CN102477159B - Amino modified silicone oil and preparation method thereof - Google Patents
Amino modified silicone oil and preparation method thereof Download PDFInfo
- Publication number
- CN102477159B CN102477159B CN 201010570456 CN201010570456A CN102477159B CN 102477159 B CN102477159 B CN 102477159B CN 201010570456 CN201010570456 CN 201010570456 CN 201010570456 A CN201010570456 A CN 201010570456A CN 102477159 B CN102477159 B CN 102477159B
- Authority
- CN
- China
- Prior art keywords
- warming
- silicone oil
- under
- 30min
- modified silicone
- 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
Abstract
The invention relates to amino modified silicone oil which has low content of metal ions and stable viscosity and a preparation method thereof. The amino modified silicone oil is prepared by using dihydroxy silicone oil and an amine coupling agent as raw materials and tetramethylammonium hydroxide as a catalyst, subjecting the above-mentioned materials to a bulk condensation reaction and adding micro-molecular compounds with active groups after the reaction lasts for 2 to 5 h. Compared to conventional methods, the invention has the following characteristics: tetramethylammonium hydroxide is used as a catalyst to substitute metallic compounds, and after the reaction is finished, temperature rises again, which enables the catalyst to be destroyed, the micro-molecular compounds to be removed, the content of metallic impurities in an obtained product of the amino modified silicone oil to be controlled and the amino modified silicone oil with low content of metals and stable viscosity to be synthesized; during utilization, the amino modified silicone oil can substantially reduce metallic impurities introduced into fibers, especially into carbon fiber precursors, thereby improving finalquality of carbon fibers, and viscosity of the silicone oil does not change in the process of storage.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to amino-modified silicone oil of a kind of low metal ion level and stable viscosity and preparation method thereof.
Background technology
Carbon fiber has a series of superior characteristic, and the most outstanding is specific tenacity, specific modulus height.Also have wear-resisting, antifatigue, creep resistance, unreactiveness etc.The high quality precursor is the key that makes high-performance carbon fibre.
Because basic metal is the oxide catalyst of carbon, in high temperature treating processess such as the preoxidation of PAN precursor, charing, can promote CO, CO
2Deng the effusion of gas, stay some cavity blemishs, and then can reduce properties of carbon; Discover that in addition iron ion also can influence the performance index such as tensile strength of former silky fibre.P.Bajaj etc. have studied metal ion in great detail to the structure of polyacrylonitrile fibril and the reason of Effect on Performance, think metal ion can replace polymeric in carboxyl (H CCOH), as:
-COOH+K
+→-COOK+H
+
Its result, to the heat release cyclisation temperature of polyacrylonitrile fibril be improved, hindered polyacrylonitrile fibril by ionic mechanism form generation cyclisation, final carbon fiber performance is reduced, the metal content of therefore controlling precursor is one of important measures that obtain the high quality precursor.
In addition, as the key link that obtains the high-performance precursor, the used spinning oil that oils also must have specific characteristics can: as good high thermal resistance, to guarantee playing the effect that can boundling can prevent the precursor adhesion again at high temperature preoxidation and carbonization initial stage; Excellent antistatic can guarantee carrying out smoothly of spinning and preoxidation process to give the good convergency of precursor and processibility; Monofilament is bonding to play good preventing at spinning and preoxidation and carbonization initial stage for excellent lubrication and anti barrier property, makes it be easy to out fibre, avoids or reduces burr and fracture of wire; The good wettability to polyacrylonitrile fibre can make and oil evenly, guarantees the homogeneous of precursor and carbon filament quality; Good film-forming properties can reduce in the process of oiling finish to the transfer of roller (roller bearing), reduces the frequency of stopping and removing, and enhances productivity; Particularly, spinning oil should high purity, and low ion and foreign matter content in order to avoid the oxidation of catalyzed carbon in the high temperature cabonization process forms residual cavity and surface imperfection, reduce the mechanical property of carbon fiber.
Amino-modified silicone oil is one of important component of spinning oil.Obviously, the amino-modified silicone oil of low metal ion level and stable viscosity suits the requirements more.
