CN103265570B - Phenoxymethyl disilane and preparation method thereof - Google Patents
Phenoxymethyl disilane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses phenoxymethyl disilane shown in formula I and preparation method thereof, the preparation method of this compound is by chlorine atom in high boiling point chlorosilane waste liquid: phenol mol ratio is that 1:1～1.5 takes raw material；Phenol is added in reactor, at 40 DEG C, high boiling point chlorosilane waste liquid is added dropwise in reactor；After dropping, it is warming up to 60～100 DEG C of reactions 8～13h until no longer there being HCl to release；By reacting rear material decompression distillation, after removing less than the 170 DEG C by-products distillated and the complete phenol of unreacted, collect 230～260 DEG C of fractions distillated and be product phenoxymethyl disilane.The present invention is with trade waste high boiling point chlorosilane waste liquid etc. as raw material, it is thus achieved that phenoxymethyl disilane there is good heat stability, non-oxidizability and high-flash, it is adaptable in hydraulic oil, diffusion pump oil and conduction oil.(RO)n Si‑Si(CH3)6‑n(I)。
Description
Technical field
The invention belongs to the compound of silicon and mainly utilize garbage to prepare the method for compound of this silicon, relating to
And one phenoxymethyl disilane and preparation method thereof.Use phenoxymethyl two silicon that the present invention obtains
Hydride compounds can be applicable to thermostability, non-oxidizability conduction oil.
Background technology
Organic silicon monomer (methylchlorosilane, phenyl chlorosilane, vinyl chlorosilane etc.) is whole organic
The basis of silicon materials industrial development, wherein the production of methylchlorosilane Silicone Industry especially
Post.At present, industrial production organosilicon mainly uses copper catalysis chloroform and silica flour to be directly synthesized and prepare methyl
Chlorosilane, and organic silicon chemical while direct method produces organosilicon product also with substantial amounts of by-product
Produce are raw (the 15% of total output～25%), wherein comprise low boiling by-product (boiling point is below 40 DEG C)
With height boiling by-product (boiling point is more than 70 DEG C).Low-boiling by-products can provide after purifying at present
Sourceization utilizes, and its Main Ingredients and Appearance is methyl trichlorosilane (accounting for the 5～8% of total output)；The most also contain
Having a certain amount of high boiling point by-products produced (accounting for the 10～15% of total output), these are high boiling point by-products produced one years old
As boiling point be 140 DEG C～190 DEG C, its Main Ingredients and Appearance be the mixed of methylchlorodisilane class organo-silicon compound
Compound, its molecular formula is as shown in formula II:
Clm Si-Si(CH3)6-m,Wherein: m=2-6
(Ⅱ)
In prior art, organosilicon industry is for this kind of high boiling point waste liquid (the most described high boiling point by-products produced)
Also there is no preferable processing method, the most in the industrial production an output substantial amounts of high boiling point waste liquid, this kind of contain
Silicon waste liquid can not directly burn, can not biodegradation, simultaneously also can hydrolyze releasing chlorination at storage process
Hydrogen, can cause harm greatly to human body and environment.Process to such waste liquid is the most all
The thorny problem that enterprise faces.Conventional processing method is by filling after hydrolyzing, be cross-linked to form solid,
This method is only capable of short-term and solves problem, can cause environment potentially hazardous simultaneously.Therefore, by this kind of waste liquid
Rationally dispose even recycling and seem the most urgent.Exploitation new technique by organic silicon waste liquid become give up into
Treasured, the problem that can not only effectively solve environmental pollution, moreover it is possible to bring extra benefit for organosilicon enterprise.
Conduction oil is the Transfer Medium of a kind of heat, due to its there is homogeneous heating, homoiothermic control temperature accurately,
Can produce under low-steam pressure that high temperature, heat-transfer effect be good, energy-conservation, conveying and the feature such as easy to operate, closely
It is widely used in various occasion over Nian, and its purposes and consumption get more and more.According to composition and manufacture
Industrial process, traditional conduction oil can be divided into synthesis type conduction oil and mineral type conduction oil.Wherein synthesize
Conduction oil mainly has alkyl benzene-type, alkylnaphthalene type, alkyl biphenyl type, biphenyl and Biphenyl Ether eutectic mixture
Types etc. are several, but these several heat conduction oil flash are all below 230 DEG C, in the environment more than 300 DEG C
Great potential safety hazard is had, it is impossible to be applicable to the needs of some special producing during work.
Organo-silicon compound have an excellent thermostability, non-oxidizability, resistance to water, weatherability, anti-shearing,
The character such as electric insulation, liquid silicone compound lubricating oil, conduction oil, insulating oil, shockproof oil,
The application that the many-side such as mould oil, defoamer, yarn fabric finishing agent succeeds, generally by this on market
Class oil is referred to as silicone oil.The structure of silicone oil is based on polysiloxanes at present, can be subdivided into alkyl silicone oil, carbon official
Energy silicone oil, functionalized silicon silicone oil and nonactive modified silicon oil, but this kind of silicone oil causes gluing owing to easily crosslinking
Degree easily increases, and typically uses not as conduction oil.The structures such as other silicone oil structure such as Si-C, carbon silicon ether because of
The short feature of molecule segment is the most difficult to be crosslinked, and its viscosity at high temperature varies less,
It is suitable for the application of high temperature heat conductive oil, but the research of this type of silicone oil is less.
Summary of the invention
The purpose of the present invention is intended to overcome deficiency of the prior art, it is provided that a kind of phenoxymethyl disilane
And preparation method thereof.Recycling of the present invention trade waste high boiling point chlorosilane waste liquid (i.e. institute
State high boiling point by-products produced, high boiling point waste liquid), pass through etherification reaction with phenol etc., it is provided that one has good
The phenoxymethyl disilane of the superperformances such as good heat stability, non-oxidizability and high-flash and system thereof
Preparation Method, this phenoxymethyl disilane can be used in hydraulic oil, diffusion pump oil or conduction oil.
Present disclosure is: phenoxymethyl disilane, it is characterized in that this compound has (I) institute
The chemical structural formula shown:
(RO)m Si-Si(CH3)6-m
(I)
In formula (I): R=C6H5-、p-CH3-C6H4-or o-CH3-C6H4-；M=2-6.
Another content of the present invention is: the preparation method of phenoxymethyl disilane, under it is characterized in that including
Row step:
A, dispensing: by chlorine atom in high boiling point chlorosilane waste liquid: the mol ratio of phenol is that 1:1～1.5 takes
Raw material high boiling point chlorosilane waste liquid and phenol, wherein: the content of chlorine atom in high boiling point chlorosilane waste liquid
(can be through acid base titration) be 13mol/L；
B, etherification reaction: phenol is equipped with constant pressure funnel, anhydrous calcium chloride drying tower, HCl
Tail connects in the reactor of device, joins in constant pressure funnel by high boiling point chlorosilane waste liquid, at 40 DEG C
At a temperature of (slowly) high boiling point chlorosilane waste liquid is added dropwise in reactor；After dropping, (by
Step) it is warming up to 60～100 DEG C and continues reaction and 8～13h device no longer has HCl release until HCl tail connects,
Terminate reaction, obtain reacting rear material；
C, separating-purifying: by reacting rear material at temperature 170～260 DEG C, the bar of pressure 5～10mmHg
Decompression distillation is carried out under part, after removing less than the 170 DEG C by-products distillated and the complete phenol of unreacted, receipts
Collect 230～260 DEG C of fractions distillated and be product phenoxymethyl disilane.
The structural characterization of product phenoxymethyl disilane is as follows: its infrared spectrum IR (KBr film, cm-1):
3049.2,2963,1597,1495,1260,864,758,720,702；1H NMR (400MHz,
CDCl3) δ: 6.82-7.20 (20H ,-ArH), 0.078-0.145 (6H ,-SiCH3).Boiling point: 230～
260℃/5mmHg；Flash-point: 300 DEG C；25 DEG C of kinematic viscosity: 342mm2/S.Initial pyrolyzation temperature:
380℃。
The chemical equation of the synthetic method of phenoxymethyl disilane is as follows:
ClmSi-Si(CH3)6-m+nC6H5OH→(C6H5O)mSi-Si(CH3)6-m+mHCl
In formula: m=2～6
The mixture that chemical composition is methylchlorodisilane of the waste liquid of high boiling point chlorosilane described in step a,
The mixture general molecular formula of this methylchlorodisilane is Clm Si-Si(CH3)6-m,Wherein: m=2-6；Described
High boiling point chlorosilane waste liquid is the chloride organic of (Sichuan Province China province) north, Luzhou Chemical Co., Ltd. offer
Silicon industrial wastes, can also be other enterprises provide chloride silicone industry waste liquid i.e. high boiling point chlorosilane
Waste liquid.
