CN111269569B - Polyaryne resin modified cyanate ester resin and preparation method thereof - Google Patents
Polyaryne resin modified cyanate ester resin and preparation method thereof Download PDFInfo
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- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
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- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/0644—Poly(1,3,5)triazines
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Abstract
The invention provides a poly aryne resin modified cyanate ester resin and a preparation method thereof, wherein the preparation method comprises the following steps: mixing the polyaryne resin and the cyanate ester resin in proportion to obtain a first mixed resin; adding a catalyst and a stabilizer into the first mixed resin, and uniformly mixing to obtain second mixed resin; and pouring the second mixed resin into a mold, and curing to obtain the polyarylacetylene resin modified cyanate resin. The method adopts a solvent-free method to prepare the polyaryne resin modified cyanate ester resin, thereby not only improving the heat resistance of the cyanate ester resin, but also giving consideration to the dielectric property of the cyanate ester resin, and being more environment-friendly.
Description
Technical Field
The invention relates to the field of materials, in particular to a polyaryne resin modified cyanate ester resin and a preparation method thereof.
Background
Cyanate ester (CE for short) refers to a phenol derivative containing Cyanate ester functional group (-OCN), and is a thermosetting resin monomer, and forms a triazine ring network structure under the action of heating and a catalyst, and the structure endows the resin with the advantages of good high temperature resistance, low moisture absorption, dielectric property, mechanical property and the like. The modification of the cyanate ester resin by using the epoxy resin, bismaleimide resin, polyimide resin or high-performance thermoplastic resin can improve the toughness of the cyanate ester resin, but the heat resistance and dielectric property of the cyanate ester resin are reduced, and in addition, a solvent with a high boiling point is generally used in the modification of the polyimide resin, which brings inconvenience to processing and use and causes environmental pollution.
Disclosure of Invention
The invention provides a poly-aryne resin modified cyanate ester resin and a preparation method thereof, which can improve the heat resistance and thermal oxidation property of the cyanate ester resin and keep the excellent dielectric property and good mechanical property of the cyanate ester resin. In addition, the cyanate ester resin is prepared by adopting an environment-friendly hot melting method, so that the pollution of the use of an organic solvent to the environment is reduced.
The invention provides a preparation method of a modified cyanate ester resin of a polyaryne resin, which comprises the following steps: mixing the polyaryne resin and the cyanate ester resin in proportion to obtain a first mixed resin; adding a catalyst and a stabilizer into the first mixed resin, and uniformly mixing to obtain second mixed resin; and pouring the second mixed resin into a mold, and curing to obtain the polyaryne resin modified cyanate ester resin.
In the above method for preparing a polyarylacetylene resin modified cyanate ester resin, the method further comprises: pre-polymerizing the polyaryne resin before mixing the polyaryne resin and the cyanate ester resin in proportion.
In the above method for preparing a polyarylalkyne resin-modified cyanate ester resin, the method further comprises: prepolymerizing the cyanate ester resin prior to mixing the polyaryne resin with the cyanate ester resin in proportion.
In the above preparation method of the aryne resin modified cyanate ester resin, the weight ratio of the aryne resin to the cyanate ester resin is 5-30:70-95.
In the above preparation method of the modified cyanate ester resin of the polyarylalkyne resin, the polyarylalkyne resin includes a monofunctional species and a bifunctional species, and the monofunctional species includes phenylacetylene and naphthylacetylene; the difunctional species include p-diacetylene benzene, m-diacetylene benzene, and diacetylene biphenyl.
In the above method for preparing a modified cyanate ester resin of a polyarylacetylene resin, the cyanate ester resin includes bisphenol a type cyanate ester, bisphenol E type cyanate ester, bisphenol F type cyanate ester, bisphenol M type cyanate ester, dicyclopentadiene type cyanate ester, and phenol type cyanate ester.
In the preparation method of the poly aryne resin modified cyanate ester resin, the catalyst comprises a mixed catalyst system of organic metal salt and nonyl phenol, an organic transition metal complex catalyst with ultraviolet light activity and an organic tin compound.
In the preparation method of the aryne resin modified cyanate ester resin, the catalyst is organic metal salt compounded with nonylphenol, the amount of the organic metal salt is 100-300ppm, and the weight ratio of the cyanate ester resin to the nonylphenol is 70-95:2-4.
