CN104231271B - Liquid silicone resin and its preparation method and application - Google Patents
Liquid silicone resin and its preparation method and application Download PDFInfo
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- CN104231271B CN104231271B CN201410543098.5A CN201410543098A CN104231271B CN 104231271 B CN104231271 B CN 104231271B CN 201410543098 A CN201410543098 A CN 201410543098A CN 104231271 B CN104231271 B CN 104231271B
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Abstract
The invention belongs to organosilicons to synthesize field, and in particular to a kind of liquid silicone resin and its preparation method and application, the liquid silicone resin are particularly suitable for preparing silicone sealant as plasticizer instead of dimethicone.The preparation method of fluid present invention silicones is carried out in the reaction kettle with agitating device and condensation reflux unit, is included the following steps：A, raw material is prepared：Mixed methyl trichlorosilane and dimethyldichlorosilane control the temperature of reaction kettle to be less than 5 DEG C；B, dropwise reaction：Concentrated hydrochloric acid is added dropwise into reaction kettle, the temperature for controlling reaction system is -10~5 DEG C；Reaction to bubble-free generates after concentrated hydrochloric acid is added dropwise, and reaction system is carried out water-oil separating；C, oil reservoir neutralizes：Into the separating obtained oil reservoirs of step b, solid alkaline matter is added in while stirring and is neutralized to oil reservoir as neutrality；D, oil reservoir is filtered：Filtration step c obtains neutral oil reservoir, and gained filtrate is primary liquid silicones.Finally through through de- low refined up to refined liquid silicone resin.
Description
Technical field
The invention belongs to organosilicons to synthesize field, and in particular to a kind of liquid silicone resin and its preparation method and application, it should
Liquid silicone resin is particularly suitable for preparing silicone sealant.
Background technology
The primary product of direct synthesis organic silicon monomer is dimethyldichlorosilane, while can generate a large amount of by-product
Object, wherein dimethyldichlorosilane and methyl trichlorosilane are most important two ingredients, account for 85%~88% and 10% respectively
~15%.
Dimethyldichlorosilane and methyl trichlorosilane have that boiling point is relatively low, readily volatilized and transport difficult, but because its from
Body molecular weight is big and easily forms vapor slugs, and meeting open fire can burn or explode, and meet water and then generate larger hydrogen chloride gas etc.
Defect is dangerous very big.Dimethyldichlorosilane can be as the raw material of DMC, for silastic elastomer or silicone oil etc. at present
Downstream product, methyl trichlorosilane are then mainly used for various silane coupling agents, silicones, waterproof material and use.
Silicone sealant will be used as plasticizer in preparation process using dimethicone at present, more to add in
Reinforced filling increases the intensity of silicone rubber products, but since the chemism of dimethicone is low, is not involved in system anti-
Should, it causes and will appear slow permeability situation during the later stage is using silicone rubber products, to the intensity and looking products of product
There is extreme influence.Therefore, the present inventor is intended to provide a kind of active liquid silicone instead of dimethicone work
For plasticizer.
Invention content
Technical problem solved by the invention is to provide a kind of liquid used instead of dimethicone as plasticizer
Silicones and preparation method thereof.
The preparation method of fluid present invention silicones, in the reaction kettle with agitating device and condensation reflux unit into
Row, includes the following steps：
A, raw material is prepared：Mixed methyl trichlorosilane and dimethyldichlorosilane control the temperature of reaction kettle to be less than 5 DEG C；
B, dropwise reaction：Concentrated hydrochloric acid is added dropwise into reaction kettle, the temperature for controlling reaction system is -10~5 DEG C；Concentrated hydrochloric acid
Reaction to bubble-free generates after being added dropwise, and reaction system is carried out water-oil separating；
C, oil reservoir neutralizes：Into the separating obtained oil reservoirs of step b, solid alkaline matter is added in while stirring and is neutralized to oil reservoir
For neutrality；
D, oil reservoir is filtered：Filtration step c obtains neutral oil reservoir, and gained filtrate is primary liquid silicones.
