CN115536849B - Titanium hybridized MQ silicon resin, anti-vertical flow heat conduction gel, preparation method thereof and electronic instrument - Google Patents
Titanium hybridized MQ silicon resin, anti-vertical flow heat conduction gel, preparation method thereof and electronic instrument Download PDFInfo
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Abstract
The application provides titanium hybridized MQ silicon resin, anti-vertical flow heat conduction gel, a preparation method thereof and an electronic instrument, and relates to the technical field of heat conduction gel. The chemical composition of the titanium hybridized MQ silicon resin provided by the application comprises an M chain element (R 3 SiO 1/2 ) Chain link Q (SiO) 4/2 ) And titanium-containing T-links (TiO 4/2 ) Wherein M: q: the molar ratio of T is (4.5-7.5): 1:2. the application also provides an anti-vertical flow heat conduction gel, which comprises the raw materials of the titanium hybridized MQ silicone resin and modified heat conduction filler treated by titanate coupling agent. The preparation method of the vertical flow resistant heat conducting gel comprises the following steps: mixing the above materials. According to the heat conduction gel, through the synergistic interaction among the raw material components, the prepared heat conduction gel is good in anti-sagging performance and adhesiveness, excellent in heat conduction performance, and free from sagging phenomenon after being impacted at high and low temperatures.
Description
Technical Field
The application relates to the technical field of heat conduction gel, in particular to titanium hybridization MQ silicon resin, anti-sagging heat conduction gel, a preparation method thereof and an electronic instrument.
Background
With the rapid development of science and technology, the demand and the demand of portable electronic products are also increasing. In order to realize portability of electronic products, related electronic components in the products are gradually developed towards integration, miniaturization and densification, however, in highly integrated electronic instruments, heat generated per unit volume is also continuously increased. Therefore, it is necessary to conduct and dissipate the heat in time, so as to avoid the damage to the instrument and equipment caused by thermal circulation. In this regard, some materials with high thermal conductivity are becoming hot spots for technical research in electronic instruments.
Among the heat conducting materials, materials such as heat conducting silicone grease, heat conducting silica gel sheets and the like can fail due to long-time use, or the heat conducting materials are only suitable for regular heat conducting interfaces, are difficult to fill irregular interfaces and the like, and are not suitable for different complex scenes, and the heat conducting gel has excellent performance, can be used for heat conducting interfaces with extremely small interface thickness or irregular interface thickness through the technologies such as smearing, dispensing and the like, and become a common heat conducting material in more and more electronic instruments. However, some electronic instruments are used in a relatively harsh environment and at relatively extreme temperatures, and the heat-conducting gel may also exhibit sagging, which makes it difficult to conduct heat effectively. Based on this, there is a need to develop a thermally conductive gel that has good adhesion, is resistant to sagging, and is resistant to high and low temperatures.
Disclosure of Invention
The invention aims to provide titanium hybridized MQ silicon resin, anti-sagging heat-conducting gel, a preparation method thereof and an electronic instrument. By selecting the titanium hybridized MQ silicon resin as the raw material of the anti-sagging heat conduction gel, the prepared heat conduction gel is ensured to have excellent anti-sagging performance, and after high-low temperature impact test, the heat conduction performance is excellent.
In order to achieve the above object, the technical scheme of the present application is as follows:
a titanium hybrid MQ silicone resin having a chemical composition comprising an M-mer, a Q-mer, and a titanium-containing T-mer, the unit-mer of which is expressed as:
[R 3 SiO 1/2 ] x [SiO 4/2 ] y [TiO 4/2 ] z ；
wherein R comprises at least one of C1-C10 linear or branched alkyl, phenyl and vinyl; x: y: z= (4.5 to 7.5): 1:2.
preferably, the source of the M mer comprises at least one of hexamethyldisiloxane, tetramethyl divinyl disiloxane, tetramethyl dihydro disiloxane;
the source of the Q chain link comprises at least one of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate;
the source of the T chain link containing titanium comprises at least one of tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, n-butyl titanate and tetraisobutyl titanate.
The application also provides the anti-vertical flow heat conduction gel, and the raw materials of the anti-vertical flow heat conduction gel comprise the titanium hybridization MQ silicone resin and the modified heat conduction filler treated by the titanate coupling agent.
Preferably, the modified thermally conductive filler satisfies at least one of the following conditions a to c:
a. the titanate coupling agent comprises at least one of tetrabutyl titanate, triisostearyl isopropyl titanate, triisopropyl titanate and diisostearyl ethyl phthalate;
b. the heat conductive filler comprises at least one of spherical aluminum oxide, zinc oxide, magnesium oxide, aluminum hydroxide, aluminum nitride, boron nitride and silicon carbide;
c. 20 g-50 g of titanate coupling agent is added into every 1000g of the heat conducting filler.
