of processing performance difference, this hair
It is bright to provide a kind of modified by cardanol itrile group phenolic resin adhesive and preparation method thereof.
Technical solution of the present invention:
A kind of modified by cardanol itrile group phenolic resin adhesive, the component including following mass parts: 100 parts of itrile group phenolic aldehyde trees
Rouge and 2.5~50 parts of anacardol cyano resins.
Further, the structural formula of the anacardol cyano resin are as follows:
Wherein, R=C15H32-n。
A kind of preparation method of modified by cardanol itrile group phenolic resin adhesive, includes the following steps:
Step 1: preparing anacardol cyano resin:
Anacardol and nitro substitution phthalonitrile are weighed by certain mol proportion and is put into organic solvent, are sufficiently stirred
It mixes to obtain uniform mixed liquor, a certain amount of basic catalyst is added in Xiang Suoshu mixed liquor, makes reaction system in certain temperature
Under react certain time while stirring, products therefrom is cooled to room temperature after reaction, stratification, collect supernatant liquid warp
Washing, solvent extraction, vacuum distillation obtain anacardol cyano resin；
Step 2: preparing phenolic resin:
Phenol and formaldehyde are uniformly mixed by certain mol proportion, catalyst a is added under certain reaction temperature, keeps reaction
Temperature is simultaneously reacted under stirring, and when reaction solution reaches cloud point temperature, reaction was completed, and reaction solution and true is washed with water
Sky dehydration, is down to room temperature for resin when the gel time of resin reaches 90~600 seconds, and solvent is added and obtains phenolic resin；
Step 3: preparing itrile group phenolic resin:
By certain mol proportion by phenolic resin made from step 2,4- nitrophthalonitrile and N,N-dimethylformamide
Catalyst b is added in mixing under certain reaction temperature, controls reaction system insulation reaction certain time under certain pH, makes anti-
System is answered to be down to room temperature and through distilled water cleaning, ethyl acetate extraction, dilute hydrochloric acid neutralization, separatory funnel separation and vacuum desolvation
Resin is down to room temperature when the gel time of gained resin reaches 90~600 seconds by agent, and solvent is added and obtains itrile group phenolic aldehyde tree
Rouge；
Step 4: preparing modified by cardanol itrile group phenolic resin adhesive:
Mass parts are pressed at room temperature by nitriles obtained by anacardol cyano resins obtained by 2.5~50 parts of step 1 and 100 parts of step 3
Base phenolic resin, which is sufficiently mixed, uniformly obtains modified by cardanol itrile group phenolic resin adhesive.
Further, nitro described in step 1 replaces phthalonitrile to be that contraposition nitro replaces phthalonitrile；The waist
Fruit phenol and nitro replace the molar ratio of phthalonitrile to be 1:(0.5~1)；The organic solvent is dimethyl sulfoxide, N, N- bis-
One of methylformamide or DMAC N,N' dimethyl acetamide；The dosage of the organic solvent is that anacardol and nitro replace adjacent benzene
2-5 times of dimethoxy nitrile total weight.
Further, basic catalyst described in step 1 is one in sodium hydroxide, barium hydroxide, sodium carbonate or potassium carbonate
Kind, the additional amount of the basic catalyst is 0.5~2.0 times that nitro replaces phthalonitrile mole；The system it is anti-
Answering temperature is 60~90 DEG C, and the reaction time is 6~16h.
Further, washing described in step 1 is that the water for being 0~25 DEG C with 8~10 times of supernatant liquid weight of temperature is washed
Supernatant liquid 3~5 times；The extraction is one of toluene, ethyl acetate, acetone or butanone with solvent.
Further, the molar ratio of phenol and formaldehyde described in step 2 is 1:(1.2~2.0), the reaction temperature is 90
~100 DEG C, the catalyst a is one of ammonium hydroxide, sodium hydroxide, potassium hydroxide or zinc oxide, the addition of the catalyst a
Amount is the 0.5~5% of phenol weight.
Further, cloud point temperature described in step 2 is 60~80 DEG C, and the vacuum degree of the vacuum dehydration is 5~10kPa,
The solvent is one of butanone, acetone or ethyl acetate.
Further, mole of phenolic resin described in step 3,4- nitrophthalonitrile and n,N-Dimethylformamide
Than for 1:(3~7): (30~80), the catalyst b are potassium carbonate or sodium carbonate, and the additional amount of the catalyst b is 4- nitro
0.5~2.0 times of phthalonitrile mole.
Further, reaction temperature described in step 3 is 60~80 DEG C, and the pH value is 9~11, when the insulation reaction
Between be 12~18h, the vacuum degree of the vacuum desolvation agent is 5~10kPa, and the solvent is in butanone, acetone or ethyl acetate
One kind.