Further, by primary liquid silicones through de- low refined up to refined liquid silicone resin.
Wherein, taking off low refine is：The primary liquid silicones that step d is obtained is carried out de- low refined, it is 120 to take off low temperature
~160 DEG C (preferably 140 DEG C), pressure are -0.06~-0.09MPa (preferably -0.085MPa), and it is (excellent for 2~4 hours to take off the low time
It selects 4 hours)；It discharges up to refined liquid silicone resin.
For efficent use of resources, the tail gas that generation is reacted in step b can also be passed through monomer absorption device, chlorine successively
Change hydrogen recovery unit, obtain more pure hydrogen chloride gas.Wherein, monomer absorption device using concentrated hydrochloric acid to escaping out
Tail gas is absorbed.
In above-mentioned technical proposal, the mass ratio of dimethyldichlorosilane and methyl trichlorosilane is 63 ︰ 7~27 in step a.
In above-mentioned technical proposal, by weight, dimethyldichlorosilane weight is concentrated hydrochloric acid to concentrated hydrochloric acid additive amount in step b
1.5-2 times (preferably 1.8 times) of dosage, methyl trichlorosilane weight are 2-3 times (preferably 2.5 times) of concentrated hydrochloric acid dosage.That is, first
The weight ratio of the mixture and concentrated hydrochloric acid of base trichlorosilane and dimethyldichlorosilane is 1.8-2.3 (preferably 2 times).
In above-mentioned technical proposal, the speed that concentrated hydrochloric acid is added dropwise in step b is 0.8~1.5kg/h；It is preferred that 1.1kg/h.Control
Rate of addition is using constant pressure dropping funnel, and control is at the uniform velocity added dropwise.Be added dropwise it is too fast can cause to react uneven, the by-product of generation
More, dropwise addition can cause that wastage of material yield is not high, and the molecular weight product of generation is larger, is unfavorable for later-stage utilization slowly.
In above-mentioned technical proposal, the reaction end of step b is to be subject to bubble-free to generate, and the usual reaction time is in 0.5-1
Hour.
In above-mentioned technical proposal, a concentration of 33~37% of concentrated hydrochloric acid described in step b.
In above-mentioned technical proposal, condensation reflux unit is the condenser pipe of jacketed, when concentrated hydrochloric acid is added dropwise, is led into chuck
Enter refrigerant and carry out heat exchange cooling.Wherein, the preferred ethylene glycol of the refrigerant.Concrete operations are that the ethylene glycol of freezing is passed through folder
It is cooled down in set.
In above-mentioned technical proposal, in step b, the temperature for controlling reaction system is to utilize the condensation for controlling condensate recycling device
Temperature is controlled less than -10 DEG C.
In above-mentioned technical proposal, in step c, alkaline matter be one kind in sodium carbonate, sodium hydroxide, sodium bicarbonate or
It is a variety of.
The refined liquid silicone resin of the present invention can replace dimethicone as plasticizer for formulas such as silicone sealants
Type silicone rubber products have extensive economic value.Since primary liquid silicones contains more lower-molecular substance or diformazan
Based polysiloxane mixed methylcyclosiloxane, therefore plasticizer should not be directly used as.In addition, chlorosilane is added drop-wise to using concentrated hydrochloric acid in preparation process
Reaction is hydrolyzed in mixed system, can farthest reduce the generation of spent acid after reaction.Preparation method of the present invention can also obtain
More pure hydrogen chloride gas is obtained, can be used as the raw material of other chemical process.
The beneficial effects of the invention are as follows：By way of concentrated hydrochloric acid is added dropwise and is reacted with mix monomer, by standing separation, in
With the measures such as filtering, de- low refined and tail gas recycle, primary liquid silicones, refined liquid silicone resin and dense salt can be obtained
Sour three kinds of products.Primary and refined liquid silicone resin tool has been widely used and higher market value, gained concentration of hydrochloric acid are big
In 33%, use can return to.Gained, which refines liquid silicone resin, can also solve dimethicone in silicone sealant preparation process
The problem of, it substitutes dimethicone and is used as plasticizer.
