CN107446097B - Preparation method of high-temperature-resistant phenolic resin with organic silicon resin as curing agent - Google Patents
Preparation method of high-temperature-resistant phenolic resin with organic silicon resin as curing agent Download PDFInfo
- Publication number
- CN107446097B CN107446097B CN201710681029.4A CN201710681029A CN107446097B CN 107446097 B CN107446097 B CN 107446097B CN 201710681029 A CN201710681029 A CN 201710681029A CN 107446097 B CN107446097 B CN 107446097B
- Authority
- CN
- China
- Prior art keywords
- resin
- temperature
- organic silicon
- phenolic resin
- heating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 54
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 54
- 229920005989 resin Polymers 0.000 title claims abstract description 51
- 239000011347 resin Substances 0.000 title claims abstract description 51
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 28
- 239000010703 silicon Substances 0.000 title claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 239000003921 oil Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000004132 cross linking Methods 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229920001709 polysilazane Polymers 0.000 claims description 8
- 229920003257 polycarbosilane Polymers 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 2
- 229920001187 thermosetting polymer Polymers 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- 150000003384 small molecules Chemical class 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 238000001723 curing Methods 0.000 description 19
- -1 aldehyde compounds Chemical class 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 238000002679 ablation Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- XXFUZSHTIOFGNV-UHFFFAOYSA-N 1-bromoprop-1-yne Chemical compound CC#CBr XXFUZSHTIOFGNV-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000013006 addition curing Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000012802 nanoclay Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a preparation method of high-temperature-resistant phenolic resin by taking organic silicon resin as a curing agent, which comprises the following steps: heating the organic silicon resin precursor in an oil bath under the protection of nitrogen, stirring and reacting to obtain an organic silicon resin prepolymer with the crosslinking degree of 10-20%, wherein the organic silicon resin prepolymer and phenolic resin are mixed according to the mass ratio of 0.1-0.3: 1 heating and uniformly mixing, injecting the mixed solution into a mold cavity, reacting under negative pressure, and then curing and demolding to obtain the high-temperature-resistant phenolic resin. The preparation method has simple process and strong operability, does not overflow small molecules in the curing process, and is suitable for industrial production; according to the invention, the organic silicon resin is used as the curing agent, the phenolic resin obtained after curing has strong instantaneous heat resistance, and the phenolic resin has high mechanical property retention rate and high carbon residue rate at high temperature.
Description
Technical Field
The invention belongs to the technical field of phenolic resin preparation, and particularly relates to a preparation method of high-temperature-resistant phenolic resin by taking organic silicon resin as a curing agent.
Background
Phenolic resins are synthetic resins prepared by condensation reaction of phenol compounds and aldehyde compounds, and are widely applied to the aspects of electronics, electrical industry, automobile manufacturing, mechanical industry and the like due to good electrical insulation performance, mechanical property, ablation resistance, corrosion resistance, higher heat resistance and good water resistance. The phenolic resin has a structure in which phenolic hydroxyl groups and methylene groups, which are easily oxidized, are present, and thus heat resistance and oxidation resistance thereof are limited. The heat resistance of the common phenolic resin cannot meet the use requirement of the common phenolic resin in the fields of aerospace and the like, when the temperature exceeds 200 ℃, the resin is obviously oxidized, when the temperature is increased to 340-360 ℃, the resin is thermally decomposed, and when the temperature is increased to 600-900 ℃, the resin is further decomposed into small molecular substances.
In order to improve the heat resistance of the phenolic resin and further widen the application range of the phenolic resin, researchers carry out a great deal of research work on improving the heat resistance of the phenolic resin. The method mainly comprises the following steps: boric acid modified phenolic resin, polysiloxane modification, nano material modification and the like.
