Long-chain alkyl-terminated side-chain phenyl silicone oil, high-temperature-resistant heat-conducting putty, preparation method of high-temperature-resistant heat-conducting putty and electronic instrument

Abstract

The invention provides long-chain alkyl-terminated side-chain phenyl silicone oil, high-temperature-resistant heat-conducting putty, a preparation method of the high-temperature-resistant heat-conducting putty and an electronic instrument, and relates to the technical field of heat-conducting materials. The structural formula of the long-chain alkyl-terminated side-chain phenyl silicone oil is # imgabs0 #, m and n are positive integers, m is greater than or equal to 1, n is greater than or equal to 1, and R is C6-C18 alkyl. By introducing long-chain alkyl, the compatibility and wettability of the long-chain alkyl terminated side-chain phenyl silicone oil and the heat-conducting powder are greatly improved, so that the prepared high-temperature-resistant heat-conducting putty is more stable and does not produce oil for a long time, and by introducing phenyl, the high-temperature-resistant heat-conducting putty can cooperate with heat-conducting filler, and the temperature resistance is better.

Description

Technical Field

[0001] The present application relates to the technical field of thermal conductive materials, and in particular to a long-chain alkyl-terminated side-chain phenyl silicone oil, a high-temperature resistant thermal conductive putty, a preparation method thereof, and an electronic instrument. Background Art

[0002] With the rapid development of science and technology, modern industry has higher and higher requirements for the heat resistance of equipment. In addition, electronic components related to industrial equipment are gradually developing in the direction of integration, miniaturization, and density. However, in highly integrated electronic instruments, the heat generated per unit volume will continue to increase. Therefore, it is necessary to conduct and dissipate this heat in time to avoid damage to the equipment caused by thermal cycles.

[0003] Thermal putty is a compressible thermal interface material made of methyl silicone oil and thermal conductive powder. However, conventional methyl silicone oil is prone to oil leakage. Therefore, there is an urgent need for a silicone oil material that is both resistant to high temperatures and not prone to oil leakage. Summary of the invention

[0004] The purpose of the present application is to provide a long-chain alkyl-terminated side-chain phenyl silicone oil, a high-temperature resistant thermally conductive putty, a preparation method thereof, and an electronic instrument to solve the above-mentioned problems.

[0005] To achieve the above objectives, the first aspect of the present application provides a long-chain alkyl-terminated side-chain phenyl silicone oil, the structural formula of which is:

[0006]

[0007] Wherein, m and n are positive integers, m≥1, n≥1, and R is a C6-C18 alkyl group.

[0008] Optionally, the raw materials of the long-chain alkyl-terminated side-chain phenyl silicone oil include double-terminal hydrogen-containing phenyl silicone oil and olefin compounds, satisfying at least one of the following conditions:

[0009] A. The chemical formula of the double-terminal hydrogen-containing phenyl silicone oil is:

[0010] H(CH3)2SiO[(CH3)2SiO] m [(C6H5)2SiO] n Si(CH3)2H;

[0011] Wherein, m and n are positive integers, m≥1, n≥1;

[0012] B. The chemical structural formula of the olefin compound is:

[0013] R-CH=CH2;

[0014] Wherein, R is a C6-C18 alkyl group;

[0015] C. The molar amount of phenyl in the double-terminal hydrogen-containing phenyl silicone oil is 5%-30%, and the mass content of hydrogen is 0.01%-0.1%.

[0016] The second aspect of the present application provides a method for preparing the long-chain alkyl-terminated side-chain phenyl silicone oil, comprising:

[0017] The double-terminal hydrogen-containing phenyl silicone oil, the olefin compound, and the platinum-based catalyst are first mixed and reacted to obtain a mixture;

[0018] The mixture is subjected to reduced pressure distillation to obtain the long-chain alkyl-terminated side-chain phenyl silicone oil.

[0019] Optionally, the preparation method of the long-chain alkyl-terminated side-chain phenyl silicone oil meets at least one of the following conditions:

[0020] A. The mass ratio of the double-terminal hydrogenated phenyl silicone oil to the olefin compound is 0.9-1.1:0.9-1.1;

[0021] B. The amount of the platinum-based catalyst used is 0.0009%-0.0011% of the total mass of the olefin compound of the double-terminal hydrogen-containing phenyl silicone oil;

[0022] B. The platinum content in the platinum-based catalyst is 3000ppm-5000ppm;

[0023] C. The first mixing comprises: performing a second mixing of the double-terminal hydrogenated phenyl silicone oil, a portion of the olefin compound, and the platinum-based catalyst, and heating to obtain a mixture A;

[0024] The mixture A and the remaining olefin compounds are mixed for the third time;

[0025] D. The reaction temperature is 120°C-130°C and the reaction time is 1h-2h;

[0026] E. The vacuum degree of the reduced pressure distillation is 0.08MPa-0.1MPa, the temperature is 120°C-130°C, and the time is 15min-30min.

