CN110105905B - Cardanol modified nitrile-based phenolic resin adhesive and preparation method thereof - Google Patents

Cardanol modified nitrile-based phenolic resin adhesive and preparation method thereof Download PDF

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CN110105905B
CN110105905B CN201910501143.3A CN201910501143A CN110105905B CN 110105905 B CN110105905 B CN 110105905B CN 201910501143 A CN201910501143 A CN 201910501143A CN 110105905 B CN110105905 B CN 110105905B
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nitrile
phenolic resin
cardanol
resin
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CN110105905A (en
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蔡学广
张大勇
刘晓辉
荣立平
王刚
李欣
朱金华
赵颖
米长虹
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Institute of Petrochemistry of Heilongjiang Academy of Sciences
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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
    • 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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Abstract

The invention relates to a cardanol modified nitrile-based phenolic resin adhesive and a preparation method thereof, and belongs to the technical field of adhesives. In order to solve the problems of large brittleness, low bonding strength, large viscosity and poor process performance of the conventional phenolic resin, the invention provides a cardanol modified nitrile-based phenolic resin adhesive, which comprises nitrile-based phenolic resin and cardanol nitrile-based resin; the preparation method comprises the steps of preparing cardanol nitrile-based resin, preparing phenolic resin, preparing nitrile-based phenolic resin and modifying the nitrile-based phenolic resin by using the cardanol nitrile-based resin to obtain the adhesive. According to the invention, by utilizing the characteristics of low viscosity and high temperature resistance activity of the cardanol nitrile-based resin, the cardanol nitrile-based resin is used for modifying the nitrile-based phenolic resin, so that the flexibility and the bonding performance of the adhesive are improved, and the viscosity of the nitrile-based phenolic resin is obviously reduced, thereby improving the processing technological performance of the high temperature resistant adhesive, reducing the usage amount of a solvent, and being an environment-friendly material.

Description

Cardanol modified nitrile-based phenolic resin adhesive and preparation method thereof
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to a cardanol modified nitrile-based phenolic resin adhesive and a preparation method thereof.
Background
The cashew nut shell oil is prepared by processing the shells of natural products cashew nuts as raw materials through multiple working procedures, the main components of the cashew nut shell oil are anacardic acid and cardol, and the anacardic acid and the cardol are further decarboxylated and subjected to reduced pressure distillation treatment to obtain the cardanol. The freshly prepared cardanol is a light yellow slightly transparent oily liquid with a slightly pungent taste and a viscosity of about 94 mPas at 25 ℃. The structural formula of the cardanol is shown as (I), the structural unit of the cardanol contains a phenolic hydroxyl group and an alkyl long-chain structure, the cardanol has the rigidity of a benzene ring and the flexibility brought by a long carbon chain, and the cardanol is a renewable resource, rich in source and low in price, so that the cardanol has a wide application field and has a very important application value. For example, the cashew nut phenolic aldehyde resin is used for synthesizing cashew nut phenolic aldehyde resin, and partially replaces phenol modified phenol formaldehyde resin, so that the performances such as toughness and the like are improved; friction property modifiers for friction materials, and the like.
Figure BDA0002090260870000011
Wherein R ═ C15H32-n。
The phenolic resin is a polymer resin variety with low price and excellent comprehensive performance, has good mechanical strength and heat resistance, particularly has outstanding instantaneous high-temperature ablation resistance, and can be used for manufacturing adhesives, coatings, composite materials and the like. However, when the working temperature exceeds 300 ℃, the phenolic resin has problems of severe oxidative decomposition and the like, and the application range is limited. The phthalonitrile resin is a novel high-temperature resistant resin, the glass transition temperature of a condensate is more than 450 ℃, the condensate has excellent mechanical property and excellent moisture resistance and chemical corrosion resistance, and the like, the high-temperature property of the phenolic resin can be obviously improved by introducing the structure of the phthalonitrile resin into a phenolic structure, but the condensate has the problems of larger brittleness, lower bonding strength and the like. The traditional method for toughening the phenolic aldehyde is to introduce a high-temperature resistant toughening agent, such as heat-resistant thermoplastic resin, heat-resistant copolymerized modified resin, nano filler and the like, and although the toughness and the bonding strength of the phenolic resin can be improved, the problems that the process viscosity of the modified resin is increased and the use process performance is poor exist.
Disclosure of Invention
The invention provides a cardanol modified nitrile-based phenolic resin adhesive and a preparation method thereof, and aims to solve the problems of high brittleness, low bonding strength, high viscosity and poor process performance of the conventional phenolic resin.
The technical scheme of the invention is as follows:
the cardanol modified nitrile-based phenolic resin adhesive comprises the following components in parts by mass: 100 parts of nitrile-based phenolic resin and 2.5-50 parts of cardanol nitrile-based resin.