In the above method for preparing a polyarylacetylene resin modified cyanate ester resin, the stabilizer comprises bisphenol a, diallyl bisphenol a and 4,4' -dihydroxy diphenyl ether.
The invention also provides the polyarylacetylene resin modified cyanate resin prepared by the preparation method.
The method adopts a solvent-free method to prepare the polyaryne resin modified cyanate ester resin, thereby not only improving the heat resistance of the cyanate ester resin, but also giving consideration to the dielectric property of the cyanate ester resin, and being more environment-friendly.
Drawings
Fig. 1 shows a flow chart of a method for preparing a polyarylalkyne resin-modified cyanate ester resin.
Detailed Description
The following examples will allow one skilled in the art to more fully understand the present invention, but do not limit the invention in any way.
As shown in fig. 1, a flow chart of a preparation method of the polyarylacetylene resin modified cyanate ester resin is shown. In this method, the pre-polymerization of the polyarylalkyne resin monomer and the pre-polymerization of the cyanate resin monomer are first performed, and then they are mixed in proportion. The cyanate resin can be one or more of bisphenol A cyanate, bisphenol E cyanate, bisphenol F cyanate, bisphenol M cyanate, dicyclopentadiene cyanate, and phenolic cyanate. The polyaryne resin monomer can be monofunctional and bifunctional, and the monofunctional can be phenylacetylene and naphthylacetylene; the bifunctional compound can be one or more of p-diacetylene benzene, m-diacetylene benzene, diacetylene biphenyl and the like.
In a modified resin system, a polyacetylene resin monomer contains alkynyl with high activity, and participates in the resin system through an addition reaction, but the polyacetylene resin has large heat release during curing, is easy to implode and is not beneficial to molding processing, and a prepolymerization reaction is carried out before general use to dissipate heat in advance. After polymerization, a resin with high crosslinking density is formed, and the resin does not contain polar groups, so that the resin has excellent heat resistance, dielectric property and ablation resistance. The general polyaryne resin monomer is low-viscosity liquid, and the viscosity of a resin system can be reduced by adding the polyaryne resin monomer into a cyanate resin system, so that the processing manufacturability of the resin is favorably improved. When the addition amount of the polyarylalkyne resin monomer is more than 50%, the cured resin has high heat resistance (has high glass transition temperature), but the mechanical property of the resin is obviously reduced, which is obviously unfavorable for application, and when the addition amount of the polyarylalkyne resin monomer is less than 5%, the heat resistance of a resin system is not obviously improved. The weight content of the polyarylalkyne monomer should therefore be between 5 and 30%.
In the modified resin system, when the content of the cyanate ester resin is lower than 50%, the mechanical property of the resin system is far lower than that of a pure cyanate ester resin system, and in order to keep the resin system to have higher dielectric property and mechanical property, the weight content of the cyanate ester monomer and the prepolymer thereof is between 70 and 95 percent.
After the polyaryne resin and the cyanate ester resin are mixed, a stabilizer and a catalyst are added, and the mixture is poured into a mold after being uniformly mixed. The stabilizer may be a high boiling point compound containing a hetero atom such as oxygen, nitrogen, phosphorus, silicon, etc., for example, a phenol compound (bisphenol a, diallyl bisphenol a, 4,4' -dihydroxydiphenyl ether, etc.). The stabilizer is added to solve the problem of phase separation of cyanate ester resin and phenylacetylene resin at room temperature, when the stabilizer is not added, the cyanate ester monomer is easy to crystallize out from the system due to strong electrostatic acting force between the cyanate ester monomers, so that the resin is layered after being placed for a long time, the performance of the cured resin cannot meet the use requirement, and after a small amount of the stabilizer is added, the electrostatic acting force between cyanate ester functional groups is eliminated or weakened, so that the resin system is kept in a homogeneous system. The amount (weight percent) of stabilizer added may be 0-5%.
