CN107557071B - A kind of organic-silicon-modified chlorinated paraffin and preparation method thereof - Google Patents
A kind of organic-silicon-modified chlorinated paraffin and preparation method thereof Download PDFInfo
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- CN107557071B CN107557071B CN201710845694.2A CN201710845694A CN107557071B CN 107557071 B CN107557071 B CN 107557071B CN 201710845694 A CN201710845694 A CN 201710845694A CN 107557071 B CN107557071 B CN 107557071B
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Abstract
The present invention relates to a kind of organic-silicon-modified chlorinated paraffins and preparation method thereof, substitution reaction generation chlorinated paraffin crude product occurs with chlorine under heat for paraffin first, then nucleophilic substitution reaction generation C-Si-C key occurs for-C-Cl key under the action of transition-metal catalyst in reactive organosilicon compounds in the active H of C-Si-H and chlorinated paraffin, up to the machine Si modification chlorinated paraffin after depickling processing.Compared with the existing technology, the invention has the following advantages that (1) described chlorinated paraffin is using organic-silicon-modified, the thermal stability of chlorinated paraffin is increased；(2) contain C-Si-C key in the organic-silicon-modified chlorinated paraffin molecular structure, therefore more lubricate, be applied to plastics, modified rubber field, toughening effect is more prominent, and hydrophobicity is also improved；(3) preparation process synthesizes under room temperature after chlorination of paraffin, simple process.
Description
Technical field
The present invention relates to a kind of organic-silicon-modified chlorinated paraffins and preparation method thereof, belong to chlorinated paraffin technical field.
Technical background
Chlorinated paraffin is using the smart wax of n-alkane containing straight chain 95% as raw material, through kelene prepared by chlorination reaction
Hydrocarbon mixture.Have many advantages, such as that low volatility, fire-retardant, electrical insulating property is good, inexpensive, can be used as fire retardant and polyvinyl chloride auxiliary
Plasticizer.Be widely used in production CABLE MATERIALS, the products such as plate, hose, artificial leather, rubber, and be applied to coating, plastic cement is run
The additive of road lubricating oil etc..
Chinese patent CN201710241789.3 discloses pressurization Light chlorimation and method is directly agitated to produce Modified Chlorinated Paraffin side
Method belongs to chlorinated paraffin technical field, in order to improve chlorinated paraffin speed of production, is adopted based on it is improved to former 87106851.6 patents
The technical solution taken is that reaction pressure increases to 1 kg/cm in kettle, and kettle is interior to install upper light source additional, and 87106851.6 devices change
Chlorine for the supply of chlorine source is directly placed into agitation device, and starting paraffin is heated to certain temperature, is then added by a certain percentage poly-
Ethylene carries out heating fusing, then puts into chlorination in kettle, provides a kind of faster production method.Chinese patent
CN201710241877.3 discloses pressurization Light chlorimation and method is agitated to produce Modified Chlorinated Paraffin method, belongs to chlorinated paraffin technology neck
Domain is adopted the technical scheme that in kettle to improve chlorinated paraffin speed of production based on it is improved to former 87106851.6 patents
Pressure increases to 1 kg/cm, and kettle is interior to install upper light source additional, starting paraffin is heated to certain temperature (110 DEG C or so), so
(5% or so) is added polyethylene and carries out heating fusing by a certain percentage afterwards, then puts into chlorination in kettle, and ensure polyethylene with heat
To melt shape, a kind of faster production method is provided.But since the essence of foregoing invention is still synthesizing paraffin chloride, chlorination
The disadvantage of the difference of thermal stability possessed by paraffin does not solve.
Summary of the invention
It is in order to overcome the shortcomings of the prior art and insufficient, the primary purpose of the present invention is that providing a kind of organic-silicon-modified chlorination
Paraffin.
Another object of the present invention is to provide a kind of preparation methods of organic-silicon-modified chlorinated paraffin.