Beneficial effects of the present invention:
The present invention introduces phthalonitrile heat resistant structure in anacardol structure, is heating and itrile group base under catalysts conditions
Polymerization crosslinking reaction can occur between group, form heat resistant structure, it is possible to reduce play the anacardol meta position long-chain pair of toughening effect
The adverse effect of modified resin heat resistance.Prepared anacardol cyano resin is a kind of novel low viscosity, high temperature resistant activity
Resin, is a kind of low-viscosity (mobile) liquid at room temperature, and viscosity at 25 DEG C is not more than 600mPas.
With the modified itrile group phenolic resin of anacardol cyano resin prepared by the present invention, can improve adhesive flexibility and
The viscosity of itrile group phenolic resin is significantly reduced while bonding property, so as to improve the processing technology of high-temperature Resistance Adhesives
Can, reduce the usage amount of solvent when in use, is a kind of environment-friendly material.
Detailed description of the invention
Fig. 1 is the infrared spectrum of anacardol cyano resin prepared by embodiment 7,8, and A is anacardol nitrile prepared by embodiment 7
Base resin, B are anacardol cyano resin prepared by embodiment 8；
Fig. 2 is the TGA curve of itrile group phenolic resin prepared by embodiment 7 and modified by cardanol itrile group phenolic resin adhesive
Comparison diagram；
Fig. 3 is the TGA curve of itrile group phenolic resin prepared by embodiment 8 and modified by cardanol itrile group phenolic resin adhesive
Comparison diagram.
Specific embodiment
Below with reference to embodiment, the following further describes the technical solution of the present invention, and however, it is not limited to this, all right
Technical solution of the present invention is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be contained
Lid is within the protection scope of the present invention.
Embodiment 1
A kind of modified by cardanol itrile group phenolic resin adhesive, the component including following mass parts: 100 parts of itrile group phenolic aldehyde trees
Rouge and 2.5~50 parts of anacardol cyano resins.
Embodiment 2
A kind of modified by cardanol itrile group phenolic resin adhesive, the component including following mass parts: 100 parts of itrile group phenolic aldehyde trees
Rouge and 2.5~50 parts of anacardol cyano resins, the wherein structural formula of anacardol cyano resin are as follows:
Wherein, R=C15H32-n。
Viscosity used in the present embodiment at 25 DEG C of anacardol cyano resin is not more than 600mPas,
Embodiment 3
The present embodiment provides a kind of preparation methods of modified by cardanol itrile group phenolic resin adhesive, include the following steps:
Step 1: preparing anacardol cyano resin:
Anacardol and nitro substitution phthalonitrile are weighed by certain mol proportion and is put into organic solvent, are sufficiently stirred
It mixes to obtain uniform mixed liquor, a certain amount of basic catalyst is added in Xiang Suoshu mixed liquor, makes reaction system in certain temperature
Under react certain time while stirring, products therefrom is cooled to room temperature after reaction, stratification, collect supernatant liquid warp
Washing, solvent extraction, vacuum distillation obtain anacardol cyano resin；
Step 2: preparing phenolic resin:
Phenol and formaldehyde are uniformly mixed by certain mol proportion, catalyst a is added under certain reaction temperature, keeps reaction
Temperature is simultaneously reacted under stirring, and when reaction solution reaches cloud point temperature, reaction was completed, and reaction solution and true is washed with water
Sky dehydration, is down to room temperature for resin when the gel time of resin reaches 90~600 seconds, and solvent is added and obtains phenolic resin；
Step 3: preparing itrile group phenolic resin:
By certain mol proportion by phenolic resin made from step 2,4- nitrophthalonitrile and N,N-dimethylformamide
Catalyst b is added in mixing under certain reaction temperature, controls reaction system insulation reaction certain time under certain pH, makes anti-
System is answered to be down to room temperature and through distilled water cleaning, ethyl acetate extraction, dilute hydrochloric acid neutralization, separatory funnel separation and vacuum desolvation
Resin is down to room temperature when the gel time of gained resin reaches 90~600 seconds by agent, and solvent is added and obtains itrile group phenolic aldehyde tree
Rouge；
Step 4: preparing modified by cardanol itrile group phenolic resin adhesive:
Mass parts are pressed at room temperature by nitriles obtained by anacardol cyano resins obtained by 2.5~50 parts of step 1 and 100 parts of step 3
Base phenolic resin, which is sufficiently mixed, uniformly obtains modified by cardanol itrile group phenolic resin adhesive.