Further, the structural formula of the cardanol nitrile resin is as follows:
Figure BDA0002090260870000021
wherein R ═ C15H32-n。
A preparation method of a cardanol modified nitrile-based phenolic resin adhesive comprises the following steps:
step one, preparation of cardanol nitrile resin:
weighing cardanol and nitro-substituted phthalonitrile according to a certain molar ratio, putting the cardanol and nitro-substituted phthalonitrile into an organic solvent, fully stirring to obtain a uniform mixed solution, adding a certain amount of alkaline catalyst into the mixed solution, stirring and reacting a reaction system at a certain temperature for a certain time, cooling an obtained product to room temperature after the reaction is finished, standing for layering, collecting upper-layer liquid, and washing, extracting with the solvent, and distilling under reduced pressure to obtain cardanol nitrile resin;
step two, preparing phenolic resin:
uniformly mixing phenol and formaldehyde according to a certain molar ratio, adding a catalyst a at a certain reaction temperature, keeping the reaction temperature, reacting in a stirring state, finishing the reaction when the reaction liquid reaches a cloud point temperature, washing the reaction liquid with water, performing vacuum dehydration, cooling the resin to the normal temperature when the gelation time of the resin reaches 90-600 seconds, and adding a solvent to obtain phenolic resin;
step three, preparing nitrile phenolic resin:
mixing the phenolic resin prepared in the second step, 4-nitrophthalonitrile and N, N-dimethylformamide according to a certain molar ratio, adding a catalyst b at a certain reaction temperature, controlling the reaction system to perform heat preservation reaction for a certain time at a certain pH value, cooling the reaction system to room temperature, washing the reaction system with distilled water, extracting with ethyl acetate, neutralizing with dilute hydrochloric acid, separating with a separating funnel and removing a solvent in vacuum, cooling the resin to room temperature when the gel time of the obtained resin reaches 90-600 seconds, and adding the solvent to obtain the nitrile-based phenolic resin;
step four, preparing the cardanol modified nitrile-based phenolic resin adhesive:
and (3) fully and uniformly mixing 2.5-50 parts of the cardanol nitrile-based resin obtained in the first step and 100 parts of nitrile-based phenolic resin obtained in the third step at room temperature according to the mass parts to obtain the cardanol modified nitrile-based phenolic resin adhesive.
Further, the nitro-substituted phthalonitrile in the step one is para-nitro-substituted phthalonitrile; the molar ratio of cardanol to nitro-substituted phthalonitrile is 1: (0.5 to 1); the organic solvent is one of dimethyl sulfoxide, N-dimethylformamide or N, N-dimethylacetamide; the dosage of the organic solvent is 2-5 times of the total weight of the cardanol and the nitro-substituted phthalonitrile.
Further, in the step one, the alkaline catalyst is one of sodium hydroxide, barium hydroxide, sodium carbonate or potassium carbonate, and the addition amount of the alkaline catalyst is 0.5-2.0 times of the molar amount of the nitro-substituted phthalonitrile; the reaction temperature of the system is 60-90 ℃, and the reaction time is 6-16 h.
Further, in the step one, washing the upper layer liquid for 3-5 times by using water with the weight 8-10 times of the weight of the upper layer liquid and the temperature of 0-25 ℃; the solvent for extraction is one of toluene, ethyl acetate, acetone or butanone.
Further, the molar ratio of the phenol to the formaldehyde in the second step is 1 (1.2-2.0), the reaction temperature is 90-100 ℃, the catalyst a is one of ammonia water, sodium hydroxide, potassium hydroxide or zinc oxide, and the addition amount of the catalyst a is 0.5-5% of the weight of the phenol.
Further, in the second step, the cloud point temperature is 60-80 ℃, the vacuum degree of vacuum dehydration is 5-10 kPa, and the solvent is one of butanone, acetone or ethyl acetate.
And further, in the third step, the molar ratio of the phenolic resin to the 4-nitrophthalonitrile to the N, N-dimethylformamide is 1 (3-7) to (30-80), the catalyst b is potassium carbonate or sodium carbonate, and the addition amount of the catalyst b is 0.5-2.0 times of the molar amount of the 4-nitrophthalonitrile.
Further, in the third step, the reaction temperature is 60-80 ℃, the pH value is 9-11, the heat preservation reaction time is 12-18 h, the vacuum degree of the vacuum desolventizing agent is 5-10 kPa, and the solvent is one of butanone, acetone or ethyl acetate.
The invention has the beneficial effects that:
according to the invention, a phthalonitrile heat-resistant structure is introduced into the cardanol structure, and a polymerization crosslinking reaction can be carried out between nitrile groups under the conditions of heating and a catalyst to form the heat-resistant structure, so that the adverse effect of a cardanol meta-position long chain with a toughening effect on the heat resistance of the modified resin can be reduced. The prepared cardanol nitrile resin is novel low-viscosity high-temperature-resistant active resin, is low-viscosity liquid at room temperature, and has viscosity of not more than 600mPa & s at 25 ℃.
The cardanol nitrile-based resin modified nitrile-based phenolic resin prepared by the invention can improve the flexibility and the bonding performance of the adhesive and simultaneously obviously reduce the viscosity of the nitrile-based phenolic resin, thereby improving the processing technological performance of the high-temperature-resistant adhesive, reducing the using amount of a solvent during use and being an environment-friendly material.
Drawings
Fig. 1 is an infrared spectrum of the cardanol nitrile-based resin prepared in examples 7 and 8, wherein a is the cardanol nitrile-based resin prepared in example 7, and B is the cardanol nitrile-based resin prepared in example 8;
FIG. 2 is a comparative TGA curve of the nitrile-based phenolic resin and cardanol modified nitrile-based phenolic resin adhesive prepared in example 7;
fig. 3 is a TGA curve comparison graph of the nitrile-based phenolic resin and cardanol modified nitrile-based phenolic resin adhesives prepared in example 8.
