Modified oxide filler, method for its production and use thereof

Abstract

This invention relates to the field of filler and coating technology, specifically to a modified oxide filler, its preparation method, and its application. The modified oxide filler comprises nano-metal oxides and polyethers, wherein the polyether has the structure shown in formula (1): Formula (1), where the ratio of m to n is 0.3-3:1; R has the structure shown in formula (2), Formula (2), where R1 is a C0-C10 alkylene group, and R2, R3, and R4 are each independently selected from C1-C3 alkyl groups. The modified oxide filler effectively promotes the dispersion of nano-oxide fillers and, when used in heat-dissipating coatings, can improve the performance of the coating.

Description

Technical Field

[0001] This invention relates to the field of filler and coating technology, specifically to a modified oxide filler, its preparation method, and its application. Background Technology

[0002] With the development of science and technology and the progress of industry, heat dissipation materials are increasingly widely used in electronic equipment, automobiles, aerospace and other fields. As an important heat dissipation material, the performance of heat dissipation coatings directly affects the service life and operational stability of equipment. Traditional heat dissipation coatings mainly consist of thermally conductive materials, binders and other additives. However, with the ever-increasing requirements for heat dissipation performance, traditional materials can no longer fully meet the needs of modern applications. Therefore, the research and development of high-performance heat dissipation coatings has become an important research direction.

[0003] The key to heat-dissipating coatings lies in the selection and modification of their thermally conductive fillers. Fillers are the main components determining the thermal conductivity of the coating, and typically include metal oxides, nitrides, and carbides. Among these, oxide fillers are widely used due to their excellent chemical stability and good thermal conductivity. For example, nano-oxides such as alumina, zinc oxide, and titanium oxide have been proven to perform excellently in improving the thermal conductivity of coatings. Nano-oxides have a larger specific surface area and higher thermal conductivity, which can significantly improve the overall heat dissipation performance of the coating.

[0004] However, relying solely on the selection of fillers is insufficient to meet the requirements of modern high-performance thermal coatings. The dispersibility and bonding strength of the fillers with the matrix also have a significant impact on the performance of the coating.

[0005] While there have been some successful applications of existing technologies, many challenges remain. Therefore, developing a novel surface polyether and exploring its application in heat dissipation coatings will be of great significance for improving the performance of heat dissipation coatings and broadening their application scope. Summary of the Invention

[0006] The purpose of this invention is to overcome the problems of easy agglomeration and uneven dispersion of fillers and unstable performance in the prior art, and to provide a modified oxide filler, its preparation method and application. The modified oxide filler can effectively promote the dispersion of nano-oxidation fillers and can improve the performance of heat dissipation coatings.

[0007] To achieve the above objectives, a first aspect of the present invention provides a modified oxide filler comprising a nano-metal oxide and a polyether, wherein the polyether has the structure shown in formula (1): Equation (1), Where the ratio of m to n is 0.3-3:1; R has the structure shown in equation (2), Equation (2), Wherein, R1 is a C0-C10 alkylene group, and R2, R3, and R4 are each independently selected from C1-C3 alkyl groups.

[0008] A second aspect of the present invention provides a method for preparing the modified oxide filler of the present invention, the method comprising: mixing nano-oxide, polyether and solvent, and drying.

[0009] A third aspect of the present invention provides the application of the modified oxide filler described herein in a heat-dissipating coating.

[0010] Through the above technical solutions, the modified nano-oxidative filler provided by the present invention, through the reasonable selection of polyether, effectively improves the dispersibility and stability of the nano-oxidative filler in the coating, overcomes the shortcomings of traditional fillers that are prone to agglomeration and uneven dispersion, and makes the filler more evenly distributed in the matrix when used in heat dissipation coatings, thus ensuring the performance stability of the coating.

[0011] The polyether described in this invention has a unique molecular structure, which not only gives it excellent defoaming properties but also effectively promotes the dispersion of nano-oxidative fillers, thereby improving the performance of the coating.

[0012] The modified nano-oxidative filler provided by this invention not only improves the overall performance of coatings, but also expands their application prospects in multiple fields such as construction, industrial equipment, and transportation vehicles, and has significant market value. Attached Figure Description

[0013] Figure 1 This is the 1H NMR spectrum of polyether A1 in Preparation Example 1; Figure 2 This is the carbon NMR spectrum of polyether A1 in Preparation Example 1; Figure 3 This is the two-dimensional HMBC NMR spectrum of polyether A1 in Preparation Example 1; Figure 4 This is the total particle flow chromatogram of the polyether A1 prepared in Example 1. Detailed Implementation

[0014] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0015] The first aspect of the present invention provides a modified oxide filler comprising a nano-metal oxide and a polyether, wherein the polyether has the structure shown in formula (1): Equation (1), Where the ratio of m to n is 0.3-3:1; R has the structure shown in equation (2), Equation (2), In this design, R1 is a C0-C10 alkylene group, and R2, R3, and R4 are each independently selected from C1-C3 alkyl groups. This modified oxide filler effectively promotes the dispersion of nano-oxidative fillers and, when used in heat-dissipating coatings, can improve the performance of the coatings.

[0016] In this invention, the alkylene group of C0 is not present, and the groups at both ends of the group are directly connected.

[0017] In the polyether described in this invention, The starting end groups introduced into the polymer structure by the polyether initiator are connected in sequence with ethylene oxide blocks and propylene oxide blocks. The other end of the polymer main chain is capped with a propylene oxide block and a hydroxyl group. Through the synergistic effect of the capping groups at both ends of the copolymer main chain, the surface tension is reduced while the defoaming effect is improved.

