CN104830240B - A kind of UV low-temperature settings silicone resin adhesive, its preparation method and application - Google Patents
A kind of UV low-temperature settings silicone resin adhesive, its preparation method and application Download PDFInfo
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- CN104830240B CN104830240B CN201510230347.XA CN201510230347A CN104830240B CN 104830240 B CN104830240 B CN 104830240B CN 201510230347 A CN201510230347 A CN 201510230347A CN 104830240 B CN104830240 B CN 104830240B
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Abstract
A kind of UV low-temperature settings silicone resin adhesive, its preparation method and application, it is related to a kind of UV low-temperature settings silicone resin adhesive, its preparation method and application.Heat resistance the present invention is to solve existing silicones is insufficient for the problem of current industrial requirement.A kind of UV low-temperature settings silicone resin adhesive of the present invention includes methacryloxypropyl trimethoxy silane, carborane and tetramethylethylenediamine；Preparation method：First, hydrolyze；2nd, polycondensation；3rd, solidify.The present invention is for preparing UV low-temperature settings silicone resin adhesive and being used for the high strength structure bonding in the sophisticated technology fields such as Aero-Space, advanced composite material (ACM) after its film-forming.
Description
Technical field
The present invention relates to a kind of UV low-temperature settings silicone resin adhesive, its preparation method and application.
Background technology
Carborane has good chemical stability, heat endurance, and has the good transparency in ultraviolet region.Be polymerized
Thing carries out combined polymerization and can be obviously improved the correlated performance of polymer, of great interest at present.Organic adhesive can
To use at high temperature, thus it is widely used in modern aerospace industry.Silicone resin adhesive based on polysiloxanes is gathered around
There are extremely outstanding heat endurance, electrical insulating property and chemical stability, thus be used as the heat-insulated of optics such as LED
Gelling agent.But, the adhesive property of existing silicones is universal low compared with carbon backbone chain high polymer, and its heat resistance is also not enough to completely
The current industrial requirement of foot.
The content of the invention
Heat resistance the present invention is to solve existing silicones is insufficient for the problem of current industrial requirement, and
There is provided a kind of UV low-temperature settings silicone resin adhesive, its preparation method and application.
A kind of UV low-temperature settings silicone resin adhesive of the present invention includes methacryloxypropyl trimethoxy silane, goes
Ionized water, carborane, silica and tetramethylethylenediamine；The methacryloxypropyl trimethoxy silane with go from
The mass ratio of sub- water is 1:(0.2~0.3)；The mass ratio of the methacryloxypropyl trimethoxy silane and carborane
It is 1:(0.05~0.2)；The mass ratio 1 of the methacryloxypropyl trimethoxy silane and silica:(0.01~
0.05)；The methacryloxypropyl trimethoxy silane is 1 with the mass ratio of tetramethylethylenediamine:(0.025~
0.1)。
A kind of preparation method of above-mentioned UV low-temperature settings silicone resin adhesive is to carry out according to the following steps：
First, hydrolyze：Methacryloxypropyl trimethoxy silane is added in there-necked flask, is added in there-necked flask
Deionized water, carries out magnetic agitation, then using watery hydrochloric acid by the pH of reaction system under conditions of being 30 DEG C~40 DEG C in temperature
Adjust to 2~5, continue to stir 30min~50min, obtain hydrolysate；The methacryloxypropyl trimethoxy silicon
Alkane is 1 with the mass ratio of deionized water:(0.2~0.3)；
2nd, polycondensation：To carborane and silica is added in hydrolysate, then temperature is warming up to from 30 DEG C~40 DEG C
55 DEG C~60 DEG C, continue to react 3h~5h, obtain transparency liquid, vacuum distillation then is carried out to transparency liquid, obtain transparent glutinous
Property product；Methacryloxypropyl trimethoxy silane described in step one is 1 with the mass ratio of carborane:(0.05~
0.2)；The mass ratio 1 of methacryloxypropyl trimethoxy silane described in step one and silica:(0.01~
0.05)；
3rd, solidify：Transparent stickiness product is dissolved in solvent, add tetramethylethylenediamine and ultrasound 10min~
20min, 5min~10min is rotated under conditions of being 60 DEG C~70 DEG C in temperature by Rotary Evaporators, obtains UV low-temperature settings
Silicone resin adhesive；The quality of the transparent stickiness product is 1g with the volume ratio of solvent:(2~3) mL；First described in step one
Base acryloxypropyl trimethoxy silane is 1 with the mass ratio of tetramethylethylenediamine:(0.025~0.1).