Preferably, the raw materials include: 80 to 95 parts of single-end-capped vinyl silicone oil, 850 to 950 parts of modified heat-conducting filler, 5 to 10 parts of titanium hybridization MQ silicone resin, 5 to 10 parts of rosin modified silane coupling agent, 2 to 3 parts of hydrogen-containing silicone oil, 0.3 to 0.6 part of catalyst and 0.1 to 0.2 part of inhibitor.
Further, the anti-vertical flow heat conducting gel satisfies at least one of the following conditions d-h:
d. the kinematic viscosity of the single-end-capped vinyl silicone oil at 25 ℃ is 500 mPas-1000 mPas;
e. the rosin modified silane coupling agent comprises rosin modified aminopropyl triethoxysilane;
f. the hydrogen content of the hydrogen-containing silicone oil is 0.1 to 0.75 weight percent;
g. the catalyst comprises platinum water, wherein the platinum content in the catalyst is 3000 ppm-5000 ppm;
h. the inhibitor comprises at least one of acetylene cyclohexanol and 1- (1-propynyl) cyclohexanol.
The application also provides a preparation method of the anti-vertical flow heat conduction gel, which comprises the following steps: and mixing raw materials comprising the titanium hybridized MQ silicon resin and the modified heat conducting filler to obtain the anti-vertical flow heat conducting gel.
Preferably, when the raw materials of the anti-vertical flow heat conduction gel further comprise single-end-capped vinyl silicone oil, rosin modified silane coupling agent, hydrogen-containing silicone oil, inhibitor and catalyst, the preparation method comprises the following steps:
firstly mixing raw materials comprising the titanium hybridization MQ silicon resin, the modified heat conduction filler, the single-end capped vinyl silicone oil, the rosin modified silane coupling agent, the hydrogen-containing silicone oil and the inhibitor to obtain a mixture;
and carrying out second mixing on the mixture and the catalyst to obtain the heat-conducting gel.
Preferably, the first mixing and the second mixing are each independently performed under vacuum conditions of-0.1 MPa to-0.08 MPa;
the first mixing time is 25-35 min, and the second mixing time is 15-25 min.
The application also provides an electronic instrument comprising the anti-vertical flow heat conduction gel.
The beneficial effects of this application:
by introducing the T chain link containing titanium into the titanium-hybridized MQ silicon resin, the temperature resistance of the silicon resin is greatly improved, so that the titanium-hybridized MQ silicon resin can still maintain the self performance in an extreme high-low temperature environment, and further, when the titanium-hybridized MQ silicon resin is applied to silicone gel or silicone rubber and other organic silicon materials, the titanium-hybridized MQ silicon resin can still have an excellent tackifying effect, and meanwhile, the temperature resistance of the organic silicon material is also improved.
According to the anti-vertical flow heat conduction gel, the titanium hybridized MQ silicon resin and the modified heat conduction filler treated by the titanate coupling agent are used as raw materials, so that the weather resistance of the heat conduction gel is greatly improved, the heat conduction gel has excellent high and low temperature resistance, the modified heat conduction filler can be combined with silicone oil in the heat conduction gel more firmly, the phenomenon that powder oil is separated from the heat conduction gel after long-time working is avoided, and the vertical flow resistance of the heat conduction gel is improved.
Furthermore, the single-end-capped vinyl silicone oil is used in the anti-vertical-flow heat-conducting gel, so that the crosslinking density of the heat-conducting gel can be reduced, the common silane coupling agent is replaced by the rosin modified silane coupling agent, the adhesiveness of the heat-conducting gel is improved, the excellent weather resistance and high and low temperature resistance of the titanium hybrid MQ silicone resin are utilized, the high and low temperature resistance of the heat-conducting gel is further improved, the titanate coupling agent is utilized to treat the heat-conducting filler, the silicone oil and the heat-conducting powder are firmly combined, and the synergistic effect of the single-end-capped vinyl silicone oil, the titanium hybrid MQ silicone resin, the modified heat-conducting filler and the rosin modified silane coupling agent is utilized, so that the finally prepared heat-conducting gel has excellent vertical-flow resistance, can be firmly adhered to an instrument even if being used in an extreme high and low temperature environment, does not generate a vertical-flow phenomenon, and has excellent heat conducting performance.
The preparation method of the anti-vertical flow heat-conducting gel has the advantages of simple process, short production period and high production efficiency, and can be used for large-scale production and preparation.
Through using the anti-vertical flow heat conduction gel of this application in the electronic instrument that this application provided, can play encapsulation, heat conduction, the effect of protection, and in extreme high low temperature environment, the adhesion of heat conduction gel still keeps better, and heat conductivility is excellent, provides stable guarantee for electronic instrument's normal work.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope of the present invention.
