CN111454576A - SiAlCN ceramic precursor modified polyurethane rubber and preparation method and application thereof - Google Patents
SiAlCN ceramic precursor modified polyurethane rubber and preparation method and application thereof Download PDFInfo
- Publication number
- CN111454576A CN111454576A CN202010378284.3A CN202010378284A CN111454576A CN 111454576 A CN111454576 A CN 111454576A CN 202010378284 A CN202010378284 A CN 202010378284A CN 111454576 A CN111454576 A CN 111454576A
- Authority
- CN
- China
- Prior art keywords
- polyurethane rubber
- aluminum
- sialcn
- modified polyurethane
- ceramic precursor
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/16—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- 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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Silicon Polymers (AREA)
Abstract
The invention relates to SiAlCN ceramic precursor modified polyurethane rubber as well as a preparation method and application thereof, belonging to the technical field of polyurethane rubber manufacturing and also belonging to the technical field of organic synthesis and modification. According to the invention, the high temperature resistance of the polyurethane rubber matrix is improved by adding the SiAlCN ceramic precursor into the polyurethane rubber matrix. The mechanical property of the modified polyurethane rubber is obviously improved, and the high-temperature heat-proof property of the modified polyurethane rubber is also obviously improved.
Description
Technical Field
The invention relates to SiAlCN ceramic precursor modified polyurethane rubber as well as a preparation method and application thereof, belonging to the technical field of polyurethane rubber manufacturing and also belonging to the technical field of organic synthesis and modification.
Background
The polyurethane rubber is an elastomer material containing more urethane groups on a polymer main chain, and is actually polyurethane rubber, which is simply referred to as polyurethane rubber or urethane rubber or polyurethane elastomer. The polymer chain contains, in addition to urethane groups, ester groups, ether groups, urea groups, aromatic groups, aliphatic chains, and the like. The polyurethane rubber can reduce self thermal conductivity through self expansion in the high temperature process, and meanwhile, the self expansion process is accompanied with the carbonization process, so that the carbonized expansion body can resist higher temperature. Therefore, the polyurethane rubber is currently used as a short-time thermal protection material in a radiant heat environment in the aerospace engine industry. However, in recent years, with the industrial progress and the rapid development of aerospace, the existing polyurethane rubber thermal protection material cannot meet the actual needs, so that new materials are required to be further developed to improve the short-time radiation heat resistance of the polyurethane rubber under the condition of not reducing the room-temperature mechanical property of the polyurethane rubber. On the other hand, the polymer precursor ceramic is a novel polymer which is directly converted into ceramic by pyrolysis of the polymer precursor, the polymer generally has good mechanical property and ductility at room temperature, has very high similarity with polyurethane rubber, and removes small molecules to form the ceramic material in the high-temperature understanding process. Such ceramics have very good mechanical properties and temperature resistance (typically melting point in excess of 2000 c) in high temperature environments. The existing research shows that the SiAlCN ceramic converted by thermal cracking of poly-aluminum silicon carbon nitrogen alkane still maintains good mechanical property and oxidation resistance at the temperature of more than 1500 ℃, particularly the melting point of the SiAlCN ceramic is higher than 2000 ℃, and the SiAlCN ceramic is widely applied to the fields of aerospace, metal smelting, chemical industry and nuclear energy.
In the present invention, the polyaluminum carboxanilium which is decomposed in a high temperature environment to generate the SiAlCN ceramic, that is, the SiAlCN ceramic precursor is added to the polyurethane rubber, the room temperature performance of the polyurethane rubber is not changed, but the high temperature resistance, especially the short-time high temperature resistance, of the polyurethane rubber can be significantly improved.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: overcomes the defects of the prior art, and provides SiAlCN ceramic precursor modified polyurethane rubber and a preparation method and application thereof.
