CN116178951A - Modified cyanate resin and preparation method thereof - Google Patents
Modified cyanate resin and preparation method thereof Download PDFInfo
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- CN116178951A CN116178951A CN202310045073.1A CN202310045073A CN116178951A CN 116178951 A CN116178951 A CN 116178951A CN 202310045073 A CN202310045073 A CN 202310045073A CN 116178951 A CN116178951 A CN 116178951A
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- cyanate
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- modified cyanate
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- 229920005989 resin Polymers 0.000 title claims abstract description 49
- 239000011347 resin Substances 0.000 title claims abstract description 49
- 150000001913 cyanates Chemical class 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 7
- -1 polysiloxane Polymers 0.000 claims abstract description 23
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 239000010703 silicon Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000007822 coupling agent Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000004643 cyanate ester Substances 0.000 claims description 11
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical group COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 6
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 4
- PVFQHGDIOXNKIC-UHFFFAOYSA-N 4-[2-[3-[2-(4-hydroxyphenyl)propan-2-yl]phenyl]propan-2-yl]phenol Chemical compound C=1C=CC(C(C)(C)C=2C=CC(O)=CC=2)=CC=1C(C)(C)C1=CC=C(O)C=C1 PVFQHGDIOXNKIC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 229920000578 graft copolymer Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 3
- 239000011157 advanced composite material Substances 0.000 abstract description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to a modified cyanate resin and a preparation method thereof, wherein the modified cyanate resin is prepared from the following raw materials in parts by weight: 100 parts of cyanate resin, 20-60 parts of solvent, 10-30 parts of polysiloxane, 0.1-5 parts of coupling agent, 0.05-0.5 part of catalyst and 1-20 parts of functionalized organosilicon surfactant. The modified cyanate resin provided by the invention is prepared by reacting polysiloxane, a catalyst, a functional organic silicon surfactant and a coupling agent, so that the technical problem of poor fracture toughness is solved, and the modified cyanate resin can be used as a resin matrix material of an advanced composite material and the like and is widely applied to the industrial fields of 5G copper-clad plates, aviation, aerospace, chip carrier plates and the like.
Description
Technical Field
The invention relates to the technical field of preparation of modified high polymer resin, in particular to modified cyanate resin and a preparation method thereof.
Background
The cyanate ester resin (CE) is a high-performance thermosetting resin containing two or more cyanate ester functional groups (-OCN), has excellent mechanical properties, high glass transition temperature (Tg=260℃), extremely low dielectric constant and dielectric loss, low moisture absorption rate and good processability, and can be applied to the high-technology fields of mechanical structural members, wave-transparent materials, 5G high-frequency high-speed circuit boards, chip (IC) carrier boards and the like in aviation materials. The composite property of the epoxy resin is superior to that of high-performance epoxy resin (EP) and bismaleimide resin (BMI), and the epoxy resin is a resin matrix with great development potential.
The curing reaction of cyanate ester resins belongs to addition polymerization reaction, but the CE is disadvantageous in that the highly crosslinked and structurally highly symmetrical triazine ring formed after the CE monomer curing reaction makes the cured product brittle. The cured product exhibits extremely high brittleness due to high crosslinking density and high molecular chain rigidity, and exhibits low fracture toughness.
Disclosure of Invention
The invention aims to provide a modified cyanate resin and a preparation method thereof, which are a method for completing the synthesis and resin blending of a toughened polymer in one step, simplify the production process and greatly improve the fracture toughness of the prepared modified cyanate resin.
The invention is realized by the following technical scheme:
a modified cyanate resin is prepared from the following raw materials in parts by weight:
100 parts of cyanate resin
20-60 parts of solvent
10-30 parts of polysiloxane
Coupling 0.1-5 parts
0.05 to 0.5 part of catalyst
1-20 parts of a functional organic silicon surfactant.
Preferably, the cyanate resin is one or a mixture of bisphenol A cyanate, bisphenol F cyanate, bisphenol M cyanate and dicyclopentadiene cyanate.
Preferably, the solvent is propylene glycol methyl ether acetate.
Preferably, the polysiloxane is a hydroxyl-terminated polydimethylsiloxane.
Preferably, the coupling agent is gamma-epoxypropyl trimethoxy silane.
Preferably, the catalyst is dibutyl tin dilaurate.