Detailed Description
The technical solutions of the present invention are further described below with reference to the following examples, but the present invention is not limited thereto, and any modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Example 1
The cardanol modified nitrile-based phenolic resin adhesive comprises the following components in parts by mass: 100 parts of nitrile-based phenolic resin and 2.5-50 parts of cardanol nitrile-based resin.
Example 2
The cardanol modified nitrile-based phenolic resin adhesive comprises the following components in parts by mass: 100 parts of nitrile-based phenolic resin and 2.5-50 parts of cardanol nitrile-based resin, wherein the structural formula of the cardanol nitrile-based resin is as follows:
Figure BDA0002090260870000041
wherein R ═ C15H32-n。
The viscosity of the cardanol nitrile-based resin used in this example at 25 ℃ is not more than 600mPa · s,
example 3
The embodiment provides a preparation method of a cardanol modified nitrile-based phenolic resin adhesive, which comprises the following steps:
step one, preparation of cardanol nitrile resin:
weighing cardanol and nitro-substituted phthalonitrile according to a certain molar ratio, putting the cardanol and nitro-substituted phthalonitrile into an organic solvent, fully stirring to obtain a uniform mixed solution, adding a certain amount of alkaline catalyst into the mixed solution, stirring and reacting a reaction system at a certain temperature for a certain time, cooling an obtained product to room temperature after the reaction is finished, standing for layering, collecting upper-layer liquid, and washing, extracting with the solvent, and distilling under reduced pressure to obtain cardanol nitrile resin;
step two, preparing phenolic resin:
uniformly mixing phenol and formaldehyde according to a certain molar ratio, adding a catalyst a at a certain reaction temperature, keeping the reaction temperature, reacting in a stirring state, finishing the reaction when the reaction liquid reaches a cloud point temperature, washing the reaction liquid with water, performing vacuum dehydration, cooling the resin to the normal temperature when the gelation time of the resin reaches 90-600 seconds, and adding a solvent to obtain phenolic resin;
step three, preparing nitrile phenolic resin:
mixing the phenolic resin prepared in the second step, 4-nitrophthalonitrile and N, N-dimethylformamide according to a certain molar ratio, adding a catalyst b at a certain reaction temperature, controlling the reaction system to perform heat preservation reaction for a certain time at a certain pH value, cooling the reaction system to room temperature, washing the reaction system with distilled water, extracting with ethyl acetate, neutralizing with dilute hydrochloric acid, separating with a separating funnel and removing a solvent in vacuum, cooling the resin to room temperature when the gel time of the obtained resin reaches 90-600 seconds, and adding the solvent to obtain the nitrile-based phenolic resin;
step four, preparing the cardanol modified nitrile-based phenolic resin adhesive:
and (3) fully and uniformly mixing 2.5-50 parts of the cardanol nitrile-based resin obtained in the first step and 100 parts of nitrile-based phenolic resin obtained in the third step at room temperature according to the mass parts to obtain the cardanol modified nitrile-based phenolic resin adhesive.
Example 4
The embodiment provides a preparation method of a cardanol modified nitrile-based phenolic resin adhesive, which comprises the following steps:
step one, preparation of cardanol nitrile resin:
according to the mol ratio of 1: (0.5-1) weighing cardanol and para-nitro-substituted phthalonitrile and putting the cardanol and para-nitro-substituted phthalonitrile into an organic solvent, wherein the organic solvent is one of dimethyl sulfoxide, N-dimethylformamide or N, N-dimethylacetamide, and the dosage of the organic solvent is 2-5 times of the total weight of the cardanol and the nitro-substituted phthalonitrile. Fully stirring to obtain a uniform mixed solution, and adding an alkaline catalyst with the molar weight 0.5-2.0 times that of the para-nitro-substituted phthalonitrile into the mixed solution, wherein the alkaline catalyst is one of sodium hydroxide, barium hydroxide, sodium carbonate or potassium carbonate. And (2) stirring the reaction system at the temperature of 60-90 ℃ for reacting for 6-16 h, cooling the obtained product to room temperature after the reaction is finished, standing for layering, collecting upper-layer liquid, washing the upper-layer liquid for 3-5 times by using water with the weight of 8-10 times of the weight of the upper-layer liquid and the temperature of 0-25 ℃, extracting by using any one of toluene, ethyl acetate, acetone or butanone as a solvent, and distilling under reduced pressure to obtain the cardanol nitrile-based resin.
Step two, preparing phenolic resin:
uniformly mixing phenol and formaldehyde according to a certain molar ratio, adding a catalyst a at a certain reaction temperature, keeping the reaction temperature, reacting in a stirring state, finishing the reaction when the reaction liquid reaches a cloud point temperature, washing the reaction liquid with water, performing vacuum dehydration, cooling the resin to the normal temperature when the gelation time of the resin reaches 90-600 seconds, and adding a solvent to obtain phenolic resin;
step three, preparing nitrile phenolic resin:
mixing the phenolic resin prepared in the second step, 4-nitrophthalonitrile and N, N-dimethylformamide according to a certain molar ratio, adding a catalyst b at a certain reaction temperature, controlling the reaction system to perform heat preservation reaction for a certain time at a certain pH value, cooling the reaction system to room temperature, washing the reaction system with distilled water, extracting with ethyl acetate, neutralizing with dilute hydrochloric acid, separating with a separating funnel and removing a solvent in vacuum, cooling the resin to room temperature when the gel time of the obtained resin reaches 90-600 seconds, and adding the solvent to obtain the nitrile-based phenolic resin;
step four, preparing the cardanol modified nitrile-based phenolic resin adhesive:
and (3) fully and uniformly mixing 2.5-50 parts of the cardanol nitrile-based resin obtained in the first step and 100 parts of nitrile-based phenolic resin obtained in the third step at room temperature according to the mass parts to obtain the cardanol modified nitrile-based phenolic resin adhesive.
