CN112341827A - Hyperbranched polysiloxane modified cyanate ester resin composite material and preparation method thereof - Google Patents
Hyperbranched polysiloxane modified cyanate ester resin composite material and preparation method thereof Download PDFInfo
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- CN112341827A CN112341827A CN202011320566.4A CN202011320566A CN112341827A CN 112341827 A CN112341827 A CN 112341827A CN 202011320566 A CN202011320566 A CN 202011320566A CN 112341827 A CN112341827 A CN 112341827A
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- cyanate ester
- ester resin
- hyperbranched polysiloxane
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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
- C08K7/10—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
Abstract
The invention relates to a method for preparing a high-toughness low-dielectric composite material by using hyperbranched polysiloxane modified cyanate ester resin. Aims to solve the problems that the cyanate resin material has large brittleness and poor toughness, and the cyanate composite material prepared by other modification methods is difficult to give consideration to both mechanical property and dielectric property. The method comprises the following steps: (1) preparing hyperbranched polysiloxane; (2) preparing hyperbranched polysiloxane modified cyanate ester resin; (3) pretreating the reinforced fibers; (4) RTM vacuum glue injection; (5) and (4) heating and curing. The hyperbranched polysiloxane modified cyanate ester resin composite material prepared by the invention has the characteristics of good toughness and excellent mechanical property. The hyperbranched polysiloxane modified cyanate ester resin prepared by the invention is used in the wave-transmitting fields of aviation, aerospace and the like.
Description
Technical Field
The invention relates to the technical field of composite material preparation, in particular to preparation of a hyperbranched polysiloxane modified cyanate ester resin composite material.
Background
In recent years, Cyanate Ester (CE) resins have been developed as a new type of thermosetting resin with unique properties. The CE resin material is very suitable for the fields of marine equipment and aerospace due to the excellent dielectric property and low water absorption of the CE. However, cyanate ester has the problems of large curing pressure, high curing temperature, large residual stress generated after curing and the like in the using process, so that the application of cyanate ester in the advanced field is limited. The cyanate has the same brittleness as other thermosetting resins, the brittleness of the cyanate severely limits the application of the cyanate in various advanced fields, and the cyanate becomes a bottleneck problem of the application of the CE resin, so the toughening modification of the cyanate is a key point in the research field of the CE resin in recent years.
Based on the above, the toughening modification is carried out at home and abroad by using different methods, such as thermosetting resin, thermoplastic resin, rubber elastomer, nano clay intercalation and the like. The methods can effectively increase the toughness of the CE resin, but often sacrifice other excellent performances of the CE resin, and are difficult to meet the new requirements of high-end fields on the excellent comprehensive performance of the CE resin. Therefore, in recent years, there is a strong demand for a new modification method that can effectively increase the toughness of CE while maintaining other excellent properties of CE.
It has been found that hyperbranched polymers (HBPs) exhibit unique properties due to their unique branched molecular structure, no entanglement between molecules, and a large number of terminal groups: such as low melt viscosity, good compatibility, easy dispersion, and solubility in organic solvents. The hyperbranched polymer has incomparable advantages in structure and performance such as low viscosity, more activation points, excellent dielectric property and the like compared with linear macromolecules. .
Therefore, in view of the above disadvantages, it is desirable to provide a method for preparing a high-toughness composite material from a hyperbranched polysiloxane-modified cyanate ester resin.
Disclosure of Invention
Technical problem to be solved
The invention aims to solve the technical problems that cyanate ester resin materials are high in brittleness and poor in toughness, and cyanate ester composite materials prepared by other modification methods are difficult to achieve both mechanical properties and dielectric properties.
(II) technical scheme
In order to solve the technical problems, the invention provides a preparation method of a hyperbranched polysiloxane modified cyanate ester resin composite material in a first aspect, wherein the preparation method comprises the following steps:
(1) preparation of hyperbranched polysiloxanes
Mixing water and polysiloxane (in a molar ratio of 1.1-1.3: 1), then dropwise adding hydrochloric acid to adjust the pH value to 1-2, carrying out prehydrolysis on a reaction system at normal temperature for 10-20 min while stirring, then heating to 50-60 ℃, refluxing for 4-10 h, and drying the obtained liquid to obtain hyperbranched polysiloxane;
(2) preparation of hyperbranched polysiloxane modified cyanate ester resin
Heating 100 parts of cyanate ester resin to be completely melted, adding 2.5-30 parts of the hyperbranched polysiloxane, and reacting to obtain hyperbranched polysiloxane modified cyanate ester resin;
(3) pretreatment of reinforcing fibers
Placing the reinforced fiber body, preferably in a fiber cloth form, in an acetone solvent, heating to 40-60 ℃, soaking for 2-4 h, drying for 12-24 h, and taking out for later use;
(4) RTM vacuum glue injection
Placing the pretreated reinforced fiber body in a mold, heating, vacuumizing, injecting the hyperbranched polysiloxane modified cyanate ester resin into the mold, and continuing vacuumizing while injecting;
(5) heat curing
And heating and curing the RTM mould with the preform, and then demoulding.