Chlorine atom in the waste liquid of high boiling point chlorosilane described in step a: the mol ratio of phenol is preferably
1:1.1。
Another content of the present invention it may also is that preparation method to methylphenoxymethyl disilane, its
Feature is to comprise the following steps:
A, dispensing: by chlorine atom in high boiling point chlorosilane waste liquid: the mol ratio of p-methyl phenol be 1:1～
1.5 take raw material high boiling point chlorosilane waste liquid and p-methyl phenol, wherein: chlorine in high boiling point chlorosilane waste liquid
The content (can be through acid base titration) of atom is 13mol/L；
B, etherification reaction: p-methyl phenol is equipped with constant pressure funnel, anhydrous calcium chloride is dried
Tower, HCl tail connect in the reactor of device, join in constant pressure funnel by high boiling point chlorosilane waste liquid,
(slowly) high boiling point chlorosilane waste liquid is added dropwise in reactor at a temperature of 40 DEG C；Drip complete
After, (progressively) is warming up to 60～100 DEG C and continues reaction 8～13h until HCl tail connects in device and no longer has
HCl releases, and terminates reaction, obtains reacting rear material；
C, separating-purifying: by reacting rear material at temperature 170～260 DEG C, the bar of pressure 5～10mmHg
Carry out decompression distillation under part, remove less than the 170 DEG C by-products distillated and the complete p-methyl phenol of unreacted
After, collect 230～260 DEG C of fractions distillated and be product to methylphenoxymethyl disilane.
Product is as follows to the structural characterization of methylphenoxymethyl disilane: (KBr is coated with its infrared spectrum IR
Film, cm-1): 3049.2,2963,1597,1495,1260,864,758,720,702；1H
NMR (400MHz, CDCl3) δ: 6.82-7.20 (20H ,-ArH), 0.078-0.145 (6H ,-SiCH3)。
Boiling point: 240～280 DEG C/5mmHg；Flash-point: 301 DEG C；25 DEG C of kinematic viscosity: 346mm2/S.Initially
Heat decomposition temperature: 370 DEG C.
The mixture that chemical composition is methylchlorodisilane of the waste liquid of high boiling point chlorosilane described in step a,
The mixture general molecular formula of this methylchlorodisilane is Clm Si-Si(CH3)6-m,Wherein: m=2-6；Described
High boiling point chlorosilane waste liquid is the chloride organic of (Sichuan Province China province) north, Luzhou Chemical Co., Ltd. offer
Silicon industrial wastes, can also be other enterprises provide chloride silicone industry waste liquid i.e. high boiling point chlorosilane
Waste liquid.
Chlorine atom in the waste liquid of high boiling point chlorosilane described in step a: the mol ratio of p-methyl phenol is preferable
For 1:1.1.
Another content of the present invention it may also is that the preparation method of o-methyl-benzene epoxide methyl disilane, its
Feature is to comprise the following steps:
A, dispensing: by chlorine atom in high boiling point chlorosilane waste liquid: the mol ratio of ortho-methyl phenol be 1:1～
1.5 take raw material high boiling point chlorosilane waste liquid and ortho-methyl phenol, wherein: chlorine in high boiling point chlorosilane waste liquid
The content (can be through acid base titration) of atom is 13mol/L；
B, etherification reaction: ortho-methyl phenol is equipped with constant pressure funnel, anhydrous calcium chloride is dried
Tower, HCl tail connect in the reactor of device, join in constant pressure funnel by high boiling point chlorosilane waste liquid,
(slowly) high boiling point chlorosilane waste liquid is added dropwise in reactor at a temperature of 40 DEG C；Drip complete
After, (progressively) is warming up to 60～100 DEG C and continues reaction 8～13h until HCl tail connects in device and no longer has
HCl releases, and terminates reaction, obtains reacting rear material；
C, separating-purifying: by reacting rear material at temperature 170～260 DEG C, the bar of pressure 5～10mmHg
Carry out decompression distillation under part, remove less than the 170 DEG C by-products distillated and the complete ortho-methyl phenol of unreacted
After, collect 230～260 DEG C of fractions distillated and be product o-methyl-benzene epoxide methyl disilane.
The structural characterization of product o-methyl-benzene epoxide methyl disilane is as follows: (KBr is coated with its infrared spectrum IR
Film, cm-1): 3049.2,2963,1597,1495,1260,864,758,720,702；1H
NMR (400MHz, CDCl3) δ: 6.82-7.20 (20H ,-ArH), 0.078-0.145 (6H ,-SiCH3)。
Boiling point: 230～270 DEG C/5mmHg；Flash-point: 301 DEG C；25 DEG C of kinematic viscosity: 344mm2/S.Initially
Heat decomposition temperature: 370 DEG C.
The mixture that chemical composition is methylchlorodisilane of high boiling point chlorosilane waste liquid described in step a, should
The mixture general molecular formula of methylchlorodisilane is Clm Si-Si(CH3)6-m,Wherein: m=2-6；Described height
Boiling point chlorosilane waste liquid is the chloride organosilicon that (Sichuan Province China province) north, Luzhou Chemical Co., Ltd. provides
Industrial wastes, can also be other enterprises provide chloride silicone industry waste liquid i.e. high boiling point chlorosilane give up
Liquid.
Chlorine atom in the waste liquid of high boiling point chlorosilane described in step a: the mol ratio of ortho-methyl phenol is preferable
For 1:1.1.
Compared with prior art, the present invention has features and a beneficial effect:
(1) present invention is used, recycling trade waste high boiling point chlorosilane waste liquid, with
Phenol etc. by etherification reaction, a synthetically prepared class novel phenoxymethyl disilane, the phenoxy group of preparation
Methyl disilane is with Si-Si as skeleton, and becomes multiple substituted radical by Si-O-C key-like, and structure can
Control, reaction process is simple, does not use organic solvent, and purification of products is convenient, and phenoxymethyl disilane has
Have prominent thermostability, boiling point and flash-point, for the exploitation of novel high-performance conduction oil provide one new
Approach；
(2) the high boiling point waste liquid that the present invention uses industrial production organosilicon common (is mainly composed of first
The mixture of base chlorine disilane class organo-silicon compound) it is raw material, by Si-Cl key and phenol or methyl
The etherification reaction of phenol, the preparation phenoxymethyl disilane compound with Si-Si bond as skeleton；, will
Organic silicon waste liquid turns waste into wealth, the problem that can not only effectively solve environmental pollution, moreover it is possible to for organosilicon enterprise
Bring extra benefit, beneficially environmental protection, for the resource recovery of the high boiling point garbage that organic silicon chemical produces
Recycling provides a good approach, and Social benefit and economic benefit is obvious；
(3) incipient degradation temperature and boiling point, the sudden strain of a muscle of the phenoxymethyl disilane of present invention acquisition are used
Point is all higher than 300 DEG C, can more than 300 DEG C steady operation under conditions of exclusion of water, and add for a long time
Under heat condition, viscosity does not increases, and meets the performance requirement of high-end heat-conducting medium, functional；
(4) organo-silicon compound (phenoxymethyl disilane etc.) using the present invention to obtain have good
Good heat stability and non-oxidizability and high-flash, be useful in hydraulic oil, diffusion pump oil and conduction oil；
(5) product preparation process of the present invention is simple, with low cost, and operation is easy, easily operates, practical
Property is strong.
Detailed description of the invention
Example given below is intended so that the invention will be further described, but is not to be construed as this
The restriction of bright protection domain, the present invention is made by person skilled in art according to the content of the invention described above
Some nonessential improvement and adjustment, still fall within protection scope of the present invention.