In the embodiment, a phthalonitrile heat-resistant structure is introduced into the cardanol structure, a polymerization crosslinking reaction can occur between nitrile groups under the conditions of heating and a catalyst, a heat-resistant structure is formed, and adverse effects of a cardanol meta-position long chain with a toughening effect on the heat resistance of the modified resin can be reduced. The prepared cardanol nitrile resin is novel low-viscosity high-temperature-resistant active resin, is low-viscosity liquid at room temperature, and has viscosity of not more than 600mPa & s at 25 ℃.
Example 5
The embodiment provides a preparation method of a cardanol modified nitrile-based phenolic resin adhesive, which comprises the following steps:
step one, preparation of cardanol nitrile resin:
according to the mol ratio of 1: (0.5-1) weighing cardanol and para-nitro-substituted phthalonitrile and putting the cardanol and para-nitro-substituted phthalonitrile into an organic solvent, wherein the organic solvent is one of dimethyl sulfoxide, N-dimethylformamide or N, N-dimethylacetamide, and the dosage of the organic solvent is 2-5 times of the total weight of the cardanol and the nitro-substituted phthalonitrile. Fully stirring to obtain a uniform mixed solution, and adding an alkaline catalyst with the molar weight 0.5-2.0 times that of the para-nitro-substituted phthalonitrile into the mixed solution, wherein the alkaline catalyst is one of sodium hydroxide, barium hydroxide, sodium carbonate or potassium carbonate. And (2) stirring the reaction system at the temperature of 60-90 ℃ for reacting for 6-16 h, cooling the obtained product to room temperature after the reaction is finished, standing for layering, collecting upper-layer liquid, washing the upper-layer liquid for 3-5 times by using water with the weight of 8-10 times of the weight of the upper-layer liquid and the temperature of 0-25 ℃, extracting by using any one of toluene, ethyl acetate, acetone or butanone as a solvent, and distilling under reduced pressure to obtain the cardanol nitrile-based resin.
Step two, preparing phenolic resin:
uniformly mixing phenol and formaldehyde according to a molar ratio of 1 (1.2-2.0), adding a catalyst a accounting for 0.5-5% of the weight of the phenol at a reaction temperature of 90-100 ℃, wherein the catalyst a is one of ammonia water, sodium hydroxide, potassium hydroxide or zinc oxide, keeping the reaction temperature and reacting under a stirring state, finishing the reaction when the reaction liquid reaches a cloud point temperature, namely 60-80 ℃, washing the reaction liquid with water, carrying out vacuum dehydration under a vacuum degree of 5-10 kPa, cooling the resin to the normal temperature when the gelation time of the resin reaches 90-600 seconds, and adding any one of butanone, acetone or ethyl acetate to obtain the phenolic resin;
step three, preparing nitrile phenolic resin:
mixing the phenolic resin prepared in the step two, 4-nitrophthalonitrile and N, N-dimethylformamide according to a molar ratio of 1 (1.2-2.0), adding a catalyst b at a certain reaction temperature, controlling a reaction system to perform heat preservation reaction for a certain time at a certain pH value, cooling the reaction system to room temperature, washing with distilled water, extracting with ethyl acetate, neutralizing with dilute hydrochloric acid, separating with a separating funnel, and removing a solvent in vacuum, cooling the resin to room temperature when the gelation time of the obtained resin reaches 90-600 seconds, and adding a solvent to obtain nitrile-based phenolic resin;
step four, preparing the cardanol modified nitrile-based phenolic resin adhesive:
and (3) fully and uniformly mixing 2.5-50 parts of the cardanol nitrile-based resin obtained in the first step and 100 parts of nitrile-based phenolic resin obtained in the third step at room temperature according to the mass parts to obtain the cardanol modified nitrile-based phenolic resin adhesive.
Example 6
The embodiment provides a preparation method of a cardanol modified nitrile-based phenolic resin adhesive, which comprises the following steps:
step one, preparation of cardanol nitrile resin:
according to the mol ratio of 1: (0.5-1) weighing cardanol and para-nitro-substituted phthalonitrile and putting the cardanol and para-nitro-substituted phthalonitrile into an organic solvent, wherein the organic solvent is one of dimethyl sulfoxide, N-dimethylformamide or N, N-dimethylacetamide, and the dosage of the organic solvent is 2-5 times of the total weight of the cardanol and the nitro-substituted phthalonitrile. Fully stirring to obtain a uniform mixed solution, and adding an alkaline catalyst with the molar weight 0.5-2.0 times that of the para-nitro-substituted phthalonitrile into the mixed solution, wherein the alkaline catalyst is one of sodium hydroxide, barium hydroxide, sodium carbonate or potassium carbonate. And (2) stirring the reaction system at the temperature of 60-90 ℃ for reacting for 6-16 h, cooling the obtained product to room temperature after the reaction is finished, standing for layering, collecting upper-layer liquid, washing the upper-layer liquid for 3-5 times by using water with the weight of 8-10 times of the weight of the upper-layer liquid and the temperature of 0-25 ℃, extracting by using any one of toluene, ethyl acetate, acetone or butanone as a solvent, and distilling under reduced pressure to obtain the cardanol nitrile-based resin.