The invention provides the hyperbranched polysiloxane modified cyanate ester resin composite material prepared by the preparation method of the first aspect of the invention.
(III) advantageous effects
The technical scheme of the invention has the following advantages:
(1) the prepared hyperbranched polysiloxane modified cyanate ester resin composite material has the advantages that hyperbranched polysiloxane and cyanate ester are copolymerized, so that the reaction activity of cyanate ester curing is increased, the curing temperature of a resin system is reduced, the curing time is shortened, and the equipment utilization rate is greatly increased.
(2) The prepared hyperbranched polysiloxane modified cyanate ester resin composite material enables hyperbranched siloxane chemical bonds to be crosslinked with CE resin through the bridging action of polyfunctional groups and hyperbranched, so that the toughness of the composite material prepared from cyanate ester resin is improved.
(3) The hyperbranched siloxane has the characteristics of low dielectric and low viscosity, and maintains the characteristic of low dielectric of a resin system while maintaining and improving the mechanical property of the CE resin composite material.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention provides a preparation method of a hyperbranched polysiloxane modified cyanate ester resin composite material, which comprises the following steps:
(1) preparation of hyperbranched polysiloxanes
Mixing water and polysiloxane (in a molar ratio of 1.1-1.3: 1), then dropwise adding hydrochloric acid to adjust the pH value to 1-2, carrying out prehydrolysis on a reaction system at normal temperature for 10-20 min while stirring, then heating to 50-60 ℃, refluxing for 4-10 h, and drying the obtained liquid to obtain hyperbranched polysiloxane;
(2) preparation of hyperbranched polysiloxane modified cyanate ester resin
Heating 100 parts of cyanate ester resin to be completely melted, adding 2.5-30 parts of the hyperbranched polysiloxane, and reacting to obtain hyperbranched polysiloxane modified cyanate ester resin;
(3) pretreatment of reinforcing fibers
Placing the reinforced fiber body, preferably in a fiber cloth form, in an acetone solvent, heating to 40-60 ℃, soaking for 2-4 h, drying for 12-24 h, and taking out for later use;
(4) RTM vacuum glue injection
Placing the pretreated reinforced fiber body in a mold, heating, vacuumizing, injecting the hyperbranched polysiloxane modified cyanate ester resin into the mold, and continuing vacuumizing while injecting;
(5) heat curing
And heating and curing the RTM mould with the preform, and then demoulding.
According to some preferred embodiments, the cyanate ester may be bisphenol E cyanate ester, bisphenol F cyanate ester, bisphenol M cyanate ester, dicyclopentadiene bisphenol cyanate ester or other polyfunctional cyanate ester; and/or
The polysiloxane is KH 570.
According to some preferred embodiments, in step (2), the cyanate ester resin is pretreated before use, and the pretreatment method is as follows: weighing cyanate ester resin, putting the cyanate ester resin into a vacuum oven, heating the cyanate ester resin to 60-80 ℃, and drying the cyanate ester resin for 18-36 h.
According to some preferred embodiments, in step (2), 100 parts of cyanate ester resin is heated to be completely melted, and then 10 to 30 parts of the hyperbranched polysiloxane (e.g., 10 parts, 15 parts, 20 parts, 25 parts, 30 parts) is put in.
According to some preferred embodiments, in step (1), the drying is carried out in a vacuum oven at 50 to 70 ℃ for 4 to 6h to remove methanol; and/or
In the step (2), the reaction is performed under stirring, the reaction temperature of the reaction is 100 ℃ and 150 ℃ (for example, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃), and the stirring time is 10-30 min.
According to some preferred embodiments, in the step (3), the fiber cloth is a quartz fiber cloth.
According to some preferred embodiments, in the step (4), the mold is a mold that is prepared in a specific shape for the RTM process according to task needs, and the heating temperature is 100 to 180 ℃ (e.g., 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃).
According to some preferred embodiments, the evacuation to RTM mold internal pressure is 0.004 to 0.006 MPa.
According to some preferred embodiments, the curing temperature of the heat curing is 100 ℃ to 170 ℃.
According to some preferred embodiments, the curing time is between 1h and 3 h.
The invention provides the hyperbranched polysiloxane modified cyanate ester resin composite material prepared by the preparation method of the first aspect of the invention.