[0027] Optionally, the preparation method of the long-chain alkyl-terminated side-chain phenyl silicone oil meets at least one of the following conditions:

[0028] A. The mass ratio of the double-terminal hydrogenated phenyl silicone oils in the second mixing and the third mixing is 0.9-1.1:8.9-9.1;

[0029] B. The terminal temperature of the heating is 90°C-100°C.

[0030] The third aspect of the present application provides a high temperature resistant thermally conductive putty, the raw materials of which, by weight, include:

[0031] 75-115 parts of long-chain alkyl-terminated side-chain phenyl silicone oil, 3-7 parts of cerium oxide, and 360-540 parts of thermal conductive filler;

[0032] The long-chain alkyl-terminated side-chain phenyl silicone oil includes the long-chain alkyl-terminated side-chain phenyl silicone oil or the long-chain alkyl-terminated side-chain phenyl silicone oil prepared by the preparation method;

[0033] The thermally conductive filler includes one or more of zinc oxide, aluminum oxide, and boron nitride.

[0034] Optionally, the high temperature resistant thermally conductive putty meets at least one of the following conditions:

[0035] A. the cerium oxide comprises nano cerium oxide;

[0036] The particle size of the nano cerium oxide is 10nm-100nm;

[0037] B. the thermally conductive filler includes the boron nitride;

[0038] C. The thermally conductive filler comprises, by parts:

[0039] 120-180 parts of zinc oxide, 220-280 parts of aluminum oxide, and 20-80 parts of boron nitride;

[0040] D. The zinc oxide includes needle-shaped zinc oxide; the particle size of the needle-shaped zinc oxide is 0.1um-1um;

[0041] E. The alumina includes one or more of angular alumina, quasi-spherical alumina, spherical alumina, and single crystal alumina;

[0042] The particle size of the aluminum oxide is 1um-20um;

[0043] F. The boron nitride includes one or more of hexagonal boron nitride, close-packed hexagonal boron nitride, cubic boron nitride, and spherical boron nitride;

[0044] The particle size of the boron nitride is 0.3um-25um.

[0045] The fourth aspect of the present application provides a method for preparing the high temperature resistant thermally conductive putty, comprising:

[0046] Under vacuum conditions, the raw materials of the high temperature resistant thermal conductive putty are subjected to a fourth mixing to prepare the high temperature resistant thermal conductive putty.

[0047] Optionally, the preparation method of the high temperature resistant thermally conductive putty satisfies at least one of the following conditions:

[0048] A. The vacuum degree of the vacuum condition is 0.08MPa-0.1MPa;

[0049] B. The fourth mixing time is 25 min-35 min.

[0050] A fifth aspect of the present application provides an electronic instrument, comprising the high temperature resistant thermally conductive putty described above or the high temperature resistant thermally conductive putty prepared by the method for preparing the high temperature resistant thermally conductive putty described above.

[0051] Compared with the prior art, the beneficial effects of this application include:

[0052] The long-chain alkyl-terminated side-chain phenyl silicone oil provided in the present application greatly improves the compatibility and wettability of the long-chain alkyl-terminated side-chain phenyl silicone oil and the thermal conductive powder by introducing a long-chain alkyl group, thereby making the high-temperature resistant thermal conductive putty prepared therefrom more stable and oil-free for a long time. Moreover, by introducing a phenyl group, it can further cooperate with the thermal conductive filler to achieve better temperature resistance.

[0053] The long-chain alkyl-terminated side-chain phenyl silicone oil and the preparation method thereof provided by the present application have simple preparation method and high production efficiency.

[0054] The high-temperature resistant thermally conductive putty provided by the present application can prevent the oxidative cross-linking and main chain cyclization degradation of long-chain alkyl-terminated side-chain phenyl silicone oil by adding cerium oxide, can prevent the free radical reaction caused by oxidation in the long-chain alkyl-terminated side-chain phenyl silicone oil within a certain temperature range, and can be regenerated under the action of O2 in the air; by absorbing certain trace acids or alkaline substances in the long-chain alkyl-terminated side-chain phenyl silicone oil that can catalyze the degradation reaction, it has a thermal stabilizing effect on the long-chain alkyl-terminated side-chain phenyl silicone oil; and, cerium oxide prevents the oxidative cross-linking and main chain cyclization degradation of the long-chain alkyl-terminated side-chain phenyl silicone oil. Under this synergistic effect, the prepared high-temperature resistant thermally conductive putty achieves the effect of long-term high temperature resistance, can play the role of packaging, heat conduction, and protection, and in an extremely high temperature environment, the state of the thermally conductive putty is maintained well, and the thermal conductivity is excellent, providing a stable guarantee for the normal operation of electronic equipment.

[0055] The preparation method of the high temperature resistant thermal conductive putty provided in the present application has a simple process, a short production cycle, and high production efficiency, and can be used for large-scale production.

[0056] The electronic instrument provided by the present application has excellent heat resistance and long service life. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for use in the embodiments will be briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present application and therefore should not be regarded as limiting the scope of the present application.