Embodiment 1:
Etherification reaction prepares phenoxymethyl disilane, and key step is as follows:
A, dispensing: take high boiling point chlorosilane waste liquid, phenol；Press chlorine in high boiling point chlorosilane waste liquid
Atom: phenol mol ratio is that 1:1.1 carries out etherification reaction；In high boiling point chlorosilane waste liquid, chlorine is former
The content of son is 13mol/L through acid base titration；
B, etherification reaction: first 538g phenol (5.72mol) is equipped with constant pressure addition
Funnel, anhydrous calcium chloride drying tower, HCl tail connect in the round-bottomed flask of device, at constant pressure funnel
The high boiling point chlorosilane waste liquid of middle addition 400mL (chloride 5.2mol), slowly will at 40 DEG C
High boiling point chlorosilane waste liquid is added dropwise in reaction unit；After dropping, progressively it is warming up to 60 DEG C
Continuing reaction 8～13h no longer has HCl to release until HCl tail connects in device；
C, separating-purifying: reaction terminate after carry out decompression distillation (5-10mmHg), remove 170 DEG C with
After lower by-product and the complete phenol of unreacted, collecting 230～260 DEG C, light yellow transparent liquid evaporates
Divide 812 grams, be product phenoxymethyl disilane, productivity 83.5%.
The structural characterization of product phenoxymethyl disilane and performance test: infrared spectrum IR (KBr
Film, cm-1): 3049.2,2963,1597,1495,1260,864,758,720,702；1H NMR (400MHz, CDCl3) δ: 6.82-7.20 (20H ,-ArH), 0.078-0.145 (6H,
-SiCH3).Boiling point: 230～260 DEG C/5mmHg；Flash-point: 300 DEG C；25 DEG C of kinematic viscositys:
342mm2/S.Initial pyrolyzation temperature: 380 DEG C.
Embodiment 2:
Etherification reaction prepares phenoxymethyl disilane, and key step is as follows:
A, dispensing: take high boiling point chlorosilane waste liquid, phenol；Press chlorine in high boiling point chlorosilane waste liquid former
Son: phenol mol ratio is that 1:1 carries out etherification reaction；The content warp of chlorine atom in high boiling point chlorosilane waste liquid
Acid base titration is 13mol/L；
B, etherification reaction: first 489g phenol (5.2mol) is equipped with constant pressure funnel,
Anhydrous calcium chloride drying tower, HCl tail connect in the round-bottomed flask of device, add 400mL in constant pressure funnel
The high boiling point chlorosilane waste liquid of (chloride 5.2mol), slowly drips high boiling point chlorosilane waste liquid at 40 DEG C
Add in reaction unit；After dropping, progressively it is warming up to 60 DEG C and continues reaction 8～13h until HCl
Tail connects no longer has HCl to release in device；
C, separating-purifying: reaction terminate after carry out decompression distillation (5-10mmHg), remove 170 DEG C with
After lower by-product and the complete phenol of unreacted, collect 230～260 DEG C of light yellow transparent liquid fractions 786.5
Gram, it is product phenoxymethyl disilane, productivity 80.0%.
The structural characterization of product phenoxymethyl disilane and performance test: infrared spectrum IR (KBr film,
cm-1): 3049.2,2963,1597,1495,1260,864,758,720,702；1H NMR (400MHz,
CDCl3) δ: 6.82-7.20 (20H ,-ArH), 0.078-0.145 (6H ,-SiCH3).Boiling point: 230～
260℃/5mmHg；Flash-point: 300 DEG C；25 DEG C of kinematic viscosity: 342mm2/S.Initial pyrolyzation temperature:
380℃。
Embodiment 3:
Etherification reaction prepares phenoxymethyl disilane, and key step is as follows:
A, dispensing: take high boiling point chlorosilane waste liquid, phenol；Press chlorine atom in high boiling point chlorosilane waste liquid:
Phenol mol ratio is that 1:1 carries out etherification reaction；In high boiling point chlorosilane waste liquid, the content of chlorine atom is through soda acid
Titration is 13mol/L；
B, etherification reaction: first 587g phenol (6.24mol) is equipped with constant pressure funnel,
Anhydrous calcium chloride drying tower, HCl tail connect in the round-bottomed flask of device, add 400mL in constant pressure funnel
The high boiling point chlorosilane waste liquid of (chloride 5.20mol), slowly by high boiling point chlorosilane waste liquid at 40 DEG C
It is added dropwise in reaction unit；After dropping, be progressively warming up to 60 DEG C continue reaction 8～13h until
HCl tail connects no longer has HCl to release in device；
C, separating-purifying: reaction terminate after carry out decompression distillation (5-10mmHg), remove 170 DEG C with
After lower by-product and the complete phenol of unreacted, collect 230～260 DEG C, light yellow transparent liquid fraction 838.6
G is product phenoxymethyl disilane, productivity 84.0%.
The structural characterization of product phenoxymethyl disilane and performance test: infrared spectrum IR (KBr film,
cm-1): 3049.2,2963,1597,1495,1260,864,758,720,702；1H NMR (400MHz,
CDCl3) δ: 6.82-7.20 (20H ,-ArH), 0.078-0.145 (6H ,-SiCH3).Boiling point: 230～
260℃/5mmHg；Flash-point: 300 DEG C；25 DEG C of kinematic viscosity: 342mm2/S.Initial pyrolyzation temperature:
380℃。
Embodiment 4:
Etherification reaction prepares phenoxymethyl disilane, and key step is as follows:
A, dispensing: take high boiling point chlorosilane waste liquid, phenol；Press chlorine atom in high boiling point chlorosilane waste liquid:
Phenol mol ratio is that 1:1 carries out etherification reaction；In high boiling point chlorosilane waste liquid, the content of chlorine atom is through soda acid
Titration is 13mol/L；
B, etherification reaction: first 5.87g phenol (62.4mmol) is equipped with constant pressure addition leakage
Bucket, anhydrous calcium chloride drying tower, HCl tail connect in the round-bottomed flask of device, add in constant pressure funnel
The high boiling point chlorosilane waste liquid of 4mL (chloride 52mmol), slowly by high boiling point chlorosilane at 40 DEG C
Waste liquid is added dropwise in reaction unit；After dropping, progressively it is warming up to 60 DEG C and continues reaction 8～13h
Device no longer there is HCl release until HCl tail connects；
C, separating-purifying: reaction terminate after carry out decompression distillation (5-10mmHg), remove 170 DEG C with
After lower by-product and the complete phenol of unreacted, collect 230～260 DEG C of colourless transparent liquid fraction 8.16g
It is product phenoxymethyl disilane, productivity 84.0%.
The structural characterization of product phenoxymethyl disilane and performance test: infrared spectrum IR (KBr film,
cm-1): 3049.2,2963,1597,1495,1260,864,758,720,702；1H NMR (400MHz,
CDCl3) δ: 6.82-7.20 (20H ,-ArH), 0.078-0.145 (6H ,-SiCH3).Boiling point: 230～
260℃/5mmHg；Flash-point: 300 DEG C；25 DEG C of kinematic viscosity: 342mm2/S.Initial pyrolyzation temperature:
380℃。
Embodiment 5:
Etherification reaction prepares phenoxymethyl disilane, and key step is as follows:
A, dispensing: take high boiling point chlorosilane waste liquid, phenol；Press chlorine atom in high boiling point chlorosilane waste liquid:
Phenol mol ratio is that 1:1 carries out etherification reaction；In high boiling point chlorosilane waste liquid, the content of chlorine atom is through soda acid
Titration is 13mol/L；
B, etherification reaction: first 6.84g phenol (72.8mmol) is equipped with constant pressure funnel,
Anhydrous calcium chloride drying tower, HCl tail connect in the round-bottomed flask of device, add 4mL in constant pressure funnel
The high boiling point chlorosilane waste liquid of (chloride 52mmol), slowly by high boiling point chlorosilane waste liquid at 40 DEG C
It is added dropwise in reaction unit；After dropping, be progressively warming up to 60 DEG C continue reaction 8～13h until
HCl tail connects no longer has HCl to release in device；
C, separating-purifying: reaction terminate after carry out decompression distillation (5-10mmHg), remove 170 DEG C with
After lower by-product and the complete phenol of unreacted, collect 230～260 DEG C of colourless transparent liquid fraction 8.65g
It is product phenoxymethyl disilane, productivity 84.5%.