A kind of application of UV low-temperature settings silicone resin adhesive of the present invention is that UV low-temperature setting silicone resin adhesives is uniform
It is coated on clean culture dish, 30s~40s is irradiated by 800W~1000W ultra-violet curing devices UV, you can film-forming.
Beneficial effects of the present invention：
The present invention improves the heat resistance of silicones by adding carborane, and several boron atoms constitute triangle facial bone in carborane
Frame, and containing great amount of hydroxy group and silicone hydroxyl, thus have good reactivity with silane compound.By introducing boron atom
Constituting polyhedron skeleton can effectively improve the heat resistance of silicones.Silica contains abundant hydroxyl, also there is efficient reaction
Activity, while the silicon oxygen bond energy to failure in silica is high, can effectively lift the heat resistance of silicones.Methacryloxy third
The introducing of the carbon-carbon double bond in base trimethoxy silicon is obviously improved the ultra-violet curing ability of silicones.Obtained novel silicon tree
Fat gelling agent contains great amount of hydroxy group, thus its cementability also obtain and be obviously improved.
Brief description of the drawings
Fig. 1 is the TG-DSC curves of commercialization silicones cured film；
Fig. 2 is the TG-DSC curves of the UV low-temperature setting silicone resin adhesive cured films that embodiment one is obtained.
Specific embodiment
Specific embodiment one：A kind of UV low-temperature settings silicone resin adhesive of present embodiment includes methacryloxy
Propyl trimethoxy silicane, deionized water, carborane, silica and tetramethylethylenediamine；The methacryloxy third
Base trimethoxy silane is 1 with the mass ratio of deionized water:(0.2~0.3)；The methacryloxypropyl trimethoxy
Silane is 1 with the mass ratio of carborane:(0.05~0.2)；The methacryloxypropyl trimethoxy silane and dioxy
The mass ratio 1 of SiClx:(0.01~0.05)；The methacryloxypropyl trimethoxy silane and tetramethylethylenediamine
Mass ratio is 1:(0.025~0.1).
Present embodiment improves the heat resistance of silicones by adding carborane, and several boron atoms constitute triangle in carborane
Facial bone frame, and containing great amount of hydroxy group and silicone hydroxyl, thus have good reactivity with silane compound.By introducing boron
Atomic building polyhedron skeleton can effectively improve the heat resistance of silicones.Silica contains abundant hydroxyl, also there is efficient
Reactivity, while the silicon oxygen bond energy to failure in silica is high, can effectively lift the heat resistance of silicones.Methacryloxypropyl
The introducing of the carbon-carbon double bond in base propyl trimethoxy silicon is obviously improved the ultra-violet curing ability of silicones.Obtained is new
Silicones gelling agent contains great amount of hydroxy group, thus its cementability also obtain and be obviously improved.
Specific embodiment two：Present embodiment from unlike specific embodiment one：The methacryloxy
Propyl trimethoxy silicane is 1 with the mass ratio of deionized water:0.24.Other are identical with specific embodiment one.
Specific embodiment three：Present embodiment from unlike specific embodiment one or two：The methacryl
Epoxide propyl trimethoxy silicane is 1 with the mass ratio of carborane:0.1.Other are identical with specific embodiment one or two.
Specific embodiment four：Unlike one of present embodiment and specific embodiment one to three：The methyl-prop
Alkene acryloxypropylethoxysilane trimethoxy silane is 1 with the mass ratio of silica:0.02.Other and specific embodiment one to three it
One is identical.
Specific embodiment five：A kind of preparation method of UV low-temperature settings silicone resin adhesive of present embodiment is by following
Step is carried out：
First, hydrolyze：Methacryloxypropyl trimethoxy silane is added in there-necked flask, is added in there-necked flask
Deionized water, carries out magnetic agitation, then using watery hydrochloric acid by the pH of reaction system under conditions of being 30 DEG C~40 DEG C in temperature
Adjust to 2~5, continue to stir 30min~50min, obtain hydrolysate；The methacryloxypropyl trimethoxy silicon
Alkane is 1 with the mass ratio of deionized water:(0.2~0.3)；
2nd, polycondensation：To carborane and silica is added in hydrolysate, then temperature is warming up to from 30 DEG C~40 DEG C
55 DEG C~60 DEG C, continue to react 3h~5h, obtain transparency liquid, vacuum distillation then is carried out to transparency liquid, obtain transparent glutinous
Property product；Methacryloxypropyl trimethoxy silane described in step one is 1 with the mass ratio of carborane:(0.05~
0.2)；The mass ratio 1 of methacryloxypropyl trimethoxy silane described in step one and silica:(0.01~
0.05)；
3rd, solidify：Transparent stickiness product is dissolved in solvent, add tetramethylethylenediamine and ultrasound 10min~
20min, 5min~10min is rotated under conditions of being 60 DEG C~70 DEG C in temperature by Rotary Evaporators, obtains UV low-temperature settings
Silicone resin adhesive；The quality of the transparent stickiness product is 1g with the volume ratio of solvent:(2~3) mL；First described in step one
Base acryloxypropyl trimethoxy silane is 1 with the mass ratio of tetramethylethylenediamine:(0.025~0.1).