Step two, preparing phenolic resin:
uniformly mixing phenol and formaldehyde according to a molar ratio of 1 (1.2-2.0), adding a catalyst a accounting for 0.5-5% of the weight of the phenol at a reaction temperature of 90-100 ℃, wherein the catalyst a is one of ammonia water, sodium hydroxide, potassium hydroxide or zinc oxide, keeping the reaction temperature and reacting under a stirring state, finishing the reaction when the reaction liquid reaches a cloud point temperature, namely 60-80 ℃, washing the reaction liquid with water, carrying out vacuum dehydration under a vacuum degree of 5-10 kPa, cooling the resin to the normal temperature when the gelation time of the resin reaches 90-600 seconds, and adding any one of butanone, acetone or ethyl acetate to obtain the phenolic resin;
step three, preparing nitrile phenolic resin:
mixing the phenolic resin prepared in the step two, 4-nitrophthalonitrile and N, N-dimethylformamide according to a molar ratio of (3-7) (30-80), adding a catalyst b accounting for 1-5% of the weight of the phenolic resin at a reaction temperature of 60-80 ℃, wherein the catalyst b is potassium carbonate or sodium carbonate, controlling the reaction system to perform heat preservation reaction for 12-18 hours under the condition that the pH value is 9-11, cooling the reaction system to room temperature, cleaning the reaction system with distilled water, extracting with ethyl acetate, neutralizing with dilute hydrochloric acid, separating with a separating funnel, and performing vacuum desolventization under the condition that the vacuum degree is 5-10 kPa, cooling the resin to room temperature when the gelation time of the obtained resin reaches 90-600 seconds, and adding any one of butanone, acetone or ethyl acetate to obtain the nitrile-based phenolic resin;
step four, preparing the cardanol modified nitrile-based phenolic resin adhesive:
and (3) fully and uniformly mixing 2.5-50 parts of the cardanol nitrile-based resin obtained in the first step and 100 parts of nitrile-based phenolic resin obtained in the third step at room temperature according to the mass parts to obtain the cardanol modified nitrile-based phenolic resin adhesive.
Example 7
The embodiment provides a specific preparation method of a cardanol modified nitrile-based phenolic resin adhesive, which comprises the following steps:
step one, preparation of cardanol nitrile resin:
weighing 40g of cardanol, 17g of 4-nitrophthalonitrile and 120g N, adding N-dimethylacetamide into a reaction bottle, fully stirring to completely dissolve 4-nitrophthalonitrile, uniformly mixing with cardanol, weighing 23g of anhydrous potassium carbonate, adding into the reaction bottle, stirring, raising the temperature to 60 ℃, reacting for 16 hours, cooling after the reaction is finished, standing, separating, pouring the upper layer liquid into 1000ml of water at 20 ℃ for washing for 3 times, adding butanone for extraction, carrying out reduced pressure distillation, removing water and butanone, and collecting the obtained product, namely the low-viscosity liquid cardanol nitrile resin, wherein the viscosity is 420mPa & s at 25 ℃.
The infrared spectrum of the cardanol nitrile-based resin measured by a coating method is shown as a curve A in figure 1, and the result shows that the cardanol nitrile-based resin is (2230-2235) cm-1A characteristic absorption peak of the-C.ident.N-group appears.
Step two, preparing phenolic resin:
weighing 100g of phenol and 146g of formaldehyde, adding the phenol and the formaldehyde into a reactor, starting stirring, heating to 97 ℃, adding 1.06g of zinc oxide, keeping the reflux temperature at 97 ℃, finishing the reaction when the cloud point temperature of the reaction solution reaches 65 ℃, wherein the reaction time is 6h, washing the reaction solution for 2 times by using water, adjusting the vacuum degree to 6kPa, heating for vacuum dehydration, cooling the resin to the normal temperature when the gel time of the resin reaches 102 seconds, adding a solvent ethyl acetate, and adding 45g of ethyl acetate to obtain a phenolic resin in a brown solution state, wherein the solid content is 69%;
step three, preparing nitrile phenolic resin:
weighing 28g of phenolic resin with the solid content of 69% prepared in the second step, 30g of 4-nitrophthalonitrile and 130g of N, N-dimethylacetamide, adding the phenolic resin, the 4-nitrophthalonitrile and the N, N-dimethylacetamide into a reactor, controlling the pH value of a reaction solution to be 11, heating to 60 ℃, stirring to dissolve, adding 33g of catalyst b potassium carbonate, keeping the temperature for reaction for 16h, cooling to room temperature, cleaning with distilled water, extracting with ethyl acetate, neutralizing with 5% dilute hydrochloric acid, separating by a separating funnel, adjusting the vacuum degree to be 6kPa, heating to remove a solvent in vacuum, cooling the resin to room temperature when the gelation time of the resin reaches 160 seconds, adding ethyl acetate, and adding 20g of the ethyl acetate to obtain the nitrile-based phenolic resin.
Step four, preparing the cardanol modified nitrile-based phenolic resin adhesive:
and (3) fully and uniformly mixing 5 parts of the cardanol nitrile-based resin obtained in the first step and 100 parts of the nitrile-based phenolic resin obtained in the third step at room temperature according to the mass parts to obtain the cardanol modified nitrile-based phenolic resin adhesive.