The structural characterization of product phenoxymethyl disilane and performance test: infrared spectrum IR (KBr film,
cm-1): 3049.2,2963,1597,1495,1260,864,758,720,702；1H NMR (400MHz,
CDCl3) δ: 6.82-7.20 (20H ,-ArH), 0.078-0.145 (6H ,-SiCH3).Boiling point: 230～
260℃/5mmHg；Flash-point: 300 DEG C；25 DEG C of kinematic viscosity: 342mm2/S.Initial pyrolyzation temperature:
380℃。
Embodiment 6:
Etherification reaction prepares phenoxymethyl disilane, and key step is as follows:
A, dispensing: take high boiling point chlorosilane waste liquid, phenol；Press chlorine atom in high boiling point chlorosilane waste liquid:
Phenol mol ratio is that 1:1 carries out etherification reaction；In high boiling point chlorosilane waste liquid, the content of chlorine atom is through soda acid
Titration is 13mol/L；
B, etherification reaction: first 7.33g phenol (78mmol) is equipped with constant pressure funnel,
Anhydrous calcium chloride drying tower, HCl tail connect in the round-bottomed flask of device, add 4mL in constant pressure funnel
The high boiling point chlorosilane waste liquid of (chloride 52mmol), slowly by high boiling point chlorosilane waste liquid at 40 DEG C
It is added dropwise in reaction unit；After dropping, be progressively warming up to 60 DEG C continue reaction 8～13h until
HCl tail connects no longer has HCl to release in device；
C, separating-purifying: reaction carries out decompression distillation (5-10mmHg) after terminating, remove a small amount of 170 DEG C
After following by-product and the complete phenol of unreacted, collect 230～260 DEG C of colourless transparent liquid fraction 9.65g
It is product phenoxymethyl disilane, productivity 84.0%.
The structural characterization of product phenoxymethyl disilane and performance test: infrared spectrum IR (KBr film,
cm-1): 3049.2,2963,1597,1495,1260,864,758,720,702；1H NMR (400MHz,
CDCl3) δ: 6.82-7.20 (20H ,-ArH), 0.078-0.145 (6H ,-SiCH3).Boiling point: 230～
260℃/5mmHg；Flash-point: 300 DEG C；25 DEG C of kinematic viscosity: 342mm2/S.Initial pyrolyzation temperature:
380℃。
Embodiment 7:
Etherification reaction prepares o-methyl-benzene epoxide methyl disilane, and key step is as follows:
A, dispensing: take high boiling point chlorosilane waste liquid, ortho-methyl phenol；Press in high boiling point chlorosilane waste liquid
Chlorine atom: ortho-methyl phenol mol ratio is that 1:1 carries out etherification reaction；In high boiling point chlorosilane waste liquid, chlorine is former
The content of son is 13mol/L through acid base titration；
B, etherification reaction: first 6.18g ortho-methyl phenol (57.2mmol) is equipped with constant voltage and drips
Liquid funnel, anhydrous calcium chloride drying tower, HCl tail connect in the round-bottomed flask of device, in constant pressure funnel
Add the high boiling point chlorosilane waste liquid of 4mL (chloride 52mmol), slowly by high boiling point chlorine at 40 DEG C
Silane waste liquid is added dropwise in reaction unit；After dropping, be progressively warming up to 60 DEG C continue reaction 8～
13h no longer has HCl to release until HCl tail connects in device；
C, separating-purifying: reaction carries out decompression distillation (5-10mmHg) after terminating, remove less than 170 DEG C
After by-product and the complete phenol of unreacted, collect 230～260 DEG C of colourless transparent liquid fraction 8.39g
It is product o-methyl-benzene epoxide methyl disilane, productivity 84.0%.
The structural characterization of product o-methyl-benzene epoxide methyl disilane is as follows: infrared spectrum IR (KBr film,
cm-1): 3049.2,2963,1597,1495,1260,864,758,720,702；1H NMR (400MHz,
CDCl3) δ: 6.82-7.20 (20H ,-ArH), 0.078-0.145 (6H ,-SiCH3).Boiling point: 230～
270℃/5mmHg；Flash-point: 301 DEG C；25 DEG C of kinematic viscosity: 344mm2/S.Initial pyrolyzation temperature:
370℃。
Embodiment 8:
Etherification reaction is prepared methylphenoxymethyl disilane, and key step is as follows:
A, dispensing: take high boiling point chlorosilane waste liquid, p-methyl phenol；Press in high boiling point chlorosilane waste liquid
Chlorine atom: p-methyl phenol mol ratio is that 1:1 carries out etherification reaction；In high boiling point chlorosilane waste liquid, chlorine is former
The content of son is 13mol/L through acid base titration；
B, etherification reaction: first 6.18g ortho-methyl phenol (57.2mmol) is equipped with constant voltage and drips
Liquid funnel, anhydrous calcium chloride drying tower, HCl tail connect in the round-bottomed flask of device, in constant pressure funnel
Add the high boiling point chlorosilane waste liquid of 4mL (chloride 52mmol), slowly by high boiling point chlorine at 40 DEG C
Silane waste liquid is added dropwise in reaction unit；After dropping, be progressively warming up to 60 DEG C continue reaction 8～
13h no longer has HCl to release until HCl tail connects in device；
C, separating-purifying: reaction carries out decompression distillation (5-10mmHg) after terminating, remove less than 170 DEG C
After by-product and the complete phenol of unreacted, collect 230～260 DEG C of colourless transparent liquid fraction 9.23g i.e.
For product to methylphenoxymethyl disilane, productivity 84.0%.
Product is as follows to the structural characterization of methylphenoxymethyl disilane: infrared spectrum IR (KBr film,
cm-1): 3049.2,2963,1597,1495,1260,864,758,720,702；1H NMR (400MHz,
CDCl3) δ: 6.82-7.20 (20H ,-ArH), 0.078-0.145 (6H ,-SiCH3).Boiling point: 240～
280℃/5mmHg；Flash-point: 301 DEG C；25 DEG C of kinematic viscosity: 346mm2/S.Initial pyrolyzation temperature:
370℃。
Embodiment 9:
Phenoxymethyl disilane, is characterized in that this compound has a chemical structural formula shown in (I):
(RO)n Si-Si(CH3)6-n
(I)
In formula (I): R=C6H5-、p-CH3-C6H4-or o-CH3-C6H4-；N=2-6.
Embodiment 10:
The preparation method of phenoxymethyl disilane, comprises the following steps:
A, dispensing: by chlorine atom in high boiling point chlorosilane waste liquid: the mol ratio of phenol is that 1:1～1.5 takes
Raw material high boiling point chlorosilane waste liquid and phenol, wherein: the content of chlorine atom in high boiling point chlorosilane waste liquid
(can be through acid base titration) be 13mol/L；
B, etherification reaction: phenol is equipped with constant pressure funnel, anhydrous calcium chloride drying tower, HCl
Tail connects in the reactor of device, joins in constant pressure funnel by high boiling point chlorosilane waste liquid, at 40 DEG C
At a temperature of (slowly) high boiling point chlorosilane waste liquid is added dropwise in reactor；After dropping, (by
Step) it is warming up to 60～100 DEG C and continues reaction and 8～13h device no longer has HCl release until HCl tail connects,
Terminate reaction, obtain reacting rear material；
C, separating-purifying: by reacting rear material at temperature 170～260 DEG C, the bar of pressure 5～10mmHg
Decompression distillation is carried out under part, after removing less than the 170 DEG C by-products distillated and the complete phenol of unreacted, receipts
Collect 230～260 DEG C of fractions distillated and be product phenoxymethyl disilane.
The structural characterization of product phenoxymethyl disilane is as follows: its infrared spectrum IR (KBr film, cm-1):
3049.2,2963,1597,1495,1260,864,758,720,702；1H NMR (400MHz,
CDCl3) δ: 6.82-7.20 (20H ,-ArH), 0.078-0.145 (6H ,-SiCH3).Boiling point: 230～
260℃/5mmHg；Flash-point: 300 DEG C；25 DEG C of kinematic viscosity: 342mm2/S.Initial pyrolyzation temperature:
380℃。
The chemical equation of the synthetic method of phenoxymethyl disilane is as follows:
ClmSi-Si(CH3)6-m+mC6H5OH→(C6H5O)mSi-Si(CH3)6-m+mHCl
In formula: m=2～6
Embodiment 11:
The preparation method of phenoxymethyl disilane, comprises the following steps:
A, dispensing: by chlorine atom in high boiling point chlorosilane waste liquid: the mol ratio of phenol is that 1:1 takes raw material
High boiling point chlorosilane waste liquid and phenol, wherein: in high boiling point chlorosilane waste liquid, the content of chlorine atom is (permissible
Through acid base titration) it is 13mol/L；
B, etherification reaction: phenol is equipped with constant pressure funnel, anhydrous calcium chloride drying tower, HCl
Tail connects in the reactor of device, joins in constant pressure funnel by high boiling point chlorosilane waste liquid, at 40 DEG C
At a temperature of (slowly) high boiling point chlorosilane waste liquid is added dropwise in reactor；After dropping, (by
Step) be warming up to 60 DEG C continue reaction 13h device no longer has HCl releases until HCl tail connects, terminate react,
Obtain reacting rear material；
C, separating-purifying: by reacting rear material at temperature 170～260 DEG C, the bar of pressure 5～10mmHg
Decompression distillation is carried out under part, after removing less than the 170 DEG C by-products distillated and the complete phenol of unreacted, receipts
Collect 230～260 DEG C of fractions distillated and be product phenoxymethyl disilane.