Synthesizing amino silicone oil has three kinds of methods usually: 1) D
4(octamethylcyclotetrasiloxane) and silane coupling agent carry out polymerization under catalyst, but the amino-modified silicone oil molecular weight distribution that this method makes is wideer, and group distributes even inadequately; 2) emulsion polymerization prepares the synthesizing amino modified organic silicon emulsion, and its weak point is to have small amounts of oligomer to be present in the emulsion, is easy to form surperficial floating oil; 3) linear body and aminosilane are coupled under the catalyzer existence and carry out condensation reaction.Polycondensation makes amino-modified silicone oil, its molecular weight of product narrowly distributing, modified group is evenly distributed, and do not produce the annular siloxane oligopolymer in the polycondensation, but shortcoming is being deposited in the process and can raise gradually with the viscosity of polycondensation product, and the speed that viscosity increases is directly proportional with amino content.It is combination catalyst that people such as this Ress are adopted hydrated barta and tertiary sodium phosphate, adds n-hexyl alcohol, nonylcarbinol 2-Ethylhexyl Alcohol and isooctadecanol etc. in reaction or after the reaction and does as viscosity stabilizer, can make the polycondensation product of stable viscosity.But do not control the metal ion content of introducing system in these methods.
In order to address the above problem, the present invention proposes the preparation method of the amino-modified silicone oil of a kind of low-metal content and stable viscosity, this silicone oil in use can reduce greatly to fiber especially carbon fibre precursor introduces metallic impurity, thereby improve the final quality of carbon fiber, and this silicone oil can viscosity not become big in put procedure.
Summary of the invention
The purpose of this invention is to provide amino-modified silicone oil of a kind of low-metal content and stable viscosity and preparation method thereof.
The preparation method of the amino-modified silicone oil of low-metal content of the present invention and stable viscosity, adopting two hydroxy silicon oils and amino coupling agent is raw material, the employing Tetramethylammonium hydroxide is catalyzer, make above-mentioned raw material carry out the body condensation reaction, behind reaction 2～5h, add the micromolecular compound that has active group, make the amino-modified silicone oil of low-metal content stable viscosity.
Described pair of hydroxy silicon oil is the two hydroxy silicon oils of low viscosity, and its range of viscosities is 30～600cSt;
Above-mentioned amino coupling agent can adopt as shown in the formula the expression compound in one or more:
Wherein: R
1, R
3Be H ,-CH
3Or-CH
2CH
3
R
2For-C
nH
2n+1, wherein n is 1～20;
R be H ,-(CH
2CH
2O)
1～20H ,-C
2H
4NH
2,-C
2H
4NHC
2H
4NH
2,
Wherein, R
4, R
5, R
6Be C
nH
2n, n is 1～20; R
7For-C
nH
2n+1, n is 1～20;
R
8, R
9For-C
nH
2n+1, n is 1～20;
R
10Be C
nH
2n, n is 1～20.
Especially, described amino coupling agent can be N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane, N-cyclohexyl-γ-aminopropyl methyl dimethoxysilane, one or more in γ-diethylenetriamine propyl group methyl dimethoxysilane.
Above-mentioned Tetramethylammonium hydroxide can adopt this area to use always, as adopting the Tetramethylammonium hydroxide by ion-exchange-resin process, substitution method (calcium hydroxide method, potassium hydroxide method, silver suboxide method), electrolytic process (monofilm method, multimembrane method) preparation, the Tetramethylammonium hydroxide that preferred electrolytic process makes.
The massfraction 0.13～4.98% that accounts for two hydroxy silicon oils and amino coupling agent total mass of ammonia element, the quality amount of Tetramethylammonium hydroxide accounts for 0.008～1.3% of total mass.
The above-mentioned micromolecular compound that has active group can be the lower alcohol of C1-C20, the low-grade amine of C1-C20, and viscosity is at one or more of the silicone oil with low viscosity of the methyl blocking of 10cSt～300cSt, and its molar mass is 0.001～0.1% of raw material total mole number.
The temperature of reaction of described condensation reaction is 70 ℃～120 ℃; And, the time of described condensation reaction is controlled at 1～10h.
Comprise also among the described preparation method that reaction is warming up to 135 ℃～150 ℃ and destroys catalyzer after finishing;
In addition, also further comprise among the described preparation method, continue to be warming up to 155 ℃～200 ℃ and remove micromolecular compound, get the clear, colorless amino-modified silicone oil.
The present invention adopts Tetramethylammonium hydroxide alternative metals compound as catalyzer, heat up again after reaction finishes and destroyed catalyzer, controlled the content of metallic impurity of the amino-modified silicone oil product of gained, thereby realized purpose of the present invention, the amino-modified silicone oil that has synthesized a kind of low-metal content stable viscosity, this kind silicone oil in use can reduce the metallic impurity of introducing to fiber especially carbon fibre precursor greatly, thereby improve the final quality of carbon fiber, and this silicone oil can viscosity not become big in put procedure.