[0058] Figure 1 The infrared spectrum of the double-terminal hydrogen-containing phenyl silicone oil provided in Example 1;

[0059] Figure 2 This is the infrared spectrum of the long-chain alkyl-terminated side-chain phenyl silicone oil prepared in Example 1;

[0060] Figure 3 This is a TGA curve diagram of the high temperature resistant thermal conductive putty prepared in Example 1. DETAILED DESCRIPTION

[0061] As used herein:

[0062] "Prepared from" is synonymous with "comprising." As used herein, the terms "comprising," "including," "having," "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises the listed elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

[0063] The conjunction "consisting of excludes any unspecified element, step, or component. If used in a claim, this phrase renders the claim closed-ended so 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 body of a claim rather than immediately following the subject matter, it limits only the elements described in that clause; other elements are not excluded from the claim as a whole.

[0064] When an amount, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper preferred values ​​and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pairing of any range upper limit or preferred value with any range lower limit or preferred value, regardless of whether the range is disclosed separately. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted as including ranges "1 to 4", "1 to 3", "1 to 2", "1 to 2 and 4 to 5", "1 to 3 and 5", etc. When a numerical range is described in this article, unless otherwise stated, the range is intended to include its end values ​​and all integers and fractions within the range.

[0065] In these examples, parts and percentages are by mass unless otherwise indicated.

[0066] "Parts by mass" refers to the basic unit of measurement for expressing the mass ratio of multiple components. 1 part can represent any unit mass, such as 1g or 2.689g. If we say that the mass of component A is a parts and the mass of component B is b parts, it means the ratio of the mass of component A to the mass of component B is a:b. Alternatively, it means that the mass of component A is aK and the mass of component B is bK (K is an arbitrary number, indicating a multiple factor). It should not be misunderstood that, unlike the mass parts, the sum of the mass of all components is not limited to 100 parts.

[0067] "And / or" is used to indicate that one or both of the stated situations may occur, for example, A and / or B includes (A and B) and (A or B).

[0068] In a first aspect, the present application provides a long-chain alkyl-terminated side-chain phenyl silicone oil, the structural formula of which is:

[0069]

[0070] Wherein, m and n are positive integers, m≥1, n≥1, and R is a C6-C18 alkyl group.

[0071] Optionally, m can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 50, 100 or any integer greater than or equal to 1, n can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 50, 100 or any integer greater than or equal to 1, and R can be C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18 or any alkyl group between C6 and C18.

[0072] In some optional embodiments, 10≤m≤1000, 10≤n≤1000.

[0073] In some embodiments, the raw materials of the long-chain alkyl-terminated side-chain phenyl silicone oil include double-terminal hydrogen-containing phenyl silicone oil and olefin compounds, satisfying at least one of the following conditions:

[0074] A. The chemical formula of the double-terminal hydrogen-containing phenyl silicone oil is:

[0075] H(CH3)2SiO[(CH3)2SiO] m [(C6H5)2SiO] n Si(CH3)2H;

[0076] Wherein, m and n are positive integers, m≥1, n≥1;

[0077] Optionally, m can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 50, 100 or any integer greater than or equal to 1, and n can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 50, 100 or any integer greater than or equal to 1.

[0078] It should be noted that the m and n values ​​in the double-terminal hydrogen-containing phenyl silicone oil are consistent with the m and n values ​​in the long-chain alkyl-terminated side-chain phenyl silicone oil.

[0079] B. The chemical structural formula of the olefin compound is:

[0080] R-CH=CH2;

[0081] Wherein, R is a C6-C18 alkyl group;

[0082] C. The molar amount of phenyl in the double-terminal hydrogen-containing phenyl silicone oil is 5%-30%, and the mass content of hydrogen is 0.01%-0.1%.

[0083] Optionally, the molar ratio of phenyl groups in the double-ended hydrogenated phenyl silicone oil can be 5%, 10%, 15%, 20%, 25%, 30% or any value between 5% and 30%, and the mass content of hydrogen can be 0.01%, 0.05%, 0.1% or any value between 0.01% and 0.1%.

[0084] It should be noted that when the benzene content in the double-ended hydrogenated phenyl silicone oil is too low, the temperature resistance is poor; when the benzene content is too high, the system viscosity is too high and powder filling is difficult; if the hydrogen content is too low, the reaction activity is low and it is difficult to react; if the hydrogen content is too high, the reaction is violent and difficult to control.

[0085] The second aspect of the present application provides a method for preparing the long-chain alkyl-terminated side-chain phenyl silicone oil, comprising:

[0086] The double-terminal hydrogen-containing phenyl silicone oil, the olefin compound, and the platinum-based catalyst are first mixed and reacted to obtain a mixture;

[0087] The mixture is subjected to reduced pressure distillation to obtain the long-chain alkyl-terminated side-chain phenyl silicone oil.

[0088] It should be noted that under the action of platinum-based catalysts, the reaction formula of double-terminal hydrogen-containing phenyl silicone oil and olefin compounds is:

[0089]

[0090] It should also be noted that the purpose of vacuum distillation is to remove low-boiling substances and obtain the final product, long-chain alkyl-terminated side-chain phenyl silicone oil.