FIG. 1 is a sample test picture of example 1 before 1000H high and low temperature cold and hot shock and after 1000H high and low temperature cold and hot shock;
FIG. 2 is a sample test image of example 2 before 1000H cold and hot shock and after 1000H cold and hot shock;
FIG. 3 is a sample test image of example 3 before 1000H cold and hot shock and after 1000H cold and hot shock;
FIG. 4 is a sample test image of the sample before 1000H cold and hot impact and after 1000H cold and hot impact in example 4;
FIG. 5 is a sample test picture of the sample before 1000H cold and hot impact and after 1000H cold and hot impact in example 5;
FIG. 6 is a sample test image of example 6 before 1000H high and low temperature cold and hot shock and after 1000H high and low temperature cold and hot shock;
FIG. 7 is a sample test picture of comparative example 1 before 1000H high and low temperature cold and hot shock and after 1000H high and low temperature cold and hot shock;
FIG. 8 is a sample test picture of comparative example 2 before 1000H high and low temperature cold and hot shock and after 1000H high and low temperature cold and hot shock;
FIG. 9 is a sample test picture of comparative example 3 before 1000H high and low temperature cold and hot shock and after 1000H high and low temperature cold and hot shock;
FIG. 10 is a graph of comparative example 4 before 1000H cold and hot shock and after 1000H cold and hot shock.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"parts by mass" means a basic unit of measurement showing the mass ratio of a plurality of components, and 1 part may be any unit mass, for example, 1g may be expressed, 2.689g may be expressed, and the like. If we say that the mass part of the a component is a part and the mass part of the B component is B part, the ratio a of the mass of the a component to the mass of the B component is represented as: b. alternatively, the mass of the A component is aK, and the mass of the B component is bK (K is an arbitrary number and represents a multiple factor). It is not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass.
"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
In a first aspect, the present application provides a titanium hybrid MQ silicone resin having a chemical composition comprising an M-mer, a Q-mer, and a titanium-containing T-mer, the unit-mer of which is expressed as: [ R ] 3 SiO 1/2 ] x [SiO 4/2 ] y [TiO 4/2 ] z ；
Wherein R comprises at least one of C1-C10 linear or branched alkyl, phenyl and vinyl; x: y: z= (4.5 to 7.5): 1:2, for example, may be 4.5:1: 2. 5.0:1: 2. 5.5:1: 2. 6.0:1: 2. 6.5:1: 2. 7.0:1: 2. 7.5:1:2 is either (4.5-7.5): 1:2.
It should be noted that MQ silicone resins are also classified into different types due to the difference in the organic groups R, and when R is all methyl, they are called methyl MQ silicone resins; when part R is H, the methyl hydrogen-containing MQ silicone resin is called; there are also methyl phenyl MQ silicone resins, vinyl MQ silicone resins, phenyl MQ silicone resins, fluorine-containing MQ silicone resins, and the like. The performance and the application range of the MQ silicone resin mainly depend on the synthesis process conditions and the types and the numbers of organic groups in molecules, namely the number ratio of M chain links to Q chain links; wherein, the M chain link containing the organic group R mainly increases the compatibility with other components, plays a role in tackifying, and the Q chain link mainly improves the strength of the composite material, thereby playing a role in reinforcing. Besides M chain links and Q chain links, the titanium-containing T chain links are added into the MQ silicon resin to form the titanium-hybridized MQ silicon resin, and structural units of Si-O-Si, si-O-Ti and Ti-O-Ti exist in the silicon resin, so that the titanium-hybridized MQ silicon resin has the characteristics of common MQ silicon resin, and meanwhile has excellent weather resistance and high and low temperature resistance, and can still keep self excellent bonding performance in extreme high and low temperature environments.
The general MQ silicone resin is mainly prepared by carrying out cohydrolytic polycondensation reaction on a compound containing M chain units and Q chain units, while the titanium hybridized MQ silicone resin contains M chain units (R 3 SiO 1/2 ) And Q chain link (SiO) 4/2 ) In addition to the reaction of the organosilicon compound of (2), contains tetrafunctional titanyl units (TiO 4/2 ) The compounds of (2) also participate in the cohydrolytic polycondensation reaction.
In some alternative embodiments, the source of the M mer comprises at least one of hexamethyldisiloxane, tetramethyl divinyl disiloxane, tetramethyl dihydro disiloxane.
In some alternative embodiments, the source of the Q mer comprises at least one of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, butyl orthosilicate.
In some alternative embodiments, the source of the titanium-containing T-mer comprises at least one of tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, n-butyl titanate, tetraisobutyl titanate.