Embodiment
Following examples are used for explanation the present invention, but are not used for limiting the scope of the invention.
Specialize as nothing, it is commercial that the present invention adopts various raw materials to be.
Embodiment 1
The alkali glue 50mg that adds two hydroxy silicon oil 30g and 2g amino silicane coupling agent 602 and Tetramethylammonium hydroxide in the 100mL there-necked flask, the drum argon gas, low vacuum vacuumizes 30min.Be warming up to 85 ℃, balanced reaction 1h under the argon shield slowly begins to vacuumize then, begin control-below the 0.02MPa, slowly gas clean-up vacuumizes 30min to-0.09MPa; Be warming up to 95 ℃ then, stirring reaction 30min; Add n-hexyl alcohol 0.01mL, continue reaction 30min; With under-0.09MPa, vacuumizing 1h with quadrat method; Remove vacuum, be warming up to 165 ℃ under the argon shield, stir 1h, destroy catalyzer, be warming up to 200 ℃ and vacuumize and remove small molecules, be cooled to room temperature.Obtain the viscosity 3750cSt of amino-modified silicone oil, the metal ion content of measuring in the product through ICP is 0.021ppm.
With above-mentioned reacting phase with condition under, Tetramethylammonium hydroxide alkali glue is changed to the alkali glue of potassium hydroxide, under the identical situation of catalyzer molar weight, the viscosity of the amino-modified silicone oil that obtains is 1980cSt, add in the acetic acid at last and potassium hydroxide, be warming up to 200 ℃ and vacuumize and remove small molecules, be cooled to room temperature.Obtain the viscosity 1750cSt of amino-modified silicone oil, the metal ion content of measuring in the product through ICP is 0.8ppm.
Embodiment 2
The alkali glue 36mg that adds two hydroxy silicon oil 30g and 2g amino silicane coupling agent 602 and Tetramethylammonium hydroxide in the 100mL there-necked flask, the drum argon gas, low vacuum vacuumizes 30min.Be warming up to 70 ℃, balanced reaction 1h under the argon shield slowly begins to vacuumize then, begin control-below the 0.02MPa, slowly gas clean-up vacuumizes 30min to-0.09MPa; Be warming up to 95 ℃ then, stirring reaction 30min; Add stearylamine 0.008mL, continue reaction 30min; With under-0.09MPa, vacuumizing 1h with quadrat method; Remove vacuum, be warming up to 165 ℃ under the argon shield, stir 1h, destroy catalyzer, be warming up to 180 ℃ and vacuumize and remove small molecules, be cooled to room temperature.Obtain the viscosity 2000cSt of amino-modified silicone oil, the metal ion content of measuring in the product through ICP is 0.022ppm.
Embodiment 3
The alkali glue 100mg that adds two hydroxy silicon oil 30g and 2g aminomethyl [N-(the 3-dimethoxy-methyl is silica-based) propyl group aminomethyl] former ripple alkane and Tetramethylammonium hydroxide in the 100mL there-necked flask, the drum argon gas, low vacuum vacuumizes 30min.Be warming up to 95 ℃, balanced reaction 1h under the argon shield slowly begins to vacuumize then, begin control-below the 0.02MPa, slowly gas clean-up vacuumizes 30min to-0.09MPa; Be warming up to 105 ℃ then, stirring reaction 30min; Add hexamethyldisiloxane 0.005mL, continue reaction 30min; With under-0.09MPa, vacuumizing 1h with quadrat method; Remove vacuum, be warming up to 165 ℃ under the argon shield, stir 1h, destroy catalyzer, be warming up to 200 ℃ and vacuumize and remove small molecules, be cooled to room temperature.Obtain the viscosity 8140cSt of amino-modified silicone oil, the metal ion content of measuring in the product through ICP is 0.021ppm.
Embodiment 4
The alkali glue 40mg that adds two hydroxy silicon oil 30g and 1g amino silicane coupling agent 602 and Tetramethylammonium hydroxide in the 100mL there-necked flask, the drum argon gas, low vacuum vacuumizes 30min.Be warming up to 85 ℃, balanced reaction 1h under the argon shield slowly begins to vacuumize then, begin control-below the 0.02MPa, slowly gas clean-up vacuumizes 30min to-0.09MPa; Be warming up to 95 ℃ then, stirring reaction 1h; Adding viscosity is the silicone oil 0.01g of the methyl blocking of 100cSt, continues reaction 30min; With under-0.09MPa, vacuumizing 1h with quadrat method; Remove vacuum, be warming up to 165 ℃ under the argon shield, stir 1h, destroy catalyzer, be warming up to 200 ℃ and vacuumize and remove small molecules, be cooled to room temperature.Obtain the viscosity 3810cSt of amino-modified silicone oil, the metal ion content of measuring in the product through ICP is 0.025ppm.
