CN111892728B - Preparation method of benzoxazine resin hot-melt prepreg for autoclave molding process - Google Patents
Preparation method of benzoxazine resin hot-melt prepreg for autoclave molding process Download PDFInfo
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- CN111892728B CN111892728B CN202010582126.XA CN202010582126A CN111892728B CN 111892728 B CN111892728 B CN 111892728B CN 202010582126 A CN202010582126 A CN 202010582126A CN 111892728 B CN111892728 B CN 111892728B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08J2361/04, C08J2361/18, and C08J2361/20
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2461/14—Modified phenol-aldehyde condensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Abstract
The invention provides a preparation method of a benzoxazine resin hot-melt prepreg for an autoclave molding process, which solves the problems of high temperature and poor manufacturability of the benzoxazine resin prepreg prepared by the existing hot-melt method by pre-polymerizing resin and adding a proper amount of organic solvent. The preparation method mainly comprises the following steps: (1) preparing a benzoxazine resin glue solution, wherein a glue solution system consists of viscosity modified benzoxazine resin, phenolic resin, a powder toughening agent and a proper amount of solvent; (2) coating the resin glue solution into a glue film with uniform thickness at a proper temperature; (3) and placing the fiber between two layers of adhesive films, and preparing the prepreg by hot-pressing compounding. The prepreg prepared by the method can be used for preparing a composite material by adopting an autoclave molding process. The prepreg prepared by the invention has the advantages of stable gel content, low volatile matter, good room temperature adhesiveness and the like, and can be used in the fields of aerospace, electronic industry and the like.
Description
Technical Field
The invention relates to a preparation method of a benzoxazine resin hot-melt prepreg for an autoclave molding process, belonging to the technical field of composite materials.
Background
Benzoxazine is a benzo-hexa-heterocyclic compound obtained by condensation reaction of a phenolic compound, formaldehyde and a primary amine compound, and is subjected to ring-opening polymerization reaction under the action of heating and a catalyst to generate benzoxazine resin, which is also called ring-opening polymerization phenolic resin. The benzoxazine resin has no release of small molecules in the curing process, so that the porosity of the product is low, the volume of the product is close to zero shrinkage in the curing process, and the internal stress is small after curing. The benzoxazine resin reserves the excellent heat resistance and flame retardant property of the phenolic resin, has better moisture resistance, and can be used for aerospace, rail transit and electronic industry.
The viscosity of the benzoxazine resin is low at high temperature, so that an autoclave molding process cannot be adopted, but the autoclave molding process has irreplaceable advantages for preparing large-size complex special-shaped composite material members, and meanwhile, the benzoxazine resin has the defects of high curing temperature, poor resin film forming property, low room-temperature viscosity and the like, so that the application of the benzoxazine resin is limited.
At present, a benzoxazine resin is mostly prepared into a prepreg by a solution method (the prepreg is a composition prepared by impregnating continuous fibers or fabrics with a resin matrix under a strictly controlled condition to prepare the resin matrix and a reinforcement, and is an intermediate material for manufacturing a composite material), and the production by the solution method has the defects of low production efficiency, serious environmental pollution, poor batch stability and the like. Compared with the solution method, the hot melting method has the advantages of high production efficiency, small environmental pollution, controllable glue content and the like, and simultaneously, the prepared composite material has low porosity and good internal quality due to low volatile matter content. However, the benzoxazine resin has the defects of poor resin film forming property, low room temperature viscosity and the like, so that the application of the benzoxazine resin in the field of hot-melt prepregs is limited.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a preparation method of a benzoxazine resin hot-melt prepreg for an autoclave molding process, and a composite material prepared from the prepreg. According to the invention, the problems of low viscosity and high curing temperature of benzoxazine resin at high temperature are solved by modifying a benzoxazine resin system, the coating temperature is reduced by adding a proper solvent into a resin glue solution, and the problems of poor resin film forming property and low prepreg room-temperature bonding property are effectively improved, so that the benzoxazine resin prepreg which has good manufacturability and is suitable for autoclave molding is obtained.
The technical scheme of the invention is as follows:
a preparation method of a benzoxazine resin hot-melt prepreg for an autoclave molding process mainly comprises the following steps:
(1) heating and melting benzoxazine resin;
(2) adding phenolic resin and a powder toughening agent into the molten benzoxazine resin, and fully stirring and uniformly mixing to obtain mixed resin;
(3) when the temperature of the mixed resin is reduced to a proper temperature, adding a proper amount of organic solvent into the mixed resin, and uniformly stirring to obtain benzoxazine resin glue solution;
(4) coating the benzoxazine resin glue solution into a glue film with uniform thickness under the condition of proper temperature;
(5) and placing the fiber between two layers of adhesive films, and performing compression roller hot-pressing compounding to obtain the prepreg.