Description of the drawings
Fig. 1 is present invention process flow chart
Specific embodiment
Illustrate below by way of specific description of embodiments of the present invention but do not limit the present invention.
As shown in Figure 1, the preparation method of liquid silicone resin of the present invention, the reaction kettle of use is with stirring and condensing reflux dress
It puts, includes the following steps：
A, raw material is prepared：Methyl trichlorosilane and dimethyl dichloro silicon 63 ︰ 7~27 in mass ratio mix to obtain mix monomer.
And the temperature of reaction kettle is reduced to less than 5 DEG C.Cooling can be used low-temperature circulating slot and carry out cooling processing to raw material.
B, dropwise reaction：Concentrated hydrochloric acid is added dropwise into reaction kettle, controls the temperature of reaction system no more than -10~5 DEG C.
Reaction to bubble-free generates after concentrated hydrochloric acid is added dropwise, and reaction system is carried out water-oil separating.
The concentration of concentrated hydrochloric acid is preferably 33~37%.The speed that concentrated hydrochloric acid is added dropwise can be suitably according to the velocity of discharge of tail gas
It is adjusted, the time that concentrated hydrochloric acid is preferably added dropwise is 2~3 hours.It is preferred that freezing is passed through to changing in condensing unit when hydrochloric acid is added dropwise
Ethylene glycol exchange heat, while control the condensation temperature of condensate recycling device below -10 DEG C.With the progress of reaction, greatly
The volatilization of amount hydrogen chloride can cause temperature of reaction system to reduce, and take part chlorosilane monomer out of, and condensing unit, which may be such that, to be taken out of
Chlorosilane monomer be condensed and return in reaction kettle until the reaction was complete.The reaction was continued 0.5~1 hour after having fed.It is quiet
It postpones and grease is detached using liquid distributing device, take oil reservoir.The reaction being substantially carried out in this step is：
C, oil reservoir neutralizes：Into the separating obtained oil reservoirs of step b, solid alkaline matter is added in while stirring and is neutralized to oil reservoir
For neutrality；
Liquid obtained by the reaction has very strong acidity in step b, is a kind of very unstable product.If it removes not in time
Go acid that can be crosslinked quickly.The alkaline matter that deacidification uses is one or more of sodium carbonate, sodium hydroxide, sodium bicarbonate,
Big stirring is preferably opened as far as possible in N-process, to accelerate to neutralize speed.
D, oil reservoir is filtered：The neutral oil reservoir obtained in step c is filtered, gained filtrate is primary liquid silicones.
The oil reservoir obtained in step c is to be mixed with a large amount of salt, the oily mater that appearance is creamy white, and is needed salinity mistake
Product can be just obtained after filter.Filtering can take natural filtration, can also use press filtration or suction filtration.Obtained filtrate is in oily
Liquid, as primary liquid silicones.
It is de- low refined：Primary liquid silicones in step d is carried out de- low refined.Specifically, rotary evaporation can be used
Instrument is handled, and takes off 120~160 DEG C of low temperature, and pressure is -0.06~-0.09MPa；Discharging obtains product.
Containing many lower-molecular substances in the primary liquid silicones obtained in step d, these substances are in later stage profit
The intensity of silicone rubber products will be reduced in, so it is low that progress high temperature is needed to take off.It is de- it is low autoclave can be selected to take off low, rotation is de-
Low, film takes off low mode.Inventor is de- low using rotation according to existence conditions, de- low condition be de- low temperature 120~
160 DEG C, pressure be -0.06~-0.09MPa, 2~4 hours time.Preferably de- low condition is to take off 140 DEG C of low temperature, pressure
For -0.085MPa, 4 hours time.
Tail gas recycle：The tail gas that generation is reacted in step b is passed through monomer absorption device, chlorination hydrogen recovery unit successively.
The gas that discharge is reacted in step b is mainly dimethyldichlorosilane, methyl trichlorosilane, hydrogen chloride.It is specific real
Shi Shi, device for absorbing tail gas contain two covering devices, respectively：A set of monomer absorption device and a set of chlorination hydrogen recovery unit.Wherein
Monomer absorption device is entrained with the monomer come for absorbing hydrogen chloride gas.