Chinese patent CN106883363A (published as 2017, 6 and 23) discloses a boron hybrid addition-cured phenolic resin and a preparation method thereof, wherein organic boric acid containing a structure similar to phenol is subjected to addition condensation reaction with formaldehyde to prepare a boron hybrid thermoplastic phenolic resin, and then the boron hybrid addition-cured phenolic resin is prepared by reacting the boron hybrid thermoplastic phenolic resin with bromopropyne. The method has the advantages that the prepared boron hybrid addition curing type phenolic resin has excellent forming and curing process performance, heat resistance and residual carbon performance, and is a high-performance composite material matrix resin with excellent high temperature resistance and ablation resistance. The disadvantages are a large increase in material and process costs and a reduction in the mechanical properties of the resin.
Chinese patent CN106317355A (published as 2017, 1 month and 11 days) discloses a high-temperature-resistant phenolic modified silicon resin and a preparation method thereof, wherein the method adopts phenol, formaldehyde aqueous solution and NaCO3Preparing phenolic resin from the aqueous solution, and adding alkoxy silane into the phenolic resin to obtain the phenolic modified organic silicon resin. Wherein the alkoxy silane is one or the combination of several of methyl trimethoxysilane, methyl triethoxysilane, methyl orthosilicate and ethyl orthosilicate. The method has the advantages that the obtained phenolic aldehyde modified silicon resin has good adhesive force, flexibility, impact resistance and high temperature resistance. The method has the disadvantages that the heat resistance is not obviously improved, the operation steps are more complicated and the required preparation time is longer.
Chinese patent CN100513480C (granted date of 2009, 7/15) discloses a method for preparing an inorganic nanomaterial-modified phenolic resin, which comprises the steps of uniformly mixing an inorganic nanomaterial and an organic surfactant, fully mixing the mixture with phenolic resin molecules, dehydrating and drying, adding a resin differential particle isolating agent and a hexamethyltetramine curing agent, and crushing to obtain the inorganic nanomaterial-modified phenolic resin. Wherein the inorganic nano material is prepared by uniformly mixing nano silicon oxide, nano aluminum oxide, nano titanium oxide, nano clay and nano barium sulfate. The method has the advantages that the obtained inorganic nano material modified phenolic resin material has the characteristics of high temperature resistance, low abrasion rate and low thermal expansion rate. The method has the disadvantages that the peel strength of the material is low and the corrosion resistance is not improved significantly.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of high-temperature-resistant phenolic resin by taking organic silicon resin as a curing agent, and the method has simple process and strong operability, and small molecules do not overflow in the curing process. The high-temperature-resistant phenolic resin with the organic silicon resin as the curing agent, which is obtained by the invention, not only can improve the high-temperature resistance of the phenolic resin, but also can keep the characteristics of basic mechanical property, electric insulation property and the like, and is a candidate material in the aerospace field.
The invention relates to a preparation method of high-temperature-resistant phenolic resin by taking organic silicon resin as a curing agent, which comprises the following steps:
(1) heating the organic silicon resin precursor in an oil bath under the protection of nitrogen, and stirring for reaction to obtain an organic silicon resin prepolymer with the crosslinking degree of 10-20%;
(2) under the protection of nitrogen, mixing the organic silicon resin prepolymer obtained in the step (1) with phenolic resin according to a mass ratio of 0.1-0.3: 1 heating and uniformly mixing, injecting the mixed solution into a mold cavity, reacting under negative pressure, and then curing and demolding to obtain the high-temperature-resistant phenolic resin.
The organic silicon resin in the step (1) is polysilazane resin, polycarbosilane resin or polyborosilazane resin.
The technological parameters of the reaction in the step (1) are as follows: the oil bath temperature is 120-170 ℃, and the stirring time is 2-6 h.
The phenolic resin in the step (2) is thermosetting phenolic resin.
The heating temperature in the step (2) is 80-85 ℃.
The technological parameters of the reaction in the step (2) are as follows: the reaction temperature is 60-80 ℃, the reaction negative pressure is-0.08-0.05 MPa, and the reaction time is 20-30 min.