[0091] In some embodiments, the preparation method of the long-chain alkyl-terminated side-chain phenyl silicone oil meets at least one of the following conditions:

[0092] A. The mass ratio of the double-terminal hydrogenated phenyl silicone oil to the olefin compound is 0.9-1.1:0.9-1.1;

[0093] Optionally, the mass ratio of the double-terminal hydrogenated phenyl silicone oil to the olefin compound can be 0.9:0.9, 1:0.9, 1.1:0.9, 0.9:1, 0.9:1.1, 1:1.1 or any value between 0.9-1.1:0.9-1.1;

[0094] B. The amount of the platinum-based catalyst used is 0.0009%-0.0011% of the total mass of the olefin compound of the double-terminal hydrogen-containing phenyl silicone oil;

[0095] Optionally, the amount of the platinum-based catalyst may be 0.0009%, 0.001%, 0.0011% or any value between 0.0009% and 0.0011% of the total mass of the olefin compound of the double-terminal hydrogenated phenyl silicone oil;

[0096] B. The platinum content in the platinum-based catalyst is 3000ppm-5000ppm;

[0097] Optionally, the platinum content in the platinum-based catalyst may be 3000 ppm, 3500 ppm, 4000 ppm, 4500 ppm, 5000 ppm or any value between 3000 ppm and 5000 ppm;

[0098] C. The first mixing comprises: performing a second mixing of the double-terminal hydrogenated phenyl silicone oil, a portion of the olefin compound, and the platinum-based catalyst, and heating to obtain a mixture A;

[0099] The mixture A and the remaining olefin compounds are mixed for the third time;

[0100] It should be noted that the addition of olefin compounds in steps and batch feeding shortens the reaction time, increases the catalytic activity, and shortens the induction period.

[0101] D. The reaction temperature is 120°C-130°C and the reaction time is 1h-2h;

[0102] Optionally, the reaction temperature may be 120°C, 125°C, 130°C or any value between 120°C and 130°C, and the reaction time may be 1h, 1.5h, 2h or any value between 1h and 2h;

[0103] E. The vacuum degree of the reduced pressure distillation is 0.08MPa-0.1MPa, the temperature is 120℃-130℃, and the time is 15min-30min.

[0104] Optionally, the vacuum degree of the reduced pressure distillation can be 0.08MPa, 0.09MPa, 0.1MPa or any value between 0.08MPa-0.1MPa, the temperature can be 120℃, 125℃, 130℃ or any value between 120℃-130℃, and the time can be 15min, 20min, 25min, 30min or any value between 15min-30min.

[0105] It should be noted that the purpose of vacuum distillation is to remove low boiling substances.

[0106] In some embodiments, the preparation method of the long-chain alkyl-terminated side-chain phenyl silicone oil meets at least one of the following conditions:

[0107] A. The mass ratio of the double-terminal hydrogenated phenyl silicone oils in the second mixing and the third mixing is 0.9-1.1:8.9-9.1;

[0108] Optionally, the mass ratio of the double-terminal hydrogenated phenyl silicone oils for the second mixing and the third mixing may be 0.9:8.9, 1:8.9, 1.1:8.9, 0.9:9, 0.9:9.1, 1.1:9.1 or any value between 0.9-1.1:8.9-9.1;

[0109] B. The terminal temperature of the heating is 90°C-100°C.

[0110] Optionally, the end point temperature of heating may be 90°C, 95°C, 100°C or any value between 90°C and 100°C.

[0111] The third aspect of the present application provides a high temperature resistant thermally conductive putty, the raw materials of which, by weight, include:

[0112] 75-115 parts of long-chain alkyl-terminated side-chain phenyl silicone oil, 3-7 parts of cerium oxide, and 360-540 parts of thermal conductive filler;

[0113] Optionally, the raw materials of the high temperature resistant thermally conductive putty are measured by weight: the long-chain alkyl-terminated side-chain phenyl silicone oil can be 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, 100 parts, 105 parts, 110 parts, 115 parts or any value between 75 parts and 115 parts; the cerium oxide can be 3 parts, 4 parts, 5 parts, 6 parts, 7 parts or any value between 3 parts and 7 parts; the thermally conductive filler can be 360 ​​parts, 380 parts, 400 parts, 420 parts, 440 parts, 460 parts, 480 parts, 500 parts, 520 parts, 540 parts or any value between 360 parts and 540 parts;

[0114] The long-chain alkyl-terminated side-chain phenyl silicone oil includes the long-chain alkyl-terminated side-chain phenyl silicone oil or the long-chain alkyl-terminated side-chain phenyl silicone oil prepared by the preparation method;

[0115] The thermally conductive filler includes one or more of zinc oxide, aluminum oxide, and boron nitride.