The specific embodiment of the present invention is described further below by embodiment, but therefore will be not of the invention
Protection domain limitation in one embodiment.
Embodiment one
The mass ratio of dimethyldichlorosilane and methyl trichlorosilane is 9 ︰ 1；0 DEG C of hydrolysis temperature；Neutralized using sodium carbonate,
De- 140 DEG C of low temperature, pressure -0.06MPa.
The mix monomer raw material of 500 volumes is added in a kettle, is cooled to 0 DEG C, and the dense of 200 volumes is added dropwise while stirring
Hydrochloric acid.It is added dropwise after 2 hours, bubble-free generates after standing 0.5 hour, and layering is released the hydrochloric acid of reactor bottom, separated
Concentration of hydrochloric acid is 35%.Sodium carbonate solid is added in into oil reservoir and is neutralized to neutrality, filtrate is filtered to take and carries out rotary distillation 3 hours,
De- 140 DEG C of the low temperature of control, pressure -0.06MPa obtain product.Viscosity is 86mm2/ s, 3 hours at 1.39,150 DEG C of index of refraction
Fugitive constituent is 1.3%.
It will be tested by de- low product for silicone sealant, obtained product tensile strength reaches 1.4MPa, fracture
Elongation reaches 650%.
Embodiment two
The mass ratio of dimethyldichlorosilane and methyl trichlorosilane is 4 ︰ 1；- 5 DEG C of hydrolysis temperature；Using in sodium bicarbonate
With de- 130 DEG C of low temperature, pressure -0.09MPa.
The mix monomer raw material of 500 volumes is added in a kettle, is cooled to -5 DEG C, while stirring from 200 volumes are added dropwise
Concentrated hydrochloric acid.It being added dropwise after 2 hours, bubble-free generates after standing 0.5 hour, layering, releases the hydrochloric acid of reactor bottom, point
The concentration of hydrochloric acid gone out is 33%.Sodium bicarbonate solid is added in into oil reservoir and is neutralized to neutrality, filtrate is filtered to take and carries out rotary distillation 3
Hour, de- 130 DEG C of low temperature, pressure -0.09MPa is controlled to obtain product.Viscosity is 115mm2/ s, at 1.41,150 DEG C of index of refraction
3 hours fugitive constituents are 1.9%.
It will be tested by de- low product for silicone sealant, obtained product tensile strength reaches 1.6MPa, fracture
Elongation reaches 620%.
Claims (15)
1. the preparation method of liquid silicone resin carries out, feature in the reaction kettle with agitating device and condensation reflux unit
It is to include the following steps：
A, raw material is prepared：Mixed methyl trichlorosilane and dimethyldichlorosilane control the temperature of reaction kettle to be less than 5 DEG C；
B, dropwise reaction：Concentrated hydrochloric acid is added dropwise into reaction kettle, the temperature for controlling reaction system is -10~5 DEG C；Concentrated hydrochloric acid is added dropwise
After reaction to bubble-free generate, reaction system is subjected to water-oil separating；
C, oil reservoir neutralizes：Into the separating obtained oil reservoirs of step b, solid alkaline matter is added in while stirring and is neutralized to during oil reservoir is
Property；
D, oil reservoir is filtered：Filtration step c obtains neutral oil reservoir, and gained filtrate is primary liquid silicones.
2. the preparation method of liquid silicone resin according to claim 1, it is characterised in that：Primary liquid silicon obtained by step d
Resin is through de- low refined up to refined liquid silicone resin.
3. the preparation method of liquid silicone resin according to claim 2, it is characterised in that：It is described de- low to refine as by step
The primary liquid silicones that d is obtained carries out de- low refined, and it is 120 ~ 160 DEG C to take off low temperature, and pressure is -0.06 ~ -0.09MPa, is taken off
The low time is 2 ~ 4 hours, is discharged up to refined liquid silicone resin.