Embodiment 5
The alkali glue 120mg that adds two hydroxy silicon oil 30g and 2g amino silicane coupling agent 602 and Tetramethylammonium hydroxide in the 100mL there-necked flask, the drum argon gas, low vacuum vacuumizes 30min.Be warming up to 105 ℃, balanced reaction 1h under the argon shield slowly begins to vacuumize then, begin control-below the 0.02MPa, slowly gas clean-up vacuumizes 30min to-0.09MPa; Be warming up to 115 ℃ then, stirring reaction 30min; Add primary isoamyl alcohol 0.006mL, continue reaction 30min; With under-0.09MPa, vacuumizing 1h with quadrat method; Remove vacuum, be warming up to 165 ℃ under the argon shield, stir 1h, destroy catalyzer, be warming up to 200 ℃ and vacuumize and remove small molecules, be cooled to room temperature.Obtain the viscosity 22000cSt of amino-modified silicone oil, the metal ion content of measuring in the product through ICP is 0.021ppm
Embodiment 6
The alkali glue 75mg that adds two hydroxy silicon oil 30g and 2g N methyl piperazine propyl group dimethoxy silane and Tetramethylammonium hydroxide in the 100mL there-necked flask, the drum argon gas, low vacuum vacuumizes 30min.Be warming up to 85 ℃, balanced reaction 1h under the argon shield slowly begins to vacuumize then, begin control-below the 0.02MPa, slowly gas clean-up vacuumizes 30min to-0.09MPa; Be warming up to 95 ℃ then, stirring reaction 30min; Add n-Butyl Amine 99 0.003mL, continue reaction 30min; With under-0.09MPa, vacuumizing 1h with quadrat method; Remove vacuum, be warming up to 165 ℃ under the argon shield, stir 1h, destroy catalyzer, be warming up to 200 ℃ and vacuumize and remove small molecules, be cooled to room temperature.Obtain the viscosity 3750cSt of amino-modified silicone oil, the metal ion content of measuring in the product through ICP is 0.021ppm.
Claims (1)
1. an amino-modified silicone oil is characterized in that, by the following method a kind of the making in:
Method one: the alkali glue 50mg that adds two hydroxy silicon oil 30g and 2g amino silicane coupling agent 602 and Tetramethylammonium hydroxide in the 100mL there-necked flask, the drum argon gas, low vacuum vacuumizes 30min, be warming up to 85 ℃, balanced reaction 1h under the argon shield slowly begins to vacuumize then, begin control-below the 0.02MPa, slowly gas clean-up vacuumizes 30min to-0.09MPa; Be warming up to 95 ℃ then, stirring reaction 30min; Add n-hexyl alcohol 0.01mL, continue reaction 30min; With under-0.09MPa, vacuumizing 1h with quadrat method; Remove vacuum, be warming up to 165 ℃ under the argon shield, stir 1h, destroy catalyzer, be warming up to 200 ℃ and vacuumize and remove small molecules, be cooled to room temperature; Obtain the viscosity 3750cSt of amino-modified silicone oil, the metal ion content of measuring in the product through ICP is 0.021ppm;
Method two: the alkali glue 36mg that adds two hydroxy silicon oil 30g and 2g amino silicane coupling agent 602 and Tetramethylammonium hydroxide in the 100mL there-necked flask, the drum argon gas, low vacuum vacuumizes 30min, be warming up to 70 ℃, balanced reaction 1h under the argon shield slowly begins to vacuumize then, begin control-below the 0.02MPa, slowly gas clean-up vacuumizes 30min to-0.09MPa; Be warming up to 95 ℃ then, stirring reaction 30min; Add stearylamine 0.008mL, continue reaction 30min; With under-0.09MPa, vacuumizing 1h with quadrat method; Remove vacuum, be warming up to 165 ℃ under the argon shield, stir 1h, destroy catalyzer, be warming up to 180 ℃ and vacuumize and remove small molecules, be cooled to room temperature; Obtain the viscosity 2000cSt of amino-modified silicone oil, the metal ion content of measuring in the product through ICP is 0.022ppm;