The catalyst may be a mixed catalyst system of an organic metal salt (octoate, naphthenate, acetylacetonate of zinc, tin, copper, cobalt, etc.) and nonylphenol (see US4, 608, 434), an organic transition metal complex catalyst active by ultraviolet light (see US5, 214, 860) and an organotin compound (dibutyltin dilaurate, bis-n-butyltin, bis-n-octyltin oxide, etc.). The catalyst is added to reduce the curing temperature of the cyanate ester resin, the organic metal salt and the nonyl phenol are not suitable to be added in large quantities, the thermal aging resistance is reduced when the adding quantity is larger, and the dielectric property is also reduced. Generally, when the activity of the resin is ensured, the addition amount is as small as possible, the catalyst is used as 100-300ppm of organic metal salt, and 2-4% of nonyl phenol is compounded.
Then, the temperature is raised and cured in a mold, for example, the curing can be performed in an electronic oven according to the temperature raising program of 110 ℃/2h +130 ℃/2h +150 ℃/2h +180 ℃/2h +200 ℃/2h. Then postcured at 230 ℃ for 4h.
The following description is given in conjunction with specific examples to provide those skilled in the art with a better understanding of the invention.
Example 1
Phenylacetylene and diethynylbenzene a 30:70 parts by weight of an alkynyl monomer which had been prepolymerized beforehand were premixed. 70 parts by weight of bisphenol A cyanate ester is weighed by a beaker and heated and stirred in an oil bath kettle at the temperature of 150 ℃ to be melted and prepolymerized for 4 hours. Then cooling to 90 ℃, adding a mixture of 30 parts of phenylacetylene and diethynylbenzene, stirring uniformly, naturally cooling to 50 ℃, adding 4% of stabilizer bisphenol A, adding a compound catalyst of 200ppm of bis-n-butyltin and 3 parts of nonylphenol, stirring uniformly at 60 ℃ by using a glass rod, pouring into a preheated metal mold coated with a mold release agent, and curing in an electronic oven according to a temperature rise program of 110 ℃/2h +130 ℃/2h +150 ℃/2h +180 ℃/2h +200 ℃/2h +2 ℃/2 h. And then post-curing for 4 hours at 230 ℃ to obtain the modified cyanate resin.
Example 2
Phenylacetylene and diethynylbenzene as 20:80 parts by weight of an alkynyl monomer which has been prepolymerized beforehand are premixed. 80 parts by weight of bisphenol E type cyanate ester is weighed by a beaker and heated and stirred in an oil bath kettle at the temperature of 150 ℃ to be melted and prepolymerized for 4 hours. Then cooling to 90 ℃, adding 20 parts of a mixture of phenylacetylene and diethynylbenzene, stirring uniformly, naturally cooling to 50 ℃, adding 3% of stabilizer diallyl bisphenol A, adding 100ppm of a compound catalyst of di-n-octyl tin oxide and 4 parts of nonyl phenol, stirring uniformly at 60 ℃ by using a glass rod, then pouring into a preheated metal mold coated with a release agent, and curing in an electronic oven according to a temperature rise program of 110 ℃/2h +130 ℃/2h +150 ℃/2h +180 ℃/2h +200 ℃/2 h. And then post-curing for 4 hours at 230 ℃ to obtain the modified cyanate resin.
Example 3
Phenylacetylene and diethynylbenzene a 10: a proportion of 90 parts by weight is premixed in which the alkynyl monomer has been prepolymerized beforehand. 90 parts by weight of bisphenol M cyanate ester is weighed by a beaker and heated and stirred in an oil bath kettle at 150 ℃ to be melted and prepolymerized for 4 hours. Then cooling to 90 ℃, adding 10 parts of a mixture of phenylacetylene and diethynylbenzene, stirring uniformly, naturally cooling to 50 ℃, adding 5% of stabilizer 4,4' -dihydroxydiphenyl ether, adding 300ppm of double n-butyltin and 2 parts of nonyl phenol compound catalyst, stirring uniformly at 60 ℃ by using a glass rod, then pouring into a preheated metal mold coated with a release agent, and curing in an electronic oven according to a temperature rise program of 110 ℃/2h +130 ℃/2h +150 ℃/2h +180 ℃/2h +200 ℃/2 h. And then post-curing for 4h at 230 ℃ to obtain the modified cyanate resin.