In some alternative embodiments, a method of preparing a titanium hybrid MQ silicone resin, comprising:
(1) Uniformly stirring raw materials including hexamethyldisiloxane, deionized water and ethanol under the conditions of pH of 1.5-2.5 and temperature of 70-90 ℃ to obtain a first solution;
(2) Adding ethyl orthosilicate and n-butyl titanate into the first solution, and continuously mixing and stirring at the temperature of 70-90 ℃ to obtain a second solution;
(3) Cooling the second solution to room temperature, adding dimethyl silicone oil, extracting, standing, layering, and discharging an acid water layer to obtain a hydrolysate;
(4) Washing the hydrolysate to neutrality, adding tetramethyl ammonium hydroxide, heating to 100-110 deg.c and polymerizing to obtain the hybridized Ti MQ silicon resin.
In a second aspect, the present application also provides an anti-sagging heat-conducting gel, the raw materials of which include the above-mentioned titanium hybrid MQ silicone resin and a modified heat-conducting filler treated by a titanate coupling agent.
It should be noted that, the specific treatment process of the modified heat conductive filler is not limited specifically, and may be: the heat-conducting filler is firstly mixed with water, then the titanate coupling agent is sprayed into the heat-conducting filler by using a spraying device, continuous stirring is required in the spraying process, stirring is also required to be continued after the spraying is finished, the heat-conducting filler and the titanate coupling agent are ensured to be fully and uniformly mixed, then the water is filtered by using a filter screen, and the powder is dried to constant weight in an oven.
In some alternative embodiments, the titanate coupling agent comprises at least one of tetrabutyl titanate, isopropyl triisostearate, isopropyl tri-titanate, and ethyl diisostearyl phthalate. More preferably, the titanate coupling agent is isopropyl triisostearate titanate.
In some alternative embodiments, the thermally conductive filler comprises at least one of spherical aluminum oxide, zinc oxide, magnesium oxide, aluminum hydroxide, aluminum nitride, boron nitride, and silicon carbide.
It can be appreciated that because the heat conductive fillers have more pores among particles, the pores can influence the heat transmission efficiency, so that in order to improve the heat conduction performance of the heat conductive gel and reduce the porosity among the fillers, the application selects the heat conductive fillers with different particle sizes for matching use, and a compact stacking structure is formed among the heat conductive fillers.
In some alternative embodiments, 20g to 50g of the titanate coupling agent is added to 1000g of the thermally conductive filler for modification treatment, for example, 20g, 25g, 30g, 35g, 40g, 45g, 50g, or any value between 20g and 50g may be added. More preferably, 25g to 35g of the titanate coupling agent is added per 1000 g.
In some alternative embodiments, the anti-vertical flow heat conducting gel comprises the following raw material components in parts by weight: 80 to 95 parts of single-end-capped vinyl silicone oil can be, for example, 80 parts, 82 parts, 84 parts, 86 parts, 88 parts, 90 parts, 92 parts, 94 parts, 95 parts or any value between 80 and 95 parts;
850-950 parts of the modified heat-conducting filler can be, for example, 850 parts, 860 parts, 870 parts, 880 parts, 890 parts, 900 parts, 910 parts, 920 parts, 930 parts, 940 parts, 950 parts or any value between 850 and 950 parts;
the titanium hybridization MQ silicon resin is 5-10 parts, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts or any value between 5 parts and 10 parts;
5 to 10 parts of rosin-modified silane coupling agent, for example, may be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts or any value between 5 and 10 parts;
2 to 3 parts of hydrogen-containing silicone oil, for example, 2 parts, 2.3 parts, 2.5 parts, 2.8 parts, 3 parts or any value between 2 and 3 parts;
0.3 to 0.6 parts of catalyst, for example, 0.3 parts, 0.35 parts, 0.4 parts, 0.45 parts, 0.5 parts or any value between 0.3 and 0.6 parts;
the inhibitor may be 0.1 to 0.2 parts, for example, 0.1 parts, 0.13 parts, 0.15 parts, 0.18 parts, 0.2 parts, or any value between 0.1 and 0.2 parts.
In some alternative embodiments, the rosin modified silane coupling agent comprises rosin modified aminopropyl triethoxysilane having a molecular structure of:
it can be understood that the rosin modified silane coupling agent is added into the heat-conducting gel, and the group on the surface of the rosin modified silane coupling agent is utilized to easily react with the group of the bonding substrate and form chemical bond connection so as to improve the adhesive force of the heat-conducting gel.
In some alternative embodiments, the kinematic viscosity of the single-ended vinyl silicone oil at 25 ℃ is from 500 mPa-s to 1000 mPa-s, for example, it may be from 500 mPa-s, 600 mPa-s, 700 mPa-s, 800 mPa-s, 900 mPa-s, 1000 mPa-s, or any value between 500 mPa-s and 1000 mPa-s.