[0116] In some embodiments, the high temperature resistant thermally conductive putty satisfies at least one of the following conditions:

[0117] A. the cerium oxide comprises nano cerium oxide;

[0118] The particle size of the nano cerium oxide is 10nm-100nm;

[0119] Optionally, the particle size of nano-cerium oxide can be 10nm, 20nm, 40nm, 60nm, 80nm, 100nm or any value between 10nm and 100nm;

[0120] B. the thermally conductive filler includes the boron nitride;

[0121] It should be noted that the π bond formed by the hybridization of B atoms and N atoms in boron nitride (BN) can interact with the phenyl side chain in phenyl silicone rubber to improve the heat resistance of the base material (about 300°C). However, the thermal putty made of phenyl silicone oil + boron nitride is prone to oil leakage, so it is necessary to introduce long-chain alkyl groups into the phenyl silicone oil. However, after the introduction of long-chain alkyl groups, the long-chain alkyl groups are easily oxidized, thereby affecting the temperature resistance. Therefore, cerium oxide needs to be introduced to prevent the oxidation cross-linking of polysiloxane. Through these synergistic effects, the thermal putty can withstand high temperatures for a long time.

[0122] C. The thermally conductive filler comprises, by parts:

[0123] 120-180 parts of zinc oxide, 220-280 parts of aluminum oxide, and 20-80 parts of boron nitride;

[0124] Optionally, the thermal conductive filler may be 120 parts, 130 parts, 140 parts, 150 parts, 160 parts, 170 parts, 180 parts or any value between 120 parts and 180 parts of zinc oxide, 220 parts, 230 parts, 240 parts, 250 parts, 260 parts, 270 parts, 280 parts or any value between 220 parts and 280 parts of aluminum oxide, and 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts or any value between 20 parts and 80 parts of boron nitride;

[0125] It should be noted that when the thermal conductive filler includes 120-180 parts of zinc oxide, 220-280 parts of aluminum oxide, and 20-80 parts of boron nitride, zinc oxide is mainly a thixotropic thermal conductive filler. In addition to the basic thermal conductive properties, it can also obtain better thixotropy. Aluminum oxide is a conventional thermal conductive filler, which mainly has the function of thermal conductivity.

[0126] D. The zinc oxide includes needle-shaped zinc oxide; the particle size of the needle-shaped zinc oxide is 0.1um-1um;

[0127] Optionally, the particle size of the needle-shaped zinc oxide can be 0.1um, 0.5um, 1um or any value between 0.1um-1um;

[0128] E. The alumina includes one or more of angular alumina, quasi-spherical alumina, spherical alumina, and single crystal alumina;

[0129] In some embodiments, the alumina comprises spherical alumina;

[0130] It should be noted that spherical alumina has lower viscosity than other shapes of alumina and is easier to add;

[0131] The particle size of the aluminum oxide is 1um-20um;

[0132] Optionally, the particle size of aluminum oxide may be 1um, 5um, 10um, 15um, 20um or any value between 1um and 20um;

[0133] F. The boron nitride includes one or more of hexagonal boron nitride, close-packed hexagonal boron nitride, cubic boron nitride, and spherical boron nitride;

[0134] In some embodiments, the boron nitride comprises hexagonal boron nitride;

[0135] It should be noted that the chemical properties of hexagonal boron nitride are extremely stable. Nitrogen and boron in hexagonal boron nitride also form a hexagonal network layer. Nitrogen and boron form a planar large π bond through sp2 hybridization, which is easier to interact with the phenyl side chain in phenyl silicone rubber.

[0136] The particle size of the boron nitride is 0.3um-25um.

[0137] Optionally, the particle size of boron nitride can be 0.3um, 1um, 5um, 10um, 15um, 20um, 25um or any value between 0.3um and 25um.

[0138] The fourth aspect of the present application provides a method for preparing the high temperature resistant thermally conductive putty, comprising:

[0139] Under vacuum conditions, the raw materials of the high temperature resistant thermal conductive putty are subjected to a fourth mixing to prepare the high temperature resistant thermal conductive putty.

[0140] It should be noted that under vacuum conditions, bubbles can be removed better.

[0141] In some embodiments, the preparation method of the high temperature resistant thermally conductive putty satisfies at least one of the following conditions:

[0142] A. The vacuum degree of the vacuum condition is 0.08MPa-0.1MPa;

[0143] Optionally, the vacuum degree of the vacuum condition may be 0.08MPa, 0.09MPa, 0.1MPa or any value between 0.08MPa and 0.1MPa;

[0144] B. The fourth mixing time is 25 min-35 min.

[0145] It should be noted that the fourth mixing time can be 25 min, 30 min, 35 min or any value between 25 min and 35 min.

[0146] A fifth aspect of the present application provides an electronic instrument, comprising the high temperature resistant thermally conductive putty described above or the high temperature resistant thermally conductive putty prepared by the method for preparing the high temperature resistant thermally conductive putty described above.

[0147] It should be noted that the electronic instrument includes but is not limited to one or more of a radiator, an image processing module, and a heating chip.