The structural characterization of product phenoxymethyl disilane is with embodiment 10.
Embodiment 12:
The preparation method of phenoxymethyl disilane, comprises the following steps:
A, dispensing: by chlorine atom in high boiling point chlorosilane waste liquid: it is former that the mol ratio of phenol is that 1:1.1 takes
Material high boiling point chlorosilane waste liquid and phenol, wherein: in high boiling point chlorosilane waste liquid, the content of chlorine atom (can
With through acid base titration) as 13mol/L；
B, etherification reaction: phenol is equipped with constant pressure funnel, anhydrous calcium chloride drying tower, HCl
Tail connects in the reactor of device, joins in constant pressure funnel by high boiling point chlorosilane waste liquid, at 40 DEG C
At a temperature of (slowly) high boiling point chlorosilane waste liquid is added dropwise in reactor；After dropping, (by
Step) it is warming up to 80 DEG C and continues reaction and 8～13h device no longer has HCl releases until HCl tail connects, end
Reaction, obtains reacting rear material；
C, separating-purifying: by reacting rear material at temperature 170～260 DEG C, the bar of pressure 5～10mmHg
Decompression distillation is carried out under part, after removing less than the 170 DEG C by-products distillated and the complete phenol of unreacted, receipts
Collect 230～260 DEG C of fractions distillated and be product phenoxymethyl disilane.
The structural characterization of product phenoxymethyl disilane is with embodiment 10.
Embodiment 13:
The preparation method of phenoxymethyl disilane, comprises the following steps:
A, dispensing: by chlorine atom in high boiling point chlorosilane waste liquid: it is former that the mol ratio of phenol is that 1:1.2 takes
Material high boiling point chlorosilane waste liquid and phenol, wherein: in high boiling point chlorosilane waste liquid, the content of chlorine atom (can
With through acid base titration) as 13mol/L；
B, etherification reaction: phenol is equipped with constant pressure funnel, anhydrous calcium chloride drying tower, HCl
Tail connects in the reactor of device, joins in constant pressure funnel by high boiling point chlorosilane waste liquid, at 40 DEG C
At a temperature of (slowly) high boiling point chlorosilane waste liquid is added dropwise in reactor；After dropping, (by
Step) it is warming up to 70 DEG C and continues reaction and 8～13h device no longer has HCl releases until HCl tail connects, end
Reaction, obtains reacting rear material；
C, separating-purifying: by reacting rear material at temperature 170～260 DEG C, the bar of pressure 5～10mmHg
Decompression distillation is carried out under part, after removing less than the 170 DEG C by-products distillated and the complete phenol of unreacted, receipts
Collect 230～260 DEG C of fractions distillated and be product phenoxymethyl disilane.
The structural characterization of product phenoxymethyl disilane is with embodiment 10.
Embodiment 14:
The preparation method of phenoxymethyl disilane, comprises the following steps:
A, dispensing: by chlorine atom in high boiling point chlorosilane waste liquid: it is former that the mol ratio of phenol is that 1:1.5 takes
Material high boiling point chlorosilane waste liquid and phenol, wherein: in high boiling point chlorosilane waste liquid, the content of chlorine atom (can
With through acid base titration) as 13mol/L；
B, etherification reaction: phenol is equipped with constant pressure funnel, anhydrous calcium chloride drying tower, HCl
Tail connects in the reactor of device, joins in constant pressure funnel by high boiling point chlorosilane waste liquid, at 40 DEG C
At a temperature of (slowly) high boiling point chlorosilane waste liquid is added dropwise in reactor；After dropping, (by
Step) it is warming up to 100 DEG C and continues reaction and 8～13h device no longer has HCl releases until HCl tail connects, tie
Shu Fanying, obtains reacting rear material；
C, separating-purifying: by reacting rear material at temperature 170～260 DEG C, the bar of pressure 5～10mmHg
Decompression distillation is carried out under part, after removing less than the 170 DEG C by-products distillated and the complete phenol of unreacted, receipts
Collect 230～260 DEG C of fractions distillated and be product phenoxymethyl disilane.
The structural characterization of product phenoxymethyl disilane is with embodiment 10.
Embodiment 15:
The preparation method of phenoxymethyl disilane, comprises the following steps:
A, dispensing: by chlorine atom in high boiling point chlorosilane waste liquid: it is former that the mol ratio of phenol is that 1:1.3 takes
Material high boiling point chlorosilane waste liquid and phenol, wherein: in high boiling point chlorosilane waste liquid, the content of chlorine atom (can
With through acid base titration) as 13mol/L；
B, etherification reaction: phenol is equipped with constant pressure funnel, anhydrous calcium chloride drying tower, HCl
Tail connects in the reactor of device, joins in constant pressure funnel by high boiling point chlorosilane waste liquid, at 40 DEG C
At a temperature of (slowly) high boiling point chlorosilane waste liquid is added dropwise in reactor；After dropping, (by
Step) it is warming up to 90 DEG C and continues reaction and 8～13h device no longer has HCl releases until HCl tail connects, end
Reaction, obtains reacting rear material；
C, separating-purifying: by reacting rear material at temperature 170～260 DEG C, the bar of pressure 5～10mmHg
Decompression distillation is carried out under part, after removing less than the 170 DEG C by-products distillated and the complete phenol of unreacted, receipts
Collect 230～260 DEG C of fractions distillated and be product phenoxymethyl disilane.
The structural characterization of product phenoxymethyl disilane is with embodiment 10.
In above-described embodiment 10～15: described in step a, the chemical composition of high boiling point chlorosilane waste liquid is first
The mixture of base chlorine disilane, the mixture general molecular formula of this methylchlorodisilane is Clm Si-Si
(CH3)6-m,Wherein: m=2-6；Described high boiling point chlorosilane waste liquid is the north, (Sichuan Province China province) Luzhou
Chloride silicone industry waste liquid that Chemical Co., Ltd. provides, can also be chloride having of providing of other enterprises
Machine silicon industrial wastes i.e. high boiling point chlorosilane waste liquid.
Embodiment 16:
Preparation method to methylphenoxymethyl disilane, comprises the following steps:
A, dispensing: by chlorine atom in high boiling point chlorosilane waste liquid: the mol ratio of p-methyl phenol be 1:1～
1.5 take raw material high boiling point chlorosilane waste liquid and p-methyl phenol, wherein: chlorine in high boiling point chlorosilane waste liquid
The content (can be through acid base titration) of atom is 13mol/L；
B, etherification reaction: p-methyl phenol is equipped with constant pressure funnel, anhydrous calcium chloride is dried
Tower, HCl tail connect in the reactor of device, join in constant pressure funnel by high boiling point chlorosilane waste liquid,
(slowly) high boiling point chlorosilane waste liquid is added dropwise in reactor at a temperature of 40 DEG C；Drip complete
After, (progressively) is warming up to 60～100 DEG C and continues reaction 8～13h until HCl tail connects in device and no longer has
HCl releases, and terminates reaction, obtains reacting rear material；
C, separating-purifying: by reacting rear material at temperature 170～260 DEG C, the bar of pressure 5～10mmHg
Carry out decompression distillation under part, remove less than the 170 DEG C by-products distillated and the complete p-methyl phenol of unreacted
After, collect 230～260 DEG C of fractions distillated and be product to methylphenoxymethyl disilane.
Product is as follows to the structural characterization of methylphenoxymethyl disilane: (KBr is coated with its infrared spectrum IR
Film, cm-1): 3049.2,2963,1597,1495,1260,864,758,720,702；1H
NMR (400MHz, CDCl3) δ: 6.82-7.20 (20H ,-ArH), 0.078-0.145 (6H ,-SiCH3)。
Boiling point: 240～280 DEG C/5mmHg；Flash-point: 301 DEG C；25 DEG C of kinematic viscosity: 346mm2/S.Initially
Heat decomposition temperature: 370 DEG C.