A kind of organic-silicon-modified chlorinated paraffin of the present invention, in molecule containing C-Si-C key, silicon content 1%~
5%, preparation method is as follows:
Smart wax is put into reaction tower, chlorine is passed through reactor by bottom distributor, gas is carried out under certain temperature and pressure
Liquid phase reactor claims liquid chlorine cylinder cummulative metering using sharp-edge orifice meter metering and pound, after liquid specific gravity reaches 1.18~1.26,
Up to chlorinated paraffin crude product；Then reaction solution is passed through into stirred tank, chlorinated paraffin crude product quality 5%~10% is added under room temperature
Reactive organosilicon compounds, chlorinated paraffin crude product quality 1%~2% 50ppm transition-metal catalyst, react 1~2h after,
Reaction solution is passed through depickling kettle and carries out depickling processing, is obtained up to a kind of organic-silicon-modified chlorinated paraffin.
The temperature of the gas-liquid phase reaction is preferably 90~100 DEG C, and pressure is preferably 100~150kPa.
The reactive organosilicon compounds are pheiiyldimetliyl silane, the hydrogeneous cyclotetrasiloxane of tetramethyl, methyl hydrogen two
Chlorosilane, tetramethyldihydrogendisiloxane, silicon oil of low hydrogen content, high containing hydrogen silicone oil, in the hydrogeneous cyclotrisiloxane of trimethyl at least
It is a kind of.
The transition-metal catalyst is RhClP (C6H5)3、RuHCl(CO)(PPh3)、HAuCl4、K2PtCl4、Ni
(CO)4、SnCl2·H2PtCl6、HCo(CO)4、Ru(SiMe2Ph)Cl(CO)(PPr3)2At least one of.
A kind of principle of organic-silicon-modified chlorinated paraffin preparation method of the present invention are as follows: first paraffin under heat with
Chlorine occurs substitution reaction and generates chlorinated paraffin；Then under the action of transition-metal catalyst, in reactive organosilicon compounds
The active H of C-Si-H and the-C-Cl key in chlorinated paraffin occur nucleophilic substitution reaction and generate C-Si-C key, obtain the machine silicon and change
Property chlorinated paraffin.
Compared with the existing technology, a kind of organic-silicon-modified chlorinated paraffin of the present invention and preparation method thereof, have with
Lower advantage: (1) chlorinated paraffin uses organic-silicon-modified, increases the thermal stability of chlorinated paraffin；(2) organosilicon changes
Property chlorinated paraffin molecular structure in contain C-Si-C key, therefore more lubricate, be applied to plastics, modified rubber field, increase
Tough effect is more prominent, and hydrophobicity is also improved；(3) preparation process synthesizes under room temperature after chlorination of paraffin, technique letter
It is single；(4) method of the invention is handled by depickling again after organic-silicon-modified, is had good continuity, is reduced life
Produce cost.
Specific embodiment
A kind of organic-silicon-modified chlorinated paraffin of the invention and its preparation process are done further below with reference to embodiment
Description.It is understood that specific embodiment described herein is used only for explaining related invention, rather than to the limit of the invention
It is fixed.
Embodiment 1
A kind of organic-silicon-modified chlorinated paraffin of the present invention contains C-Si-C key in molecule, and preparation process is as follows:
Smart wax is put into reaction tower, chlorine is passed through reactor by bottom distributor, carries out gas-liquid under 90 DEG C and 150kPa
Phase reaction claims liquid chlorine cylinder cummulative metering using sharp-edge orifice meter metering and pound, after liquid specific gravity reaches 1.18~1.20, i.e.,
Obtain chlorinated paraffin crude product；Then reaction solution is passed through into stirred tank, the phenyl of chlorinated paraffin crude product quality 5% is added under room temperature
Transition-metal catalyst RuHCl (CO) (PPh of the 50ppm of dimethylsilane, chlorinated paraffin crude product quality 2%3), 1h after reaction
Afterwards, reaction solution is passed through depickling kettle and carries out depickling processing to get a kind of organic-silicon-modified chlorinated paraffin.
