CN110256677A - Epoxy-modified trifluoro propyl silicone oil and preparation method thereof - Google Patents
Epoxy-modified trifluoro propyl silicone oil and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of epoxy-modified trifluoro propyl silicone oil and preparation method thereof.The epoxy-modified trifluoro propyl silicone oil has the structure feature as shown in following formula (I): where a:b:c:d=1:0.5-2:0.1-1:0-0.1；R1、R2For silicone oil end-capping group.The epoxy-modified trifluoro propyl silicone oil, trifluoro propyl and epoxy group compatibility are rationally and segment distribution is uniform, have good reactivity, are able to ascend the protective performance of protective coating.
Description
Technical field
The present invention relates to technical field of polymer materials, more particularly to a kind of epoxy-modified trifluoro propyl silicone oil and its system
Preparation Method.
Background technique
The Performance And Reliability and environment of electronics have close relationship, such as chemistry, vibration, Gao Chen, salt fog, humidity
Wiring board circuit is caused event occur the problems such as may softening to wiring board generation burn into, deform, go mouldy with environment such as high temperature
Barrier.The moisture proof of product, salt spray proof, mould proof technology are often known as " three proofings " technology by electronics industry, specially apply three-proofing coating
It is overlying on PCB surface, forms one layer of three proofings protective film.Containing chemical substance (such as: fuel, coolant etc.), vibration,
Moisture, salt spray, the moist wiring board with three-proofing coating unused under high-temperature condition there may be burn into fungus growth and generate short circuit
The problems such as, cause circuit to break down, damage can be protected the circuit from using three-proofing coating, so that the reliability of wiring board is improved,
Increase its safety coefficient and guarantees its service life.
Common three-proofing coating is acrylic acid three-proofing coating, polyurethane three-proofing coating, epoxy three-proofing coating and organosilicon currently on the market
Three-proofing coating etc..Acrylic acid, polyurethane, epoxy three-proofing coating quality are more crisp, compare under, organosilicon three-proofing coating has soft bullet
Property, it can release stress well, while high temperature resistance is good, but price is costly.Therefore, organosilicon-modified acrylic is commonly used
Resin, polyurethane resin or epoxy resin are used as three-proofing coating, but they have the shortcomings that it is common: salt spray proof, anti-chemical corruption
Corrosion can be not good enough.
Fluorine containing silicone oil refers to key containing F-C in polymer, Si-O-Si key and Si-C key, and is free of Si-F key and fluorinated carbon
Group is not directly coupled on silicon atom, and centre must have a quasi polymer of " hydrocarbon abutment " or spacer group.Fluorinated polysiloxane
Backbone structure is submissive organosilicon chain, side chain is property is stable and surface tension is extremely low organic fluorine chain, wherein exploitation earliest,
Most widely used is the trifluoro propyl silicone oil of the side chain containing trifluoro propyl.Trifluoro propyl silicone oil is mainly used as fabric, leather, paper
The disadvantages of chemical corrosion resistance of finishing agent, the lower temperature resistance difference and organosilicon material that overcome organic fluorine material is poor has resistance to
The excellent properties such as high/low temperature, resistant to chemical etching, oil resistant solvent resistant, low surface tension and low-k, and just because of trifluoro
These excellent performances of propyl silicone oil make it have excellent three proofings effect, especially salt spray proof, anti-chemical corrosive nature excellent
It is different.
Epoxy-modified trifluoro propyl silicone oil, due to the presence of the three-membered ring of the high deformability of epoxy group and the pole of charge
Change effect makes it have the high feature of easy open loop, reactivity, can be with-OH ,-NH2, the groups reaction such as-COOH, therefore by its
The additive that can be used as three-proofing coating uses, and the flexibility of three-proofing coating not only can be improved, and greatly promotes its moisture proof, dust-proof, anti-
Mould, salt spray proof, anti-chemical corrosive nature, can also enhance the adhesive property between three-proofing coating and appliance component, substrate, mention
The reliability of elevated track plate increases its safety coefficient, and guarantees its service life.In addition, epoxy-modified trifluoro propyl silicone oil
It can be adapted for the use of the fields such as electronics coating glue.