Example 1
(1) Preparation of hyperbranched polysiloxanes
Weighing deionized water and KH570 (the molar ratio is 1.1: 1), pouring into a three-neck flask for mixing, gradually dropwise adding hydrochloric acid into the three-neck flask, adjusting the pH value to be 1-2, continuously stirring, carrying out prehydrolysis for 15min at normal temperature, heating to 55 ℃, refluxing for 7h to obtain colorless transparent liquid, putting the liquid into a 60 ℃ vacuum drying oven, carrying out vacuum drying for 5h, and removing methanol to obtain hyperbranched polysiloxane;
(2) preparation of hyperbranched polysiloxane modified cyanate ester resin
Weighing cyanate (bisphenol E type cyanate), putting into a vacuum oven, heating to 70 ℃, drying for 24h, and taking out for later use. Weighing 100 parts of bisphenol E cyanate, putting the bisphenol E cyanate into a three-neck flask with mechanical stirring, heating the bisphenol E cyanate to be completely molten, then putting 10 parts of hyperbranched polysiloxane (KH570), adjusting the temperature to 140 ℃, stirring the mixture for 30min, and taking the mixture out;
(3) pretreatment of reinforcing fibers
Placing quartz fiber in acetone solvent, heating to 50 deg.C, soaking for 2h, taking out, placing in vacuum oven, drying for 12h, and taking out;
(4) RTM vacuum glue injection
Preparing a mould with a specific shape for an RTM process according to task requirements, laying pretreated reinforcing fibers in the mould, closing the mould and locking the mould. Putting the mold and the injection glue tank into an oven, adjusting the temperature of the oven to 100 ℃, vacuumizing until the internal pressure of the RTM mold is 0.5MPa, injecting resin into the mold, and continuously vacuumizing while injecting;
(5) heat curing
And removing the connection between the glue injection tank and the mold, and placing the RTM mold with the prefabricated body in an oven to finish demolding treatment after heating and curing. The curing process temperature is 170 ℃ and the curing time is 1.5 h.
Example 2
This example 2 is substantially the same as example 1 except that: in the step (2), the cyanate ester resin is bisphenol M type cyanate ester, and the mass part of the hyperbranched polysiloxane is 2.5 parts.
Example 3
This example 3 is substantially the same as example 1 except that: in step (2), the curing temperature was 200 ℃.
Example 4
This example 4 is substantially the same as example 1 except that: in the step (2), the mass part of the hyperbranched polysiloxane is 30 parts.
Example 5
This example 5 is substantially the same as example 1 except that: in step (2), except that the curing temperature was 160 ℃.
Example 6
This example 6 is substantially the same as example 1 except that: in step (2), no hyperbranched polysiloxane was added.
TABLE 1 Properties of the examples and the composites prepared
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a hyperbranched polysiloxane modified cyanate ester resin composite material is characterized by comprising the following steps:
(1) preparation of hyperbranched polysiloxanes
Mixing water and polysiloxane (in a molar ratio of 1.1-1.3: 1), then dropwise adding hydrochloric acid to adjust the pH value to 1-2, carrying out prehydrolysis on a reaction system at normal temperature for 10-20 min while stirring, then heating to 50-60 ℃, refluxing for 4-10 h, and drying the obtained liquid to obtain hyperbranched polysiloxane;
(2) preparation of hyperbranched polysiloxane modified cyanate ester resin
Heating 100 parts of cyanate ester resin to be completely melted, adding 2.5-30 parts of the hyperbranched polysiloxane, and reacting to obtain hyperbranched polysiloxane modified cyanate ester resin;
(3) pretreatment of reinforcing fibers
Placing the reinforced fiber body, preferably in a fiber cloth form, in an acetone solvent, heating to 40-60 ℃, soaking for 2-4 h, drying for 12-24 h, and taking out for later use;
(4) RTM vacuum glue injection
Placing the pretreated reinforced fiber body in a mold, heating, vacuumizing, injecting the hyperbranched polysiloxane modified cyanate ester resin into the mold, and continuing vacuumizing while injecting;
(5) heat curing
And heating and curing the RTM mould with the preform, and then demoulding.
2. The method of claim 1, wherein:
the cyanate is selected from the group consisting of bisphenol E cyanate, bisphenol F cyanate, bisphenol M cyanate, and dicyclopentadiene bisphenol cyanate; and/or
The polysiloxane is KH 570.
3. The method of claim 1, wherein:
in the step (2), the cyanate ester resin is pretreated before use, and the pretreatment method comprises the following steps: weighing cyanate ester resin, putting the cyanate ester resin into a vacuum oven, heating the cyanate ester resin to 60-80 ℃, and drying the cyanate ester resin for 18-36 h.
4. The method of claim 1, wherein:
in the step (2), 100 parts of cyanate ester resin is heated to be completely melted, and 10 to 30 parts of the hyperbranched polysiloxane is added.
5. The method of claim 1, wherein:
in step (1), the drying is carried out in a vacuum drying oven at 50 to 70 ℃ for 4 to 6 hours to remove methanol; and/or
In the step (2), the reaction is carried out under stirring, the reaction temperature of the reaction is 100-150 ℃, and the stirring time of the stirring is 10-30 min.
6. The method of claim 1, wherein:
in the step (3), the fiber cloth is quartz fiber cloth.
7. The method of claim 1, wherein:
in the step (4), the heating temperature is 100-180 ℃.
8. The method of claim 1, wherein:
in the step (4), vacuumizing is carried out until the internal pressure of the RTM mold is 0.4-0.6 MPa.
9. The method of claim 1, wherein:
in the step (5), the curing temperature of the heating curing is 100-170 ℃; the curing time is 1-3 h.
10. The hyperbranched polysiloxane-modified cyanate ester resin composite material prepared by the preparation method according to any one of claims 1 to 9.
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Cited By (1)
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| CN113402880A (en) * | 2021-06-18 | 2021-09-17 | 西北工业大学 | High-performance fluorine-containing cyanate resin system and preparation method thereof |
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