The technical solution of the invention is as follows:
a modified polyurethane rubber of SiAlCN ceramic precursor comprises a polyurethane rubber matrix and poly-silicon aluminum carbon nitrogen alkyl;
the polyurethane rubber substrate is polyurethane rubber EU 2400;
the poly-silicon aluminum carbon nitrogen alkane is poly-vinyl silicon aluminum carbon nitrogen alkane, and the preparation method of the poly-vinyl silicon aluminum carbon nitrogen alkane comprises the following steps:
phenyl vinyl dichlorosilane and vinyl trichlorosilane are subjected to ammonolysis reaction in an ammonia atmosphere, secondary butyl alcohol aluminum is added after the ammonolysis reaction is finished to continue the reaction for 2 to 5 hours, and the polyvinyl aluminum carbon nitrogen alkane is obtained and is viscous and transparent yellow liquid;
the molar ratio of the phenyl vinyl dichlorosilane to the vinyl trichlorosilane is 1.1-1.5: 1, carrying out ammonolysis reaction at the temperature of 25-45 ℃ for 4-10h, continuously stirring reactants in the ammonolysis reaction process at the stirring speed of 100-200 r/min, adding aluminum sec-butoxide at the speed of 1-5 d/s, wherein the adding amount of the aluminum sec-butoxide is as follows: the molar ratio of the total mole number of silicon atoms in the phenyl vinyl dichlorosilane and the vinyl trichlorosilane to the mole number of aluminum atoms in the secondary aluminum butoxide is 1.5-2.0: 1.
a preparation method of SiAlCN ceramic precursor modified polyurethane rubber comprises the steps of mixing polyvinyl silanylaluminum carbonitridine and a polyurethane rubber substrate, stirring for 30-90 min, adding a chloroplatinic acid catalyst, and continuing stirring for 3-10 min to obtain modified polyurethane rubber; the stirring speed is 200-300 r/min;
the mass ratio of the polyvinyl aluminum silicon carbonitride alkyl to the polyurethane rubber matrix is 1-10: 1, the mass ratio of the chloroplatinic acid catalyst to the polyurethane rubber matrix is 0.01-0.2: 1.
brushing the obtained modified polyurethane rubber in a mold at 60-80 DEG CHeating for 10-30 minutes at the temperature of (1) to obtain a flexible rubber sheet with the thickness of 2mm, testing the mechanical property and the high-temperature heat-proof property of the obtained flexible rubber sheet with the thickness of 2mm, wherein the mechanical property is mainly used for measuring the tearing strength and the tensile strength, the tearing strength test adopts the measurement of the tearing strength of GB/T529-1999 vulcanized rubber or thermoplastic rubber, the measurement of the tensile stress strain property of GB/T528-1998 vulcanized rubber or thermoplastic rubber, and the high-temperature heat-proof property adopts 200kw/m2The heat flow of (2) mm thick rubber sheet was irradiated for 60s, and the temperature rise at the back of the rubber sheet was measured.
The application of the SiAlCN ceramic precursor modified polyurethane rubber is characterized in that the modified polyurethane rubber is coated on the surface of a base material to be protected in a brush mode, and the heat resistance of the surface of the base material to be protected is improved.
Advantageous effects
(1) According to the invention, the high temperature resistance of the polyurethane rubber matrix is improved by adding the SiAlCN ceramic precursor into the polyurethane rubber matrix.
(2) The mechanical property of the modified polyurethane rubber is obviously improved, and the high-temperature heat-proof property of the modified polyurethane rubber is also obviously improved.
Detailed Description
The invention is further illustrated by the following examples, without restricting its application to the examples given.