Embodiment 4
The present embodiment provides a kind of preparation methods of modified by cardanol itrile group phenolic resin adhesive, include the following steps:
Step 1: preparing anacardol cyano resin:
1:(0.5~1 in molar ratio) it weighs anacardol and contraposition nitro substitution phthalonitrile and is put into organic molten
In agent, organic solvent is one in dimethyl sulfoxide, n,N-Dimethylformamide or n,N-dimethylacetamide in the present embodiment
Kind, dosage is 2-5 times that anacardol and nitro replace phthalonitrile total weight.It is sufficiently stirred to obtain uniform mixed liquor,
The basic catalyst that contraposition nitro replaces 0.5~2.0 times of phthalonitrile mole, the present embodiment are added into the mixed liquor
Neutral and alkali catalyst is one of sodium hydroxide, barium hydroxide, sodium carbonate or potassium carbonate.Make reaction system in 60~90 DEG C of temperature
6~16h is reacted under degree while stirring, is after reaction cooled to room temperature products therefrom, stratification collects supernatant liquid,
Supernatant liquid 3~5 times is washed, with toluene, ethyl acetate, third with the water that 8~10 times of supernatant liquid weight of temperature are 0~25 DEG C
Any one of ketone or butanone are extracted as solvent, are evaporated under reduced pressure to obtain anacardol cyano resin.
Step 2: preparing phenolic resin:
Phenol and formaldehyde are uniformly mixed by certain mol proportion, catalyst a is added under certain reaction temperature, keeps reaction
Temperature is simultaneously reacted under stirring, and when reaction solution reaches cloud point temperature, reaction was completed, and reaction solution and true is washed with water
Sky dehydration, is down to room temperature for resin when the gel time of resin reaches 90~600 seconds, and solvent is added and obtains phenolic resin；
Step 3: preparing itrile group phenolic resin:
By certain mol proportion by phenolic resin made from step 2,4- nitrophthalonitrile and N,N-dimethylformamide
Catalyst b is added in mixing under certain reaction temperature, controls reaction system insulation reaction certain time under certain pH, makes anti-
System is answered to be down to room temperature and through distilled water cleaning, ethyl acetate extraction, dilute hydrochloric acid neutralization, separatory funnel separation and vacuum desolvation
Resin is down to room temperature when the gel time of gained resin reaches 90~600 seconds by agent, and solvent is added and obtains itrile group phenolic aldehyde tree
Rouge；
Step 4: preparing modified by cardanol itrile group phenolic resin adhesive:
Mass parts are pressed at room temperature by nitriles obtained by anacardol cyano resins obtained by 2.5~50 parts of step 1 and 100 parts of step 3
Base phenolic resin, which is sufficiently mixed, uniformly obtains modified by cardanol itrile group phenolic resin adhesive.
The present embodiment introduces phthalonitrile heat resistant structure in anacardol structure, is heating and itrile group under catalysts conditions
Polymerization crosslinking reaction can occur between group, form heat resistant structure, it is possible to reduce play the anacardol meta position long-chain of toughening effect
To the adverse effect of modified resin heat resistance.Prepared anacardol cyano resin is that a kind of novel low viscosity, high temperature resistant are living
Property resin, be a kind of low-viscosity (mobile) liquid at room temperature, viscosity at 25 DEG C is not more than 600mPas.
Embodiment 5
The present embodiment provides a kind of preparation methods of modified by cardanol itrile group phenolic resin adhesive, include the following steps:
Step 1: preparing anacardol cyano resin:
1:(0.5~1 in molar ratio) it weighs anacardol and contraposition nitro substitution phthalonitrile and is put into organic molten
In agent, organic solvent is one in dimethyl sulfoxide, n,N-Dimethylformamide or n,N-dimethylacetamide in the present embodiment
Kind, dosage is 2-5 times that anacardol and nitro replace phthalonitrile total weight.It is sufficiently stirred to obtain uniform mixed liquor,
The basic catalyst that contraposition nitro replaces 0.5~2.0 times of phthalonitrile mole, the present embodiment are added into the mixed liquor
Neutral and alkali catalyst is one of sodium hydroxide, barium hydroxide, sodium carbonate or potassium carbonate.Make reaction system in 60~90 DEG C of temperature
6~16h is reacted under degree while stirring, is after reaction cooled to room temperature products therefrom, stratification collects supernatant liquid,
Supernatant liquid 3~5 times is washed, with toluene, ethyl acetate, third with the water that 8~10 times of supernatant liquid weight of temperature are 0~25 DEG C
Any one of ketone or butanone are extracted as solvent, are evaporated under reduced pressure to obtain anacardol cyano resin.