The curing process parameters in the step (2) are as follows: vacuumizing at room temperature, heating to 100-120 ℃ at a heating rate of 15-20 ℃/min, and keeping the temperature for 0.5-1.5 h; then heating to 130-150 ℃ at a heating rate of 3-5 ℃/min, keeping the pressure at 0.2-0.4 MPa, and keeping the temperature for 1-2 h; then increasing the pressure to 0.4-0.6 MPa; heating to 180-190 ℃ at a heating rate of 5-10 ℃/min, and preserving heat for 1-2 h.
Advantageous effects
(1) The preparation method has simple process and strong operability, does not overflow small molecules in the curing process, and is suitable for industrial production;
(2) according to the invention, the organic silicon resin is used as the curing agent, the phenolic resin obtained after curing has strong instantaneous heat resistance, and the phenolic resin has high mechanical property retention rate and high carbon residue rate at high temperature.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
(1) Placing the polysilazane resin precursor in a container, heating to 120 ℃ by using an oil bath under the protection of nitrogen, and stirring for 6 hours to obtain a polysilazane resin prepolymer with the crosslinking degree of 10%;
(2) mixing the polysilazane resin prepolymer obtained in the step (1) with phenolic resin in a mass ratio of 1: 10, uniformly mixing at 80 ℃, then injecting the mixed solution into a mold cavity, keeping the negative pressure of-0.06 MPa for 30min at 60 ℃, then carrying out curing treatment, vacuumizing at room temperature, heating to 100 ℃ at the heating rate of 15 ℃/min, and keeping the temperature for 1.5 h; then heating to 130 ℃ at the heating rate of 3 ℃/min, keeping the pressure at 0.3MPa, and keeping the temperature for 2 h; then the pressure is increased to 0.6 MPa; heating to 180 ℃ at the heating rate of 5 ℃/min, preserving heat for 2h, and demoulding to obtain the high-temperature-resistant phenolic resin.
The high-temperature-resistant phenolic resin taking the organic silicon resin as the curing agent prepared by the embodiment has the initial decomposition temperature of 302 ℃, the weight loss process mainly occurs at 400-650 ℃, the main decomposition temperature is 566 ℃, the carbon residue rate is higher than 53.6 percent, the carbon residue rate is increased by 6.6 percent compared with the common phenolic resin, the tensile strength is higher than 74.8MPa, and the shear strength is higher than 10.8 MPa.
Example 2
(1) Placing the polycarbosilane resin precursor in a container, heating to 140 ℃ by using an oil bath under the protection of nitrogen, and stirring for 4 hours to obtain a polycarbosilane resin prepolymer with the crosslinking degree of 15%;
(2) mixing the polycarbosilane resin prepolymer obtained in the step (1) with phenolic resin in a mass ratio of 2: 10, uniformly mixing at 83 ℃, then injecting the mixed solution into a mold cavity, keeping the negative pressure of-0.07 MPa for 25min at 70 ℃, then carrying out curing treatment, vacuumizing at room temperature, heating to 110 ℃ at the heating rate of 17 ℃/min, and keeping the temperature for 1 h; then heating to 140 ℃ at the heating rate of 4 ℃/min, keeping the pressure at 0.3MPa, and keeping the temperature for 1.5 h; then the pressure is increased to 0.5 MPa; heating to 185 ℃ at the heating rate of 7 ℃/min, preserving the heat for 1.5h, and then demoulding to obtain the high-temperature resistant phenolic resin.
The high-temperature-resistant phenolic resin taking the organic silicon resin as the curing agent prepared by the embodiment has the initial decomposition temperature of 311 ℃, the weight loss process mainly occurs at 450-700 ℃, the main decomposition temperature is about 582 ℃, the carbon residue rate is more than 55.1 percent, the carbon residue rate is increased by 8.1 percent compared with the common phenolic resin, the tensile strength is more than 76.1MPa, and the shear strength is more than 11.2 MPa.