Examples
The first step is as follows: synthesizing polyvinyl silicon aluminum carboazane: the molar mass ratio of phenyl vinyl dichlorosilane (0.11mol) to vinyl trichlorosilane (0.10mol) is 1.1: 1, ammonolyzing at 25 ℃ in the presence of ammonia gas at a mechanical stirring speed of 100 revolutions per minute for 10 hours to obtain polyvinylsilazane, then, starting to dropwise add aluminum sec-butoxide at a stirring speed of 1 drop/second, wherein the molar mass ratio of silicon atoms to aluminum atoms in the system is controlled to be 1.5: 1 (the total amount of the secondary butanol aluminum is 0.14mol), continuously reacting for 5 hours after the dropwise adding is finished to obtain viscous and transparent yellow liquid, namely the polyvinyl aluminum carboazane;
the second step is that: adding 10 parts by weight of polyvinyl silicon aluminum carbon nitrogen alkane into 1 part by weight of polyurethane rubber EU2400, continuously stirring for 90 minutes at the stirring speed of 200 revolutions per minute, then adding 0.2 part by weight of chloroplatinic acid serving as a catalyst, and then stirring for 3 minutes and taking out for later use;
the third step: coating the modified polyurethane rubber in the second step in a mold, and putting the mold in an oven at 80 ℃ for 10 minutes to obtain a flexible rubber sheet with the thickness of 2 mm;
the fourth step: mechanical properties the tear strength and tensile strength are mainly measured: the tearing performance test adopts GB/T529-1999 determination of tearing strength of vulcanized rubber or thermoplastic rubber, GB/T528-1998 determination of tensile stress strain performance of vulcanized rubber or thermoplastic rubber, and the high-temperature heat-proof performance adopts 200kw/m2The heat flow of (2) mm thick rubber sheet was irradiated for 60s, and the temperature rise at the back of the rubber sheet was measured. Thus, the thermal protective properties of the compounded rubber sheet in a high temperature environment were measured. For comparison, the same tests were performed on a polyurethane rubber without the addition of the polyvinylsilylaluminum carboazane.
The test result shows that: the tensile strength of the polyurethane rubber EU2400 without the addition of the polyvinyl-silicon-aluminum-carbon nitrogen alkane is 25.4MPa, the tear strength is 45.1kN/m, and the high-temperature heat-proof performance adopts 200kw/m2Irradiating a rubber sheet with the thickness of 2mm for 60s by using the heat flow, and measuring the temperature rise of the back surface of the rubber sheet to be 145 ℃; the tensile strength of the modified polyurethane rubber added with the polyvinyl aluminum carboazane is 42.9MPa, the tearing strength is 73.8kN/m, and the high-temperature heat-proof performance adopts 200kw/m2The heat flux of (2) mm thick rubber sheet was irradiated for 60 seconds, and the temperature rise at the back of the rubber sheet was measured to be 11 ℃.
Claims (10)
1. A SiAlCN ceramic precursor modified polyurethane rubber is characterized in that: the raw materials of the modified polyurethane rubber comprise a polyurethane rubber matrix and polysilicone aluminum carbonitride;
the poly-silicon aluminum carbon nitrogen alkane is poly-vinyl silicon aluminum carbon nitrogen alkane, and the preparation method of the poly-vinyl silicon aluminum carbon nitrogen alkane comprises the following steps:
and (3) carrying out ammonolysis reaction on phenyl vinyl dichlorosilane and vinyl trichlorosilane in an ammonia atmosphere, and adding aluminum sec-butoxide to continue the reaction after the ammonolysis reaction is finished to obtain the polyvinyl aluminum carbonitride.
2. The SiAlCN ceramic precursor modified polyurethane rubber as defined in claim 1, wherein: the polyurethane rubber substrate is polyurethane rubber EU 2400.
3. The SiAlCN ceramic precursor modified polyurethane rubber as defined in claim 1, wherein: the obtained polyvinyl-silicon-aluminum-carbon nitrogen alkane is viscous and transparent yellow liquid.
4. The SiAlCN ceramic precursor modified polyurethane rubber as defined in claim 1, wherein: the molar ratio of the phenyl vinyl dichlorosilane to the vinyl trichlorosilane is 1.1-1.5: 1.
5. the SiAlCN ceramic precursor modified polyurethane rubber as defined in claim 1, wherein: the ammonolysis reaction temperature is 25-45 ℃, and the ammonolysis reaction time is 4-10 h.
6. The SiAlCN ceramic precursor modified polyurethane rubber as defined in claim 1, wherein: the reactants are continuously stirred in the ammonolysis reaction process, and the stirring speed is 100-200 r/min.