Embodiment 2
A kind of organic-silicon-modified chlorinated paraffin of the present invention contains C-Si-C key in molecule, and preparation process is as follows:
Smart wax is put into reaction tower, chlorine is passed through reactor by bottom distributor, carries out gas-liquid under 100 DEG C and 100kPa
Phase reaction claims liquid chlorine cylinder cummulative metering using sharp-edge orifice meter metering and pound, will after liquid specific gravity reaches 1.24~1.26
Reaction solution is passed through depickling kettle and carries out depickling processing to get chlorinated paraffin crude product；Then reaction solution is passed through into stirred tank, room temperature
It is lower be added the hydrogeneous cyclotetrasiloxane of tetramethyl of chlorinated paraffin crude product quality 10%, chlorinated paraffin crude product quality 1% 50ppm mistake
Cross metallic catalyst HAuCl4, after reacting 2h, it is organic to get described one kind that reaction solution is passed through the progress depickling processing of depickling kettle
Si modification chlorinated paraffin.
Embodiment 3
A kind of organic-silicon-modified chlorinated paraffin of the present invention contains C-Si-C key in molecule, and preparation process is as follows:
Smart wax is put into reaction tower, chlorine is passed through reactor by bottom distributor, carries out gas-liquid under 95 DEG C and 140kPa
Phase reaction claims liquid chlorine cylinder cummulative metering using sharp-edge orifice meter metering and pound, will after liquid specific gravity reaches 1.18~1.20
Reaction solution is passed through depickling kettle and carries out depickling processing to get chlorinated paraffin crude product；Then reaction solution is passed through into stirred tank, room temperature
The lower 50ppm that the silicon oil of low hydrogen content of chlorinated paraffin crude product quality 7.2%, chlorinated paraffin crude product quality 1.6% is added
SnCl2·H2PtCl6, after reacting 2h, reaction solution is passed through the progress depickling processing of depickling kettle and is changed to get a kind of organosilicon
Property chlorinated paraffin.
Embodiment 4
A kind of organic-silicon-modified chlorinated paraffin of the present invention contains C-Si-C key in molecule, and preparation process is as follows:
Smart wax is put into reaction tower, chlorine is passed through reactor by bottom distributor, carries out gas-liquid under 98 DEG C and 140kPa
Phase reaction claims liquid chlorine cylinder cummulative metering using sharp-edge orifice meter metering and pound, after liquid specific gravity reaches 1.24~1.26, i.e.,
Obtain chlorinated paraffin crude product；Then reaction solution is passed through into stirred tank, the three of chlorinated paraffin crude product quality 7.9% is added under room temperature
Methyl hydrogen cyclotrisiloxane, chlorinated paraffin crude product quality 1.2% 50ppm HCo (CO)4, after reacting 1.8h, by reaction solution
It is passed through depickling kettle and carries out depickling processing to get a kind of organic-silicon-modified chlorinated paraffin.