Further, the benzoxazine resin glue solution comprises the following components in parts by weight: the benzoxazine resin is 65-90 parts by weight, the phenolic resin is 5-20 parts by weight, the powder toughening agent is 1-5 parts by weight, and the organic solvent is 4-10 parts by weight.
Further, the benzoxazine resin in step (1) in the present invention includes at least one of a dihydric phenol type benzoxazine or a dihydric amine type benzoxazine.
The structure of the binary phenol type benzoxazine is as follows:
wherein: x is-CH 2 -，-C(CH 3 ) 2 -，-SO 2 -one of O-; r1 and R2 are alkyl, one of aryl (R1, R2 may both be alkyl or both aryl, or one is alkyl and the other is aryl).
Diamine type benzoxazine, the compound structure of which is as follows:
wherein: x is-CH 2 -，-SO 2 -one of O-; r1 and R2 are hydrogen, one of the alkyl groups (R1, R2 may both beHydrogen is either both alkyl or one is hydrogen and the other is alkyl).
Further, the benzoxazine resin in the step (1) is heated at 80-120 ℃ for 2-4 hours for prepolymerization, so that viscosity modification is realized, the minimum viscosity of the modified resin is more than 3000mP & s, and the molding requirement of an autoclave is met.
Further, the phenolic resin in the step (2) of the invention is barium phenolic resin, and the powder toughening agent is at least one of nano silicon dioxide or nano titanium dioxide.
Further, in the step (3) of the invention, when the temperature of the mixed resin is reduced to 30-50 ℃, a proper amount of organic solvent is added, wherein the organic solvent is at least one of acetone, butanone and 1, 4-dioxane.
Further, in the step (4), the benzoxazine resin glue solution is coated at 40-60 ℃, and the surface density of the glue film is adjusted by controlling the roll spacing of a hot melting machine and the coating speed, so that the resin content of the prepreg prepared in the step (5) is controlled at 35-45%.
Further, the speed of the hot-pressing compounding of the press roller in the step (5) of the invention is controlled to be 3-5 m/min.
Further, the fibers used in step (5) of the present invention include unidirectional fibers, fiber fabric, chopped fibers or long-cut fibers, and the fiber type is at least one of carbon fibers, glass fibers, aramid fibers and quartz fibers.
The invention further improves the benzoxazine resin hot-melt prepreg prepared by the method for the autoclave molding process.
A further improvement of the present invention is to provide a method of making a composite material using a prepreg made by the above method: the composite material is prepared by using benzoxazine resin prepreg and adopting an autoclave molding process.
Further, the curing temperature of the autoclave molding process is 160-200 ℃, the curing time is 4-10h, and the autoclave molding process is cooled to room temperature after curing.
A further development of the invention consists in providing a composite material which is produced by the above-described process.
Compared with the prior art, the invention has the following beneficial effects:
(1) aiming at the problem of low high-temperature viscosity of benzoxazine resin, the invention realizes viscosity modification by pre-polymerization of the benzoxazine resin, and the minimum viscosity of the modified resin is more than 3000mP & s, thereby meeting the molding requirement of an autoclave.
(2) According to the invention, the phenolic resin is added into the benzoxazine resin system, so that the reactivity and the thermal stability of the resin system are effectively improved, and the curing and forming temperature of the resin system is reduced.
(3) The preparation method of the benzoxazine resin hot-melt prepreg for the autoclave molding process provided by the invention avoids the problems of low efficiency and large pollution of the prepreg prepared by a solution method, reduces the coating temperature by adding a proper solvent into the resin glue solution, effectively improves the room temperature adhesiveness of the prepreg, and improves the manufacturability of the prepreg.
Detailed Description
In order to enhance the understanding of the present invention, the present invention will be described in further detail with reference to the following examples, which are provided for the purpose of illustration only and are not intended to limit the scope of the present invention.
Example 1:
heating 65 parts of benzoxazine resin to 80 ℃ for melting, keeping the temperature for 4 hours, stopping heating, adding 20 parts of phenolic resin and 5 parts of nano-silica toughening agent, uniformly mixing by using a high-speed mixer, adding 10 parts of acetone solvent when the temperature of the resin is reduced to 30 ℃, and uniformly stirring to obtain a resin glue solution. Coating the benzoxazine resin glue solution at the temperature of 40 ℃, controlling the roller distance of a hot melting machine and the coating speed to adjust the surface density of the glue film, and obtaining the resin glue film with uniform thickness. SW280 glass is arranged between two layers of adhesive films, and the prepreg is prepared by hot-pressing and compounding through a pressing roller, wherein the speed is controlled at 3 m/min. The prepared prepreg was tested for volatiles and resin content, with the volatiles of 0.8% and the resin content of 40.5%.