But the epoxy-modified trifluoro propyl silicone oil reactivity being prepared at present is not satisfactory, and as three-proofing coating is wanted
It asks with preferable levelability, it is therefore desirable to lower system viscosity, and the epoxy-modified trifluoropropyl that can be prepared at present
Base silicon oil viscosity range is relatively narrow, and whether low viscosity or highly viscous product are difficult to obtain, and limits epoxy-modified trifluoropropyl
The application of base silicone oil.
Summary of the invention
Based on this, it is necessary to a kind of epoxy-modified trifluoro propyl silicone oil is provided, trifluoro propyl and epoxy group compatibility rationally and
Segment distribution is uniform, has good reactivity, is able to ascend the protective performance of protective coating.
A kind of epoxy-modified trifluoro propyl silicone oil has the structure feature as shown in following formula (I):
Wherein, a:b:c:d=1:0.5-2:0.1-1:0-0.1；
R1、R2For silicone oil end-capping group.
The present invention also provides a kind of preparation methods of epoxy-modified trifluoro propyl silicone oil, include the following steps:
By dimethicone, trifluoro propyl cyclotrisiloxane, hydrogen-containing siloxane and vinylcyclosiloxanes according to silicon
The molar ratio of atom is that 1:0.5-2:0.1-1:0-0.1 is mixed, and end-capping reagent is then added, carries out ring-opening polymerization, obtains
Hydrogeneous fluorosilicon oil；
The hydrogeneous fluorosilicon oil is mixed with allyl alkyl ether according to molar ratio 1:1.2-1.6, it is anti-to carry out Si―H addition reaction
It answers.
The present invention also provides a kind of protective coating, raw material composition includes the epoxy-modified trifluoro propyl silicone oil, or, institute
The epoxy-modified trifluoro propyl silicone oil that the preparation method stated is prepared.
Compared with prior art, the invention has the following beneficial effects:
In the structure of epoxy-modified trifluoro propyl silicone oil of the invention, trifluoro propyl and epoxy group compatibility are rationally and chain link
It is evenly distributed, there is good reactivity.The epoxy-modified trifluoro propyl silicone oil is applied to protective coating (such as three-proofing coating),
Salt spray proof, anti-chemical corrosive nature and the flexibility that protective coating can effectively be promoted have protective coating preferably anti-
Moist, dust-proof, mould proof, salt spray proof and anti-chemical corrosive nature.
Specific embodiment
Epoxy-modified trifluoro propyl silicone oil of the invention and preparation method thereof is made below in conjunction with specific embodiment further
Detailed description.
The embodiment of the present invention provides a kind of epoxy-modified trifluoro propyl silicone oil, has the structure as shown in following formula (I) special
Sign:
Wherein, a:b:c:d=1:0.5-2:0.1-1:0-0.1；
R1、R2For silicone oil end-capping group.
In the structure of epoxy-modified trifluoro propyl silicone oil of the invention, trifluoro propyl and epoxy group compatibility are rationally and chain link
It is evenly distributed, there is good reactivity, be able to ascend the protective performance of protective coating.Wherein, a, b, c and d are rationally controlled
Between ratio, that is, adjust structure epoxy group and trifluoro propyl content and proportion, keep epoxy group " neutralization " appropriate
Trifluoro propyl it is highly polar, be able to ascend the compatibility of protective coating and substrate, enhance protective coating and appliance component, substrate
Between adhesive property, improve the reliability, safety coefficient and service life of wiring board.
In addition, the viscosity of the epoxy-modified trifluoro propyl silicone oil can tied by increasing or decreasing a, b, c and d respective link
Total content in structure is adjusted.In a specific embodiment, the viscosity of the epoxy-modified trifluoro propyl silicone oil can be in 50-
Adjustment in 50000cs (25 DEG C) range.