Step 2: preparing phenolic resin:
1:(1.2~2.0 in molar ratio) phenol and formaldehyde are uniformly mixed, benzene is added under 90~100 DEG C of reaction temperatures
The catalyst a of the 0.5%~5% of phenol weight, catalyst a is ammonium hydroxide, sodium hydroxide, potassium hydroxide or zinc oxide in the present embodiment
One of, keep reaction temperature simultaneously to be reacted under stirring, when reaction solution reaches cloud point temperature, i.e., at 60~80 DEG C
Reaction was completed, reaction solution and vacuum dehydration under conditions of vacuum degree is 5~10kPa is washed with water, when the gel time of resin
Resin is down to room temperature when reaching 90~600 seconds, any one of butanone, acetone or ethyl acetate is added, obtains phenolic resin；
Step 3: preparing itrile group phenolic resin:
1:(1.2~2.0 in molar ratio) by phenolic resin made from step 2,4- nitrophthalonitrile and N, N- diformazan
The mixing of base formamide, is added catalyst b under certain reaction temperature, controls reaction system one timing of insulation reaction under certain pH
Between, so that reaction system is down to room temperature and neutralized through distilled water cleaning, ethyl acetate extraction, dilute hydrochloric acid, separatory funnel separates and true
Resin is down to room temperature when the gel time of gained resin reaches 90~600 seconds by empty desolventizing, and solvent is added and obtains itrile group phenol
Urea formaldehyde；
Step 4: preparing modified by cardanol itrile group phenolic resin adhesive:
Mass parts are pressed at room temperature by nitriles obtained by anacardol cyano resins obtained by 2.5~50 parts of step 1 and 100 parts of step 3
Base phenolic resin, which is sufficiently mixed, uniformly obtains modified by cardanol itrile group phenolic resin adhesive.
Embodiment 6
The present embodiment provides a kind of preparation methods of modified by cardanol itrile group phenolic resin adhesive, include the following steps:
Step 1: preparing anacardol cyano resin:
1:(0.5~1 in molar ratio) it weighs anacardol and contraposition nitro substitution phthalonitrile and is put into organic molten
In agent, organic solvent is one in dimethyl sulfoxide, n,N-Dimethylformamide or n,N-dimethylacetamide in the present embodiment
Kind, dosage is 2-5 times that anacardol and nitro replace phthalonitrile total weight.It is sufficiently stirred to obtain uniform mixed liquor,
The basic catalyst that contraposition nitro replaces 0.5~2.0 times of phthalonitrile mole, the present embodiment are added into the mixed liquor
Neutral and alkali catalyst is one of sodium hydroxide, barium hydroxide, sodium carbonate or potassium carbonate.Make reaction system in 60~90 DEG C of temperature
6~16h is reacted under degree while stirring, is after reaction cooled to room temperature products therefrom, stratification collects supernatant liquid,
Supernatant liquid 3~5 times is washed, with toluene, ethyl acetate, third with the water that 8~10 times of supernatant liquid weight of temperature are 0~25 DEG C
Any one of ketone or butanone are extracted as solvent, are evaporated under reduced pressure to obtain anacardol cyano resin.
Step 2: preparing phenolic resin:
1:(1.2~2.0 in molar ratio) phenol and formaldehyde are uniformly mixed, benzene is added under 90~100 DEG C of reaction temperatures
The catalyst a of the 0.5%~5% of phenol weight, catalyst a is ammonium hydroxide, sodium hydroxide, potassium hydroxide or zinc oxide in the present embodiment
One of, keep reaction temperature simultaneously to be reacted under stirring, when reaction solution reaches cloud point temperature, i.e., at 60~80 DEG C
Reaction was completed, reaction solution and vacuum dehydration under conditions of vacuum degree is 5~10kPa is washed with water, when the gel time of resin
Resin is down to room temperature when reaching 90~600 seconds, any one of butanone, acetone or ethyl acetate is added, obtains phenolic resin；
Step 3: preparing itrile group phenolic resin:
1:(3~7 in molar ratio): (30~80) by phenolic resin made from step 2,4- nitrophthalonitrile and N,
Dinethylformamide mixing, is added 1~5% catalyst b of phenolic resin weight, this reality under 60~80 DEG C of reaction temperatures
Applying catalyst b in example is potassium carbonate or sodium carbonate, controls reaction system 12~18h of insulation reaction under conditions of pH is 9~11,
Reaction system is set to be down to room temperature and through distilled water cleaning, ethyl acetate extraction, dilute hydrochloric acid neutralization, separatory funnel separation and vacuum degree
For vacuum desolvation agent under the conditions of 5~10kPa, resin is down to room temperature when the gel time of gained resin reaches 90~600 seconds,
Any one of butanone, acetone or ethyl acetate is added, obtains itrile group phenolic resin；
Step 4: preparing modified by cardanol itrile group phenolic resin adhesive:
Mass parts are pressed at room temperature by nitriles obtained by anacardol cyano resins obtained by 2.5~50 parts of step 1 and 100 parts of step 3
Base phenolic resin, which is sufficiently mixed, uniformly obtains modified by cardanol itrile group phenolic resin adhesive.
Embodiment 7
The present embodiment provides a kind of specific preparation methods of modified by cardanol itrile group phenolic resin adhesive, including walk as follows
It is rapid:
Step 1: preparing anacardol cyano resin:
It weighs 40g anacardol, 17g 4- nitrophthalonitrile and 120g n,N-dimethylacetamide and reaction flask is added,
Being sufficiently stirred is completely dissolved 4- nitrophthalonitrile, and after mixing with anacardol, weighs the addition of 23g Anhydrous potassium carbonate
Temperature under stirring, is risen to 60 DEG C, reacts 16h by reaction flask, after reaction, cooling, is stood, supernatant liquid is poured into liquid separation
It is washed 3 times in 20 DEG C of 1000ml water, butanone extraction is added, vacuum distillation removes moisture and butanone, and it is as low to collect gains
Viscous liquid anacardol cyano resin, viscosity is 420mPas at 25 DEG C.