4. according to the preparation method of claim 1-3 any one of them liquid silicone resins, it is characterised in that：Diformazan in step a
The mass ratio of base dichlorosilane and methyl trichlorosilane is 63 ︰ 7~27.
5. according to the preparation method of claim 1-3 any one of them liquid silicone resins, it is characterised in that：Methyl trichlorosilane
It is 1.8-2.3 with the mixture of dimethyldichlorosilane and the weight ratio of concentrated hydrochloric acid.
6. the preparation method of liquid silicone resin according to claim 5, it is characterised in that：Methyl trichlorosilane and dimethyl
The mixture of dichlorosilane and the weight ratio of concentrated hydrochloric acid are 2.
7. according to the preparation method of claim 1-3 any one of them liquid silicone resins, it is characterised in that：It is added dropwise in step b
The speed of concentrated hydrochloric acid is 0.8 ~ 1.5kg/h.
8. the preparation method of liquid silicone resin according to claim 7, it is characterised in that：Concentrated hydrochloric acid is added dropwise in step b
Speed is 1.1kg/h.
9. according to the preparation method of claim 1-3 any one of them liquid silicone resins, it is characterised in that：It is added dropwise in step b
It is passed through refrigerant during concentrated hydrochloric acid and exchanges heat to changing in condensing unit.
10. the preparation method of liquid silicone resin according to claim 9, it is characterised in that：The refrigerant is ethylene glycol.
11. according to the preparation method of claim 1-3 any one of them liquid silicone resins, it is characterised in that：Described in step b
The temperature of control reaction system is using the condensation temperature of condensate recycling device is controlled to be controlled less than -10 DEG C.
12. according to the preparation method of claim 1-3 any one of them liquid silicone resins, it is characterised in that：Described in step c
Alkaline matter is one or more of sodium carbonate, sodium hydroxide, sodium bicarbonate.
13. claim 1-12 any one of them preparation method prepares gained liquid silicone resin.
14. application of the liquid silicone resin described in claim 13 as plasticizer.
15. application of the liquid silicone resin described in claim 13 as the plasticizer for preparing silicone sealant.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105906810B (en) | 2016-04-26 | 2019-08-06 | 广东标美硅氟新材料有限公司 | A kind of preparation method of organopolysiloxane resins |
| CN106629604B (en) * | 2016-11-28 | 2019-07-16 | 昆明理工大学 | A method of gas phase chlorination hydrogen is produced using chlorosilane raffinate |
| CN111868142B (en) * | 2018-12-28 | 2022-08-16 | 浙江三时纪新材科技有限公司 | Preparation method of spherical silicon resin powder or connected body thereof and spherical silicon resin powder or connected body thereof obtained by preparation method |
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| CN102220011A (en) * | 2011-05-30 | 2011-10-19 | 黄山市强路新材料有限公司 | Addition type flame retardant liquid silicon resin and preparation method thereof |
| CN103204993A (en) * | 2013-04-16 | 2013-07-17 | 江苏大学 | Preparation method of methyl silicone resin |
| CN103484056A (en) * | 2013-09-09 | 2014-01-01 | 广州市高士实业有限公司 | Dealcoholized silicone sealant and preparation method thereof |
| CN103881100A (en) * | 2014-02-20 | 2014-06-25 | 常州市嘉诺有机硅有限公司 | Toughened organic silicone high-temperature adhesive resin and preparation process thereof |
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| CN101875726A (en) * | 2009-04-30 | 2010-11-03 | 中国石油天然气股份有限公司 | Method for preparing polysiloxane by hydrolyzing dimethyl dichlorosilane |
| CN102220011A (en) * | 2011-05-30 | 2011-10-19 | 黄山市强路新材料有限公司 | Addition type flame retardant liquid silicon resin and preparation method thereof |
| CN103204993A (en) * | 2013-04-16 | 2013-07-17 | 江苏大学 | Preparation method of methyl silicone resin |
| CN103484056A (en) * | 2013-09-09 | 2014-01-01 | 广州市高士实业有限公司 | Dealcoholized silicone sealant and preparation method thereof |
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