FIG. 2 is a TGA curve comparison graph of the nitrile-based phenolic resin and cardanol modified nitrile-based phenolic resin adhesive prepared in the embodiment under nitrogen atmosphere; as shown in fig. 2, when 5 parts of cardanol nitrile-based resin is added by mass, TGA test results show that the 5% weight loss temperature of the cured adhesive in nitrogen atmosphere is 397 ℃, the residual carbon at 800 ℃ is 70%, and the 5% weight loss temperature and the residual carbon at 800 ℃ of the unmodified nitrile-based phenolic resin are 399 ℃ and 73% respectively; the bonding performance test result shows that the room-temperature shear strength of the modified resin adhesive is 9.07MPa, which is improved by 22% compared with that before modification, the shear strengths at 300 ℃ and 350 ℃ are respectively 10.87MPa and 5.22MPa, and the strength retention rates before modification are respectively 100% and 109%.
Example 8
The embodiment provides a specific preparation method of a cardanol modified nitrile-based phenolic resin adhesive, which comprises the following steps:
step one, preparation of cardanol nitrile resin:
weighing 40g of cardanol, 23g of 4-nitrophthalonitrile and 140g N, adding N-dimethylacetamide into a reaction bottle, fully stirring to completely dissolve 4-nitrophthalonitrile, uniformly mixing with cardanol, weighing 30g of anhydrous potassium carbonate, adding into the reaction bottle, stirring, raising the temperature to 60 ℃, reacting for 16 hours, cooling after the reaction is finished, standing, separating, pouring the upper layer liquid into 1000ml of cold water at 20 ℃ for washing for 3 times, adding butanone for extraction, carrying out reduced pressure distillation, removing water and solvent, and collecting the obtained product to obtain low-viscosity liquid cardanol nitrile resin, wherein the viscosity is 600mPa & s at 25 ℃.
The infrared spectrum of the product measured by the coating method is shown as a curve B in figure 1, and the result shows that the cardanol nitrile-based resin is (2230-2235) cm-1Where a-C.ident.N-based absorption peak appears.
Step two, preparing phenolic resin:
weighing 100g of phenol and 146g of formaldehyde, adding the phenol and the formaldehyde into a reactor, starting stirring, heating to 97 ℃, adding 1.06g of zinc oxide, keeping the reflux temperature at 97 ℃, finishing the reaction when the cloud point temperature of the reaction solution reaches 65 ℃, wherein the reaction time is 6h, then washing the reaction solution for 2 times by using water, adjusting the vacuum degree to 6kPa, heating for vacuum dehydration, cooling the resin to the normal temperature when the gel time of the resin reaches 102 seconds, adding a solvent ethyl acetate, and adding 45g of ethyl acetate to obtain the phenolic resin in a brown solution state, wherein the solid content is 69%.
Step three, preparing nitrile phenolic resin:
weighing 28g of phenolic resin with the solid content of 69% prepared in the second step, 30g of 4-nitrophthalonitrile and 130g of N, N-dimethylacetamide, adding the phenolic resin, the 4-nitrophthalonitrile and the N, N-dimethylacetamide into a reactor, controlling the pH value of a reaction solution to be 11, heating to 60 ℃, stirring to dissolve, adding 33g of catalyst b potassium carbonate, keeping the temperature for reaction for 16h, cooling to room temperature, cleaning with distilled water, extracting with ethyl acetate, neutralizing with 5% dilute hydrochloric acid, separating by a separating funnel, adjusting the vacuum degree to be 6kPa, heating to remove a solvent in vacuum, cooling the resin to room temperature when the gelation time of the resin reaches 160 seconds, adding ethyl acetate, and adding 20g of the ethyl acetate to obtain the nitrile-based phenolic resin.
Step four, preparing the cardanol modified nitrile-based phenolic resin adhesive:
and (3) fully and uniformly mixing 5 parts of the cardanol nitrile-based resin obtained in the first step and 100 parts of the nitrile-based phenolic resin obtained in the third step at room temperature according to the mass parts to obtain the cardanol modified nitrile-based phenolic resin adhesive.
Fig. 3 is a TGA curve comparison graph of the nitrile-based phenolic resin and the cardanol modified nitrile-based phenolic resin adhesive prepared in example 8 under nitrogen atmosphere, and as shown in fig. 3, when 5 parts of cardanol nitrile-based resin is added by mass, TGA test results show that the 5% weight loss temperature of the cured adhesive under nitrogen atmosphere is 380 ℃, the residual carbon at 800 ℃ is 72%, and the 5% weight loss temperature of the unmodified nitrile-based phenolic resin and the residual carbon at 800 ℃ are 399 ℃ and 73%, respectively; the bonding performance test result shows that the room-temperature shear strength of the adhesive is 9.79MPa, which is improved by 32% compared with that before modification, the shear strengths at 300 ℃ and 350 ℃ are respectively 10.97MPa and 5.55MPa, and the retention rates of the resin before modification are respectively 102% and 116%.