Embodiment 17:
Preparation method to methylphenoxymethyl disilane, comprises the following steps:
A, dispensing: by chlorine atom in high boiling point chlorosilane waste liquid: the mol ratio of p-methyl phenol is 1:1
Take raw material high boiling point chlorosilane waste liquid and p-methyl phenol, wherein: in high boiling point chlorosilane waste liquid, chlorine is former
The content (can be through acid base titration) of son is 13mol/L；
B, etherification reaction: p-methyl phenol is equipped with constant pressure funnel, anhydrous calcium chloride is dried
Tower, HCl tail connect in the reactor of device, join in constant pressure funnel by high boiling point chlorosilane waste liquid,
(slowly) high boiling point chlorosilane waste liquid is added dropwise in reactor at a temperature of 40 DEG C；Drip complete
After, (progressively) is warming up to 100 DEG C of continuation reactions 8～13h no longer has HCl until HCl tail connects in device
Release, terminate reaction, obtain reacting rear material；
C, separating-purifying: by reacting rear material at temperature 170～260 DEG C, the bar of pressure 5～10mmHg
Carry out decompression distillation under part, remove less than the 170 DEG C by-products distillated and the complete p-methyl phenol of unreacted
After, collect 230～260 DEG C of fractions distillated and be product to methylphenoxymethyl disilane.
Product to the structural characterization of methylphenoxymethyl disilane with embodiment 16.
Embodiment 18:
Preparation method to methylphenoxymethyl disilane, comprises the following steps:
A, dispensing: by chlorine atom in high boiling point chlorosilane waste liquid: the mol ratio of p-methyl phenol is 1:
1.5 take raw material high boiling point chlorosilane waste liquid and p-methyl phenol, wherein: chlorine in high boiling point chlorosilane waste liquid
The content (can be through acid base titration) of atom is 13mol/L；
B, etherification reaction: p-methyl phenol is equipped with constant pressure funnel, anhydrous calcium chloride is dried
Tower, HCl tail connect in the reactor of device, join in constant pressure funnel by high boiling point chlorosilane waste liquid,
(slowly) high boiling point chlorosilane waste liquid is added dropwise in reactor at a temperature of 40 DEG C；Drip complete
After, (progressively) is warming up to 60 DEG C of continuation reactions 8～13h no longer has HCl to put until HCl tail connects in device
Go out, terminate reaction, obtain reacting rear material；
C, separating-purifying: by reacting rear material at temperature 170～260 DEG C, the bar of pressure 5～10mmHg
Carry out decompression distillation under part, remove less than the 170 DEG C by-products distillated and the complete p-methyl phenol of unreacted
After, collect 230～260 DEG C of fractions distillated and be product to methylphenoxymethyl disilane.
Product to the structural characterization of methylphenoxymethyl disilane with embodiment 16.
Embodiment 19:
Preparation method to methylphenoxymethyl disilane, comprises the following steps:
A, dispensing: by chlorine atom in high boiling point chlorosilane waste liquid: the mol ratio of p-methyl phenol is 1:1.4
Take raw material high boiling point chlorosilane waste liquid and p-methyl phenol, wherein: in high boiling point chlorosilane waste liquid, chlorine is former
The content (can be through acid base titration) of son is 13mol/L；
B, etherification reaction: p-methyl phenol is equipped with constant pressure funnel, anhydrous calcium chloride is dried
Tower, HCl tail connect in the reactor of device, join in constant pressure funnel by high boiling point chlorosilane waste liquid,
(slowly) high boiling point chlorosilane waste liquid is added dropwise in reactor at a temperature of 40 DEG C；Drip complete
After, (progressively) is warming up to 70 DEG C of continuation reactions 8～13h no longer has HCl to put until HCl tail connects in device
Go out, terminate reaction, obtain reacting rear material；
C, separating-purifying: by reacting rear material at temperature 170～260 DEG C, the bar of pressure 5～10mmHg
Carry out decompression distillation under part, remove less than the 170 DEG C by-products distillated and the complete p-methyl phenol of unreacted
After, collect 230～260 DEG C of fractions distillated and be product to methylphenoxymethyl disilane.
Product to the structural characterization of methylphenoxymethyl disilane with embodiment 16.
Embodiment 20:
Preparation method to methylphenoxymethyl disilane, comprises the following steps:
A, dispensing: by chlorine atom in high boiling point chlorosilane waste liquid: the mol ratio of p-methyl phenol is 1:1.3
Take raw material high boiling point chlorosilane waste liquid and p-methyl phenol, wherein: in high boiling point chlorosilane waste liquid, chlorine is former
The content (can be through acid base titration) of son is 13mol/L；
B, etherification reaction: p-methyl phenol is equipped with constant pressure funnel, anhydrous calcium chloride is dried
Tower, HCl tail connect in the reactor of device, join in constant pressure funnel by high boiling point chlorosilane waste liquid,
(slowly) high boiling point chlorosilane waste liquid is added dropwise in reactor at a temperature of 40 DEG C；Drip complete
After, (progressively) is warming up to 90 DEG C of continuation reactions 8～13h no longer has HCl to put until HCl tail connects in device
Go out, terminate reaction, obtain reacting rear material；
C, separating-purifying: by reacting rear material at temperature 170～260 DEG C, the bar of pressure 5～10mmHg
Carry out decompression distillation under part, remove less than the 170 DEG C by-products distillated and the complete p-methyl phenol of unreacted
After, collect 230～260 DEG C of fractions distillated and be product to methylphenoxymethyl disilane.
Product to the structural characterization of methylphenoxymethyl disilane with embodiment 16.
Embodiment 21:
Preparation method to methylphenoxymethyl disilane, comprises the following steps:
A, dispensing: by chlorine atom in high boiling point chlorosilane waste liquid: the mol ratio of p-methyl phenol is 1:1.1
Take raw material high boiling point chlorosilane waste liquid and p-methyl phenol, wherein: in high boiling point chlorosilane waste liquid, chlorine is former
The content (can be through acid base titration) of son is 13mol/L；
B, etherification reaction: p-methyl phenol is equipped with constant pressure funnel, anhydrous calcium chloride is dried
Tower, HCl tail connect in the reactor of device, join in constant pressure funnel by high boiling point chlorosilane waste liquid,
(slowly) high boiling point chlorosilane waste liquid is added dropwise in reactor at a temperature of 40 DEG C；Drip complete
After, (progressively) is warming up to 80 DEG C of continuation reactions 8～13h no longer has HCl to put until HCl tail connects in device
Go out, terminate reaction, obtain reacting rear material；
C, separating-purifying: by reacting rear material at temperature 170～260 DEG C, the bar of pressure 5～10mmHg
Carry out decompression distillation under part, remove less than the 170 DEG C by-products distillated and the complete p-methyl phenol of unreacted
After, collect 230～260 DEG C of fractions distillated and be product to methylphenoxymethyl disilane.
Product to the structural characterization of methylphenoxymethyl disilane with embodiment 16.
In above-described embodiment 16～21: described in step a, the chemical composition of high boiling point chlorosilane waste liquid is first
The mixture of base chlorine disilane, the mixture general molecular formula of this methylchlorodisilane is Clm Si-Si
(CH3)6-m,Wherein: m=2-6；Described high boiling point chlorosilane waste liquid is the north, (Sichuan Province China province) Luzhou
Chloride silicone industry waste liquid that Chemical Co., Ltd. provides, can also be chloride having of providing of other enterprises
Machine silicon industrial wastes i.e. high boiling point chlorosilane waste liquid.
Embodiment 22:
The preparation method of o-methyl-benzene epoxide methyl disilane, comprises the following steps:
A, dispensing: by chlorine atom in high boiling point chlorosilane waste liquid: the mol ratio of ortho-methyl phenol be 1:1～
1.5 take raw material high boiling point chlorosilane waste liquid and ortho-methyl phenol, wherein: chlorine in high boiling point chlorosilane waste liquid
The content (can be through acid base titration) of atom is 13mol/L；
B, etherification reaction: ortho-methyl phenol is equipped with constant pressure funnel, anhydrous calcium chloride is dried
Tower, HCl tail connect in the reactor of device, join in constant pressure funnel by high boiling point chlorosilane waste liquid,
(slowly) high boiling point chlorosilane waste liquid is added dropwise in reactor at a temperature of 40 DEG C；Drip complete
After, (progressively) is warming up to 60～100 DEG C and continues reaction 8～13h until HCl tail connects in device and no longer has
HCl releases, and terminates reaction, obtains reacting rear material；
C, separating-purifying: by reacting rear material at temperature 170～260 DEG C, the bar of pressure 5～10mmHg
Carry out decompression distillation under part, remove less than the 170 DEG C by-products distillated and the complete ortho-methyl phenol of unreacted
After, collect 230～260 DEG C of fractions distillated and be product o-methyl-benzene epoxide methyl disilane.