[0148] The embodiments of the present application will be described in detail below in conjunction with specific examples, but it will be appreciated by those skilled in the art that the following examples are only used to illustrate the present application and should not be considered as limiting the scope of the present application. If specific conditions are not specified in the examples, they are carried out according to normal conditions or the conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0149] Example 1

[0150] In a first aspect, the present embodiment provides a long-chain alkyl-terminated side-chain phenyl silicone oil having the structural formula:

[0151]

[0152] Wherein, R is a C12 alkyl group;

[0153] Among them, the raw materials of long-chain alkyl-terminated side-chain phenyl silicone oil include double-terminal hydrogen-containing phenyl silicone oil and olefin compounds;

[0154] The chemical formula of double-terminal hydrogen-containing phenyl silicone oil is:

[0155] H(CH3)2SiO[(CH3)2SiO] m [(C6H5)2SiO] n Si(CH3)2H,

[0156] Among them, the number of m and n is consistent with that in the structural formula of the long-chain alkyl-terminated side-chain phenyl silicone oil, with a mass content of 10% for phenyl, a mass content of 0.05% for hydrogen, a viscosity of 350cps, selected from Shandong Dayi Chemical Co., Ltd., model DY-PH201;

[0157] The chemical structure of olefin compounds is:

[0158] CH3(CH2) 11 -CH=CH2.

[0159] The second aspect of this embodiment provides a method for preparing a long-chain alkyl-terminated side-chain phenyl silicone oil, comprising:

[0160] In a four-necked flask equipped with a stirrer, a dropping funnel, a thermometer and a condenser, the above-mentioned double-ended hydrogen-containing phenyl silicone oil and part of the olefin compounds (accounting for 10% of the total mass of the olefin compounds) and 5000ppm of platinum catalyst are added, and the remaining olefin compounds (accounting for 90% of the total mass of the olefin compounds by mole) are added dropwise when heated to 90°C. After the addition of the olefin compounds is completed, the reaction is continued at 120°C-130°C for 1.5h, and then the low-boiling substances are removed by reduced pressure distillation. The vacuum degree of the reduced pressure distillation is 0.08MPa-0.1MPa, the temperature is 120°C-130°C, and the time is 15min-30min, to obtain a long-chain alkyl-terminated side-chain phenyl silicone oil;

[0161] The amount of platinum catalyst used is 0.001% of the total mass of the olefin compound of the double-terminal hydrogen-containing phenyl silicone oil.

[0162] Infrared test of double-terminal hydrogenated phenyl silicone oil Figure 1 As shown, among them, 1412.54 is a phenyl group, and 2127.58 is a hydrogen-containing Si-H bond;

[0163] The infrared test of the long-chain alkyl-terminated side-chain phenyl silicone oil is as follows Figure 2 As shown, compared Figure 1 , the hydrogen-containing Si-H bond at 2127.58 is significantly reduced, proving that the reaction is carried out effectively.

[0164] A third aspect of the present embodiment provides a high temperature resistant thermally conductive putty, the raw materials of which, measured by weight, include:

[0165] 90g of the above-mentioned long-chain alkyl-terminated side-chain phenyl silicone oil, 5g of cerium oxide, and 450 parts of thermal conductive filler;

[0166] Thermally conductive fillers, by parts, include:

[0167] 150g zinc oxide, 250g aluminum oxide, 50g boron nitride;

[0168] Cerium oxide includes nano-cerium oxide, the particle size of which is 30 nm, purchased from Xuancheng Jingrui New Materials Co., Ltd.

[0169] Zinc oxide includes needle-shaped zinc oxide, the particle size of which is 0.6 μm and is purchased from Japan Shirasu Chemical;

[0170] Alumina includes spherical alumina, the particle size of spherical alumina is 20 μm, purchased from Ya'an Baitu High-tech Materials Co., Ltd., model BAK-20;

[0171] Boron nitride includes hexagonal boron nitride, and the particle size of hexagonal boron nitride is 1 um, which is purchased from Liaoning Boronda Technology Co., Ltd.

[0172] A fourth aspect of the present embodiment provides a method for preparing a high temperature resistant thermally conductive putty, comprising:

[0173] Under the condition of a vacuum degree of 0.08MPa-0.1MPa, the raw materials of the high temperature resistant thermal conductive putty are added into a vacuum planetary mixer, stirred for 30 minutes at -0.08MPa and a rotation speed of 10rpm to obtain the high temperature resistant thermal conductive putty.

[0174] The prepared high temperature resistant thermal conductive putty was subjected to thermogravimetric test, and the obtained TGA curve is as follows Figure 1 As shown, in fact, the test was carried out using a thermogravimetric analyzer, and the test conditions were: under nitrogen, from room temperature to 800°C, with a heating rate of 20°C / min, a gas flow rate of 60mL / min, and a balance gas flow rate of 40mL / min.

[0175] Example 2

[0176] The difference from Example 1 is that the added amount of cerium oxide is 7 g.

[0177] Example 3

[0178] The difference from Example 1 is that the added amount of zinc oxide is 120 g.

[0179] Example 4

[0180] The difference from Example 1 is that the amount of aluminum oxide added is 280 g.

[0181] Example 5

[0182] The difference from Example 1 is that the added amount of boron nitride is 30 g.