In a wherein specific embodiment, a:b:c:d=1:0.5-1:0.2-1:0-0.1.
In a wherein specific embodiment, a:b:c:d=1:0.5-0.7:0.8-1:0.02-0.08.
In a wherein specific embodiment, R1、R2It is independently selected from following silicone oil end-capping group:
The preparation method of above-mentioned epoxy-modified trifluoro propyl silicone oil, includes the following steps:
By dimethicone, trifluoro propyl cyclotrisiloxane, hydrogen-containing siloxane and vinylcyclosiloxanes according to silicon
The molar ratio of atom is that 1:0.5-2:0.1-1:0-0.1 is mixed, and end-capping reagent is then added, carries out ring-opening polymerization, obtains
Hydrogeneous fluorosilicon oil；
The hydrogeneous fluorosilicon oil is mixed with allyl alkyl ether according to molar ratio 1:1.2-1.6, it is anti-to carry out Si―H addition reaction
It answers.
The present invention has found that existing epoxy-modified trifluoro propyl silicone oil reactivity is not satisfactory in the course of the research, into
And it is limited to the promotion of protective coating performance, and the relatively narrow reason of range of viscosities essentially consists in: traditional epoxy-modified trifluoro
Propyl silicone oil preparation method causes.
Specifically, traditional epoxy-modified trifluoro propyl silicone oil is such as to use eight first using the method for equilibrium polymerization reaction
Basic ring tetrasiloxane, 3- [the third oxygen of (2,3)-epoxy] hydroxypropyl methyl dimethoxysilane, trifluoro propyl methyl cyclotrisiloxane exist
It is balanced reaction under basic catalyst effect, prepares epoxy-modified trifluoro propyl silicone oil, this method is difficult to prepare high trifluoropropyl
The epoxy-modified trifluoro propyl silicone oil of the content of base and epoxy group.In the reaction process, such as increase trifluoro propyl and epoxy group
Content cause balanced reaction conversion ratio low since trifluoro propyl and epoxy group steric hindrance are larger, yield is small, and chain element point
Cloth is easy uneven.Simultaneously as have epoxy silane hydrolytic condensation step, therefore this method is difficult to prepare the product of low viscosity,
And due to trifluoro propyl and the strong steric effect of epoxy group, also makes this method be difficult to prepare the high product of viscosity, lead to epoxy
The range of viscosities of modified trifluoro propyl silicone oil is narrow.
Based on this study found that preparation method of the invention: the first step uses fluorine-containing cyclosiloxane, dimethicone
The hydrogeneous fluorosilicon oil of side chain is prepared with the direct ring-opening polymerisation of hydrogeneous cyclosiloxane；Second step passes through the hydrogeneous fluorine of side chain being prepared
Silicone oil and the direct addition of allyl polyoxy alkyl glycidyl ether obtain epoxy-modified trifluoro propyl silicone oil.The preparation method can
The steric effect between trifluoro propyl and epoxy group is avoided well, and needs not move through epoxy silane hydrolytic condensation step, thus
It can make in the structure for the epoxy-modified trifluoro propyl silicone oil being prepared the content of trifluoro propyl and epoxy group is adjustable (can be high and can
It is low), and segment distribution is more evenly.Meanwhile the preparation method also has the advantages of high conversion rate, high income, controllability is strong, can
The broader product of range of viscosities is prepared, while fluorine content, epoxy content and end-capping reagent type are adjustable, can meet difference
Application demand, greatly expand the application range of epoxy-modified trifluoro propyl silicone oil.
Again on the basis of this, together with dimethicone, appropriate vinylcyclosiloxanes can be also added less, in polymer
A small amount of vinyl groups is introduced on side chain, to improve the reactivity of epoxy-modified trifluoro propyl silicone oil, its application of further expansion
Range.It is to be appreciated that vinylcyclosiloxanes can not also be added.