Specific embodiment six：Present embodiment from unlike specific embodiment five：Methyl-prop described in step one
Alkene acryloxypropylethoxysilane trimethoxy silane is 1 with the mass ratio of deionized water:0.24.Other are identical with specific embodiment five.
Specific embodiment seven：Present embodiment from unlike specific embodiment five or six：It is molten described in step 3
Agent is ethanol or acetone.Other are identical with specific embodiment five or six.
Specific embodiment eight：Unlike one of present embodiment and specific embodiment five to seven：Add in step 3
Enter tetramethylethylenediamine and ultrasound 15min.Other are identical with one of specific embodiment five to seven.
Specific embodiment nine：A kind of application of UV low-temperature settings silicone resin adhesive of present embodiment is by UV low-temperature solids
SiClx Resin adhesive is evenly applied on clean culture dish, by 800W~1000W ultra-violet curing devices UV irradiate 30s~
40s, you can film-forming.
Effect of the invention is verified by following examples：
Embodiment one：A kind of preparation method of UV low-temperature settings silicone resin adhesive is to carry out according to the following steps：
First, hydrolyze：10g methacryloxypropyl trimethoxy silanes are added in there-necked flask, in there-necked flask
3g deionized waters are added, magnetic agitation is carried out under conditions of being 30 DEG C in temperature, then using watery hydrochloric acid by the pH of reaction system
Adjust to 2, continue to stir 30min, obtain hydrolysate；
2nd, polycondensation：To 0.05g carboranes and 0.01g silica is added in 20g hydrolysates, then by temperature from 30
55 DEG C DEG C are warming up to, continue to react 4h, obtain transparency liquid, vacuum distillation then is carried out to transparency liquid, obtain transparent stickiness
Product；
3rd, solidify：The transparent stickiness products of 5g are dissolved in 10mL ethanol, 0.05g tetramethylethylenediamines and ultrasound is added
10min, removal ethanol is rotated under conditions of being 60 DEG C in temperature by Rotary Evaporators, obtains UV low-temperature setting silicones gluings
Agent.
The UV low-temperature setting silicone resin adhesives that embodiment one is obtained are evenly applied on clean culture dish, are passed through
1000W ultra-violet curing devices UV irradiates 30s, you can film-forming.Differential thermal-thermogravimetric analysis is carried out to cured film.By commercialization
Methyl silicon resin is evenly applied on clean culture dish, irradiates 30s by 1000W ultra-violet curing devices UV, you can be solidified into
Film.Differential thermal-thermogravimetric analysis is carried out to cured film.Fig. 1 is the TG-DSC curves of commercialization silicones cured film；Fig. 2 is embodiment
The TG-DSC curves of the one UV low-temperature setting silicone resin adhesive cured films for obtaining.Both contrasts understand the UV obtained through the present invention
The heat resistance of low-temperature setting silicone resin adhesive increases, and commercialization silicones cured film starts weightlessness at 198 DEG C, and UV is low
Warm constitutes of silicones adhesive cured film starts weightless at 243 DEG C.It can thus be appreciated that it is obtained can UV low-temperature settings silicones
The heat resistance of adhesive is greatly improved.
Claims (9)
1. a kind of UV low-temperature settings silicone resin adhesive, it is characterised in that UV low-temperature settings silicone resin adhesive includes metering system
Acryloxypropylethoxysilane trimethoxy silane, deionized water, carborane, silica and tetramethylethylenediamine；The methacryl
Epoxide propyl trimethoxy silicane is 1 with the mass ratio of deionized water:(0.2~0.3)；The methacryloxypropyl three
Methoxy silane is 1 with the mass ratio of carborane:(0.05~0.2)；The methacryloxypropyl trimethoxy silane
With the mass ratio 1 of silica:(0.01~0.05)；The methacryloxypropyl trimethoxy silane and tetramethyl second
The mass ratio of diamines is 1:(0.025~0.1).
2. a kind of UV low-temperature settings silicone resin adhesive according to claim 1, it is characterised in that the methacryl
Epoxide propyl trimethoxy silicane is 1 with the mass ratio of deionized water:0.24.
