CN102477159A - Amino modified silicone oil and preparation method thereof - Google Patents
Amino modified silicone oil and preparation method thereof Download PDFInfo
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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 final quality 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
Thomel has a series of superior characteristic, and the most outstanding is that specific tenacity, specific modulus are high.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 process 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 metals ion in great detail to the structure of polyacrylonitrile fibril and the reason of Effect on Performance, think metals ion can replace polymeric in carboxyl (H CCOH), as:
-COOH+K
+→-COOK+H
+
Its result; The heat release cyclisation temperature that makes polyacrylonitrile fibril is improved; Hindered polyacrylonitrile fibril through ionic mechanism form generation cyclisation, final thomel 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: like 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 good convergency of precursor and processibility; Monofilament is bonding to play good preventing at spinning and preoxidation and carbonization initial stage for excellent lubrication property 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 thomel.
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 MWD broad that this method makes, 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; The modification group is evenly distributed; And do not produce the annular siloxane oligopolymer in the polycondensation, but shortcoming is being deposited rising gradually in the process 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 tsp, 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 to fiber especially carbon fibre precursor greatly introduces metallic impurity; Thereby improve the final quality of thomel, 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 TMAH is a catalyzer; Make above-mentioned raw material carry out the body condensation reaction, behind reaction 2～5h, add the micromolecular compound that has reactive group, make the amino-modified silicone oil of low-metal content stable viscosity.
Said pair of hydroxy silicon oil is the two hydroxy silicon oils of LV, 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.
Special, said 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 TMAH can adopt this area to use always; As can adopt the TMAH by ion-exchange-resin process, substitution method (calcium hydroxide method, potassium hydroxide method, silver suboxide method), electrolytic process (monofilm method, multimembrane method) preparation, the TMAH 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 TMAH accounts for 0.008～1.3% of total mass.
The above-mentioned micromolecular compound that has reactive 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 a 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 said preparation method that reaction is warming up to 135 ℃～150 ℃ and destroys catalyzer after finishing;
In addition, also further comprise among the said 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 TMAH 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 the object of the invention, synthesized a kind of amino-modified silicone oil 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 thomel, and this silicone oil can viscosity not become big in put procedure.
Embodiment
Following examples are used to explain the present invention, but are not used for limiting scope of the present invention.
Specialize like 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 TMAH 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, begins to be controlled at-below the 0.02MPa, and 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; Use with quadrat method and under-0.09MPa, vacuumize 1h; 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; TMAH alkali glue is changed to the alkali glue of Pottasium Hydroxide; Under the identical situation of catalyzer molar weight, the viscosity of the amino-modified silicone oil that obtains is 1980cSt, adds in the acetic acid at last and Pottasium 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 in the 100mL there-necked flask, adds two hydroxy silicon oil 30g and 2g amino silicane coupling agent 602 and TMAH, 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, begins to be controlled at-below the 0.02MPa, and 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; Use with quadrat method and under-0.09MPa, vacuumize 1h; 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 in the 100mL there-necked flask, adds two hydroxy silicon oil 30g and 2g aminomethyl [N-(the 3-dimethoxy-methyl is silica-based) propyl group aminomethyl] former ripple alkane and TMAH, 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, begins to be controlled at-below the 0.02MPa, and slowly gas clean-up vacuumizes 30min to-0.09MPa; Be warming up to 105 ℃ then, stirring reaction 30min; Add SWS-F 221 0.005mL, continue reaction 30min; Use with quadrat method and under-0.09MPa, vacuumize 1h; 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 in the 100mL there-necked flask, adds two hydroxy silicon oil 30g and 1g amino silicane coupling agent 602 and TMAH, 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, begins to be controlled at-below the 0.02MPa, and 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; Use with quadrat method and under-0.09MPa, vacuumize 1h; 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 in the 100mL there-necked flask, adds two hydroxy silicon oil 30g and 2g amino silicane coupling agent 602 and TMAH, 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, begins to be controlled at-below the 0.02MPa, and 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; Use with quadrat method and under-0.09MPa, vacuumize 1h; 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 in the 100mL there-necked flask, adds two hydroxy silicon oil 30g and 2g N methyl piperazine propyl group dimethoxy silane and TMAH, 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, begins to be controlled at-below the 0.02MPa, and 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; Use with quadrat method and under-0.09MPa, vacuumize 1h; 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 (10)
1. amino-modified silicone oil; It is characterized in that adopting two hydroxy silicon oils and amino coupling agent is raw material, the employing TMAH is a catalyzer; Make above-mentioned raw material carry out the body condensation reaction, add the micromolecular compound that has reactive group behind reaction 2～5h and make.