Method three: the alkali glue 40mg that adds two hydroxy silicon oil 30g and 1g amino silicane coupling agent 602 and Tetramethylammonium hydroxide in the 100mL there-necked flask, the drum argon gas, low vacuum vacuumizes 30min, be warming up to 85 ℃, balanced reaction 1h under the argon shield slowly begins to vacuumize then, begin control-below the 0.02MPa, slowly gas clean-up vacuumizes 30min to-0.09MPa; Be warming up to 95 ℃ then, stirring reaction 1h; Adding viscosity is the silicone oil 0.01g of the methyl blocking of 100cSt, continues reaction 30min; With under-0.09MPa, vacuumizing 1h with quadrat method; Remove vacuum, be warming up to 165 ℃ under the argon shield, stir 1h, destroy catalyzer, be warming up to 200 ℃ and vacuumize and remove small molecules, be cooled to room temperature; Obtain the viscosity 3810cSt of amino-modified silicone oil, the metal ion content of measuring in the product through ICP is 0.025ppm;
Method four: the alkali glue 120mg that adds two hydroxy silicon oil 30g and 2g amino silicane coupling agent 602 and Tetramethylammonium hydroxide in the 100mL there-necked flask, the drum argon gas, low vacuum vacuumizes 30min, be warming up to 105 ℃, balanced reaction 1h under the argon shield slowly begins to vacuumize then, begin control-below the 0.02MPa, slowly gas clean-up vacuumizes 30min to-0.09MPa; Be warming up to 115 ℃ then, stirring reaction 30min; Add primary isoamyl alcohol 0.006mL, continue reaction 30min; With under-0.09MPa, vacuumizing 1h with quadrat method; Remove vacuum, be warming up to 165 ℃ under the argon shield, stir 1h, destroy catalyzer, be warming up to 200 ℃ and vacuumize and remove small molecules, be cooled to room temperature; Obtain the viscosity 22000cSt of amino-modified silicone oil, the metal ion content of measuring in the product through ICP is 0.021ppm;
Method five: the alkali glue 75mg that adds two hydroxy silicon oil 30g and 2g N methyl piperazine propyl group dimethoxy silane and Tetramethylammonium hydroxide in the 100mL there-necked flask, the drum argon gas, low vacuum vacuumizes 30min, be warming up to 85 ℃, balanced reaction 1h under the argon shield slowly begins to vacuumize then, begin control-below the 0.02MPa, slowly gas clean-up vacuumizes 30min to-0.09MPa; Be warming up to 95 ℃ then, stirring reaction 30min; Add n-Butyl Amine 99 0.003mL, continue reaction 30min; With under-0.09MPa, vacuumizing 1h with quadrat method; Remove vacuum, be warming up to 165 ℃ under the argon shield, stir 1h, destroy catalyzer, be warming up to 200 ℃ and vacuumize and remove small molecules, be cooled to room temperature; Obtain the viscosity 3750cSt of amino-modified silicone oil, the metal ion content of measuring in the product through ICP is 0.021ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010570456 CN102477159B (en) | 2010-11-26 | 2010-11-26 | Amino modified silicone oil and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010570456 CN102477159B (en) | 2010-11-26 | 2010-11-26 | Amino modified silicone oil and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102477159A CN102477159A (en) | 2012-05-30 |
| CN102477159B true CN102477159B (en) | 2013-09-04 |
Family
ID=46089947
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010570456 Expired - Fee Related CN102477159B (en) | 2010-11-26 | 2010-11-26 | Amino modified silicone oil and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102477159B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775792B (en) * | 2012-08-15 | 2014-05-07 | 广州市回天精细化工有限公司 | Modified hydrogen-containing silicone oil, preparation method and application thereof, and silicon rubber containing modified hydrogen-containing silicone oil |
| CN105111444A (en) * | 2015-08-25 | 2015-12-02 | 射阳天源化工有限公司 | Manufacturing method of brightening and smoothening agent |
| CN107698764B (en) * | 2017-10-21 | 2021-05-14 | 湖北三江航天江河化工科技有限公司 | Cyanoethyl grafted aminoalkyl silicone oil for composite solid propellant and synthetic method thereof |
| CN108676165A (en) * | 2018-05-10 | 2018-10-19 | 浙江科峰新材料有限公司 | A kind of preparation process of amido silicon oil crude oil |
| WO2020175159A1 (en) * | 2019-02-25 | 2020-09-03 | 日産化学株式会社 | Inorganic oxide particle, inorganic oxide particle dispersion and preparation method thereof, and method for producing surface modifier |