[0183] Comparative Example 1

[0184] The difference from Example 1 is that long-chain alkyl-terminated side-chain phenyl silicone oil and its preparation method are not provided, and the long-chain alkyl-terminated side-chain phenyl silicone oil in the high-temperature resistant thermally conductive putty is replaced by methyl-terminated side-chain phenyl silicone oil of the same viscosity, and the methyl-terminated side-chain phenyl silicone oil is purchased from Guangdong Chensi New Material Technology Co., Ltd., model CX360.

[0185] Comparative Example 2

[0186] The difference from Example 1 is that the double-terminal hydrogen-containing phenyl silicone oil is replaced by a double-terminal hydrogen-containing silicone oil purchased from Shandong Dayi Chemical Co., Ltd., model DY-H201.

[0187] Comparative Example 3

[0188] The difference from Example 1 is that cerium oxide is not added.

[0189] Comparative Example 4

[0190] The difference from Example 1 is that the boron nitride is replaced by 1 um alumina purchased from Ya'an Baitu High-tech Materials Co., Ltd., model number NSM-1S.

[0191] The performance test of the high temperature resistant thermal conductive putty prepared in the above embodiment and comparative example is carried out. The test results are shown in Table 1. The specific test standards are as follows:

[0192] Thermal conductivity: According to the standard of ASTM D5470-2017, the unit is W / m·k;

[0193] Thermal resistance: According to the standard of ASTM D5470-2017, the unit is ℃in2 / W;

[0194] Dispensing rate: Tested by the mass of extrusion at 90psi, 1mm nozzle, 1min, in g;

[0195] Specific gravity: in accordance with the standard in ASTM D792-2007 Plastics Density and Relative Density Test Method, the unit is g / cc;

[0196] Oil discharge: Pour 110mm high temperature resistant thermal putty into a 15mm×150mm test tube, store it at room temperature and pressure for 30 days, observe the separation of oil and powder in the rubber, and then characterize it by measuring the total height of the oil-powder separation layer (unit: mm);

[0197] High temperature resistance test: According to GB / T 2423.2-2008 Environmental testing for electric and electronic products Part 2: Test method Test B: Test at 300℃ for 1000h.

[0198] Table 1 Performance test

[0199]

[0200] It can be seen from Table 1 that the high temperature resistant thermally conductive putty provided by the present application has excellent thermal conductivity, good high temperature resistance, and good anti-oiling effect, indicating that the present application uses the synergistic interaction of long-chain alkyl-terminated side-chain phenyl silicone oil, cerium oxide and thermally conductive filler to make the prepared thermally conductive putty have excellent high temperature resistance, and there will be no obvious change even at a high temperature of 300°C for 1000 hours.

[0201] From Comparative Example 1, it can be seen that phenyl silicone oil plus boron nitride plus cerium oxide has good heat resistance, but the lack of long-chain alkyl has poor oil resistance, so pure phenyl silicone oil is not suitable for making oil-free thermal putty. Comparative Example 2 shows that silicone oil lacking phenyl has poor heat resistance, Comparative Example 3 shows that silicone oil lacking cerium oxide has poor heat resistance, and Comparative Example 4 shows that boron nitride has poor heat resistance.

[0202] However, this application requires a high-temperature resistant thermal putty (target is 300℃1000H). Simple silicone rubber is not good at high temperature resistance, so phenyl silicone oil is used, but the temperature resistance of simple phenyl silicone oil is still not ideal, so it is necessary to introduce boron nitride. The π bond formed by the hybridization of B atoms and N atoms in BN can interact with the phenyl side chain in phenyl silicone rubber, which is beneficial to improve the heat resistance of the matrix material. However, the thermal putty made of phenyl silicone oil + boron nitride is prone to oil leakage, so it is necessary to introduce long-chain alkyl groups into phenyl silicone oil. However, after the introduction of long-chain alkyl groups, the long-chain alkyl groups are easily oxidized, thereby affecting the temperature resistance, so it is necessary to introduce cerium oxide to prevent polysiloxane from oxidative cross-linking. Through the above-mentioned synergistic effect, the high-temperature resistant thermal putty can withstand 300℃ (1000H) for a long time.

[0203] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit it. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present application.

[0204] In addition, those skilled in the art will appreciate that, although some embodiments herein include certain features included in other embodiments but not other features, the combination of features of different embodiments is meant to be within the scope of the present application and form different embodiments. For example, in the above claims, any one of the claimed embodiments may be used in any combination. The information disclosed in this background technology section is intended only to deepen the understanding of the overall background technology of the present application and should not be regarded as an admission or in any form of implication that the information constitutes prior art known to those skilled in the art.

Claims

1. A long-chain alkyl-terminated side-chain phenyl silicone oil, characterized in that: Its structural formula is: Wherein, m and n are positive integers, m≥1, n≥1, and R is a C6-C18 alkyl group.