The benzoxazine resin prepreg is cured by an autoclave molding process to prepare a composite material laminated board, the curing condition is kept for 10 hours at 160 ℃, the internal quality of the prepared composite material laminated board is good, the tensile strength test is carried out, and the performance data of the prepreg and the composite material are shown in table 1.
Example 2:
heating 80 parts of benzoxazine resin to 100 ℃ for melting, keeping the temperature for 3 hours, stopping heating, adding 10 parts of phenolic resin and 3 parts of nano-silica toughening agent, uniformly mixing by using a high-speed stirrer, adding 7 parts of butanone solvent when the temperature of the resin is reduced to 40 ℃, and uniformly stirring to obtain a resin glue solution. Coating the benzoxazine resin glue solution at the temperature of 50 ℃, controlling the roller distance of a hot melting machine and the coating speed to adjust the surface density of the glue film, and obtaining the resin glue film with uniform thickness. SW280 glass is arranged between two layers of adhesive films, and the prepreg is prepared by hot-pressing and compounding through a pressing roller, wherein the speed is controlled at 4 m/min. The prepared prepreg is tested for volatile content and resin content, the volatile content of the prepreg is 0.7%, and the resin content is 39.8%.
The benzoxazine resin prepreg is cured by an autoclave molding process to prepare a composite material laminated board, the curing condition is kept for 7 hours at 180 ℃, the internal quality of the prepared composite material laminated board is good, the tensile strength test is carried out, and the performance data of the prepreg and the composite material are shown in table 1.
Example 3:
heating 90 parts of benzoxazine resin to 120 ℃ for melting, keeping the temperature for 2 hours, stopping heating, adding 5 parts of phenolic resin and 1 part of nano-silica toughening agent, uniformly mixing by using a high-speed mixer, adding 4 parts of dioxane solvent when the temperature of the resin is reduced to 50 ℃, and uniformly stirring to obtain a resin glue solution. Coating the benzoxazine resin glue solution at the temperature of 60 ℃, controlling the roller distance of a hot melting machine and the coating speed to adjust the surface density of the glue film, and obtaining the resin glue film with uniform thickness. SW280 glass is arranged between two layers of adhesive films, and the prepreg is prepared by hot-pressing and compounding through a pressing roller, wherein the speed is controlled at 5 m/min. The prepared prepreg is tested for volatile content and resin content, and the volatile content of the prepreg is 0.5%, and the resin content is 40.2%.
The benzoxazine resin prepreg is cured by an autoclave molding process to prepare a composite material laminated board, the curing condition is kept for 4 hours at 200 ℃, the internal quality of the prepared composite material laminated board is good, a tensile strength test is carried out, and the performance data of the prepreg and the composite material are shown in table 1.
Example 4:
heating 80 parts of benzoxazine resin to 120 ℃ for melting, keeping the temperature for 2 hours, stopping heating, adding 10 parts of phenolic resin and 3 parts of nano-silica toughening agent, uniformly mixing by using a high-speed mixer, adding 7 parts of dioxane solvent when the temperature of the resin is reduced to 40 ℃, and uniformly stirring to obtain a resin glue solution. Coating the benzoxazine resin glue solution at the temperature of 50 ℃, controlling the roller distance of a hot melting machine and the coating speed to adjust the surface density of the glue film, and obtaining the resin glue film with uniform thickness. And (3) placing the T700 carbon fiber unidirectional fabric between two layers of adhesive films, and preparing the prepreg by hot-pressing and compounding through a compression roller, wherein the speed is controlled at 4 m/min. The prepared prepreg is tested for volatile content and resin content, the volatile content of the prepreg is 0.8%, and the resin content is 39.2%.
The benzoxazine resin prepreg is cured by an autoclave molding process to prepare a composite material laminated board, the curing condition is kept for 7 hours at 180 ℃, the internal quality of the prepared composite material laminated board is good, a tensile strength test is carried out, and the performance data of the prepreg and the composite material are shown in table 1.
TABLE 1 benzoxazine resin prepreg and cured product properties thereof
As can be seen from Table 1, the prepreg prepared by the method has low volatile content and controllable resin content, is suitable for preparing prepregs with different fiber types, and the composite material prepared by the prepreg has excellent mechanical property, which indicates that the internal quality of the composite material is good.