It can be appreciated that, compared with the double-end-capped vinyl silicone oil, the side-chain vinyl silicone oil and the side-end vinyl silicone oil, the single-end-capped vinyl silicone oil in the application has smaller crosslinking density after an addition reaction, and can reduce the hardness of the heat-conducting gel, thereby reducing the stress of the heat-conducting gel on an electronic instrument during use.
In some alternative embodiments, the hydrogen content of the hydrogen-containing silicone oil is 0.1wt% to 0.75wt%, for example, may be 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.75wt%, or any value between 0.1wt% and 0.75 wt%. More preferably, the hydrogen content of the hydrogen-containing silicone oil is 0.18wt%.
The hydrogen-containing silicone oil of the present application includes at least one of a side-chain hydrogen-containing silicone oil and a terminal-side hydrogen-containing silicone oil. Obviously, the terminal hydrogen-containing silicone oil has hydrogen bonds at the end-capping position and the side chain position, so that the crosslinking density of the heat-conducting gel is easily increased and the hardness is increased when the addition reaction is carried out. Therefore, side chain hydrogen containing silicone oils and single end hydrogen containing silicone oils are preferred for use in this application.
In some alternative embodiments, the catalyst comprises platinum water, and the platinum content in the catalyst is 3000ppm to 5000ppm, for example, may be 3000ppm, 4000ppm, 5000ppm, or any value between 3000ppm and 5000 ppm. The catalyst can be also called as platinum catalyst and Karste catalyst, is light yellow liquid and can rapidly catalyze the addition crosslinking reaction between vinyl-containing siloxane and hydrogen-containing siloxane.
In some alternative embodiments, the inhibitor comprises at least one of ethynyl cyclohexanol, 1- (1-propynyl) cyclohexanol.
In a third aspect, the present application further provides a preparation method of the above anti-sagging heat-conducting gel, including: and mixing raw materials comprising the modified heat-conducting filler and the titanium hybridized MQ silicone resin to obtain the heat-conducting gel.
Further, when the raw materials of the anti-vertical flow heat conduction gel further comprise single-end-capped vinyl silicone oil, rosin modified silane coupling agent, hydrogen-containing silicone oil, inhibitor and catalyst, the preparation method comprises the following steps:
(1) Firstly mixing raw materials comprising the titanium hybridization MQ silicon resin, the modified heat conduction filler, the single-end capped vinyl silicone oil, the rosin modified silane coupling agent, the hydrogen-containing silicone oil and the inhibitor to obtain a mixture;
(2) And carrying out second mixing on the mixture and the catalyst to obtain the heat-conducting gel.
It should be noted that, when preparing the heat-conducting gel, stirring can be performed by using vacuum stirrers of different types on the market. Wherein, when the first mixing and the second mixing are carried out, the first mixing and the second mixing are carried out under vacuum conditions, and the vacuum conditions are-0.1 MPa to-0.08 MPa. This is mainly to ensure that the raw materials are mixed in the process of removing bubbles in the stirred raw materials as much as possible, and prevent the subsequent heat-conducting gel from influencing the final performance due to bubbles in the gel during use.
In some alternative embodiments, the time required to perform the first mixing is 25min to 35min, for example, may be 25min, 28min, 30min, 32min, 35min, or any value between 25min and 35 min; in the second mixing, the time required is 15 to 25 minutes, and may be, for example, 15 minutes, 18 minutes, 20 minutes, 22 minutes, 25 minutes, or any value between 15 and 25 minutes.
Embodiments of the present invention will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
This example provides a titanium hybrid MQ silicone resin with the unit links shown below:
[R 3 SiO 1/2 ] x [SiO 4/2 ] y [TiO 4/2 ] z ；
wherein R is-CH 3 ；x：y：z＝6：1：2。
The M: q: t molar ratio is 6:1:2, the preparation method of the titanium hybridization MQ silicon resin comprises the following steps:
(1) 162.38g of hexamethyldisiloxane, 200g of deionized water and 50g of absolute ethyl alcohol are stirred for 60min under the condition that the pH is 2 and the temperature is 80 ℃ to obtain a first solution;
(2) 34.721g of ethyl orthosilicate and 69.442g of n-butyl titanate are added into the first solution, and stirring is continued for 5 hours at 80 ℃ to obtain a second solution;
(3) Cooling the second solution to room temperature, adding 200g of dimethyl silicone oil (viscosity of 50 mPas), extracting, standing, layering, and discharging an acid water layer to obtain a hydrolysate;
(4) Washing the hydrolysate to neutrality, adding 0.02g of tetramethyl ammonium hydroxide, heating to 100 ℃, and performing polymerization reaction for 3 hours to obtain M: q: t molar ratio is 6:1:2, titanium hybrid MQ silicone resin.