Comparative example 1
100 parts by weight of bisphenol A cyanate ester is weighed by a beaker and heated and stirred in an oil bath kettle at 100 ℃ to be melted and prepolymerized for 4 hours. Naturally cooling to 50 ℃, adding a compound catalyst of 200ppm of bis-n-butyltin and 3 parts of nonyl phenol, uniformly stirring at 60 ℃ by using a glass rod, then pouring into a preheated metal mold coated with a release agent, and curing in an electronic oven according to a temperature rise program of 110 ℃/2h +130 ℃/2h +150 ℃/2h +180 ℃/2h +200 ℃/2 h. And then post-curing for 4h at 230 ℃ to obtain the cyanate ester resin.
Comparative example 2
100 parts by weight of bisphenol E type cyanate ester is weighed by a beaker and heated and stirred in an oil bath kettle at 150 ℃ to be melted and prepolymerized for 4 hours. Naturally cooling to 50 ℃, adding 3% of stabilizer diallyl bisphenol A, adding 100ppm of compound catalyst of bis-n-octyl tin oxide and 4 parts of nonyl phenol, uniformly stirring at 60 ℃ by using a glass rod, then pouring into a preheated metal mold coated with a mold release agent, and curing in an electronic oven according to the temperature rise program of 110 ℃/2h +130 ℃/2h +150 ℃/2h +180 ℃/2h +200 ℃/2 h. And then post-curing for 4h at 230 ℃ to obtain the cyanate ester resin.
The films obtained in the above examples and comparative examples were measured by the following methods:
the mechanical property testing method comprises the following steps: the test standard is GB/T2567-2008, the bending strength is tested by an American Instron universal material testing machine, and the impact strength is tested by a Zhang science and technology Limited company simply supported beam impact testing machine.
Thermal performance test method: the glass transition temperature of the modified resin was measured by a TA Q-800 dynamic mechanical thermal analyzer, and the size of the test specimen was 50mm × 10mm × 3mm.
The dielectric property test method comprises the following steps: the coaxial resonant cavity method (japanese AET high frequency dielectric constant tester) includes the dielectric constant and dielectric loss.
The test results are shown in table 1 below:
TABLE 1
It can be seen from comparing examples 1-3 with comparative examples 1-2 that the present invention utilizes the polyarylalkyne resin to modify the cyanate ester resin, thereby increasing the glass transition temperature of the resin system, decreasing the flexural strength, increasing the flexural modulus, and also improving the dielectric constant of the resin system without much change in dielectric loss.
The method adopts a solvent-free method to prepare the polyaryne resin modified cyanate ester resin, so that the heat resistance of the cyanate ester resin is improved, the dielectric property of the cyanate ester resin is also considered, and the problem of phase separation of a polyaryne resin monomer and a cyanate ester monomer at room temperature is well solved by using the stabilizer. The polyareneyne resin modified cyanate ester resin obtained by the invention can be applied to a wave-transparent radome of a high-speed aircraft. The polyarylalkyne resin has higher crosslinking density than bismaleimide resin, has higher heat resistance, and the glass transition temperature thereof reaches the level of thermosetting polyimide, but the polyarylalkyne resin has better manufacturability than the thermosetting polyimide. The raw materials such as phenylacetylene, diacetylene benzene and the like have far lower cost than phenylacetylene silane, and a large amount of solvent is not used in the preparation process, so the production cost of the invention is low.
The resin system disclosed by the invention has high temperature resistance and low dielectric property, and can meet the use requirement of an antenna cover in a radome system of a high-speed aircraft. When the speed of the aerospace high-speed aircraft reaches 3 Mach number, the surface temperature of the material reaches more than 260 ℃, the influence on the heat resistance and the dielectric property of the radome material caused by the increase of the flight Mach number can be improved, and the problem of performance reduction of the radome structure caused by the increase of the speed of the aircraft can be solved. The resin system has excellent high-temperature oxidation resistance and dielectric property, can particularly bear 300 ℃ brazing, can be applied to high-speed printed circuit boards in the electronic information industry, and solves the thermal oxidation problem caused by long-time work of the circuit boards.
Those skilled in the art will appreciate that the above embodiments are merely exemplary embodiments and that various changes, substitutions, and alterations can be made without departing from the spirit and scope of the application.