Example 3
(1) Placing the precursor of the polysilazane resin in a container, heating to 165 ℃ by using an oil bath under the protection of nitrogen, and stirring for 2 hours to obtain a polysilazane resin prepolymer with the crosslinking degree of 20%;
(2) mixing the polysilazane resin prepolymer obtained in the step (1) with phenolic resin in a mass ratio of 3: 10, uniformly mixing at 85 ℃, then injecting the mixed solution into a mold cavity, keeping the negative pressure of-0.08 MPa at 80 ℃ for 20min, then carrying out curing treatment, vacuumizing at room temperature, heating to 110 ℃ at the heating rate of 20 ℃/min, and keeping the temperature for 1 h; then heating to 150 ℃ at the heating rate of 5 ℃/min, keeping the pressure at 0.3MPa, and keeping the temperature for 1 h; then the pressure is increased to 0.4 MPa; heating to 190 ℃ at the heating rate of 10 ℃/min, preserving heat for 1h, and demoulding to obtain the high-temperature-resistant phenolic resin.
The high-temperature resistant phenolic resin taking the organic silicon resin as the curing agent prepared by the embodiment has the initial decomposition temperature of 317 ℃, the weight loss process is mainly carried out at 450-720 ℃, the main decomposition temperature is about 590 ℃, the carbon residue rate is about 57.2 percent, the carbon residue rate is increased by 10.2 percent compared with the common phenolic resin, the tensile strength is greater than 78.0MPa, and the shear strength is greater than 12.0 MPa.
Claims (4)
1. A preparation method of high-temperature resistant phenolic resin with organic silicon resin as a curing agent comprises the following steps:
(1) heating the organic silicon resin precursor in an oil bath under the protection of nitrogen, and stirring for reaction to obtain an organic silicon resin prepolymer with the crosslinking degree of 10-20%; wherein the organic silicon resin is polysilazane resin, polycarbosilane resin or polysilaborazine resin; the technological parameters of the reaction are as follows: the oil bath temperature is 120-170 ℃, and the stirring time is 2-6 h;
(2) under the protection of nitrogen, mixing the organic silicon resin prepolymer obtained in the step (1) with phenolic resin according to a mass ratio of 0.1-0.3: 1, heating and uniformly mixing, injecting the mixed solution into a mold cavity, reacting under negative pressure, and then curing and demolding to obtain high-temperature-resistant phenolic resin; wherein the technological parameters of the reaction are as follows: the reaction temperature is 60-80 ℃, the reaction negative pressure is-0.08-0.05 MPa, and the reaction time is 20-30 min.
2. The preparation method of the high-temperature resistant phenolic resin with the organic silicon resin as the curing agent according to claim 1, is characterized in that: the phenolic resin in the step (2) is thermosetting phenolic resin.
3. The preparation method of the high-temperature resistant phenolic resin with the organic silicon resin as the curing agent according to claim 1, is characterized in that: the heating temperature in the step (2) is 80-85 ℃.
4. The preparation method of the high-temperature resistant phenolic resin with the organic silicon resin as the curing agent according to claim 1, is characterized in that: the curing process parameters in the step (2) are as follows: vacuumizing at room temperature, heating to 100-120 ℃ at a heating rate of 15-20 ℃/min, and keeping the temperature for 0.5-1.5 h; then heating to 130-150 ℃ at a heating rate of 3-5 ℃/min, keeping the pressure at 0.2-0.4 MPa, and keeping the temperature for 1-2 h; then increasing the pressure to 0.4-0.6 MPa; heating to 180-190 ℃ at a heating rate of 5-10 ℃/min, and preserving heat for 1-2 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710681029.4A CN107446097B (en) | 2017-08-10 | 2017-08-10 | Preparation method of high-temperature-resistant phenolic resin with organic silicon resin as curing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710681029.4A CN107446097B (en) | 2017-08-10 | 2017-08-10 | Preparation method of high-temperature-resistant phenolic resin with organic silicon resin as curing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107446097A CN107446097A (en) | 2017-12-08 |
| CN107446097B true CN107446097B (en) | 2019-12-31 |
Family
ID=60491563