The infrared spectroscopy of anacardol cyano resin is measured as shown in figure 1 shown in A curve with coating method, as the result is shown anacardol nitrile
Base resin is in (2230~2235) cm-1Locate appearance-C ≡ N- base characteristic absorption peak.
Step 2: preparing phenolic resin:
It weighs 100g phenol and 146g formaldehyde is added in reactor, start stirring, be warming up to 97 DEG C, 1.06g oxygen is added
Change zinc, maintain the reflux for temperature be 97 DEG C, react when reaction solution cloud point temperature reaches 65 DEG C terminates, at this time reaction used in the time be
Then 6h is washed with water reaction solution 2 times, then adjust vacuum degree and reach 6kPa, and heating carries out vacuum dehydration, when the gel of resin
Between resin is down to room temperature when reaching 102 seconds, solvent ethyl acetate is added, additional amount 45g obtains the phenol of brown solution shape
Urea formaldehyde, solid content 69%；
Step 3: preparing itrile group phenolic resin:
The phenolic resin of the solid content 69% of 28g step 2 preparation, the N of 30g4- nitrophthalonitrile and 130g are weighed,
N- dimethyl acetamide is added in reactor, and control reaction solution pH is 11, is warming up to 60 DEG C, 33g is added after stirring and dissolving
Catalyst b potassium carbonate, insulation reaction 16h are cleaned with distilled water after dropping to room temperature, then are extracted with ethyl acetate, are used
The dilute hydrochloric acid that concentration is 5% neutralizes, and separates through separatory funnel, adjusts vacuum degree and reaches 6kPa, and heating carries out vacuum desolvation agent, when
Resin is down to room temperature when the gel time of resin reaches 160 seconds, ethyl acetate is added, additional amount 20g obtains itrile group phenolic aldehyde
Resin.
Step 4: preparing modified by cardanol itrile group phenolic resin adhesive:
Mass parts are pressed at room temperature by itrile group phenolic aldehyde obtained by anacardol cyano resins obtained by 5 parts of step 1 and 100 parts of step 3
Resin, which is sufficiently mixed, uniformly obtains modified by cardanol itrile group phenolic resin adhesive.
Fig. 2 is itrile group phenolic resin and modified by cardanol itrile group phenolic resin gluing manufactured in the present embodiment under nitrogen atmosphere
The TGA curve comparison figure of agent；As shown in Fig. 2, when anacardol cyano resin is added 5 parts by mass fraction, TGA test result table
Bright, 5% weightless temperature of adhesive solidfied material nitrogen atmosphere is 397 DEG C, and 800 DEG C of carbon residues are 70%, the itrile group phenol not being modified
5% weightless temperature of urea formaldehyde and 800 DEG C of carbon residues are respectively 399 DEG C and 73%；Adhesive property test result shows modified resin
The room temperature shear strength of adhesive is 9.07MPa, improves 22% more before modified, 300 DEG C and 350 DEG C of shear strength is respectively
10.87MPa and 5.22MPa, strength retention is respectively 100% and 109% more before modified.
Embodiment 8
The present embodiment provides a kind of specific preparation methods of modified by cardanol itrile group phenolic resin adhesive, including walk as follows
It is rapid:
Step 1: preparing anacardol cyano resin:
It weighs 40g anacardol, 23g 4- nitrophthalonitrile and 140g n,N-dimethylacetamide and reaction flask is added,
Being sufficiently stirred is completely dissolved 4- nitrophthalonitrile, and after mixing with anacardol, weighs the addition of 30g Anhydrous potassium carbonate
Temperature under stirring, is risen to 60 DEG C, reacts 16h by reaction flask, after reaction, cooling, is stood, supernatant liquid is poured into liquid separation
It is washed 3 times in 20 DEG C of 1000ml cold water, butanone extraction is added, vacuum distillation removes moisture and solvent, collects gains, obtains
Low-viscosity (mobile) liquid anacardol cyano resin, viscosity is 600mPas at 25 DEG C.
The infrared spectroscopy of product is measured as shown in figure 1 shown in B curve with coating method, and anacardol cyano resin exists as the result is shown
(2230~2235) cm-1Locate appearance-C ≡ N- base absorption peak.
Step 2: preparing phenolic resin:
It weighs 100g phenol and 146g formaldehyde is added in reactor, start stirring, be warming up to 97 DEG C, 1.06g oxygen is added
Change zinc, maintain the reflux for temperature be 97 DEG C, react when reaction solution cloud point temperature reaches 65 DEG C terminates, at this time reaction used in the time be
Then 6h is washed with water reaction solution 2 times, then adjust vacuum degree and reach 6kPa, and heating carries out vacuum dehydration, when the gel of resin
Between resin is down to room temperature when reaching 102 seconds, solvent ethyl acetate is added, additional amount 45g obtains the phenol of brown solution shape
Urea formaldehyde, solid content 69%.