Example 9
The embodiment provides a specific preparation method of a cardanol modified nitrile-based phenolic resin adhesive, which comprises the following steps:
step one, preparation of cardanol nitrile resin:
weighing 40g of cardanol, 14g of 4-nitrophthalonitrile and 210g N, adding N-dimethylacetamide into a reaction bottle, fully stirring to completely dissolve 4-nitrophthalonitrile, uniformly mixing with cardanol, weighing 40g of anhydrous sodium hydroxide, adding into the reaction bottle, stirring, raising the temperature to 70 ℃, reacting for 10 hours, cooling after the reaction is finished, standing, separating, pouring the upper layer liquid into 1000ml of cold water at 20 ℃ for washing for 3 times, adding toluene for extraction, carrying out reduced pressure distillation, removing water and a solvent, and collecting the obtained substance to obtain the low-viscosity liquid cardanol nitrile resin.
Step two, preparing phenolic resin:
weighing 100g of phenol and 160g of formaldehyde, adding the phenol and the formaldehyde into a reactor, starting stirring, heating to 98 ℃, adding 3.2g of sodium hydroxide, keeping the reflux temperature at 98 ℃, finishing the reaction when the cloud point temperature of the reaction solution reaches 70 ℃, wherein the reaction time is 6.5h, then washing the reaction solution for 2 times by using water, adjusting the vacuum degree to 7kPa, heating for vacuum dehydration, cooling the resin to the normal temperature when the gel time of the resin reaches 200 seconds, adding a solvent ethyl acetate, and adding 45g of ethyl acetate to obtain the phenolic resin in a brown solution state, wherein the solid content is 73%.
Step three, preparing nitrile phenolic resin:
weighing 28g of phenolic resin with the solid content of 73% prepared in the second step, 40g of 4-nitrophthalonitrile and 140g of N, N-dimethylacetamide, adding the phenolic resin, the 4-nitrophthalonitrile and the N, N-dimethylacetamide into a reactor, controlling the pH of a reaction solution to be 9, heating to 65 ℃, stirring to dissolve, adding 33g of catalyst b potassium carbonate, keeping the temperature for reaction for 15 hours, cooling to room temperature, cleaning with distilled water, extracting with ethyl acetate, neutralizing with 5% dilute hydrochloric acid, separating by a separating funnel, adjusting the vacuum degree to be 7kPa, heating to remove a solvent in vacuum, cooling the resin to room temperature when the gelation time of the resin reaches 130 seconds, adding ethyl acetate, and adding 26g of the ethyl acetate to obtain the nitrile-based phenolic resin.
Step four, preparing the cardanol modified nitrile-based phenolic resin adhesive:
and (3) fully and uniformly mixing 20 parts of the cardanol nitrile-based resin obtained in the first step and 100 parts of the nitrile-based phenolic resin obtained in the third step at room temperature according to the mass parts to obtain the cardanol modified nitrile-based phenolic resin adhesive.
Example 10
The embodiment provides a specific preparation method of a cardanol modified nitrile-based phenolic resin adhesive, which comprises the following steps:
step one, preparation of cardanol nitrile resin:
weighing 40g of cardanol, 25g of 4-nitrophthalonitrile and 240g N, adding N-dimethylacetamide into a reaction bottle, fully stirring to completely dissolve 4-nitrophthalonitrile, uniformly mixing with cardanol, weighing 50g of anhydrous barium hydroxide, adding into the reaction bottle, stirring, raising the temperature to 80 ℃, reacting for 14 hours, cooling after the reaction is finished, standing, separating, pouring the upper layer liquid into 1000ml of cold water at 20 ℃ for washing for 3 times, adding acetone for extraction, carrying out reduced pressure distillation, removing water and a solvent, and collecting the obtained substance to obtain the low-viscosity liquid cardanol nitrile resin.
Step two, preparing phenolic resin:
weighing 100g of phenol and 180 g of formaldehyde, adding the phenol and the formaldehyde into a reactor, starting stirring, heating to 99 ℃, adding 3.6g of potassium hydroxide, keeping the reflux temperature at 99 ℃, finishing the reaction when the cloud point temperature of the reaction solution reaches 75 ℃, wherein the reaction time is 7h, then washing the reaction solution for 2 times by using water, adjusting the vacuum degree to 8kPa, heating for vacuum dehydration, cooling the resin to the normal temperature when the gel time of the resin reaches 300 seconds, adding a solvent ethyl acetate, and adding 47g of ethyl acetate to obtain the phenolic resin in a brown solution state, wherein the solid content is 56%.
Step three, preparing nitrile phenolic resin:
weighing 28g of phenolic resin with the solid content of 56% prepared in the second step, 50g of 4-nitrophthalonitrile and 150g of N, N-dimethylacetamide, adding the phenolic resin, the 4-nitrophthalonitrile and the N, N-dimethylacetamide into a reactor, controlling the pH of a reaction solution to be 10, heating to 70 ℃, stirring to dissolve, adding 33g of catalyst b potassium carbonate, keeping the temperature for reaction for 14h, cooling to room temperature, cleaning with distilled water, extracting with ethyl acetate, neutralizing with 5% dilute hydrochloric acid, separating by a separating funnel, adjusting the vacuum degree to 8kPa, heating to remove a solvent in vacuum, cooling the resin to room temperature when the gelation time of the resin reaches 190 seconds, adding ethyl acetate, and adding 34g of the ethyl acetate to obtain the nitrile-based phenolic resin.
Step four, preparing the cardanol modified nitrile-based phenolic resin adhesive:
and (3) fully and uniformly mixing 35 parts of the cardanol nitrile-based resin obtained in the first step and 100 parts of the nitrile-based phenolic resin obtained in the third step at room temperature according to the mass parts to obtain the cardanol modified nitrile-based phenolic resin adhesive.