Claims (8)
1. A preparation method of a poly aryne resin modified cyanate ester resin is characterized by comprising the following steps:
mixing the polyaryne resin and the cyanate ester resin in proportion to obtain a first mixed resin;
adding a catalyst and a stabilizer into the first mixed resin, and uniformly mixing to obtain second mixed resin;
pouring the second mixed resin into a mould, and curing to obtain the polyaryne resin modified cyanate resin,
wherein the polyaryne resin is subjected to prepolymerization before being mixed with the cyanate ester resin in proportion,
wherein the stabilizer comprises bisphenol A, diallyl bisphenol A and 4,4' -dihydroxy diphenyl ether.
2. The method for preparing a polyarylalkyne resin-modified cyanate ester resin according to claim 1, further comprising:
prepolymerizing the cyanate ester resin prior to mixing the polyaryne resin with the cyanate ester resin in proportion.
3. The method for preparing a polyarylacetylene resin modified cyanate ester resin according to claim 1, wherein the weight ratio of the polyarylacetylene resin to the cyanate ester resin is 5 to 30:70-95.
4. The method for preparing a polyarylalkyne resin-modified cyanate ester resin according to claim 1, wherein the polyarylalkyne resin comprises a monofunctional species and a bifunctional species, the monofunctional species comprising phenylacetylene and naphthylacetylene; the difunctional species include p-diacetylene benzene, m-diacetylene benzene and diacetylene biphenyl.
5. The method for preparing a polyarylacetylene resin modified cyanate ester resin according to claim 1, wherein said cyanate ester resin comprises bisphenol a type cyanate ester, bisphenol E type cyanate ester, bisphenol F type cyanate ester, bisphenol M type cyanate ester, dicyclopentadiene type cyanate ester, and phenol type cyanate ester.
6. The method for preparing a polyarylalkyne resin-modified cyanate ester resin according to claim 1, wherein the catalyst comprises a mixed catalyst system of an organic metal salt and nonylphenol, an organic transition metal complex catalyst that is ultraviolet-active, and an organotin compound.
7. The method for preparing the polyarylene resin modified cyanate ester resin according to claim 6, wherein the catalyst is an organic metal salt compound nonylphenol, the amount of the organic metal salt is 100 to 300ppm, and the weight ratio of the cyanate ester resin to the nonylphenol is 70 to 95:2-4.
8. A polyarylalkyne resin-modified cyanate ester resin produced by the method for producing a polyarylalkyne resin-modified cyanate ester resin according to any one of claims 1 to 7.
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| CN114685988A (en) * | 2020-12-29 | 2022-07-01 | 洛阳尖端技术研究院 | Modified bismaleimide resin and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2000034406A (en) * | 1998-07-17 | 2000-02-02 | Sumitomo Chem Co Ltd | Polyfunctional cyanic ester resin composition and copper foil-clad adhesive sheet |
| CN101117383A (en) * | 2007-07-10 | 2008-02-06 | 华东理工大学 | Aryl radical acetylene and cyanate resin copolymer |
| CN101864076A (en) * | 2010-05-14 | 2010-10-20 | 华东理工大学 | Cyanate resin modified by phenylacetylene base silane resin and preparation method thereof |
| CN108395532A (en) * | 2018-02-12 | 2018-08-14 | 华东理工大学 | Modified cyanic acid ester resin and preparation method thereof |
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| FR2862307B1 (en) * | 2003-11-13 | 2006-04-28 | Commissariat Energie Atomique | POLYETHYNYLENE PHENYLENE ETHYNYLENE SILYLENE MODIFIED POLYMERS), COMPOSITIONS CONTAINING SAME, PROCESSES FOR PREPARING THE SAME, AND CURED PRODUCTS. |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000034406A (en) * | 1998-07-17 | 2000-02-02 | Sumitomo Chem Co Ltd | Polyfunctional cyanic ester resin composition and copper foil-clad adhesive sheet |
| CN101117383A (en) * | 2007-07-10 | 2008-02-06 | 华东理工大学 | Aryl radical acetylene and cyanate resin copolymer |
| CN101864076A (en) * | 2010-05-14 | 2010-10-20 | 华东理工大学 | Cyanate resin modified by phenylacetylene base silane resin and preparation method thereof |
| CN108395532A (en) * | 2018-02-12 | 2018-08-14 | 华东理工大学 | Modified cyanic acid ester resin and preparation method thereof |
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