The embodiment also provides a vertical flow resistant heat conductive gel, comprising: 87g of singly-blocked vinyl silicone oil, 897.5g of modified heat-conducting filler, 5g of rosin modified silane coupling agent and 8g of M: q: t molar ratio is 6:1:2, 2g of side chain hydrogen silicone oil, 0.1g of acetylene cyclohexanol and 0.3g of platinum water.
The preparation method of the modified heat-conducting filler comprises the following steps: 200g of 1 μm spherical alumina, 300g of 5 μm spherical alumina and 500g of 20 μm spherical alumina were mixed with 10kg of distilled water, stirred at 500rpm for 10min, 30g of titanate coupling agent was added with a spray device, then mixing was continued at 2000rpm for 20min, then the mixed material was filtered off water with a filter screen, filtered, and then put in a vacuum oven, dried at 105 ℃ to constant weight, to obtain a modified heat conductive filler.
The preparation method of the vertical flow resistant heat conducting gel comprises the following steps:
(1) 87g of a singly-blocked vinyl silicone oil having a kinematic viscosity of 500 mPas, 8g of M: q: t molar ratio is 6:1:2, 2g of side chain hydrogen silicone oil with the hydrogen content of 0.18wt%, 897.5g of modified heat conducting filler, 5g of rosin modified silane coupling agent and 0.1g of acetylene cyclohexanol, and adding the materials into a vacuum planetary stirrer, and stirring for 30min at the rotating speed of-0.08 MPa and 10rpm to obtain a mixture;
(2) 0.3g of 5000ppm platinum water is added into the mixture, and the mixture is stirred for 20min at the rotating speed of-0.08 MPa and 10rpm, and the heat-conducting gel is obtained after full reaction.
Example 2
The same as in example 1, except that the kinematic viscosity of the monoblocked vinyl silicone oil was changed to 1000 mPas.
Example 3
As in example 1, the difference M is: q: t molar ratio is 4:1:2, wherein the addition amount of hexamethyldisiloxane is 108.25g.
Example 4
The procedure of example 1 was repeated except that the addition amount of the side-chain hydrogen-containing silicone oil was changed to 3g.
Example 5
The same as in example 1, except that the addition amount of the monoblocked vinyl silicone oil was changed to 82g, and the addition amount of the modified heat conductive filler was 902.5g.
Example 6
The same as in example 1, except that the addition amount of the monoblocked vinyl silicone oil was changed to 82g, while the addition amount of the rosin-modified silane coupling agent was changed to 10g.
Comparative example 1
The procedure of example 1 was repeated except that the rosin-modified silane coupling agent was replaced with a silane coupling agent of gamma-aminopropyl triethoxysilane.
Comparative example 2
As in example 1, except that the titanium hybrid MQ silicone resin was replaced with a conventional M: the molar ratio of Q is 4: MQ silicone of 5.
Comparative example 3
The procedure is as in example 1, except that the monoblocked vinylsilicone oil having a kinematic viscosity of 500 mPas is replaced by a doubly blocked vinylsilicone oil having a kinematic viscosity of 500 mPas.
Comparative example 4
The same as in example 1, except that the modified heat conductive filler was obtained by treating the heat conductive filler with a titanate coupling agent, instead of treating the heat conductive filler with a conventional silane coupling agent of γ - (2, 3-glycidoxy) propyltrimethoxysilane.
And detecting the performance of the prepared heat conducting gel, wherein the specific detection standard is as follows:
thermal conductivity coefficient: according to the standard in ASTM D5470-2017, the unit is W/m.k;
thermal resistance: according to the standard in ASTM D5470-2017, in units of℃in2/W;
dispensing rate: the extrusion quality in g was measured in terms of 90psi,1mm of gum mouth, 1 min;
specific gravity after curing: according to the standards in ASTM D792-2007 plastics Density and relative Density test method, in g/cc;
vertical flow test: the method for testing slump of a sealant according to ASTM D2202-2000 (2006) was followed while increasing the high and low temperature cold and hot impact. Wherein, the cold and hot impact conditions of high and low temperature are: testing the cured heat-conducting gel for 1000H at the circulation temperature of-40-150 ℃, wherein the time of each high-low temperature circulation is 10min. The vertical flow test is mainly used for simulating the sagging of the product caused by the gravity possibly applied to the product during the use under different high and low temperature environments and examining the anti-gravity capability of the product under high and low temperature impact. Typically, because adhesive articles cure, sagging is tested for their ability to resist gravity at ordinary temperatures, but the thermally conductive gel is always in a gel state, sagging may occur due to gravity during use. The vertical flow test of the thermally conductive gel requires the addition of high and low temperature cold and hot impact conditions as a reference standard.