7. The SiAlCN ceramic precursor modified polyurethane rubber as defined in claim 1, wherein: the adding speed is 1-5 drops/s when the secondary butyl alcohol aluminum is added, and the adding amount of the secondary butyl alcohol aluminum is as follows: the molar ratio of the total mole number of silicon atoms in the phenyl vinyl dichlorosilane and the vinyl trichlorosilane to the mole number of aluminum atoms in the secondary aluminum butoxide is 1.5-2.0: 1.
8. the SiAlCN ceramic precursor modified polyurethane rubber as defined in claim 1, wherein: adding aluminum sec-butoxide and continuing the reaction for 2-5 h.
9. A preparation method of SiAlCN ceramic precursor modified polyurethane rubber is characterized by comprising the following steps: mixing the polyvinyl-silicon-aluminum-carbon nitrogen alkane and the polyurethane rubber matrix, stirring for 30-90 min, adding a chloroplatinic acid catalyst, and continuing stirring for 3-10 min to obtain modified polyurethane rubber; the stirring speed is 200-300 r/min;
the mass ratio of the polyvinyl aluminum silicon carbonitride alkyl to the polyurethane rubber matrix is 1-10: 1, the mass ratio of the chloroplatinic acid catalyst to the polyurethane rubber matrix is 0.01-0.2: 1.
10. an application of SiAlCN ceramic precursor modified polyurethane rubber is characterized in that: and brushing the modified polyurethane rubber on the surface of the base material to be protected.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010378284.3A CN111454576B (en) | 2020-05-07 | 2020-05-07 | SiAlCN ceramic precursor modified polyurethane rubber and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010378284.3A CN111454576B (en) | 2020-05-07 | 2020-05-07 | SiAlCN ceramic precursor modified polyurethane rubber and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111454576A true CN111454576A (en) | 2020-07-28 |
| CN111454576B CN111454576B (en) | 2021-10-01 |
Family
ID=71677968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010378284.3A Active CN111454576B (en) | 2020-05-07 | 2020-05-07 | SiAlCN ceramic precursor modified polyurethane rubber and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111454576B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0543753A1 (en) * | 1991-11-21 | 1993-05-26 | Neyrpic | Wear-resistant composite material and method for its manufacture |
| CN101844870A (en) * | 2010-04-30 | 2010-09-29 | 北京航空航天大学 | Preparation method of SiC-SiAlCN glass ceramics |
| CN101870585A (en) * | 2010-07-06 | 2010-10-27 | 中国人民解放军国防科学技术大学 | Preparation method of Si-Al-C-N ceramic precursor |
| CN104479609A (en) * | 2014-06-18 | 2015-04-01 | 广东新展化工新材料有限公司 | Silane-terminated modified polyurethane sealant and preparation method thereof |
| CN105084903A (en) * | 2015-05-26 | 2015-11-25 | 郑州大学 | SiAlCN polymer precursor ceramic temperature sensor and preparation method thereof |
| CN105272266A (en) * | 2015-11-27 | 2016-01-27 | 厦门大学 | Preparation method of precursor converted silicon carbide foam ceramics |
| CN105967725A (en) * | 2016-05-06 | 2016-09-28 | 陈昌 | Foam-type porous ceramic material and preparation method thereof |
| CN108794941A (en) * | 2018-07-03 | 2018-11-13 | 西南交通大学 | A kind of high-dielectric constant inorganic/organic composite material film and preparation method thereof |
| CN109406038A (en) * | 2018-11-26 | 2019-03-01 | 闽南师范大学 | A kind of flat membrane structure SiAlCN wireless and passive pressure sensor and preparation method thereof |
-
2020
- 2020-05-07 CN CN202010378284.3A patent/CN111454576B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0543753A1 (en) * | 1991-11-21 | 1993-05-26 | Neyrpic | Wear-resistant composite material and method for its manufacture |
| CN101844870A (en) * | 2010-04-30 | 2010-09-29 | 北京航空航天大学 | Preparation method of SiC-SiAlCN glass ceramics |
| CN101870585A (en) * | 2010-07-06 | 2010-10-27 | 中国人民解放军国防科学技术大学 | Preparation method of Si-Al-C-N ceramic precursor |
| CN104479609A (en) * | 2014-06-18 | 2015-04-01 | 广东新展化工新材料有限公司 | Silane-terminated modified polyurethane sealant and preparation method thereof |