Claims (9)

1. The cardanol modified nitrile-based phenolic resin adhesive is characterized by comprising the following components in parts by mass: 100 parts of nitrile-based phenolic resin and 2.5-50 parts of cardanol nitrile-based resin, wherein the structural formula of the cardanol nitrile-based resin is as follows:
Figure FDA0003087468080000011
wherein R ═ C15H31-nAnd n is 0, 2, 4 or 6.
2. The preparation method of the cardanol modified nitrile-based phenolic resin adhesive as claimed in claim 1, characterized by comprising the following steps:
step one, preparation of cardanol nitrile resin:
weighing cardanol and nitro-substituted phthalonitrile according to a certain molar ratio, putting the cardanol and nitro-substituted phthalonitrile into an organic solvent, fully stirring to obtain a uniform mixed solution, adding a certain amount of alkaline catalyst into the mixed solution, stirring and reacting a reaction system at a certain temperature for a certain time, cooling an obtained product to room temperature after the reaction is finished, standing for layering, collecting upper-layer liquid, and washing, extracting with the solvent, and distilling under reduced pressure to obtain cardanol nitrile resin;
step two, preparing phenolic resin:
uniformly mixing phenol and formaldehyde according to a certain molar ratio, adding a catalyst a at a certain reaction temperature, keeping the reaction temperature, reacting in a stirring state, finishing the reaction when the reaction liquid reaches a cloud point temperature, washing the reaction liquid with water, performing vacuum dehydration, cooling the resin to the normal temperature when the gelation time of the resin reaches 90-600 seconds, and adding a solvent to obtain phenolic resin;
step three, preparing nitrile phenolic resin:
mixing the phenolic resin prepared in the second step, 4-nitrophthalonitrile and N, N-dimethylformamide according to a certain molar ratio, adding a catalyst b at a certain reaction temperature, controlling the reaction system to perform heat preservation reaction for a certain time at a certain pH value, cooling the reaction system to room temperature, washing the reaction system with distilled water, extracting with ethyl acetate, neutralizing with dilute hydrochloric acid, separating with a separating funnel and removing a solvent in vacuum, cooling the resin to room temperature when the gel time of the obtained resin reaches 90-600 seconds, and adding the solvent to obtain the nitrile-based phenolic resin;
step four, preparing the cardanol modified nitrile-based phenolic resin adhesive:
and (3) fully and uniformly mixing 2.5-50 parts of the cardanol nitrile-based resin obtained in the first step and 100 parts of nitrile-based phenolic resin obtained in the third step at room temperature according to the mass parts to obtain the cardanol modified nitrile-based phenolic resin adhesive.
3. The preparation method of the cardanol modified nitrile-based phenolic resin adhesive according to claim 2, wherein in the first step, the nitro-substituted phthalonitrile is para-nitro-substituted phthalonitrile; the molar ratio of cardanol to nitro-substituted phthalonitrile is 1: (0.5 to 1); the organic solvent is one of dimethyl sulfoxide, N-dimethylformamide or N, N-dimethylacetamide; the dosage of the organic solvent is 2-5 times of the total weight of the cardanol and the nitro-substituted phthalonitrile.
4. The preparation method of the cardanol modified nitrile-based phenolic resin adhesive according to claim 2 or 3, wherein in the first step, the alkaline catalyst is one of sodium hydroxide, barium hydroxide, sodium carbonate or potassium carbonate, and the addition amount of the alkaline catalyst is 0.5-2.0 times of the molar amount of nitro-substituted phthalonitrile; the reaction temperature of the system is 60-90 ℃, and the reaction time is 6-16 h.
5. The preparation method of the cardanol modified nitrile-based phenolic resin adhesive according to claim 4, wherein in the step one, the upper layer liquid is washed for 3-5 times by water at 0-25 ℃ and 8-10 times the weight of the upper layer liquid; the solvent for extraction is one of toluene, ethyl acetate, acetone or butanone.
6. The preparation method of the cardanol modified nitrile-based phenolic resin adhesive according to claim 5, wherein in the second step, the molar ratio of phenol to formaldehyde is 1 (1.2-2.0), the reaction temperature is 90-100 ℃, the catalyst a is one of ammonia water, sodium hydroxide, potassium hydroxide or zinc oxide, and the addition amount of the catalyst a is 0.5-5% of the weight of phenol.
7. The preparation method of the cardanol modified nitrile-based phenolic resin adhesive according to claim 6, wherein in the second step, the cloud point temperature is 60-80 ℃, the vacuum degree of vacuum dehydration is 5-10 kPa, and the solvent is one of butanone, acetone or ethyl acetate.
8. The preparation method of the cardanol modified nitrile-based phenolic resin adhesive as claimed in claim 7, wherein in step three, the molar ratio of the phenolic resin to the 4-nitrophthalonitrile to the N, N-dimethylformamide is 1 (3-7) (30-80), the catalyst b is potassium carbonate or sodium carbonate, and the addition amount of the catalyst b is 0.5-2.0 times of the molar amount of the 4-nitrophthalonitrile.
9. The preparation method of the cardanol modified nitrile-based phenolic resin adhesive according to claim 8, wherein in the third step, the reaction temperature is 60-80 ℃, the pH value is 9-11, the heat preservation reaction time is 12-18 h, the vacuum degree of the vacuum desolvation is 5-10 kPa, and the solvent is one of butanone, acetone or ethyl acetate.
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