In the vertical flow test condition, two pieces of glass are used for sandwiching a heat conducting gel with the diameter of 10-20 mm and the height of 2mm for high-temperature and low-temperature cold and hot impact test. The product of the same embodiment uses 6 or 7 samples for testing before and after vertical flow, if all the samples are still in the center of the glass after being subjected to high and low temperature cold and hot impact test, and the position does not deviate, namely the test result is judged as follows: no vertical flow exists; if any one of the samples has a certain deviation after the high-low temperature impact test is finished, judging that the test result is: and (5) vertical flow. The results of the specific vertical flow test can be seen in the accompanying drawings.
Fig. 1 is a photograph of the heat conductive gel prepared in example 1 before and after high and low temperature cold and hot impact. The upper row in fig. 1 is the samples before the cold-hot impact at high and low temperatures, and the lower row is the samples after the cold-hot impact at high and low temperatures (the up-down arrangement sequence of the samples corresponding to the samples before and after the cold-hot impact at high and low temperatures in fig. 2-10 is the same as that in fig. 1). Fig. 2,3, 4, 5, and 6 correspond to the pictures before and after the high and low temperature cold and hot impact of the heat conductive gel prepared in examples 2 to 6, respectively. From the sample cases of fig. 1 to 6, it is apparent that these heat conductive gel samples prepared in the present application do not have sagging phenomenon even after being subjected to high and low temperature cold and hot impact.
Fig. 7, 8, 9 and 10 correspond to the pictures before and after the high and low temperature cold and hot impact of the heat conductive gel prepared in comparative examples 1 to 4, respectively. From fig. 7 to fig. 10, it is obvious that all samples in fig. 7 slip downwards from the original positions after being subjected to high and low temperature cold and hot impact, which indicates that the samples have poor adhesion after being subjected to high and low temperature cold and hot impact and have sagging; the samples in fig. 8 have obvious sagging phenomenon after high and low temperature cold and hot impact, and some samples have poor adhesion and are directly detached from the glass plate; although some of the samples in fig. 9 and 10 remained good after the cold and hot impact at high and low temperatures, there was still some shift in the positions of the individual samples, indicating that the samples prepared by the formulation still had sagging after the cold and hot impact at high and low temperatures.
The results of the measurements of the different properties of examples 1 to 6 and comparative examples 1 to 4 are shown in Table 1.
TABLE 1
As can be seen from Table 1, the heat conductive gel prepared by the method has excellent heat conductive performance and good anti-sagging performance. Furthermore, the prepared heat-conducting gel has good adhesiveness and excellent sagging resistance through the synergistic interaction of the single-ended vinyl silicone oil, the titanium hybridized MQ silicone resin, the modified heat-conducting filler and the rosin modified silane coupling agent, and the sagging phenomenon can not occur even if the heat-conducting gel is subjected to high-temperature and low-temperature cold-hot impact for 1000 hours.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (8)
1. The anti-vertical flow heat conduction gel is characterized by comprising the following raw materials: 80 to 95 parts of single-end capped vinyl silicone oil, 850 to 950 parts of modified heat-conducting filler treated by titanate coupling agent, 5 to 10 parts of titanium hybridization MQ silicon resin, 5 to 10 parts of rosin modified silane coupling agent, 2 to 3 parts of hydrogen-containing silicone oil, 0.3 to 0.6 part of catalyst and 0.1 to 0.2 part of inhibitor;
the chemical composition of the titanium hybrid MQ silicon resin comprises an M chain link, a silicon-containing Q chain link and a titanium-containing Q chain link, and the unit chain links are expressed as follows:
[R 3 SiO 1/2 ] x [SiO 4/2 ] y [TiO 4/2 ] z ；
wherein R comprises at least one of C1-C10 linear or branched alkyl, phenyl and vinyl; x: y: z= (4.5 to 7.5): 1:2;
the rosin modified silane coupling agent comprises rosin modified aminopropyl triethoxysilane.
2. The anti-vertical flow thermally conductive gel of claim 1, wherein the source of M mer comprises at least one of hexamethyldisiloxane, tetramethyl divinyl disiloxane, tetramethyl dihydro disiloxane;
the source of the silicon-containing Q chain link comprises at least one of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate;
the source of the titanium-containing Q chain element comprises at least one of tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, n-butyl titanate and tetraisobutyl titanate.
3. The anti-vertical flow thermally conductive gel of claim 1, wherein at least one of the following conditions a-c is satisfied:
a. the titanate coupling agent comprises at least one of tetrabutyl titanate, triisostearyl isopropyl titanate, triisopropyl titanate and diisostearyl ethyl phthalate;
b. the heat conductive filler comprises at least one of spherical aluminum oxide, zinc oxide, magnesium oxide, aluminum hydroxide, aluminum nitride, boron nitride and silicon carbide;
c. 20 g-50 g of titanate coupling agent is added into every 1000g of the heat conducting filler.