Step 3: preparing itrile group phenolic resin:
The phenolic resin of the solid content 69% of 28g step 2 preparation, the N of 30g4- nitrophthalonitrile and 130g are weighed,
N- dimethyl acetamide is added in reactor, and control reaction solution pH is 11, is warming up to 60 DEG C, 33g is added after stirring and dissolving
Catalyst b potassium carbonate, insulation reaction 16h are cleaned with distilled water after dropping to room temperature, then are extracted with ethyl acetate, are used
The dilute hydrochloric acid that concentration is 5% neutralizes, and separates through separatory funnel, adjusts vacuum degree and reaches 6kPa, and heating carries out vacuum desolvation agent, when
Resin is down to room temperature when the gel time of resin reaches 160 seconds, ethyl acetate is added, additional amount 20g obtains itrile group phenolic aldehyde
Resin.
Step 4: preparing modified by cardanol itrile group phenolic resin adhesive:
Mass parts are pressed at room temperature by itrile group phenolic aldehyde obtained by anacardol cyano resins obtained by 5 parts of step 1 and 100 parts of step 3
Resin, which is sufficiently mixed, uniformly obtains modified by cardanol itrile group phenolic resin adhesive.
Fig. 3 is the itrile group phenolic resin and modified by cardanol itrile group phenolic resin gluing that under nitrogen atmosphere prepared by embodiment 8
The TGA curve comparison figure of agent, as shown in figure 3, when anacardol cyano resin is added 5 parts by mass fraction, TGA test result table
Bright, 5% weightless temperature of adhesive solidfied material nitrogen atmosphere is 380 DEG C, and 800 DEG C of carbon residues are 72%, the itrile group phenol not being modified
5% weightless temperature of urea formaldehyde and 800 DEG C of carbon residues are respectively 399 DEG C and 73%；Adhesive property test result shows adhesive
Room temperature shear strength is 9.79MPa, improves 32% more before modified, 300 DEG C and 350 DEG C of shear strength be respectively 10.97MPa with
5.55MPa, resin conservation rate is respectively 102% and 116% more before modified.
Embodiment 9
The present embodiment provides a kind of specific preparation methods of modified by cardanol itrile group phenolic resin adhesive, including walk as follows
It is rapid:
Step 1: preparing anacardol cyano resin:
It weighs 40g anacardol, 14g 4- nitrophthalonitrile and 210g n,N-dimethylacetamide and reaction flask is added,
Being sufficiently stirred is completely dissolved 4- nitrophthalonitrile, and after mixing with anacardol, weighs 40g and add without water sodium hydroxide
Enter reaction flask, under stirring, temperature is risen to 70 DEG C, reacts 10h, it is after reaction, cooling, it stands, supernatant liquid is fallen in liquid separation
Entering in 20 DEG C of 1000ml cold water and wash 3 times, toluene extraction is added, vacuum distillation removes moisture and solvent, gains are collected,
Obtain low-viscosity (mobile) liquid anacardol cyano resin.
Step 2: preparing phenolic resin:
It weighs 100g phenol and 160g formaldehyde is added in reactor, start stirring, be warming up to 98 DEG C, 3.2g hydrogen-oxygen is added
Change sodium, maintain the reflux for temperature be 98 DEG C, react when reaction solution cloud point temperature reaches 70 DEG C terminates, at this time reaction used in the time be
Then 6.5h is washed with water reaction solution 2 times, then adjust vacuum degree and reach 7kPa, and heating carries out vacuum dehydration, when the gel of resin
Resin is down to room temperature when time reaches 200 seconds, solvent ethyl acetate is added, additional amount 45g obtains brown solution shape
Phenolic resin, solid content 73%.
Step 3: preparing itrile group phenolic resin:
The phenolic resin of the solid content 73% of 28g step 2 preparation, the N of 40g4- nitrophthalonitrile and 140g are weighed,
N- dimethyl acetamide is added in reactor, and control reaction solution pH is 9, is warming up to 65 DEG C, and 33g is added after stirring and dissolving and urges
Agent b potassium carbonate, insulation reaction 15h are cleaned with distilled water after dropping to room temperature, then are extracted with ethyl acetate, and use is dense
Degree neutralizes for 5% dilute hydrochloric acid, separates through separatory funnel, adjusts vacuum degree and reaches 7kPa, heating carries out vacuum desolvation agent, works as tree
Resin is down to room temperature when the gel time of rouge reaches 130 seconds, ethyl acetate is added, additional amount 26g obtains itrile group phenolic aldehyde tree
Rouge.