Preferably, the functionalized silicone surfactant is a graft copolymer of a functionalized organopolysiloxane and a polyether, the chemical structure of which is as follows:
the invention also provides a preparation method of the modified cyanate resin, which comprises the following steps:
(1) Adding the solvent and the cyanate ester resin with the formula amount into a reaction kettle, heating to 70 ℃, and preserving heat until stirring is uniform;
(2) And (3) adding polysiloxane, a catalyst and a functional organic silicon surfactant in sequence at the reaction temperature of 70 ℃, dispersing and stirring for 30 minutes, adding a coupling agent, dispersing and stirring for 60 minutes, evaporating out a solvent, and discharging for standby.
The beneficial effects of the invention are as follows: the modified cyanate resin provided by the invention is prepared by reacting polysiloxane, a catalyst, a functional organic silicon surfactant and a coupling agent, so that the technical problem of poor fracture toughness is solved, and the modified cyanate resin can be used as a resin matrix material of an advanced composite material and the like and is widely applied to the industrial fields of 5G copper-clad plates, aviation, aerospace, chip carrier plates and the like.
Description of the embodiments
The following detailed description of the preferred embodiments of the invention will provide those skilled in the art with a better understanding of the invention with its advantages and features, and thus define the scope of the invention more clearly and clearly.
Examples
The modified CE resin is prepared from the following raw materials in parts by weight: 100 parts of bisphenol A cyanate, 50 parts of propylene glycol methyl ether acetate, 8 parts of hydroxyl-terminated polydimethylsiloxane, 1.0 part of gamma-epoxypropyl trimethoxysilane, 0.1 part of dibutyltin dilaurate and 2 parts of functional organic silicon surfactant.
Adding 100 parts of bisphenol A cyanate and 50 parts of propylene methyl ether acetate into a reaction kettle, heating to 70 ℃, and preserving heat until stirring is uniform;
sequentially adding hydroxyl-terminated polydimethylsiloxane, dibutyl tin dilaurate and functional organosilicon surfactant at the reaction temperature of 70 ℃, dispersing and stirring for 30 minutes, adding gamma-epoxypropyl trimethoxy silane, dispersing and stirring for 30 minutes, and evaporating out the solvent.
Pouring the obtained modified CE resin into a preheated pouring die, carrying out vacuum defoaming for 2 hours at 150 ℃, respectively carrying out solidification and post-treatment according to the processes of 180 ℃/2h+200 ℃/2h+220 ℃/2h and 240 ℃/4h, naturally cooling, and demoulding to obtain the solidified modified CE resin, and cooling to room temperature and measuring fracture toughness by using ASTM D5645.
Examples
The modified CE resin is prepared from the following raw materials in parts by weight: 100 parts of bisphenol F cyanate, 50 parts of propylene glycol methyl ether acetate, 9 parts of hydroxyl-terminated polydimethylsiloxane, 1.0 part of gamma-epoxypropyl trimethoxysilane, 0.15 part of dibutyltin dilaurate and 2.5 parts of functional organic silicon surfactant.
Adding 100 parts of bisphenol F cyanate and 50 parts of propylene methyl ether acetate into a reaction kettle, heating to 70 ℃, and preserving heat until stirring is uniform;
sequentially adding hydroxyl-terminated polydimethylsiloxane, dibutyl tin dilaurate and functional organosilicon surfactant at the reaction temperature of 70 ℃, dispersing and stirring for 30 minutes, adding gamma-epoxypropyl trimethoxy silane, dispersing and stirring for 30 minutes, and evaporating out the solvent.
Pouring the obtained modified CE resin into a preheated pouring die, carrying out vacuum defoaming for 2 hours at 150 ℃, respectively carrying out solidification and post-treatment according to the processes of 180 ℃/2h+200 ℃/2h+220 ℃/2h and 240 ℃/4h, naturally cooling, and demoulding to obtain the solidified modified CE resin, and cooling to room temperature and measuring fracture toughness by using ASTM D5645.
Examples
The modified CE resin is prepared from the following raw materials in parts by weight: 100 parts of bisphenol M cyanate, 45 parts of propylene glycol methyl ether acetate, 10 parts of hydroxyl-terminated polydimethylsiloxane, 1.0 part of gamma-epoxypropyl trimethoxysilane, 0.1 part of dibutyltin dilaurate and 3 parts of functional organic silicon surfactant.
Adding 100 parts of bisphenol M cyanate and 45 parts of propylene methyl ether acetate into a reaction kettle, heating to 70 ℃, and preserving heat until stirring is uniform;
sequentially adding hydroxyl-terminated polydimethylsiloxane, dibutyl tin dilaurate and functional organosilicon surfactant at the reaction temperature of 70 ℃, dispersing and stirring for 30 minutes, adding gamma-epoxypropyl trimethoxy silane, dispersing and stirring for 30 minutes, and evaporating out the solvent.