2. The long-chain alkyl-terminated side-chain phenyl silicone oil according to claim 1, characterized in that The raw materials of the long-chain alkyl-terminated side-chain phenyl silicone oil include double-terminal hydrogen-containing phenyl silicone oil and olefin compounds, and meet at least one of the following conditions: A. The chemical formula of the double-terminal hydrogen-containing phenyl silicone oil is: <h2 style=";text-align:left;direction:ltr">H(CH3)2SiO[(CH3)2SiO]<h2 style=";text-align:left;direction:ltr"> m <h2 style=";text-align:left;direction:ltr"> [(C6H5)2SiO]<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr"> Si(CH3)2H; Wherein, m and n are positive integers, m≥1, n≥1; B. The chemical structural formula of the olefin compound is: R-CH=CH2; Wherein, R is a C6-C18 alkyl group; C. The molar amount of phenyl in the double-terminal hydrogen-containing phenyl silicone oil is 5%-30%, and the mass content of hydrogen is 0.01%-0.1%.

3. A method for preparing the long-chain alkyl-terminated side-chain phenyl silicone oil according to claim 1 or 2, characterized in that: include: The double-terminal hydrogen-containing phenyl silicone oil, the olefin compound, and the platinum-based catalyst are first mixed and reacted to obtain a mixture; The mixture is subjected to reduced pressure distillation to obtain the long-chain alkyl-terminated side-chain phenyl silicone oil.

4. The method for preparing a long-chain alkyl-terminated side-chain phenyl silicone oil according to claim 3, characterized in that: At least one of the following conditions is met: A. The mass ratio of the double-terminal hydrogenated phenyl silicone oil to the olefin compound is 0.9-1.1:0.9-1.1; B. The amount of the platinum-based catalyst used is 0.0009%-0.0011% of the total mass of the olefin compound of the double-terminal hydrogen-containing phenyl silicone oil; B. The platinum content in the platinum-based catalyst is 3000ppm-5000ppm; C. The first mixing comprises: performing a second mixing of the double-terminal hydrogenated phenyl silicone oil, a portion of the olefin compound, and the platinum-based catalyst, and heating to obtain a mixture A; The mixture A and the remaining olefin compounds are mixed for the third time; D. The reaction temperature is 120°C-130°C and the reaction time is 1h-2h; E. The vacuum degree of the reduced pressure distillation is 0.08MPa-0.1MPa, the temperature is 120℃-130℃, and the time is 15min-30min.

5. The method for preparing the long-chain alkyl-terminated side-chain phenyl silicone oil according to claim 4, characterized in that: At least one of the following conditions is met: A. The mass ratio of the double-terminal hydrogenated phenyl silicone oils in the second mixing and the third mixing is 0.9-1.1:8.9-9.1; B. The terminal temperature of the heating is 90°C-100°C.

6. A high temperature resistant thermally conductive putty, characterized in that: The raw materials, calculated by mass, include: 75-115 parts of long-chain alkyl-terminated side-chain phenyl silicone oil, 3-7 parts of cerium oxide, and 360-540 parts of thermal conductive filler; The long-chain alkyl-terminated side-chain phenyl silicone oil comprises the long-chain alkyl-terminated side-chain phenyl silicone oil according to claim 1 or 2 or the long-chain alkyl-terminated side-chain phenyl silicone oil according to any one of claims 3 to 5. The thermally conductive filler includes one or more of zinc oxide, aluminum oxide, and boron nitride.

7. The high temperature resistant thermally conductive putty according to claim 6, characterized in that: At least one of the following conditions is met: A. the cerium oxide comprises nano cerium oxide; The particle size of the nano cerium oxide is 10nm-100nm; B. the thermally conductive filler includes the boron nitride; C. The thermally conductive filler comprises, by parts: 120-180 parts of zinc oxide, 220-280 parts of aluminum oxide, and 20-80 parts of boron nitride; D. The zinc oxide includes needle-shaped zinc oxide; the particle size of the needle-shaped zinc oxide is 0.1um-1um; E. The alumina includes one or more of angular alumina, quasi-spherical alumina, spherical alumina, and single crystal alumina; The particle size of the aluminum oxide is 1um-20um; F. The boron nitride includes one or more of hexagonal boron nitride, close-packed hexagonal boron nitride, cubic boron nitride, and spherical boron nitride; The particle size of the boron nitride is 0.3um-25um.

8. A method for preparing the high temperature resistant thermally conductive putty according to claim 6 or 7, characterized in that: include: Under vacuum conditions, the raw materials of the high temperature resistant thermal conductive putty are subjected to a fourth mixing to prepare the high temperature resistant thermal conductive putty.

9. The method for preparing the high temperature resistant thermally conductive putty according to claim 8, characterized in that: At least one of the following conditions is met: A. The vacuum degree of the vacuum condition is 0.08MPa-0.1MPa; B. The fourth mixing time is 25 min-35 min.

10. An electronic device, characterized in that: The invention relates to a high temperature resistant thermally conductive putty prepared by the high temperature resistant thermally conductive putty according to claim 6 or 7 or the high temperature resistant thermally conductive putty prepared by the preparation method of the high temperature resistant thermally conductive putty according to claim 8 or 9.

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