In addition, the entire technical process of the preparation method is simple and efficient, reaction condition is mild, is easy to control, convenient for operating,
Suitable for industrialized production.
In a wherein specific embodiment, by dimethicone, trifluoro propyl cyclotrisiloxane, Silicon Containing Hydrogen oxygen
Alkane and vinylcyclosiloxanes are mixed according to the molar ratio of silicon atom for 1:0.5-1:0.2-1:0-0.1.
In a wherein specific embodiment, by dimethicone, trifluoro propyl cyclotrisiloxane, Silicon Containing Hydrogen oxygen
Alkane and vinylcyclosiloxanes are mixed according to the molar ratio of silicon atom for 1:0.5-0.7:0.8-1:0.02-0.08.
In a wherein specific embodiment, the end-capping reagent is hexamethyldisiloxane (MM) and 1,1,3,3- tetramethyl
At least one of base disiloxane.
In a wherein specific embodiment, the dimethicone is hexamethyl cyclotrisiloxane (D3), eight
Methyl cyclotetrasiloxane (D4), decamethylcyclopentaandoxane (D5), ten diformazan basic rings, six siloxanes (D6) and dimethyl siloxane
At least one of mixed methylcyclosiloxane (DMC).
In a wherein specific embodiment, the allyl alkyl ether is allyl glycidyl ether, allyl is poly-
At least one of ethylene oxide epoxy group ether and allyl polyoxypropylene epoxy group ether.
In a wherein specific embodiment, the vinylcyclosiloxanes are selected from four silicon oxygen of tetramethyl tetravinyl ring
At least one of alkane and trimethyl trivinyl cyclotrisiloxane.
In a wherein specific embodiment, the hydrogen-containing siloxane is selected from tetramethyl tetrahydro cyclotetrasiloxane (D4H)
At least one of with 202 containing hydrogen silicone oils.
Between above-mentioned end-capping reagent, dimethicone, hydrogen-containing siloxane, vinylcyclosiloxanes and allyl alkyl ether
The epoxy-modified trifluoro propyl silicone oil can be prepared in welcome selection compatibility by above-mentioned preparation method.
In a wherein specific embodiment, the ring-opening polymerization is catalyzed using acidic catalyst, described
Acidic catalyst is at least one of storng-acid cation exchange resin, Emathlite and trifluoromethanesulfonic acid；And/or it is described
Hydrosilylation is catalyzed using platinum catalyst.More specifically, the dosage of the acidic catalyst is this step reaction
The 0.5~10% of raw material gross weight；The dosage of the platinum catalyst is the 2-15ppm of this step reaction raw material gross weight.
In a wherein specific embodiment, the reaction condition of the ring-opening polymerization are as follows: reaction temperature 40-80
DEG C, reaction time 1-4h.
In a wherein specific embodiment, the reaction condition of the hydrosilylation are as follows: reaction temperature 80-120
DEG C, reaction time 60-90min.
In a wherein specific embodiment, before carrying out the hydrosilylation, first to the hydrogeneous fluorosilicon oil with
Allyl alkyl ether is dehydrated.More specifically, the method for the dehydration are as follows: be dehydrated under the conditions of vacuum degree -0.08MPa
1h。
It the following is specific embodiment, each raw material used in the examples is commercial product.
Embodiment 1:
The present embodiment is a kind of preparation method of epoxy-modified trifluoro propyl silicone oil, and steps are as follows:
1) preparation of hydrogeneous fluorosilicon oil: by dimethicone, trifluoro propyl cyclotrisiloxane (D3F), tetramethyl four
Hydrogen cyclotetrasiloxane (D4H it) is added in reactor by silicon atom molar ratio 1:1:0.2, then by the end-capping reagent (pregnancy of 5 parts by weight
Base disiloxane) it is added in reactor, 3h is reacted at 70 DEG C under cation exchange resin effect, filters out catalyst, in
Low 3h is taken off at 120 DEG C, is deviate from low molecule, is obtained hydrogeneous fluorosilicon oil.Conversion ratio 81.0%.