The structural characterization of product o-methyl-benzene epoxide methyl disilane is as follows: (KBr is coated with its infrared spectrum IR
Film, cm-1): 3049.2,2963,1597,1495,1260,864,758,720,702；1H
NMR (400MHz, CDCl3) δ: 6.82-7.20 (20H ,-ArH), 0.078-0.145 (6H ,-SiCH3)。
Boiling point: 230～270 DEG C/5mmHg；Flash-point: 301 DEG C；25 DEG C of kinematic viscosity: 344mm2/S.Initially
Heat decomposition temperature: 370 DEG C.
Embodiment 23:
The preparation method of o-methyl-benzene epoxide methyl disilane, comprises the following steps:
A, dispensing: by chlorine atom in high boiling point chlorosilane waste liquid: the mol ratio of ortho-methyl phenol is 1:1
Take raw material high boiling point chlorosilane waste liquid and ortho-methyl phenol, wherein: in high boiling point chlorosilane waste liquid, chlorine is former
The content (can be through acid base titration) of son is 13mol/L；
B, etherification reaction: ortho-methyl phenol is equipped with constant pressure funnel, anhydrous calcium chloride is dried
Tower, HCl tail connect in the reactor of device, join in constant pressure funnel by high boiling point chlorosilane waste liquid,
(slowly) high boiling point chlorosilane waste liquid is added dropwise in reactor at a temperature of 40 DEG C；Drip complete
After, (progressively) is warming up to 60 DEG C of continuation reactions 8～13h no longer has HCl to put until HCl tail connects in device
Go out, terminate reaction, obtain reacting rear material；
C, separating-purifying: by reacting rear material at temperature 170～260 DEG C, the bar of pressure 5～10mmHg
Carry out decompression distillation under part, remove less than the 170 DEG C by-products distillated and the complete ortho-methyl phenol of unreacted
After, collect 230～260 DEG C of fractions distillated and be product o-methyl-benzene epoxide methyl disilane.
The structural characterization of product o-methyl-benzene epoxide methyl disilane is with embodiment 22.
Embodiment 24:
The preparation method of o-methyl-benzene epoxide methyl disilane, comprises the following steps:
A, dispensing: by chlorine atom in high boiling point chlorosilane waste liquid: the mol ratio of ortho-methyl phenol is 1:1.1
Take raw material high boiling point chlorosilane waste liquid and ortho-methyl phenol, wherein: in high boiling point chlorosilane waste liquid, chlorine is former
The content (can be through acid base titration) of son is 13mol/L；
B, etherification reaction: ortho-methyl phenol is equipped with constant pressure funnel, anhydrous calcium chloride is dried
Tower, HCl tail connect in the reactor of device, join in constant pressure funnel by high boiling point chlorosilane waste liquid,
(slowly) high boiling point chlorosilane waste liquid is added dropwise in reactor at a temperature of 40 DEG C；Drip complete
After, (progressively) is warming up to 70 DEG C of continuation reactions 8～13h no longer has HCl to put until HCl tail connects in device
Go out, terminate reaction, obtain reacting rear material；
C, separating-purifying: by reacting rear material at temperature 170～260 DEG C, the bar of pressure 5～10mmHg
Carry out decompression distillation under part, remove less than the 170 DEG C by-products distillated and the complete ortho-methyl phenol of unreacted
After, collect 230～260 DEG C of fractions distillated and be product o-methyl-benzene epoxide methyl disilane.
The structural characterization of product o-methyl-benzene epoxide methyl disilane is with embodiment 22.
Embodiment 25:
The preparation method of o-methyl-benzene epoxide methyl disilane, comprises the following steps:
A, dispensing: by chlorine atom in high boiling point chlorosilane waste liquid: the mol ratio of ortho-methyl phenol is 1:1.2
Take raw material high boiling point chlorosilane waste liquid and ortho-methyl phenol, wherein: in high boiling point chlorosilane waste liquid, chlorine is former
The content (can be through acid base titration) of son is 13mol/L；
B, etherification reaction: ortho-methyl phenol is equipped with constant pressure funnel, anhydrous calcium chloride is dried
Tower, HCl tail connect in the reactor of device, join in constant pressure funnel by high boiling point chlorosilane waste liquid,
(slowly) high boiling point chlorosilane waste liquid is added dropwise in reactor at a temperature of 40 DEG C；Drip complete
After, (progressively) is warming up to 90 DEG C of continuation reactions 8～13h no longer has HCl to put until HCl tail connects in device
Go out, terminate reaction, obtain reacting rear material；
C, separating-purifying: by reacting rear material at temperature 170～260 DEG C, the bar of pressure 5～10mmHg
Carry out decompression distillation under part, remove less than the 170 DEG C by-products distillated and the complete ortho-methyl phenol of unreacted
After, collect 230～260 DEG C of fractions distillated and be product o-methyl-benzene epoxide methyl disilane.
The structural characterization of product o-methyl-benzene epoxide methyl disilane is with embodiment 22.
Embodiment 26:
The preparation method of o-methyl-benzene epoxide methyl disilane, comprises the following steps:
A, dispensing: by chlorine atom in high boiling point chlorosilane waste liquid: the mol ratio of ortho-methyl phenol is 1:
1.5 take raw material high boiling point chlorosilane waste liquid and ortho-methyl phenol, wherein: chlorine in high boiling point chlorosilane waste liquid
The content (can be through acid base titration) of atom is 13mol/L；
B, etherification reaction: ortho-methyl phenol is equipped with constant pressure funnel, anhydrous calcium chloride is dried
Tower, HCl tail connect in the reactor of device, join in constant pressure funnel by high boiling point chlorosilane waste liquid,
(slowly) high boiling point chlorosilane waste liquid is added dropwise in reactor at a temperature of 40 DEG C；Drip complete
After, (progressively) is warming up to 80 DEG C of continuation reactions 8～13h no longer has HCl to put until HCl tail connects in device
Go out, terminate reaction, obtain reacting rear material；
C, separating-purifying: by reacting rear material at temperature 170～260 DEG C, the bar of pressure 5～10mmHg
Carry out decompression distillation under part, remove less than the 170 DEG C by-products distillated and the complete ortho-methyl phenol of unreacted
After, collect 230～260 DEG C of fractions distillated and be product o-methyl-benzene epoxide methyl disilane.
The structural characterization of product o-methyl-benzene epoxide methyl disilane is with embodiment 22.
Embodiment 27:
The preparation method of o-methyl-benzene epoxide methyl disilane, comprises the following steps:
A, dispensing: by chlorine atom in high boiling point chlorosilane waste liquid: the mol ratio of ortho-methyl phenol is 1:1.3
Take raw material high boiling point chlorosilane waste liquid and ortho-methyl phenol, wherein: in high boiling point chlorosilane waste liquid, chlorine is former
The content (can be through acid base titration) of son is 13mol/L；
B, etherification reaction: ortho-methyl phenol is equipped with constant pressure funnel, anhydrous calcium chloride is dried
Tower, HCl tail connect in the reactor of device, join in constant pressure funnel by high boiling point chlorosilane waste liquid,
(slowly) high boiling point chlorosilane waste liquid is added dropwise in reactor at a temperature of 40 DEG C；Drip complete
After, (progressively) is warming up to 100 DEG C of continuation reactions 8～13h no longer has HCl until HCl tail connects in device
Release, terminate reaction, obtain reacting rear material；
C, separating-purifying: by reacting rear material at temperature 170～260 DEG C, the bar of pressure 5～10mmHg
Carry out decompression distillation under part, remove less than the 170 DEG C by-products distillated and the complete ortho-methyl phenol of unreacted
After, collect 230～260 DEG C of fractions distillated and be product o-methyl-benzene epoxide methyl disilane.
The structural characterization of product o-methyl-benzene epoxide methyl disilane is with embodiment 22.
Embodiment 28:
The preparation method of o-methyl-benzene epoxide methyl disilane, comprises the following steps:
A, dispensing: by chlorine atom in high boiling point chlorosilane waste liquid: the mol ratio of ortho-methyl phenol is 1:1.4
Take raw material high boiling point chlorosilane waste liquid and ortho-methyl phenol, wherein: in high boiling point chlorosilane waste liquid, chlorine is former
The content (can be through acid base titration) of son is 13mol/L；
B, etherification reaction: ortho-methyl phenol is equipped with constant pressure funnel, anhydrous calcium chloride is dried
Tower, HCl tail connect in the reactor of device, join in constant pressure funnel by high boiling point chlorosilane waste liquid,
(slowly) high boiling point chlorosilane waste liquid is added dropwise in reactor at a temperature of 40 DEG C；Drip complete
After, (progressively) is warming up to 80 DEG C of continuation reactions 8～13h no longer has HCl to put until HCl tail connects in device
Go out, terminate reaction, obtain reacting rear material；
C, separating-purifying: by reacting rear material at temperature 170～260 DEG C, the bar of pressure 5～10mmHg
Carry out decompression distillation under part, remove less than the 170 DEG C by-products distillated and the complete ortho-methyl phenol of unreacted
After, collect 230～260 DEG C of fractions distillated and be product o-methyl-benzene epoxide methyl disilane.
The structural characterization of product o-methyl-benzene epoxide methyl disilane is with embodiment 22.
In above-described embodiment 22～28: described in step a, the chemical composition of high boiling point chlorosilane waste liquid is first
The mixture of base chlorine disilane, the mixture general molecular formula of this methylchlorodisilane is Clm Si-Si
(CH3)6-m,Wherein: m=2-6；Described high boiling point chlorosilane waste liquid is the north, (Sichuan Province China province) Luzhou
Chloride silicone industry waste liquid that Chemical Co., Ltd. provides, can also be chloride having of providing of other enterprises
Machine silicon industrial wastes i.e. high boiling point chlorosilane waste liquid.
In above-described embodiment: each raw material used is commercially available prod in addition to high boiling point chlorosilane waste liquid.
In above-described embodiment: in the percentage used, indicate the most especially, be mass percent
Example；Described weight (quality) part can be all gram or kilogram.
In above-described embodiment: technological parameter (temperature, time, concentration etc.) and each component in each step are used
Numerical quantities etc. are scope, and any point is the most applicable.
The technology contents being not specifically delineated in present invention and above-described embodiment is compared with technology.
The invention is not restricted to above-described embodiment, described in present invention, all can implement and have described good effect
Really.
Claims (6)
1. the preparation method of phenoxymethyl disilane, is characterized in that comprising the following steps:
A, dispensing: by chlorine atom in high boiling point chlorosilane waste liquid: the mol ratio of phenol is 1:1～1.5
Take raw material high boiling point chlorosilane waste liquid and phenol, wherein: chlorine atom in high boiling point chlorosilane waste liquid
Content is 13mol/L；
The mixture that chemical composition is methylchlorodisilane of described high boiling point chlorosilane waste liquid, this methyl
The mixture general molecular formula of chlorine disilane is Clm Si-Si(CH3)6-m,Wherein: m=2-6；
B, etherification reaction: phenol is equipped with constant pressure funnel, anhydrous calcium chloride drying tower,
HCl tail connects in the reactor of device, joins in constant pressure funnel by high boiling point chlorosilane waste liquid,
At a temperature of 40 DEG C, high boiling point chlorosilane waste liquid is added dropwise in reactor；After dropping, heat up
Continuing reaction 8～13h to 60～100 DEG C no longer has HCl to release until HCl tail connects in device, terminate
Reaction, obtains reacting rear material；
C, separating-purifying: by reacting rear material at temperature 170～260 DEG C, pressure 5～10mmHg
Under the conditions of carry out decompression distillation, after removing less than the 170 DEG C by-products distillated and the complete phenol of unreacted,
Collect 230～260 DEG C of fractions distillated and be product phenoxymethyl disilane；The change of this compound
Structural formula is:
(RO)n Si-Si(CH3)6-n
In formula: R=C6H5-；N=2-6.
2. the preparation method of phenoxymethyl disilane as described in claim 1, is characterized in that: step
Chlorine atom in high boiling point chlorosilane waste liquid described in rapid a: the mol ratio of phenol is 1:1.1.
3. the preparation method of pair methylphenoxymethyl disilane, is characterized in that comprising the following steps:
A, dispensing: by chlorine atom in high boiling point chlorosilane waste liquid: the mol ratio of p-methyl phenol is
1:1～1.5 takes raw material high boiling point chlorosilane waste liquid and p-methyl phenol, wherein: high boiling point chlorosilane
In waste liquid, the content of chlorine atom is 13mol/L；
The mixture that chemical composition is methylchlorodisilane of described high boiling point chlorosilane waste liquid, this methyl
The mixture general molecular formula of chlorine disilane is Clm Si-Si(CH3)6-m,Wherein: m=2-6；
B, etherification reaction: p-methyl phenol is equipped with constant pressure funnel, anhydrous calcium chloride is done
Dry tower, HCl tail connect in the reactor of device, and high boiling point chlorosilane waste liquid is joined constant pressure funnel
In, at a temperature of 40 DEG C, high boiling point chlorosilane waste liquid is added dropwise in reactor；After dropping,
Being warming up to 60～100 DEG C of continuation reactions 8～13h no longer has HCl to release until HCl tail connects in device,
Terminate reaction, obtain reacting rear material；
C, separating-purifying: by reacting rear material at temperature 170～260 DEG C, pressure 5～10mmHg
Under the conditions of carry out decompression distillation, remove less than the 170 DEG C by-products distillated and unreacted complete to methyl
After phenol, collect 230～260 DEG C of fractions distillated and be product to methylphenoxymethyl disilane；
The chemical structural formula of this compound is:
(RO)n Si-Si(CH3)6-n
In formula: R=p-CH3-C6H4-；N=2-6.
4. preparation method to methylphenoxymethyl disilane as described in claim 3, its feature
It is: chlorine atom in the waste liquid of high boiling point chlorosilane described in step a: the mol ratio of p-methyl phenol is
1:1.1。
5. the preparation method of o-methyl-benzene epoxide methyl disilane, is characterized in that comprising the following steps:
A, dispensing: by chlorine atom in high boiling point chlorosilane waste liquid: the mol ratio of ortho-methyl phenol is
1:1～1.5 takes raw material high boiling point chlorosilane waste liquid and ortho-methyl phenol, wherein: high boiling point chlorosilane
In waste liquid, the content of chlorine atom is 13mol/L；
The mixture that chemical composition is methylchlorodisilane of described high boiling point chlorosilane waste liquid, this methyl
The mixture general molecular formula of chlorine disilane is Clm Si-Si(CH3)6-m,Wherein: m=2-6；
B, etherification reaction: ortho-methyl phenol is equipped with constant pressure funnel, anhydrous calcium chloride is done
Dry tower, HCl tail connect in the reactor of device, and high boiling point chlorosilane waste liquid is joined constant pressure funnel
In, at a temperature of 40 DEG C, high boiling point chlorosilane waste liquid is added dropwise in reactor；After dropping,
Being warming up to 60～100 DEG C of continuation reactions 8～13h no longer has HCl to release until HCl tail connects in device,
Terminate reaction, obtain reacting rear material；
C, separating-purifying: by reacting rear material at temperature 170～260 DEG C, pressure 5～10mmHg
Under the conditions of carry out decompression distillation, remove less than the 170 DEG C by-products distillated and the complete adjacent methyl of unreacted
After phenol, collect 230～260 DEG C of fractions distillated and be product o-methyl-benzene epoxide methyl disilane；
The chemical structural formula of this compound is:
(RO)n Si-Si(CH3)6-n
In formula: R=o-CH3-C6H4-；N=2-6.
6. the preparation method of o-methyl-benzene epoxide methyl disilane, its feature as described in claim 5
It is: chlorine atom in the waste liquid of high boiling point chlorosilane described in step a: the mol ratio of ortho-methyl phenol is
1:1.1。
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| Method to prepare functional substituted oligosilanes;Uhlig Wolfram等，;《Zeitschrift fuer Chemie》;19891231;第29卷(第9期);第335-336页，尤其是第335页 * |
| Preparation, thermal decomposition,and some reactions of poly(methyldisilanylsesquiazanes) [Si2Me3(NH)1.5]n and [Si2Me2(NH)2]n;Semenov V. V.等，;《Zhurnal Obshchei Khimii》;19911231;第61卷(第5期);第1195-1202页，尤其是第1199页 * |
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