The physical property of paraffin is as follows: in embodiment
It is required according to GB 1680-81, organic-silicon-modified chlorinated paraffin and commercially available chlorinated paraffin -52 in testing example
Thermal decomposition temperature, data are as follows:
Organic-silicon-modified chlorinated paraffin and commercially available chlorinated paraffin -52 in 45g embodiment is taken to be respectively placed in 25mm × 125mm examination
In pipe, it is put into ultraviolet light accelerated aging test case, ageing oven temperature 50 C, revolving speed 3r/min；Primary, the note every 5min observation
The color of record stable type chlorinated paraffin starts the time of variation, is as follows:
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Commercially available top grade chlorinated paraffin -52 | Commercially available top grade chlorinated paraffin -42 | |
| Start Coloring Time | 95min | 90min | 95min | 90 min | 70min | 75min |
Claims (4)
1. a kind of organic-silicon-modified chlorinated paraffin, which is characterized in that contain C- in the organic-silicon-modified chlorinated paraffin molecule
Si-C key, the organic-silicon-modified chlorinated paraffin silicon content 1%-5%；
The preparation method of the organic-silicon-modified chlorinated paraffin, comprising the following steps: smart wax is put into reaction tower, chlorine is by bottom
Distributor is passed through reactor, and gas-liquid phase reaction is carried out under certain temperature and pressure, claims liquid using sharp-edge orifice meter metering and pound
Chlorine steel cylinder cummulative metering, to get chlorinated paraffin crude product after liquid specific gravity reaches 1.18-1.26；Then by reaction solution be passed through to
In stirred tank, reactive organosilicon compounds, the chlorinated paraffin crude product quality of chlorinated paraffin crude product quality 5%-10% are added under room temperature
Reaction solution after reacting 1-2h, is passed through depickling kettle and carries out depickling processing to get institute by the transition-metal catalyst of the 50ppm of 1%-2%
A kind of organic-silicon-modified chlorinated paraffin stated.
2. a kind of organic-silicon-modified chlorinated paraffin according to claim 1, which is characterized in that the temperature of the gas-liquid phase reaction
Preferred 90-100 DEG C is spent, pressure is preferably 100-150kPa.
3. a kind of organic-silicon-modified chlorinated paraffin according to claim 1, which is characterized in that the active organosilicon
Conjunction object be pheiiyldimetliyl silane, the hydrogeneous cyclotetrasiloxane of tetramethyl, methyl hydrogen dichlorosilane, tetramethyldihydrogendisiloxane,
At least one of silicon oil of low hydrogen content, high containing hydrogen silicone oil, the hydrogeneous cyclotrisiloxane of trimethyl.
4. a kind of organic-silicon-modified chlorinated paraffin according to claim 1, which is characterized in that the transition metal is urged
Agent is RhClP (C6H5)3、RuHCl(CO)(PPh3)、HAuCl4、K2PtCl4、Ni(CO)4、SnCl2·H2PtCl6、HCo
(CO)4、Ru(SiMe2Ph)Cl(CO)(PPr3)2At least one of.
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| CN108728163B (en) * | 2018-05-03 | 2020-10-20 | 南京国威化工有限公司 | Organic silicon tackifying chlorinated paraffin |
| CN109082129A (en) * | 2018-07-14 | 2018-12-25 | 合肥艾飞新材料有限公司 | A kind of Modified Chlorinated Paraffin and preparation method thereof |
| CN109021648B (en) * | 2018-07-18 | 2020-09-01 | 安徽星鑫化工科技有限公司 | Preparation method of special super-hydrophobic anti-corrosion chlorinated paraffin for coating |
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| CN105602391B (en) * | 2016-02-25 | 2018-05-11 | 中山诺顿科研技术服务有限公司 | Antirust coating |
| CN106995721A (en) * | 2017-04-04 | 2017-08-01 | 林群祥 | The hot method production method of Modified Chlorinated Paraffin 70 of air cooling is directly agitated in catalysis pressurization |
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Denomination of invention: Organic silicon modified chlorinated paraffin and preparation method thereof Effective date of registration: 20191227 Granted publication date: 20190315 Pledgee: Huoqiu County Industrial Finance Company Limited by Guarantee Pledgor: Anhui Xingxin Chemical Science & Technology Co., Ltd. Registration number: Y2019980001349 |
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Address after: 237451 Huhu Town, Huoqiu County, Lu'an City, Anhui Province Patentee after: Anhui Xingxin Material Technology Co.,Ltd. Address before: 237451 Huhu Town, Huoqiu County, Lu'an City, Anhui Province Patentee before: ANHUI XINGXIN CHEMICAL TECHNOLOGY Co.,Ltd. |