2) hydrogeneous fluorosilicon oil and allyl glycidyl ether epoxy-modified trifluoro propyl silicone oil preparation: are pressed to the ratio of 1:1.3
Example is added in reactor, is opened vacuum to -0.08MPa and is dehydrated 1h, is warming up to 90 DEG C after eliminating vacuum with nitrogen, is then added
5ppm platinum catalyst reacts 90min, is evaporated under reduced pressure out excessive allyl alkyl ether and obtains epoxy-modified trifluoro propyl silicone oil,
Excessive allyl alkyl ether is collected after distilling out and is reused as reaction raw materials.
As a result: yield 99.2%, in product structure, a:b:c=1:1:0.2, end-capping group isViscosity
253cs。
Embodiment 2:
The present embodiment is a kind of preparation method of epoxy-modified trifluoro propyl silicone oil, and steps are as follows:
1) preparation of hydrogeneous fluorosilicon oil: by dimethicone, trifluoro propyl cyclotrisiloxane (D3F), tetramethyl four
Hydrogen cyclotetrasiloxane (D4H), reaction is added by silicon atom molar ratio 1:0.5:1:0.05 in trimethyl trivinyl cyclotrisiloxane
In device, then the end-capping reagent of 1 parts by weight (1,1,3,3- tetramethyl disiloxane) is added in reactor, in cation exchange tree
4h is reacted at 60 DEG C under rouge effect, filters out catalyst, low 3h is taken off at 120 DEG C, deviates from low molecule, obtains hydrogeneous fluorine silicon
Oil.Conversion ratio 83.2%.
2) hydrogeneous fluorosilicon oil and allyl glycidyl ether epoxy-modified trifluoro propyl silicone oil preparation: are pressed to the ratio of 1:1.2
Example be added in reactor, open vacuum to -0.08MPa be dehydrated 1h, with nitrogen eliminate vacuum after be warming up to 120 DEG C, then plus
Enter 2ppm platinum catalyst reaction 80min, is evaporated under reduced pressure out excessive allyl alkyl ether and obtains epoxy-modified trifluoro propyl silicon
Oil, excessive allyl alkyl ether are collected after distilling out and are reused as reaction raw materials.
As a result: yield 99.0%, in product structure, a:b:c:d=1:0.5:1:0.05, end-capping group isProduct viscosity 10536cs.
Embodiment 3:
The present embodiment is a kind of preparation method of epoxy-modified trifluoro propyl silicone oil, and steps are as follows:
1) preparation of hydrogeneous fluorosilicon oil: by dimethicone, trifluoro propyl cyclotrisiloxane (D3F), 202 is high hydrogeneous
Silicone oil is added in reactor by silicon atom molar ratio 1:0.7:0.3, then by the end-capping reagent of 0.5 parts by weight (two silicon oxygen of hexamethyl
Alkane) it is added in reactor, 4h is reacted at 70 DEG C under cation exchange resin effect, filters out catalyst, is taken off at 120 DEG C
Low 3h deviates from low molecule, obtains hydrogeneous fluorosilicon oil.Conversion ratio 84.1%.
2) hydrogeneous fluorosilicon oil and allyl glycidyl ether epoxy-modified trifluoro propyl silicone oil preparation: are pressed to the ratio of 1:1.2
Example is added in reactor, is opened vacuum to -0.08MPa and is dehydrated 1h, is warming up to 80 after eliminating vacuum with nitrogen, is then added
15ppm platinum catalyst reacts 60min, is evaporated under reduced pressure out excessive allyl alkyl ether and obtains epoxy-modified trifluoro propyl silicon
Oil, excessive allyl alkyl ether are collected after distilling out and are used as reaction raw materials.