The particular embodiments of the present invention disclosed above are illustrative only and are not intended to be limiting, since various alternatives, modifications, and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The invention should not be limited to the disclosure of the embodiments in the present specification, but the scope of the invention is defined by the appended claims.
Claims (9)
1. A preparation method of a benzoxazine resin hot-melt prepreg for an autoclave molding process is characterized by comprising the following steps:
(1) heating and melting benzoxazine resin;
(2) adding phenolic resin and a powder toughening agent into the molten benzoxazine resin, and fully stirring and uniformly mixing to obtain mixed resin;
(3) when the temperature of the mixed resin is reduced to a proper temperature, adding a proper amount of organic solvent into the mixed resin, and uniformly stirring to obtain benzoxazine resin glue solution;
(4) coating the benzoxazine resin glue solution into a glue film with uniform thickness under the condition of proper temperature;
(5) arranging fibers between two layers of adhesive films, and performing compression roller hot-pressing compounding to obtain a prepreg;
wherein, the benzoxazine resin in the step (1) is heated at 80-120 ℃ for 2-4 hours for prepolymerization, so as to realize viscosity modification, the minimum viscosity of the modified resin is more than 3000mP & s, and the molding requirement of an autoclave is met;
wherein, in the step (3), when the temperature of the mixed resin is reduced to 30-50 ℃, a proper amount of organic solvent is added, and the organic solvent is at least one of acetone, butanone and 1, 4-dioxane;
wherein, the benzoxazine resin glue solution in the step (4) is coated at 40-60 ℃, and the surface density of the glue film is adjusted by controlling the roll distance and the coating speed of a hot melting machine, so that the resin content of the prepreg prepared in the step (5) is controlled at 35-45%.
2. The method according to claim 1, wherein the benzoxazine resin glue solution comprises the following components in parts by weight: the benzoxazine resin is 65-90 parts by weight, the phenolic resin is 5-20 parts by weight, the powder toughening agent is 1-5 parts by weight, and the organic solvent is 4-10 parts by weight.
3. The method according to claim 1, wherein the benzoxazine resin in step (1) comprises at least one of a dihydric phenol type benzoxazine or a dihydric amine type benzoxazine, and the compound has the following structure:
dihydric phenol type benzoxazine:
wherein: x is-CH 2 -，-C(CH 3 ) 2 -，-SO 2 -one of O-; r1 and R2 are one of alkyl and aryl;
diamine type benzoxazine:
wherein: x is-CH 2 -，-SO 2 -one of O-; r1 and R2 are hydrogen or alkyl.
4. The method of claim 1, wherein the phenolic resin in step (2) is a barium phenolic resin and the powder toughening agent is at least one of nano silica or nano titania.
5. The method according to claim 1, wherein the speed of the roll thermocompression bonding in the step (5) is controlled to be 3-5 m/min; the fibers in the step (5) comprise unidirectional fibers, fiber fabrics, chopped fibers or long-cut fibers, and the types of the fibers are at least one of carbon fibers, glass fibers, aramid fibers and quartz fibers.
6. A benzoxazine resin hot melt prepreg for an autoclave molding process prepared according to the method of any one of claims 1-5.
7. A method for preparing a composite material is characterized in that the benzoxazine resin prepreg prepared by the method of any one of claims 1-5 is used for preparing the composite material by an autoclave molding process.
8. The method as claimed in claim 7, wherein the autoclave molding process has a curing temperature of 160-200 ℃, a curing time of 4-10h, and cooling to room temperature after curing.
9. A composite material prepared according to the method of claim 7 or 8.
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| CN114316322A (en) * | 2022-01-10 | 2022-04-12 | 长春长光宇航复合材料有限公司 | Ablation-resistant benzoxazine prepreg, composite material and preparation method of composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884376A (en) * | 2006-05-19 | 2006-12-27 | 四川大学 | Thermostable benzoxazine resin compound and its preparation method and uses |
| CN105038224A (en) * | 2015-07-23 | 2015-11-11 | 江苏恒神股份有限公司 | Benzoxazine prepreg composite and preparation method |
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| US7666938B2 (en) * | 2004-12-03 | 2010-02-23 | Henkel Corporation | Nanoparticle silica filled benzoxazine compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884376A (en) * | 2006-05-19 | 2006-12-27 | 四川大学 | Thermostable benzoxazine resin compound and its preparation method and uses |
| CN105038224A (en) * | 2015-07-23 | 2015-11-11 | 江苏恒神股份有限公司 | Benzoxazine prepreg composite and preparation method |
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