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710681029.4A Expired - Fee Related CN107446097B (en) | 2017-08-10 | 2017-08-10 | Preparation method of high-temperature-resistant phenolic resin with organic silicon resin as curing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107446097B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116144239A (en) * | 2022-12-29 | 2023-05-23 | 蚌埠凌空科技有限公司 | Phenolic resin-based thermal protection coating and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5089552A (en) * | 1989-12-08 | 1992-02-18 | The B. F. Goodrich Company | High char yield silazane-modified phenolic resins |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921565B (en) * | 2010-08-31 | 2013-02-27 | 黑龙江省科学院石油化学研究院 | Preparation method of solvent-free and high temperature-resistant adhesive |
| CN105647108B (en) * | 2016-03-30 | 2018-07-17 | 西安交通大学 | A kind of sweat connecting technique silicone-modified phenolic resin and preparation method thereof |
| CN105801785A (en) * | 2016-05-06 | 2016-07-27 | 黑龙江省科学院石油化学研究院 | Vinyl polycarbosilane modified phenol-formaldehyde adhesive and preparation method thereof |
-
2017
- 2017-08-10 CN CN201710681029.4A patent/CN107446097B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5089552A (en) * | 1989-12-08 | 1992-02-18 | The B. F. Goodrich Company | High char yield silazane-modified phenolic resins |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107446097A (en) | 2017-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106867363B (en) | Solvent-free graphene modified epoxy resin mortar of a kind of humid zone rust and preparation method thereof | |
| CN106810286B (en) | Boron nitride fiber reinforced cordierite ceramic matrix composite and preparation method thereof | |
| CN110282993B (en) | Preparation method of ceramic matrix composite containing interface phase | |
| CN101891957B (en) | Organic silicon resin-based heat-resisting wave-penetrating composite material and preparation method thereof | |
| CN110330350B (en) | Preparation method of fiber-toughened alumina ceramic | |
| CN107446097B (en) | Preparation method of high-temperature-resistant phenolic resin with organic silicon resin as curing agent | |
| CN111019297A (en) | Glass fiber reinforced resin matrix composite material and preparation method thereof | |
| EP3400203A1 (en) | Refractory molded body, compounds, binders, and method for producing same | |
| CN109836557B (en) | Toughened hydrophobic epoxy resin and preparation method thereof | |
| Wielage et al. | A cost effective route for the densification of carbon–carbon composites | |
| CN108975949B (en) | AlON-AlN porous material based on in-situ foaming and preparation method thereof | |
| CN110256093A (en) | A kind of reduction infiltration process preparation SiCfThe method of remaining silicone content in/SiC ceramic matrix composite material | |
| CN107619282B (en) | Preparation method of high-toughness titanium silicon carbide-silicon carbide complex phase ceramic special-shaped part | |
| CN104086729B (en) | A kind of dimethylbenzene phenol-formaldehyde resin modified and the method preparing water discharging board thereof | |
| CN104194257A (en) | Glass-fiber reinforced molded plastic of heat-resistant environment-friendly phenolic resin | |
| CN105503229A (en) | Preparation method of Al2O3f/SiOC radar wave-absorbing composite material | |
| CN113667162B (en) | Method for improving high temperature resistance of silicone resin and composite material thereof | |
| CN109180887B (en) | Preparation method of molybdenum phenolic resin for water-soluble rock wool, adhesive and application thereof | |
| CN109096753B (en) | Nitrile resin composite material and preparation method thereof | |
| CN113004655A (en) | Preparation method of glass fiber reinforced thermosetting resin prepreg | |
| CN104803695A (en) | High-strength carbon fiber enhanced boron nitride ceramic matrix composite and preparation method thereof | |
| CN107778020A (en) | A kind of method of carbon fiber-reinforced epoxy resin-matrix industry alkali lignin wood ceramics | |
| CN113861362A (en) | Method for rapidly curing and simultaneously toughening benzoxazine resin | |
| CN107573076B (en) | High-toughness titanium silicon carbide-silicon carbide complex phase ceramic special-shaped piece | |
| CN109096488B (en) | Phthalonitrile resin composition and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20191231 |