| CN111875802B (en) * | 2020-06-19 | 2022-06-14 | 上海抚佳精细化工有限公司 | Application of amine stabilizer in preparation of hydrophilic silicone oil with stable viscosity and preparation method of hydrophilic silicone oil |
| CN112280041B (en) * | 2020-11-23 | 2022-05-27 | 江西蓝星星火有机硅有限公司 | Preparation method of amino silicone oil with low organosilicon ring body content |
| CN112897928A (en) * | 2021-01-22 | 2021-06-04 | 夏梅 | Concrete additive and preparation method thereof |
| TWI763566B (en) * | 2021-07-23 | 2022-05-01 | 臺灣塑膠工業股份有限公司 | Manufacturing method for carbon fiber |
| CN113667127A (en) * | 2021-09-08 | 2021-11-19 | 威海拓展纤维有限公司 | Preparation method of amino modified silicone oil |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101357993A (en) * | 2007-08-01 | 2009-02-04 | 瓦克化学股份公司 | Multi-stage method of preparing organopolysiloxane containing amino alkyl group |
-
2010
- 2010-11-26 CN CN 201010570456 patent/CN102477159B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101357993A (en) * | 2007-08-01 | 2009-02-04 | 瓦克化学股份公司 | Multi-stage method of preparing organopolysiloxane containing amino alkyl group |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102477159A (en) | 2012-05-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102477159B (en) | Amino modified silicone oil and preparation method thereof | |
| US3907954A (en) | Production of fibers containing silicon-oxygen bonds | |
| CN108035011B (en) | Melt direct spinning colored polyester fiber and preparation method thereof | |
| CN105133085A (en) | Preparation method of environmentally-friendly flame-retardant polyester bulked continuous filament | |
| US8399591B2 (en) | Amino-mercapto functional organopolysiloxanes | |
| KR100492279B1 (en) | Curable Polymethylsilsesuccioxane Composition | |
| CN101812743B (en) | Spinning solution for industrially producing pure chitosan fiber and preparation method thereof | |
| CN107937997B (en) | Preparation method of high-strength low-elongation polyester industrial yarn | |
| FR2726551A1 (en) | PROCESS FOR THE PREPARATION OF CERAMIC MATERIALS AND DEPARTURE COMPOSITION THAT CAN BE IMPLEMENTED IN THIS PROCESS | |
| EP1349807A1 (en) | Mineral compounds, method for preparing same and use thereof in thermoplastic materials | |
| EP1866364B1 (en) | Use of a specific platinum compound in order to improve the resistance of silicon elastomers to degradation caused by very high temperatures | |
| CN114539530B (en) | Preparation method of alkane amino modified silicone oil and emulsion thereof for carbon fiber oiling agent | |
| Xu et al. | Effect of a bio-based copolymer containing lysine, dopamine and triazine on flame retardancy and mechanical properties of thermoplastic polyurethane/ammonium polyphosphate | |
| CN107964788B (en) | Oil agent and preparation method thereof | |
| CN101397519B (en) | Drawing oil special for annealed aluminum wire and method for producing the same | |
| CN109837752A (en) | The preparation method of spinning oil high molecular weight polyether | |
| FR2583744A1 (en) | PROCESS FOR MANUFACTURING CERAMIC SHAPED ARTICLES CONTAINING SILICON NITRIDE | |
| US3122585A (en) | Production of dimethylamine-borane | |
| CN115716917B (en) | Novel method for preparing zirconium-containing polycarbosilane | |
| CN114891274B (en) | Modified molybdenum disulfide wear-resistant agent, preparation method, wear-resistant agent composition, nylon material and application | |
| Wu et al. | Polyethylene-octene elastomer/silica hybrids prepared by a sol-gel process using tetraethoxysiliane | |
| CN115710826B (en) | Giant tow carbon fiber precursor oiling agent and preparation method thereof | |
| Cherepanov et al. | Synthesis of Disiloxanes and MQ Resins with Sydnonyl Substituents | |
| JPH0351319A (en) | Treating agent for pitch-based carbon fiber | |
| FR2613347A1 (en) | AQUEOUS SOLUTION CONTAINING ZIRCONIUM AND PROCESS FOR PRODUCING ZIRCONIA FIBERS |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130904 Termination date: 20151126 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |