CN104558015B - A kind of preparation method of high-purity organosilicon monomer - Google Patents
A kind of preparation method of high-purity organosilicon monomer Download PDFInfo
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- CN104558015B CN104558015B CN201510033653.4A CN201510033653A CN104558015B CN 104558015 B CN104558015 B CN 104558015B CN 201510033653 A CN201510033653 A CN 201510033653A CN 104558015 B CN104558015 B CN 104558015B
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Abstract
The invention provides a kind of preparation method of high-purity organosilicon monomer, specifically, with industrial organic silicon monomer, by steps such as multiple rectifying, membrane filtration, multiple sub-boiling distillations, electronic grade high-purity organic silicon monomer is made in the present invention.The inventive method technological operation is simple, safe, obtained organic silicon monomer purity is more than 99.99%, single impurity metal ion content is less than 0.1ppb, more than or equal to 0.5 μm solid particle is less than 5/ml, and product quality is stable, and can meet great scale integrated circuit prepares needs.
Description
Technical field
The invention provides a kind of preparation method for producing high-purity organosilicon monomer, and in particular to one kind is used for semiconductor row
The purification process of the organosilicon liquid source monomer of industry.
Background technology
Organosilan is because being the important original needed for super large-scale integration manufacturing process with excellent dielectric properties
Material, is one of indispensable micro-electronics chemicals.The purity of organosilane product directly affects the performance of integrated circuit, product
The presence of middle impurity especially metal ion, it is easy to cause the generation of staggered floor, thus increase leakage current, cause to puncture and reduce
In the life-span of carrier, for nanometer-grade IC, several metal ions or dust granule are just enough to scrap whole circuit.
Therefore, the high-purity organosilicon liquid source of the growth requirement electron level of super large-scale integration.
The purification process of high-purity organosilicon alkane mainly includes the removal of machine impurity, metal ion and solia particle.Wherein,
The removal of organic impurities is main using the method absorbed with rectifying, and solia particle is then removed by filter process, but metal
The removal difficulty of ion is larger, and conventional purification process is not obvious to metal ion removal effect, is extremely difficult to below ppm, but
For the silane of high-end chip, require control within 10ppb metal ion content, it is therefore desirable to which one kind production high-purity has
The purification technique of machine silicon monomer.
United States Patent (USP) US2008314728A1 discloses a kind of method for purifying trichlorosilicane and silicon tetrachloride, by adding
Complexing agent complexation of metal ions formation polymer precipitation, the method then purified again by rectifying, the last metal ion of this method
Content can only achieve 0.1ppm, it is impossible to meet the preparation requirement of electronic grade high-purity siloxanes.
United States Patent (USP) US5312947A discloses a kind of method of increase ionic crystals size exclusion, by silane systems
Middle introducing polar solvent, evaporates after being sufficiently stirred at a certain temperature, is filtered out based on the increase of metal ion crystalline size to realize
Purpose, but this method can only by metal ion control in ppm ranks.
United States Patent (USP) US20050054211A1 discloses a kind of method of absorption tower absorption purification organosilicon, passes through silane
It is dissolved in solvent, is then filtered by the absorption tower equipped with adsorbent, then re-evaporation and concentration repeats and reached removing
The purpose of metal ion.This method removes metal ion effect with certain, but needs a large amount of organic solvents to be used as carrier, raw
Low yield is produced, and processing procedure needs real-time monitoring, is repeated several times, processing procedure poor controllability, it is impossible to applied to industrial metaplasia
Production.
Chinese patent CN102245618A discloses a kind of side that silicon compound is purified by adsorbent adsorbing metal ions
Method, this method has certain removal effect to particular kind of metal ion, but only can not by simple physisorptive filter
Guarantee pair is so the metal ion removal of species, cannot guarantee that other are miscellaneous caused by activated carbon of sorbent or diatomaceous addition
The introducing of matter.
Therefore, in the urgent need to a kind of technological operation is simple, the economical and efficient method for removing metal ion in organosilicon, with
Electronic grade high-purity organosilicon is obtained, is particularly useful for the high-purity organosilicon liquid source of large scale integrated circuit.
The content of the invention
It is an object of the invention to provide a kind of purifying for the organosilicon liquid source monomer that technological operation is simple, product quality is high
Method.
There is provided a kind of preparation method of high-purity organosilicon monomer, described preparation method bag for the first aspect of the present invention
Include following steps：
(1), industrial organic silicon monomer is made by multiple rectifying column, so as to carry out multiple rectifying to it, obtaining the first purifying has
Machine silicon monomer；
(2) described first is purified organic silicon monomer by the first film filter, so as to carry out coarse filtration, obtain second pure
Change organic silicon monomer；
(3) described second is purified organic silicon monomer and enter multiple sub-boiling distillation device, multiple sub-boiling distillation is carried out to it,
And cut is collected, obtain the 3rd purifying organic silicon monomer；
(4), make the described 3rd to purify organic silicon monomer to be filtered by the second film filter, obtain that product is high-purity to be had
Machine silicon monomer.
In another preference, described organic silicon monomer is organosilan, preferably liquid organosilicon alkane.
In another preference, described multiple rectifying column has the rectifying column of 1~10 group of serial or parallel connection, preferably has
There is the rectifying column of 2~8 groups of serial or parallel connections；Wherein, there are more than the 2 rectifying king-posts being serially connected inside every group of rectifying column
Body.
In another preference, in described multiple rectifying column, the cylinder of each rectifying column, which is each independently, to be selected from the group
Cylinder：Stainless steel column, quartzy cylinder, PFA liner cylinders, or its combination；And/or
In described multiple rectifying column, the filler in each rectifying column or rectifying column cylinder is each independently what is be selected from the group
Filler：Stainless steel structured packing, stainless steel random packing, quartzy structured packing, quartzy random packing, regular the filling out of PFA claddings
The random packing of material, PFA claddings, or its combination.
In another preference, in described step (1), described multiple rectifying is entered under 0.02~0.1MPa pressure
OK.
In another preference, the first described film filter and the second film filter are PP film filters or PTFE film mistake
Filter；Preferably, the aperture of the first described film filter and the second film filter is 0.002~0.5 μm.
In another preference, the aperture of the first described film filter is 0.05-0.5 μm.
In another preference, the aperture of the second described film filter is 0.002-0.1 μm.
In another preference, described step (3) is carried out under the conditions of ultra-clean；And/or described step (3) is in inertia
Carried out under atmosphere.
In another preference, described step is referred in described step under an inert atmosphere, in purifying environment
(being preferably in multiple sub-boiling distillation device) has inert atmosphere protection.
In another preference, described inert atmosphere is nitrogen atmosphere or argon gas atmosphere.
In another preference, described multiple sub-boiling distillation utensil has the sub-boiling distillation device of multigroup serial or parallel connection, excellent
Sub-boiling distillation device of the choosing with 2~8 groups of serial or parallel connections；Preferably, described sub-boiling distillation device body uses PFA liners not
Become rusty steel or high purity quartz material.
In another preference, described sub-boiling distillation device be can accurate temperature controlling sub-boiling distillation device.
In another preference, also include in described step (3)：Collect the cut of (T-100)~T DEG C；Wherein, it is described
T be target organic silicon monomer boiling point；Preferably, the cut of (T-80)~(T-5) DEG C of collection.
The second aspect of the present invention includes there is provided a kind of high-purity organosilicon monomer production plant, the equipment：Multiple essence
Evaporate tower assembly, the first film filter component, multiple sub-boiling distillation device assembly, the second film filter component；And lead between each component
Transfer pipeline is crossed to be connected.
In another preference, described transfer pipeline is stainless steel, quartz, the stainless steel of PFA liners or PTFE materials
Pipeline.
In another preference, the first described film filter component includes：First film filter, and intermediate products storage
Groove.
In another preference, described multiple sub-boiling distillation device assembly includes：Multiple sub-boiling distillation devices being serially connected,
And the 3rd intermediate products storage tank.
In another preference, described multiple rectifying tower assembly has the rectifying column of 1~10 group of serial or parallel connection, preferably
Ground has the rectifying column of 2~8 groups of serial or parallel connections；Wherein, there are more than 2 rectifying columns being serially connected inside every group of rectifying column
Cylinder；
Preferably, in described multiple rectifying column, the cylinder of each rectifying column is each independently the cylinder being selected from the group：No
Become rusty steel column, quartzy cylinder, PFA liner cylinders, or its combination；And/or
In described multiple rectifying column, the filler of each rectifying column is each independently the filler being selected from the group：Stainless steel is advised
What whole filler, stainless steel random packing, quartzy structured packing, quartzy random packing, the structured packing of PFA claddings, PFA were coated dissipates
Heap filler, or its combination.
In another preference, in described multiple rectifying tower assembly, each rectifying column also there are tower reactor, front-end volatiles to store up
Groove, the first intermediate products storage tank and tails storage tank.
In another preference, the first described film filter and the second film filter are PP film filters or PTFE film
Filter；Preferably, the aperture of the first described film filter and the second film filter is 0.002~0.5 μm.
In another preference, the aperture of the first described film filter is 0.05-0.5 μm.
In another preference, the aperture of the second described film filter is 0.002-0.01 μm.
In another preference, described multiple sub-boiling distillation utensil has the sub-boiling distillation device of multigroup serial or parallel connection, excellent
Sub-boiling distillation device of the choosing with 2~8 groups of serial or parallel connections.
In another preference, described sub-boiling distillation device be can accurate temperature controlling sub-boiling distillation device.
In another preference, described sub-boiling distillation device body uses the stainless steel or high purity quartz material of PFA liners.
It should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the invention and have in below (eg embodiment)
It can be combined with each other between each technical characteristic of body description, so as to constitute new or preferred technical scheme.As space is limited, exist
This no longer tires out one by one states.
Brief description of the drawings
Fig. 1 is the schematic device of the present invention, and in figure, each legend is as follows：
111st, 112 rectifying column
121st, 122 tower reactor
131st, 132 front-end volatiles storage tank
141st, 142 first intermediate products storage tank
23 second intermediate products storage tanks
34 the 3rd intermediate products storage tanks
151st, 152 tails storage tank
161st, 21,31,41 measuring pump
22 first film filters
31st, 32 sub-boiling distillation device
42 second film filters.
Embodiment
The present inventor's in-depth study by long-term, it has unexpectedly been found that, organosilicon liquid source is by rectifying, and coarse filtration is sub-
Boiling distillation, is refiltered, and can obtain high-purity (purity is more than 99.99%), (single impurity metal ion content is small for low metal ion
In 0.1ppb) product, meet preparation requirement of the great scale integrated circuit to high-purity organosilicon liquid source.Based on above-mentioned hair
Existing, inventor completes the present invention.
Term
As used herein, term " multiple rectifying column " refers to the component of the rectifying column with more than one group serial or parallel connection, its
In, every group of rectifying column is respectively provided with the rectifying column cylinder that two or more are mutually in series.
The preparation of high-purity organosilicon monomer
The invention provides a kind of preparation method of high-purity organosilicon monomer, described preparation method comprises the following steps：
(1), industrial organic silicon monomer is made by multiple rectifying column, so as to carry out multiple rectifying to it, obtaining the first purifying has
Machine silicon monomer；
(2) described first is purified organic silicon monomer by the first film filter, so as to carry out coarse filtration, obtain second pure
Change organic silicon monomer；
(3) described second is purified organic silicon monomer and enter multiple sub-boiling distillation device, it is distilled, and collection evaporates
Point, obtain the 3rd purifying organic silicon monomer；
(4), make the described 3rd to purify organic silicon monomer to be filtered by the second film filter, obtain that product is high-purity to be had
Machine silicon monomer.
In another preference, described organic silicon monomer is organosilan, preferably liquid organosilicon alkane.It is resulting
Product high-purity organosilicon monomer output after can directly be packed.
Described multiple rectifying column is preferably the cylinder with 2~10 series connection, preferably has the post of 2~8 series connection
Body.Produce high-purity organosilicon monomer when, by regulate and control flow to, make industrial organic silicon monomer by more than one rectifying column so as to
Carry out multiple rectifying.Described multiple rectifying column can also have multigroup rectifying column in parallel, and (every group of rectifying column is mutual comprising more than 2
The rectifying column being in series), in production, each group rectifying column in parallel is passed through industrial organic silicon monomer and carries out multiple rectifying simultaneously.
In described multiple rectifying column, the cylinder of each rectifying column is not particularly limited, and for example (but being not limited to) is each only
It is on the spot the cylinder being selected from the group：Stainless steel column, quartzy cylinder, PFA liner cylinders, or its combination.
In described multiple rectifying column, the filler of each rectifying column has no particular limits, and can be structured packing or scattered
Heap filler.In another preference, the filler of each rectifying column is each independently the filler being selected from the group：Stainless steel is regular to be filled out
Material, stainless steel random packing, quartzy structured packing, quartzy random packing, the structured packing of PFA claddings, the scattered landfill of PFA claddings
Material, or its combination.
In the preferred embodiments of the present invention, multiple rectifying in described step (1) can under normal pressure or reduced pressure,
Carried out for example under 0.02~0.1MPa pressure.In a preferred embodiment of the invention, first carry out at ambient pressure one group or
Multigroup rectifying, then carries out one or more groups of rectifying again at reduced pressure conditions.
In described step (1), in described multiple rectification step, by collecting intermediate products (i.e. (T-3)~(T+
DEG C 3) cut；More preferably (T-2)~(T+2) DEG C of cut), the first purifying organic silicon monomer needed for obtaining.Wherein,
Described T is that the T values under boiling point of the target organic silicon monomer under corresponding pressure, normal pressure can be by those skilled in the art's root
Determined according to the species of target organic silicon monomer, the T values under reduced pressure can pass through this area by those skilled in the art
Conventional calculation is drawn.
In described step (2) and (4), the first described film filter and the species of the second film filter be not special
Limitation, can select any appropriate film filter, such as PP film filters or PTFE film filter；Preferably, described
The aperture of one film filter and the second film filter is 0.002~0.5 μm.
In another preference, the first described film filter and the aperture of the second film filter are different, for example, the
One film filter (being used for coarse filtration) is from the film filter that aperture is 0.05-0.5 μm, and the second film filter (is filtrated to get again
End-product) from the film filter that aperture is 0.002-0.1 μm.
In another preference, described step (3) is carried out under the conditions of ultra-clean；And/or described step (3) is in inertia
Carried out under atmosphere.
In another preference, described step is referred in described step under an inert atmosphere, and purifying environment is (excellent
Elect multiple sub-boiling distillation device as) in have inert atmosphere protection.
In another preference, described inert atmosphere is nitrogen atmosphere or argon gas atmosphere.
In another preference, described multiple sub-boiling distillation utensil has the sub-boiling distillation device of multigroup serial or parallel connection, excellent
Sub-boiling distillation device of the choosing with 2~8 groups of serial or parallel connections.Described sub-boiling distillation device be preferably can the sub- boiling of accurate temperature controlling steam
Evaporate device.
In another preference, described sub-boiling distillation device body uses the stainless steel or high purity quartz material of PFA liners.
After distillation is finished in described step (3), the cut of (T-100)~T DEG C is preferably collected；Wherein, described T is
The boiling point of target organic silicon monomer；It is highly preferred that collecting (T-80)~(T-5) DEG C of cut.
In described preparation process, the flow of liquid phase has no particular limits, and can be adjusted according to output of products flow,
Specifically, it can be set according to the size of distiller, such adjustment is that those skilled in the art are reading the present invention
It can be become apparent from after disclosure.In particularly preferred embodiment of the present invention, the flow control of liquid phase exists
Make the inventory flowed into and out in each reaction member (such as multiple sub-boiling distillation device) substantially suitable, for example, multiple sub-boiling distillation
The second purifying organic silicon monomer being passed through in device is suitable or substantially suitable with the amount of the 3rd purifying organic silicon monomer of outflow.
Described method can obtain that the electron level organosilicon liquid source of large scale integrated circuit can be applied to, in this hair
In some bright preferred embodiments, preparation-obtained product purity is more than 99.99%, and single impurity metal ion content is less than
0.1ppb, particle diameter >=0.5 μm solid particle is less than 5/ml.
High-purity organosilicon monomer production plant
Present invention also offers a kind of high-purity organosilicon monomer production plant suitable for the inventive method, the equipment bag
Include：Multiple rectifying tower assembly, the first film filter component, multiple sub-boiling distillation device assembly, the second film filter component；And each group
It is connected between part by transfer pipeline.
In another preference, described transfer pipeline is the pipeline being selected from the group：Stainless steel pipeline, quartzy pipeline, PFA
The stainless steel pipeline of liner, or PTFE materials pipeline.
In another preference, described multiple rectifying column is preferably the cylinder with 2~10 series connection, is preferably had
The cylinder of 2~8 series connection.Described multiple rectifying column can also have multigroup rectifying column in parallel (every group of rectifying column comprising 2 with
On the rectifying column that is mutually in series).
In another preference, in described multiple rectifying column, the cylinder of each rectifying column, which is each independently, to be selected from the group
Cylinder：Stainless steel column, quartzy cylinder, PFA liner cylinders, or its combination.
In another preference, in described multiple rectifying column, the filler of each rectifying column, which is each independently, to be selected from the group
Filler：It is regular that stainless steel structured packing, stainless steel random packing, quartzy structured packing, quartzy random packing, PFA are coated
The random packing of filler, PFA claddings, or its combination.
In another preference, the first described film filter and the second film filter are PP film filters or PTFE film mistake
Filter；Preferably, the aperture of the first described film filter and the second film filter is 0.002~0.5 μm.In another preference
In, the aperture of the first described film filter is 0.05-0.5 μm；The aperture of the second described film filter is 0.002-0.1 μ
m。
In another preference, described multiple sub-boiling distillation utensil has the sub-boiling distillation device of multigroup serial or parallel connection, excellent
Sub-boiling distillation device of the choosing with 2~8 groups of serial or parallel connections.
In another preference, described sub-boiling distillation device be can accurate temperature controlling sub-boiling distillation device.
In another preference, described sub-boiling distillation device body uses the stainless steel or high purity quartz material of PFA liners.
In a preferred embodiment of the invention, described production equipment has structure as shown in Figure 1 (herein only
Schematically to illustrate the structure of the application production equipment, and not show most preferred situation).Wherein, described equipment bag
Two groups of rectifying columns 111,112 are included, each group of rectifying column, which includes tower reactor (tower reactor 121,122 i.e. in figure), front-end volatiles storage tank, (schemes
In front-end volatiles storage tank 131,132), intermediate products storage tank (the intermediate products storage tank 141,142 i.e. in figure) and tails storage tank
(the tails storage tank 151,152 i.e. in figure).Front-end volatiles obtained by distillation process are stored in described front-end volatiles storage tank,
Tails is stored in tails storage tank, and required cut is stored in each the first intermediate products storage tank and by transfer pipeline
Into the relevant device of subsequent step.Described equipment also includes one first film filter, and the first described film filter has
One is used to store the second intermediate products storage tank 23 that second obtained after membrane filtration purifies organic silicon monomer.The second described purifying
Organic silicon monomer is entered by transfer pipeline has multiple series connection in multiple sub-boiling distillation device, described multiple sub-boiling distillation device
Sub-boiling distillation device (the sub-boiling distillation device 31,32 i.e. in figure), and it is organic for storing the obtained after sub-boiling distillation the 3rd purifying
3rd intermediate products storage tank 34 of silicon monomer.The 3rd described purifying organic silicon monomer enters the second membrane filtration by transfer pipeline
Device, obtains final products high-purity organosilicon monomer by membrane filtration after purification.
In the apparatus, one or more measuring pumps are preferably also included, so as to control material flow velocity.A kind of preferred
In the case of, described equipment includes：Measuring pump on connection intermediate products storage tank 141 and the connecting pipeline of tower reactor 122
161st, positioned at connection intermediate products storage tank 142 with the measuring pump 21 on the connecting pipeline of the first film filter 22, in connecting
Between product storage tank 23 and the measuring pump 31 on the connecting pipeline of multiple sub-boiling distillation device 31 with positioned at connecting intermediate products storage tank 34
With the measuring pump 41 on the connecting pipeline of the second film filter 42.
Compared with prior art, main advantages of the present invention include：
(1) method that the present invention is provided is applied to the organosilicon liquid source required for prepared by all integrated circuits, adaptability
Extensively.
(2) present invention is by rectifying, and coarse filtration, sub-boiling distillation is refiltered, simple to operate, process control, and stable yield can
For industrialized production.
(3) product purity is high (purity is more than 99.99%), and metal ion content is low, and (single impurity metal ion content is small
In 0.1ppb), solid particle is few (>=0.5 μm of particle is less than 5/ml), and fully meet large scale integrated circuit has to electron level
The requirement of machine silicon liquid source.
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.The experimental method of unreceipted actual conditions in the following example, generally according to conventional strip
Part, or according to the condition proposed by manufacturer.Unless otherwise indicated, otherwise percentage and number are calculated by weight.
The preparation of the high-purity octamethylcy-clotetrasiloxane of embodiment 1
(1) rectifying
Under atmospheric pressure state, Contained In Commercial OctamethylcyclotetraOnloxane is added in reactor, then passes through four groups of rectifying columns
Series connection continuous rectification, control split ratio and column temperature, the cut of 173-175 DEG C of collection.
(2) coarse filtration
The cut being collected into is passed through into 0.5 μm of film filter by measuring pump.
(3) sub-boiling distillation
Under nitrogen protection, by measuring pump toward sub-boiling distillation device continuous sample introduction, two groups of sub-boiling distillation device series connection, heating is warm
Degree is raised to 150~155 DEG C of collection cuts.
(4) refined filtration
The cut of collection, by 0.005 μm of film filter, is then output to directly filling by measuring pump.
Product detects that product purity is 99.999% through GC, ICP-MS and PMS, and single metal ion content is less than 1ppb,
More than or equal to 0.5 μm particle is less than 5/ml.
The preparation of the high-purity octamethylcy-clotetrasiloxane of embodiment 2
(1) rectifying
Under atmospheric pressure state, Contained In Commercial OctamethylcyclotetraOnloxane is added in reactor, then passes through five groups of rectifying columns
Series connection continuous rectification, control split ratio and column temperature, the cut of 173-175 DEG C of collection.
(2) coarse filtration
The cut being collected into is passed through into 0.1 μm of film filter by measuring pump.
(3) sub-boiling distillation
Under nitrogen protection, by measuring pump toward sub-boiling distillation device continuous sample introduction, three groups of sub-boiling distillation device series connection, heating is warm
Degree is raised to 140~145 DEG C of collection cuts.
(4) refined filtration
The cut of collection, by 0.005 μm of film filter, is then exported directly filling by measuring pump.
Product detects that product purity is 99.9999%, and single metal ion content is less than through GC, ICP-MS and PMS
0.1ppb, more than or equal to 0.5 μm particle is less than 5/ml.
The preparation of the high-purity octamethylcy-clotetrasiloxane of embodiment 3
(1) rectifying
Under atmospheric pressure state, Contained In Commercial OctamethylcyclotetraOnloxane is added in reactor, then passes through two groups of rectifying columns
Series connection continuous rectification, control split ratio and column temperature, the cut of 173-175 DEG C of collection, then by two groups of rectifying columns in 0.015MPa
Lower rectifying, the cut of 107-110 DEG C of collection.
(2) coarse filtration
The cut being collected into is passed through into 0.1 μm of film filter by measuring pump.
(3) sub-boiling distillation
Under nitrogen protection, continuous sample introduction is distinguished to three groups of sub-boiling distillation devices in parallel by measuring pump, then be connected in series to another
Group sub-boiling distillation device, heating-up temperature is raised to 145~150 DEG C of collection cuts.
(4) refined filtration
The cut of collection, by 0.005 μm of film filter, is then exported directly filling by measuring pump.
Product detects that product purity is 99.999%, and single metal ion content is less than through GC, ICP-MS and PMS
0.5ppb, more than or equal to 0.5 μm particle is less than 5/ml.
The preparation of the high-purity MTES of embodiment 4
(1) rectifying
Under atmospheric pressure state, technical grade methyl triethoxysilane is added in reactor, then passes through three groups of rectifying columns
Series connection continuous rectification, control split ratio and column temperature, the cut of 141-143 DEG C of collection.
(2) coarse filtration
The cut being collected into is passed through into 0.1 μm of film filter by measuring pump.
(3) sub-boiling distillation
Under nitrogen protection, by measuring pump toward sub-boiling distillation device continuous sample introduction, three groups of sub-boiling distillation device series connection, heating is warm
Degree is raised to 120~125 DEG C of collection cuts.
(4) refined filtration
The cut of collection, by 0.002 μm of film filter, is then exported directly filling by measuring pump.
Product detects that product purity is 99.99%, and single metal ion content is less than through GC, ICP-MS and PMS
0.1ppb, more than or equal to 0.5 μm particle is less than 5/ml.
The preparation of the high-purity dimethyldimethoxysil,ne of embodiment 5
(1) rectifying
Under atmospheric pressure state, technical grade dimethyldimethoxysil,ne is added in reactor, then passes through three groups of rectifying
Post series connection continuous rectification, control split ratio and column temperature, the cut of 81-82 DEG C of collection.
(2) coarse filtration
The cut being collected into is passed through into 0.2 μm of film filter by measuring pump.
(3) sub-boiling distillation
Under nitrogen protection, by measuring pump toward sub-boiling distillation device continuous sample introduction, three groups of sub-boiling distillation device series connection, heating is warm
Degree is warming up to 65~70 DEG C of collection cuts.
(4) refined filtration
The cut of collection, by 0.005 μm of film filter, is then exported directly filling by measuring pump.
Product detects that product purity is 99.99%, and single metal ion content is less than through GC, ICP-MS and PMS
0.1ppb, more than or equal to 0.5 μm particle is less than 5/ml.
The preparation of the high-purity octamethylcy-clotetrasiloxane of comparative example
(1) rectifying
Under atmospheric pressure state, Contained In Commercial OctamethylcyclotetraOnloxane is added in reactor, then passes through four groups of rectifying columns
Series connection continuous rectification, control split ratio and column temperature, the cut of 173-175 DEG C of collection.
(2) filter
Then the cut being collected into is exported directly filling by measuring pump by 0.005 μm of film filter.
Product detects that product purity is 99.98% through GC, ICP-MS and PMS, and single metal ion content is higher than 60ppb,
More than or equal to 0.5 μm particle is 18/ml.
The production technology that can be seen that the application by above-mentioned comparative example and embodiment is that extremely advantageous high-purity of a class has
Organic siloxane production technology, when one in production technology or several steps are omitted, resulting organosiloxane product
Quality be very big difference occur, it is impossible to reach the requirement needed for integrated circuit.
All documents referred in the present invention are all incorporated as reference in this application, independent just as each document
It is incorporated as with reference to such.In addition, it is to be understood that after the above-mentioned instruction content of the present invention has been read, those skilled in the art can
To be made various changes or modifications to the present invention, these equivalent form of values equally fall within the model that the application appended claims are limited
Enclose.
Claims (20)
1. a kind of preparation method of high-purity organosilicon monomer, it is characterised in that described preparation method comprises the following steps：
(1), make industrial organic silicon monomer by multiple rectifying column, so as to carry out multiple rectifying to it, obtain the first purifying organosilicon
Monomer；
(2) described first is purified organic silicon monomer by the first film filter, so as to carry out coarse filtration, obtaining the second purifying has
Machine silicon monomer；
(3) described second is purified organic silicon monomer and enter multiple sub-boiling distillation device, multiple sub-boiling distillation is carried out to it, and receive
Collect cut, obtain the 3rd purifying organic silicon monomer；
(4), make described the 3rd purify organic silicon monomer to be filtered by the second film filter, obtain product high-purity organosilicon
Monomer.
2. the method as described in claim 1, it is characterised in that described multiple rectifying column has 1~10 group of serial or parallel connection
Rectifying column.
3. method as claimed in claim 2, it is characterised in that described multiple rectifying column has 2~8 groups of serial or parallel connections
Rectifying column.
4. have inside method as claimed in claim 2 or claim 3, it is characterised in that in described multiple rectifying column, every group of rectifying column
There are more than 2 rectifying column being serially connected cylinders.
5. the method as described in claim 1-3 is any, it is characterised in that in described multiple rectifying column, the post of each rectifying column
Body is each independently the cylinder being selected from the group：Stainless steel column, quartzy cylinder, PFA liner cylinders, or its combination；And/or
In described multiple rectifying column, the filler in each rectifying column or rectifying column cylinder is each independently filling out of being selected from the group
Material：Stainless steel structured packing, stainless steel random packing, quartzy structured packing, quartzy random packing, the structured packing of PFA claddings,
The random packing of PFA claddings, or its combination.
6. the method as described in claim 1, it is characterised in that the first described film filter and the second film filter are PP films
Filter or PTFE film filter.
7. the method as described in claim 1, it is characterised in that the first described film filter and the aperture of the second film filter
For 0.002~0.5 μm.
8. the method as described in claim 1, it is characterised in that described multiple sub-boiling distillation utensil has multigroup serial or parallel connection
Sub-boiling distillation device.
9. the method as described in claim 1, it is characterised in that described multiple sub-boiling distillation utensil has 2~8 groups of series connection or simultaneously
The sub-boiling distillation device of connection.
10. the method as described in claim 1, it is characterised in that the body of described multiple sub-boiling distillation device uses PFA liners
Stainless steel or high purity quartz material.
11. the method as described in claim 1, it is characterised in that also include in described step (3)：Collect (T-100)~T
DEG C cut；Wherein, described T is the boiling point of target organic silicon monomer.
12. the method as described in claim 1, it is characterised in that also include in described step (3)：Collect (T-80)~(T-
DEG C 5) cut.
13. a kind of high-purity organosilicon monomer production plant, it is characterised in that the equipment includes：Multiple rectifying tower assembly, first
Film filter component, multiple sub-boiling distillation device assembly, the second film filter component；And pass through transfer pipeline phase between each component
Even.
14. production equipment as claimed in claim 13, it is characterised in that described multiple rectifying tower assembly has 1~10 group
The rectifying column of serial or parallel connection.
15. production equipment as claimed in claim 13, it is characterised in that described multiple rectifying tower assembly has 2~8 groups of strings
Connection or the rectifying column of parallel connection；Wherein, there are more than the 2 rectifying column cylinders being serially connected inside every group of rectifying column.
16. production equipment as claimed in claim 13, it is characterised in that in described multiple rectifying column, the post of each rectifying column
Body is each independently the cylinder being selected from the group：Stainless steel column, quartzy cylinder, PFA liner cylinders, or its combination；And/or
In described multiple rectifying column, the filler of each rectifying column is each independently the filler being selected from the group：Stainless steel is regular to be filled out
Material, stainless steel random packing, quartzy structured packing, quartzy random packing, the structured packing of PFA claddings, the scattered landfill of PFA claddings
Material, or its combination.
17. production equipment as claimed in claim 13, it is characterised in that described the first film filter and the second film filter
For PP film filters or PTFE film filter.
18. production equipment as claimed in claim 13, it is characterised in that described the first film filter and the second film filter
Aperture be 0.002~0.5 μm.
19. production equipment as claimed in claim 13, it is characterised in that described multiple sub-boiling distillation utensil has multigroup series connection
Or sub-boiling distillation device in parallel.
20. production equipment as claimed in claim 13, it is characterised in that the sub-boiling distillation with 2~8 groups of serial or parallel connections
Device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510033653.4A CN104558015B (en) | 2015-01-22 | 2015-01-22 | A kind of preparation method of high-purity organosilicon monomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510033653.4A CN104558015B (en) | 2015-01-22 | 2015-01-22 | A kind of preparation method of high-purity organosilicon monomer |
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| Publication Number | Publication Date |
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| CN104558015A CN104558015A (en) | 2015-04-29 |
| CN104558015B true CN104558015B (en) | 2017-11-07 |
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| CN201510033653.4A Expired - Fee Related CN104558015B (en) | 2015-01-22 | 2015-01-22 | A kind of preparation method of high-purity organosilicon monomer |
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| CN109912636B (en) * | 2019-04-11 | 2020-04-07 | 苏州金宏气体股份有限公司 | Production method of high-purity ethyl orthosilicate |
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| ITRM20040570A1 (en) * | 2004-11-19 | 2005-02-19 | Memc Electronic Materials | PROCEDURE AND PLANT FOR THE PURIFICATION OF TRICHLOROSILANE AND SILICON TETRACLORIDE. |
| CN103113401B (en) * | 2013-03-20 | 2016-05-18 | 中国科学院上海高等研究院 | Produce method and the device of high-purity organosilicon |
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