| CN105084903A (en) * | 2015-05-26 | 2015-11-25 | 郑州大学 | SiAlCN polymer precursor ceramic temperature sensor and preparation method thereof |
| CN105272266A (en) * | 2015-11-27 | 2016-01-27 | 厦门大学 | Preparation method of precursor converted silicon carbide foam ceramics |
| CN105967725A (en) * | 2016-05-06 | 2016-09-28 | 陈昌 | Foam-type porous ceramic material and preparation method thereof |
| CN108794941A (en) * | 2018-07-03 | 2018-11-13 | 西南交通大学 | A kind of high-dielectric constant inorganic/organic composite material film and preparation method thereof |
| CN109406038A (en) * | 2018-11-26 | 2019-03-01 | 闽南师范大学 | A kind of flat membrane structure SiAlCN wireless and passive pressure sensor and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| KATJA SCHELM，等: "Mechanical and Surface-Chemical Properties of Polymer Derived Ceramic Replica Foams", 《MATERIALS》 * |
| 马彦，等: "先驱体转化法制备多孔陶瓷的发展现状", 《材料工程》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111454576B (en) | 2021-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114085537B (en) | Dynamic double-network solid-liquid polysiloxane elastomer and preparation method thereof | |
| CN109867965A (en) | A kind of high-temperature-resisting silicon rubber material and the preparation method and application thereof | |
| JP2016525601A (en) | Polyketone polymerization catalyst | |
| CN109400649B (en) | Preparation of single-component intumescent flame retardant and application of single-component intumescent flame retardant in flame-retardant epoxy resin | |
| CN111454576B (en) | SiAlCN ceramic precursor modified polyurethane rubber and preparation method and application thereof | |
| CN110964202B (en) | Preparation method of polysiloxane/diphenol benzoxazine | |
| Bao et al. | Preparation, characterization, and curing kinetics of elevated and cryogenic temperature-resistant epoxy resin composites | |
| CN111732730A (en) | High-temperature-resistant borosilicate rubber raw rubber and synthetic method thereof | |
| CN110511572A (en) | A kind of silicon hybridization composite flame-retardant agent of carbonaceous material and its preparation method and application | |
| CN113248788B (en) | Polyhydroxy rosin modified organosilane coupling agent, and preparation method and application thereof | |
| CN112322244A (en) | High-temperature-resistant adhesive and preparation method thereof | |
| CN112210131A (en) | Flame-retardant rubber and preparation method thereof | |
| CN116396695A (en) | High-protection mica composite material for cable wrapping filling and preparation method thereof | |
| CN111662541B (en) | Silicon-boron-nitrogen-alkane modified high-temperature-resistant polyurethane rubber and preparation method thereof | |
| Tian et al. | Preparation and properties of a new polytriazole resin made from dialkyne and triazide compounds and its composite | |
| WO2022111288A1 (en) | Weather-resistant silazane rubber with three-dimensional network structure and preparation method therefor | |
| CN116478628A (en) | Wear-resistant noise-reducing mica composite material for wrapping wire harnesses of new energy automobiles and preparation method thereof | |
| CN111548443B (en) | Polyvinyl silaborazine and preparation method thereof | |
| CN102234375A (en) | Polyphenylacetylene silicon oxide borane and preparation method thereof | |
| CN114044867B (en) | Method for preparing benzoxazine resin based on waste optical disc | |
| CN108707232A (en) | A kind of preparation method of room temperature condensed type nitrile silicone rubber | |
| CN115074027A (en) | Organic-inorganic composite high-temperature heat-insulating coating and preparation method thereof | |
| CN107142072A (en) | A kind of fluorine-containing corrosion-resistant organosilicon adhesive and preparation method thereof | |
| CN111944145A (en) | Thermosetting polytriazole ester resin, composite material thereof and preparation method thereof | |
| CN111362827A (en) | Process for catalytically synthesizing N, N-dimethylacrylamide |
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 |