4. The anti-vertical flow thermally conductive gel of claim 1, wherein at least one of the following conditions is satisfied:
d. the kinematic viscosity of the single-end-capped vinyl silicone oil at 25 ℃ is 500 mPas-1000 mPas;
f. the hydrogen content of the hydrogen-containing silicone oil is 0.1 to 0.75 weight percent;
g. the catalyst comprises platinum water, wherein the platinum content in the catalyst is 3000 ppm-5000 ppm;
h. the inhibitor comprises at least one of acetylene cyclohexanol and 1- (1-propynyl) cyclohexanol.
5. A method of preparing the anti-vertical flow heat conducting gel according to any one of claims 1 to 4, comprising: and mixing raw materials comprising the titanium hybridized MQ silicon resin and the modified heat conducting filler to obtain the anti-vertical flow heat conducting gel.
6. The method of manufacturing as claimed in claim 5, comprising:
firstly mixing raw materials comprising the titanium hybridization MQ silicon resin, the modified heat conduction filler, the single-end capped vinyl silicone oil, the rosin modified silane coupling agent, the hydrogen-containing silicone oil and the inhibitor to obtain a mixture;
and carrying out second mixing on the mixture and the catalyst to obtain the heat-conducting gel.
7. The method of claim 6, wherein the first mixing and the second mixing are each independently performed under vacuum conditions of-0.1 MPa to-0.08 MPa;
the first mixing time is 25-35 min, and the second mixing time is 15-25 min.
8. An electronic device comprising the anti-sagging heat conductive gel according to any one of claims 1 to 4.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5596060A (en) * | 1994-04-01 | 1997-01-21 | Dow Corning Asia, Ltd. | Curable polytitanosiloxane compositions and method for preparing cured polytitanosiloxanes using said compositions |
| CN103265703A (en) * | 2013-05-06 | 2013-08-28 | 北京化工大学 | High refractive index titanium hybrid silicon resin and preparation method thereof |
| CN105399956A (en) * | 2015-11-25 | 2016-03-16 | 烟台德邦先进硅材料有限公司 | High-temperature-resistant high-refractive-index Ti-containing organic silicon resin and preparation method thereof |
| CN105399958A (en) * | 2015-11-25 | 2016-03-16 | 烟台德邦先进硅材料有限公司 | Hybrid organic silicon resin with framework structure containing Zr or containing Zr and Ti simultaneously and preparation method of organic silicon resin |
| CN106867024A (en) * | 2017-02-23 | 2017-06-20 | 中国林业科学研究院林产化学工业研究所 | A kind of Abietyl modified organosilane cross-linking agent of dealcoholized type room temperature vulcanized silicone rubber and preparation method thereof |
| CN107099265A (en) * | 2017-05-27 | 2017-08-29 | 浙江固特热熔胶有限公司 | A kind of Hot melt adhesive for automobile interior trim part and preparation method thereof |
| CN113248788A (en) * | 2021-05-12 | 2021-08-13 | 仲恺农业工程学院 | Polyhydroxy rosin modified organosilane coupling agent, and preparation method and application thereof |
-
2022
- 2022-10-12 CN CN202211247227.7A patent/CN115536849B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5596060A (en) * | 1994-04-01 | 1997-01-21 | Dow Corning Asia, Ltd. | Curable polytitanosiloxane compositions and method for preparing cured polytitanosiloxanes using said compositions |
| CN103265703A (en) * | 2013-05-06 | 2013-08-28 | 北京化工大学 | High refractive index titanium hybrid silicon resin and preparation method thereof |
| CN105399956A (en) * | 2015-11-25 | 2016-03-16 | 烟台德邦先进硅材料有限公司 | High-temperature-resistant high-refractive-index Ti-containing organic silicon resin and preparation method thereof |
| CN105399958A (en) * | 2015-11-25 | 2016-03-16 | 烟台德邦先进硅材料有限公司 | Hybrid organic silicon resin with framework structure containing Zr or containing Zr and Ti simultaneously and preparation method of organic silicon resin |
| CN106867024A (en) * | 2017-02-23 | 2017-06-20 | 中国林业科学研究院林产化学工业研究所 | A kind of Abietyl modified organosilane cross-linking agent of dealcoholized type room temperature vulcanized silicone rubber and preparation method thereof |
| CN107099265A (en) * | 2017-05-27 | 2017-08-29 | 浙江固特热熔胶有限公司 | A kind of Hot melt adhesive for automobile interior trim part and preparation method thereof |
| CN113248788A (en) * | 2021-05-12 | 2021-08-13 | 仲恺农业工程学院 | Polyhydroxy rosin modified organosilane coupling agent, and preparation method and application thereof |
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