3. a kind of UV low-temperature settings silicone resin adhesive according to claim 1, it is characterised in that the methacryl
Epoxide propyl trimethoxy silicane is 1 with the mass ratio of carborane:0.1.
4. a kind of UV low-temperature settings silicone resin adhesive according to claim 1, it is characterised in that the methacryl
Epoxide propyl trimethoxy silicane is 1 with the mass ratio of silica:0.02.
5. a kind of preparation method of UV low-temperature settings silicone resin adhesive as claimed in claim 1, it is characterised in that UV low temperature
The preparation method of constitutes of silicones adhesive is to carry out according to the following steps：
First, hydrolyze：Methacryloxypropyl trimethoxy silane is added in there-necked flask, in there-necked flask add go from
Sub- water, magnetic agitation is carried out under conditions of being 30 DEG C~40 DEG C in temperature, is then adjusted the pH of reaction system using watery hydrochloric acid
To 2~5, continue to stir 30min~50min, obtain hydrolysate；The methacryloxypropyl trimethoxy silane with
The mass ratio of deionized water is 1:(0.2~0.3)；
2nd, polycondensation：To carborane and silica is added in hydrolysate, temperature is then warming up to 55 DEG C from 30 DEG C~40 DEG C
~60 DEG C, continue to react 3h~5h, obtain transparency liquid, vacuum distillation then is carried out to transparency liquid, obtain transparent stickiness and produce
Thing；Methacryloxypropyl trimethoxy silane described in step one is 1 with the mass ratio of carborane described in step 2:
(0.05~0.2)；Methacryloxypropyl trimethoxy silane described in step one and silica described in step 2
Mass ratio 1:(0.01~0.05)；
3rd, solidify：Transparent stickiness product is dissolved in solvent, tetramethylethylenediamine and ultrasound 10min~20min is added, led to
Cross under conditions of Rotary Evaporators are 60 DEG C~70 DEG C in temperature and rotate 5min~10min, obtain UV low-temperature setting silicon resin glues
Glutinous agent；The quality of the transparent stickiness product is 1g with the volume ratio of solvent:(2~3) mL；Methacryl described in step one
Epoxide propyl trimethoxy silicane is 1 with the mass ratio of tetramethylethylenediamine described in step 3:(0.025~0.1).
6. a kind of preparation method of UV low-temperature settings silicone resin adhesive according to claim 5, it is characterised in that step
Methacryloxypropyl trimethoxy silane described in one is 1 with the mass ratio of deionized water:0.24.
7. a kind of preparation method of UV low-temperature settings silicone resin adhesive according to claim 5, it is characterised in that step
Solvent described in three is ethanol or acetone.
8. a kind of preparation method of UV low-temperature settings silicone resin adhesive according to claim 5, it is characterised in that step
Tetramethylethylenediamine and ultrasound 15min are added in three.
9. a kind of application of UV low-temperature settings silicone resin adhesive as claimed in claim 1, it is characterised in that UV low-temperature settings
The application of silicone resin adhesive is that UV low-temperature setting silicone resin adhesives are evenly applied on clean culture dish, by 800W
~1000W ultra-violet curing devices UV irradiates 30s~40s, you can film-forming.
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| SU757577A1 (en) * | 1978-08-17 | 1980-08-23 | Sev Vadim V | Adhesive composition |
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| CN101875727A (en) * | 2009-10-23 | 2010-11-03 | 北京化工大学 | Method for preparing carborane-siloxane polymer under catalysis of Lewis acid |
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| CN102634031A (en) * | 2012-04-06 | 2012-08-15 | 中国科学院化学研究所 | Heat-resisting poly (silazane-siloxane) polymer and preparation method thereof |
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2015
- 2015-05-07 CN CN201510230347.XA patent/CN104830240B/en active Active
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| US4069083A (en) * | 1975-12-22 | 1978-01-17 | Combustion Engineering, Inc. | Bonding material and method |
| SU757577A1 (en) * | 1978-08-17 | 1980-08-23 | Sev Vadim V | Adhesive composition |
| US5264285A (en) * | 1992-06-08 | 1993-11-23 | Hughes Aircraft Company | Method of bonding using polycarborane siloxane polymers |
| CN101875727A (en) * | 2009-10-23 | 2010-11-03 | 北京化工大学 | Method for preparing carborane-siloxane polymer under catalysis of Lewis acid |
| CN102167832A (en) * | 2011-03-02 | 2011-08-31 | 中国科学院化学研究所 | Poly(carborane-siloxane/silazane) polymer and preparation method thereof |
| CN102634031A (en) * | 2012-04-06 | 2012-08-15 | 中国科学院化学研究所 | Heat-resisting poly (silazane-siloxane) polymer and preparation method thereof |
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