Pouring the obtained modified CE resin into a preheated pouring die, carrying out vacuum defoaming for 2 hours at 150 ℃, respectively carrying out solidification and post-treatment according to the processes of 180 ℃/2h+200 ℃/2h+220 ℃/2h and 240 ℃/4h, naturally cooling, and demoulding to obtain the solidified modified CE resin, and cooling to room temperature and measuring fracture toughness by using ASTM D5645.
Examples
The modified CE resin is prepared from the following raw materials in parts by weight: 100 parts of dicyclopentadiene cyanate, 40 parts of propylene glycol methyl ether acetate, 6 parts of hydroxyl-terminated polydimethylsiloxane, 0.8 part of gamma-epoxypropyl trimethoxysilane, 0.075 part of dibutyltin dilaurate and 1.5 parts of functional organic silicon surfactant.
Adding 100 parts of dicyclopentadiene cyanate and 40 parts of propylene methyl ether acetate into a reaction kettle, heating to 70 ℃, and preserving heat until stirring is uniform;
sequentially adding hydroxyl-terminated polydimethylsiloxane, dibutyl tin dilaurate and functional organosilicon surfactant at the reaction temperature of 70 ℃, dispersing and stirring for 30 minutes, adding gamma-epoxypropyl trimethoxy silane, dispersing and stirring for 30 minutes, and evaporating out the solvent.
Pouring the obtained modified CE resin into a preheated pouring die, carrying out vacuum defoaming for 2 hours at 150 ℃, respectively carrying out solidification and post-treatment according to the processes of 180 ℃/2h+200 ℃/2h+220 ℃/2h and 240 ℃/4h, naturally cooling, and demoulding to obtain the solidified modified CE resin, and cooling to room temperature and measuring fracture toughness by using ASTM D5645.
The test data are shown in the following table:
| breaking energy G 1c （J/m2） | Flexural Strength (MPa) | Tg（℃） | |
| Comparative example | 60 | 95 | 247 |
| Example 1 | 350 | 106 | 242 |
| Example 2 | 570 | 112 | 239 |
| Example 3 | 720 | 105 | 236 |
| Example 4 | 330 | 98 | 241 |
From the results, it was found that the fracture energy (G 1c ) The fracture energy is increased by more than 5 times compared with that of unmodified resin, namely the fracture toughness is greatly improved, and the glass transition temperature is hardly changed.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention.
Claims (8)
1. The modified cyanate resin is characterized by being prepared from the following raw materials in parts by weight:
100 parts of cyanate resin
20-60 parts of solvent
10-30 parts of polysiloxane
0.1-5 parts of coupling agent
0.05 to 0.5 part of catalyst
1-20 parts of a functional organic silicon surfactant.
2. The modified cyanate resin of claim 1, wherein the cyanate resin is one or a mixture of bisphenol a cyanate, bisphenol F cyanate, bisphenol M cyanate, and dicyclopentadiene cyanate.
3. The modified cyanate ester resin of claim 1, wherein the solvent is propylene glycol methyl ether acetate.
4. The modified cyanate ester resin of claim 1, wherein the polysiloxane is a hydroxyl-terminated polydimethylsiloxane.
5. The modified cyanate ester resin of claim 1, wherein the coupling agent is gamma-epoxypropyltrimethoxysilane.
6. The modified cyanate ester resin of claim 1, wherein the catalyst is dibutyltin dilaurate.
7. The modified cyanate ester resin of claim 1, wherein the functionalized silicone surfactant is a graft copolymer of a functionalized organopolysiloxane and a polyether.
8. A method for producing the modified cyanate ester resin according to any one of claims 1 to 7, comprising the steps of:
(1) Adding the solvent and the cyanate ester resin with the formula amount into a reaction kettle, heating to 70 ℃, and preserving heat until stirring is uniform;
(2) And (3) adding polysiloxane, a catalyst and a functional organic silicon surfactant in sequence at the reaction temperature of 70 ℃, dispersing and stirring for 30 minutes, adding a coupling agent, dispersing and stirring for 60 minutes, evaporating out a solvent, and discharging for standby.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310045073.1A CN116178951A (en) | 2023-01-30 | 2023-01-30 | Modified cyanate resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310045073.1A CN116178951A (en) | 2023-01-30 | 2023-01-30 | Modified cyanate resin and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116178951A true CN116178951A (en) | 2023-05-30 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310045073.1A Pending CN116178951A (en) | 2023-01-30 | 2023-01-30 | Modified cyanate resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116178951A (en) |
-
2023
- 2023-01-30 CN CN202310045073.1A patent/CN116178951A/en active Pending
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