Step 4: preparing modified by cardanol itrile group phenolic resin adhesive:
Mass parts are pressed at room temperature by itrile group phenolic aldehyde obtained by anacardol cyano resins obtained by 20 parts of step 1 and 100 parts of step 3
Resin, which is sufficiently mixed, uniformly obtains modified by cardanol itrile group phenolic resin adhesive.
Embodiment 10
The present embodiment provides a kind of specific preparation methods of modified by cardanol itrile group phenolic resin adhesive, including walk as follows
It is rapid:
Step 1: preparing anacardol cyano resin:
It weighs 40g anacardol, 25g 4- nitrophthalonitrile and 240g n,N-dimethylacetamide and reaction flask is added,
Being sufficiently stirred is completely dissolved 4- nitrophthalonitrile, and after mixing with anacardol, weighs 50g anhydrous barium hydroxide and adds
Enter reaction flask, under stirring, temperature is risen to 80 DEG C, reacts 14h, it is after reaction, cooling, it stands, supernatant liquid is fallen in liquid separation
Entering in 20 DEG C of 1000ml cold water and wash 3 times, acetone extract is added, vacuum distillation removes moisture and solvent, gains are collected,
Obtain low-viscosity (mobile) liquid anacardol cyano resin.
Step 2: preparing phenolic resin:
It weighs 100g phenol and 180 formaldehyde is added in reactor, start stirring, be warming up to 99 DEG C, 3.6g hydrogen-oxygen is added
Change potassium, maintain the reflux for temperature be 99 DEG C, react when reaction solution cloud point temperature reaches 75 DEG C terminates, at this time reaction used in the time be
Then 7h is washed with water reaction solution 2 times, then adjust vacuum degree and reach 8kPa, and heating carries out vacuum dehydration, when the gel of resin
Between resin is down to room temperature when reaching 300 seconds, solvent ethyl acetate is added, additional amount 47g obtains the phenol of brown solution shape
Urea formaldehyde, solid content 56%.
Step 3: preparing itrile group phenolic resin:
The phenolic resin of the solid content 56% of 28g step 2 preparation, the N of 50g4- nitrophthalonitrile and 150g are weighed,
N- dimethyl acetamide is added in reactor, and control reaction solution pH is 10, is warming up to 70 DEG C, 33g is added after stirring and dissolving
Catalyst b potassium carbonate, insulation reaction 14h are cleaned with distilled water after dropping to room temperature, then are extracted with ethyl acetate, are used
The dilute hydrochloric acid that concentration is 5% neutralizes, and separates through separatory funnel, adjusts vacuum degree and reaches 8kPa, and heating carries out vacuum desolvation agent, when
Resin is down to room temperature when the gel time of resin reaches 190 seconds, ethyl acetate is added, additional amount 34g obtains itrile group phenolic aldehyde
Resin.
Step 4: preparing modified by cardanol itrile group phenolic resin adhesive:
Mass parts are pressed at room temperature by itrile group phenolic aldehyde obtained by anacardol cyano resins obtained by 35 parts of step 1 and 100 parts of step 3
Resin, which is sufficiently mixed, uniformly obtains modified by cardanol itrile group phenolic resin adhesive.
Claims (10)
1. a kind of modified by cardanol itrile group phenolic resin adhesive, which is characterized in that the component including following mass parts: 100 parts
Itrile group phenolic resin and 2.5~50 parts of anacardol cyano resins.
2. a kind of modified by cardanol itrile group phenolic resin adhesive according to claim 1, which is characterized in that the anacardol
The structural formula of cyano resin are as follows:
Wherein, R=C15H32-n。
3. a kind of preparation method of modified by cardanol itrile group phenolic resin adhesive as claimed in claim 1 or 2, feature exist
In including the following steps:
Step 1: preparing anacardol cyano resin:
Anacardol and nitro substitution phthalonitrile are weighed by certain mol proportion and is put into organic solvent, are sufficiently stirred
To uniform mixed liquor, a certain amount of basic catalyst is added in Xiang Suoshu mixed liquor, makes reaction system side at a certain temperature
It stirs side and reacts certain time, be after reaction cooled to room temperature products therefrom, stratification, collect supernatant liquid through water
It washes, solvent extraction, vacuum distillation obtain anacardol cyano resin；
Step 2: preparing phenolic resin:
Phenol and formaldehyde are uniformly mixed by certain mol proportion, catalyst a is added under certain reaction temperature, keeps reaction temperature
And reacted under stirring, when reaction solution reaches cloud point temperature, reaction was completed, and reaction solution is washed with water and vacuum is de-
Resin is down to room temperature when the gel time of resin reaches 90~600 seconds by water, and solvent is added and obtains phenolic resin；
Step 3: preparing itrile group phenolic resin:
Phenolic resin made from step 2,4- nitrophthalonitrile and N,N-dimethylformamide are mixed by certain mol proportion
It closes, catalyst b is added under certain reaction temperature, control reaction system insulation reaction certain time under certain pH, make to react
System is down to room temperature and is extracted through distilled water cleaning, ethyl acetate, dilute hydrochloric acid neutralizes, separatory funnel separates and vacuum desolvation agent,
Resin is down to room temperature when the gel time of gained resin reaches 90~600 seconds, solvent is added and obtains itrile group phenolic resin；
Step 4: preparing modified by cardanol itrile group phenolic resin adhesive:
Mass parts are pressed at room temperature by itrile group phenol obtained by anacardol cyano resins obtained by 2.5~50 parts of step 1 and 100 parts of step 3
Urea formaldehyde, which is sufficiently mixed, uniformly obtains modified by cardanol itrile group phenolic resin adhesive.