As a result: yield 99.5%, in product structure, a:b:c=1:0.7:0.3, end-capping group isIt produces
Product viscosity 19725cs.
Epoxy-modified trifluoro propyl silicone oil (in table referred to as " embodiment 1-3 ") progressive that embodiment 1-3 is prepared
It can test, and be compared with traditional epoxy-modified trifluoro propyl silicone oil (in table referred to as " tradition "), as a result as shown in the table:
Wherein, the structural formula of traditional epoxy-modified trifluoro propyl silicone oil is as follows:
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of epoxy-modified trifluoro propyl silicone oil, which is characterized in that have the structure feature as shown in following formula (I):
Wherein, a:b:c:d=1:0.5-2:0.1-1:0-0.1；
R1、R2For silicone oil end-capping group.
2. epoxy-modified trifluoro propyl silicone oil according to claim 1, which is characterized in that a:b:c:d=1:0.5-1:
0.2-1:0-0.1.
3. epoxy-modified trifluoro propyl silicone oil according to claim 1 or 2, which is characterized in that R1、R2Choosing independently
From following silicone oil end-capping group:
4. a kind of preparation method of epoxy-modified trifluoro propyl silicone oil, which comprises the steps of:
By dimethicone, trifluoro propyl cyclotrisiloxane, hydrogen-containing siloxane and vinylcyclosiloxanes according to silicon atom
Molar ratio be that 1:0.5-2:0.1-1:0-0.1 is mixed, be then added end-capping reagent, carry out ring-opening polymerization, obtain hydrogeneous
Fluorosilicon oil；
The hydrogeneous fluorosilicon oil is mixed with allyl alkyl ether according to molar ratio 1:1.2-1.6, hydrosilylation is carried out.
5. the preparation method of epoxy-modified trifluoro propyl silicone oil according to claim 4, which is characterized in that by diformazan basic ring
Siloxanes, trifluoro propyl cyclotrisiloxane, hydrogen-containing siloxane and vinylcyclosiloxanes are 1 according to the molar ratio of silicon atom:
0.5-1:0.2-1:0-0.1 is mixed.
6. the preparation method of epoxy-modified trifluoro propyl silicone oil according to claim 4, which is characterized in that the end-capping reagent
For hexamethyldisiloxane and 1, at least one of 1,3,3- tetramethyl disiloxane.
7. according to the preparation method of the described in any item epoxy-modified trifluoro propyl silicone oil of claim 4-6, which is characterized in that institute
Stating dimethicone is hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, decamethylcyclopentaandoxane, ten dimethyl
At least one of six siloxanes of ring and dimethyl siloxane mixed methylcyclosiloxane.
8. according to the preparation method of the described in any item epoxy-modified trifluoro propyl silicone oil of claim 4-6, which is characterized in that institute
Stating allyl alkyl ether is allyl glycidyl ether, allyl polyethenoxy epoxy group ether and allyl polyoxypropylene epoxy group
At least one of ether.
9. according to the preparation method of the described in any item epoxy-modified trifluoro propyl silicone oil of claim 4-6, which is characterized in that institute
It states ring-opening polymerization to be catalyzed using acidic catalyst, the acidic catalyst is storng-acid cation exchange resin, acid
Property at least one of carclazyte and trifluoromethanesulfonic acid；And/or
The hydrosilylation is catalyzed using platinum catalyst.
10. a kind of protective coating, which is characterized in that raw material composition includes claim 1-3 described in any item epoxy-modified three
Fluoropropyl silicone oil, or, the epoxy-modified trifluoro propyl silicone oil that the described in any item preparation methods of claim 4-9 are prepared.
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| CN201910635350.8A CN110256677B (en) | 2019-07-15 | 2019-07-15 | Epoxy modified trifluoropropyl silicone oil and preparation method thereof |
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| CN201910635350.8A CN110256677B (en) | 2019-07-15 | 2019-07-15 | Epoxy modified trifluoropropyl silicone oil and preparation method thereof |
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