2. amino-modified silicone oil as claimed in claim 1 is characterized in that, the consumption of said raw material is: the massfraction 0.13～4.98% that accounts for two hydroxy silicon oils and amino coupling agent total mass of ammonia element; The quality of said TMAH accounts for 0.008～1.3% of two hydroxy silicon oils and amino coupling agent total mass.
3. according to claim 1 or claim 2 amino-modified silicone oil is characterized in that the temperature of reaction of described condensation reaction is 70 ℃～120 ℃, and the time of condensation reaction is controlled at 1～10h.
4. like the arbitrary described amino-modified silicone oil of claim 1-3, it is characterized in that, also comprise among the said preparation method that reaction is warming up to 135 ℃～150 ℃ and destroys catalyzer after finishing.
5. amino-modified silicone oil as claimed in claim 4 is characterized in that, also further comprises among the said preparation method, continues to be warming up to 155 ℃～200 ℃ and removes micromolecular compound, gets the clear, colorless amino-modified silicone oil.
6. amino-modified silicone oil as claimed in claim 1 is characterized in that, said pair of hydroxy silicon oil is the two hydroxy silicon oils of LV, and its range of viscosities is 30～600cSt.
7. amino-modified silicone oil as claimed in claim 1 is characterized in that, said amino coupling agent be 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.
8. like claim 1 or 7 described amino-modified silicone oils; It is characterized in that; Said amino coupling agent is N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane; N-cyclohexyl-γ-aminopropyl methyl dimethoxysilane, one or more in γ-diethylenetriamine propyl group methyl dimethoxysilane.
9. amino-modified silicone oil as claimed in claim 1; It is characterized in that; The said micromolecular compound that has reactive group is 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, its molar mass is 0.001～0.1% of a raw material total mole number.
10. like the preparation method of the arbitrary described amino-modified silicone oil of claim 1-9; It is characterized in that adopting two hydroxy silicon oils and amino coupling agent is raw material, the employing TMAH is a catalyzer; Make above-mentioned raw material carry out the body condensation reaction; Behind reaction 2～5h, add the micromolecular compound that has reactive group and make, reaction is warming up to 135 ℃-150 ℃ after finishing, and destroys catalyzer; Be warming up to 155 ℃-200 ℃ subsequently, remove micromolecular compound and make;
The massfraction 0.13～4.98% that accounts for two hydroxy silicon oils and amino coupling agent total mass of ammonia element wherein, the quality of TMAH is 0.008～1.3% of pair hydroxy silicon oils and an amino coupling agent total mass; The said molar mass that has the micromolecular compound of reactive group is 0.001～0.1% of a raw material total mole number;
The temperature of reaction of said condensation reaction is 70 ℃～120 ℃; Reaction times is controlled at 1～10h.
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| CN102775792A (en) * | 2012-08-15 | 2012-11-14 | 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 |
| CN107698764A (en) * | 2017-10-21 | 2018-02-16 | 湖北三江航天江河化工科技有限公司 | Cyanoethyl for composite solidpropellant is grafted ammonia alkyl silicone oil and synthetic method |
| 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 |
| CN111875802A (en) * | 2020-06-19 | 2020-11-03 | 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 |
| CN112280041A (en) * | 2020-11-23 | 2021-01-29 | 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 |
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| 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 |
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| 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 |
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2010
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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| 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 |
| CN102775792A (en) * | 2012-08-15 | 2012-11-14 | 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 |
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| 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 |
| CN113474288A (en) * | 2019-02-25 | 2021-10-01 | 日产化学株式会社 | Inorganic oxide particles, inorganic oxide particle dispersion liquid, method for producing inorganic oxide particle dispersion liquid, and method for producing surface modifier |
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| CN111875802A (en) * | 2020-06-19 | 2020-11-03 | 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 |
| CN112280041A (en) * | 2020-11-23 | 2021-01-29 | 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 |
| 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 |
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| CN114059198A (en) * | 2021-07-23 | 2022-02-18 | 台湾塑胶工业股份有限公司 | Method for producing carbon fiber |
| CN114059198B (en) * | 2021-07-23 | 2024-02-13 | 台湾塑胶工业股份有限公司 | Method for producing carbon fiber |
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