4. a kind of preparation method of modified by cardanol itrile group phenolic resin adhesive according to claim 3, which is characterized in that
Nitro described in step 1 replaces phthalonitrile to be that contraposition nitro replaces phthalonitrile；The anacardol and nitro replace adjacent benzene
The molar ratio of dimethoxy nitrile is 1:(0.5~1)；The organic solvent is dimethyl sulfoxide, N,N-dimethylformamide or N, N- bis-
One of methylacetamide；The dosage of the organic solvent is the 2-5 that anacardol and nitro replace phthalonitrile total weight
Times.
5. according to a kind of preparation method of modified by cardanol itrile group phenolic resin adhesive of claim 3 or 4, feature exists
In basic catalyst described in step 1 is one of sodium hydroxide, barium hydroxide, sodium carbonate or potassium carbonate, and the alkalinity is urged
The additional amount of agent is 0.5~2.0 times that nitro replaces phthalonitrile mole；The reaction temperature of the system is 60~90
DEG C, the reaction time is 6~16h.
6. a kind of preparation method of modified by cardanol itrile group phenolic resin adhesive according to claim 5, which is characterized in that
Washing described in step 1 is that the water for being 0~25 DEG C with 8~10 times of supernatant liquid weight of temperature is washed supernatant liquid 3~5 times；Institute
It is one of toluene, ethyl acetate, acetone or butanone that extraction, which is stated, with solvent.
7. a kind of preparation method of modified by cardanol itrile group phenolic resin adhesive according to claim 6, which is characterized in that
The molar ratio of phenol and formaldehyde described in step 2 is 1:(1.2~2.0), the reaction temperature is 90~100 DEG C, the catalyst
A is one of ammonium hydroxide, sodium hydroxide, potassium hydroxide or zinc oxide, and the additional amount of the catalyst a is the 0.5 of phenol weight
~5%.
8. a kind of preparation method of modified by cardanol itrile group phenolic resin adhesive according to claim 7, which is characterized in that
Cloud point temperature described in step 2 is 60~80 DEG C, and the vacuum degree of the vacuum dehydration is 5~10kPa, and the solvent is butanone, third
One of ketone or ethyl acetate.
9. a kind of preparation method of modified by cardanol itrile group phenolic resin adhesive according to claim 8, which is characterized in that
The molar ratio of phenolic resin described in step 3,4- nitrophthalonitrile and N,N-dimethylformamide is 1:(3~7): (30~
80), the catalyst b is potassium carbonate or sodium carbonate, and the additional amount of the catalyst b is 4- nitrophthalonitrile mole
0.5~2.0 times.
10. a kind of preparation method of modified by cardanol itrile group phenolic resin adhesive, feature exist according to claim 9
In reaction temperature described in step 3 is 60~80 DEG C, and the pH value is 9~11, and the insulation reaction time is 12~18h, institute
The vacuum degree for stating vacuum desolvation agent is 5~10kPa, and the solvent is one of butanone, acetone or ethyl acetate.
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| CN113136106A (en) * | 2021-05-18 | 2021-07-20 | 湖南飞鸿达新材料有限公司 | Thin-sheet type heat-conducting wave-absorbing composite material |
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|---|---|---|---|---|
| CN106753100A (en) * | 2016-12-08 | 2017-05-31 | 黑龙江省科学院石油化学研究院 | Inorganic nano particle hybridization synvaren and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106753100A (en) * | 2016-12-08 | 2017-05-31 | 黑龙江省科学院石油化学研究院 | Inorganic nano particle hybridization synvaren and preparation method thereof |
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| GIUSEPPE VASAPOLLO等: ""Cardanol-Based Materials as Natural Precursors for Olefin Metathesis"", 《MOLECULES》 * |
| 刘国际等: "腰果酚的应用研究进展", 《材料导报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113136106A (en) * | 2021-05-18 | 2021-07-20 | 湖南飞鸿达新材料有限公司 | Thin-sheet type heat-conducting wave-absorbing composite material |
| CN113136106B (en) * | 2021-05-18 | 2021-12-21 | 湖南飞鸿达新材料有限公司 | Thin-sheet type heat-conducting wave-absorbing composite material |
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