[0018] In this invention, the structure of the polyether can be confirmed by NMR analysis. In the two-dimensional C-H NMR spectrum of the polyether, there are three carbon signals related to the hydrogen of the terminal hydroxyl group, that is, there are three spatially adjacent carbons near the hydroxyl group, proving that the terminal hydroxyl group comes from the propylene oxide block.

[0019] According to a preferred embodiment of the present invention, R1 is selected from -(CH2). x1 -、-CH2-CH(CH3)-(CH2) x2 -, -CH2-C(CH3)2-(CH2) x3 -、-CH(CH3)-(CH2) x4 -、-C(CH3)2-(CH2) x5 -、-C(CH3)(CH2CH3)-(CH2) x6 -or -C(CH3)(C3H7)-(CH2) x7 - where x1-x7 are each independently selected from 0, 1, 2, 3 or 4; this is beneficial for improving the dispersibility of nano-oxidation fillers.

[0020] In this invention, R2, R3, and R4 are each independently selected from C1-C3 alkyl groups, wherein the alkyl group can be a straight-chain or branched alkyl group, including but not limited to methyl, ethyl, n-propyl, or isopropyl. More preferably, R2, R3, and R4 are all methyl. Using the above-mentioned preferred structural composition is beneficial for accelerating the disappearance of foam.

[0021] According to a preferred embodiment of the present invention, the ratio of m to n is 0.5-2:1, which is beneficial to improving the dispersibility of the nano-oxidation filler.

[0022] In the context of this specification, including in the embodiments, the degree of polymerization is obtained by NMR analysis.

[0023] According to a preferred embodiment of the present invention, m is 1-14, preferably 3-9; n is 1-14, preferably 3-9, which is beneficial to reduce surface tension and make it easier to defoam, thereby improving the dispersibility of nano-oxidation fillers.

[0024] According to a preferred embodiment of the present invention, R is selected from -CH2CH2CH(CH3)CH2C(CH3)2CH3, -C(CH2CH3)(CH2CH2CH3)CH3, -CH2CH2C(CH3)2CH2CH3 or -C(CH3)2CH2CH3; preferably -CH2CH2CH(CH3)CH2C(CH3)2CH3.

[0025] According to a preferred embodiment of the present invention, the weight-average molecular weight of the polyether does not exceed 2000 g / mol, preferably 450-1500 g / mol, for example, it can be 450 g / mol, 500 g / mol, 550 g / mol, 600 g / mol, 650 g / mol, 700 g / mol, 750 g / mol, 800 g / mol, 850 g / mol, 900 g / mol, 950 g / mol, 1000 g / mol, 1100 g / mol, 1200 g / mol, 1300 g / mol, 1400 g / mol, 1500 g / mol, or a value between two points. Within the above-mentioned preferred molecular weight range, it is beneficial to reduce the viscosity of the polyether and improve its dispersion performance.

[0026] In the context of this invention specification, including the examples, the molecular weight is obtained by gas chromatography-mass spectrometry analysis; the molecular weight of polyether is tested using gas chromatography-mass spectrometry under the following conditions: HP-5MS column, column temperature 50(5)-10-300(20), injection volume 1 μL, split ratio 50:1, injection port temperature 300 ℃, carrier gas flow rate 1 mL / min, and total particle flow of standard sample is collected as a reference.

[0027] According to a preferred embodiment of the present invention, the polyether has a viscosity of 50 to 1000 centipoise (cP) at 25°C, preferably 500-1000 centipoise, which is beneficial to improving the dispersibility of the nano-oxidation filler.

[0028] According to a preferred embodiment of the present invention, the hydrophilic-lipophilic balance (HLB) value of the polyether is 8 to 15, which is beneficial to improving the dispersibility of the nano-oxidative filler.

[0029] In this invention, the surface tension reduction effect of the polyether can be determined by the surface tension of the aqueous solution of the polyether.

[0030] According to one embodiment of the present invention, the polyether is mixed with water to obtain an aqueous solution of the polyether, wherein the mass concentration of the polyether is 0.1%, and the static surface tension of the aqueous solution of the polyether is 23-40 mN / m, preferably 25-30 mN / m.

[0031] According to one embodiment of the present invention, the polyether is mixed with water to obtain an aqueous solution of the polyether, wherein the mass concentration of the polyether is 0.1%, and the dynamic surface tension of the aqueous solution of the polyether is 20-45 mN / m, preferably 25-30 mN / m.

[0032] In the context of this specification, including the embodiments, the static surface tension is obtained by testing with a static surface tension meter, and the dynamic surface tension is obtained by testing with a dynamic surface tension meter.

[0033] According to a preferred embodiment of the present invention, the polyether is selected from at least one of (CH3)3CCH2CH(CH3)CH2CH2O(C2H4O)3(C3H6O)3H, CH3(CH2CH2CH3)(CH2CH3)CO(C2H4O)3(C3H6O)6H, CH3CH2C(CH3)2CH2CH2O(C2H4O)8(C3H6O)4H, and CH3CH2(CH3)2CO(C2H4O)4(C3H6O)8H, preferably (CH3)3CCH2CH(CH3)CH2CH2O(C2H4O)3(C3H6O)3H.

[0034] According to a preferred embodiment of the present invention, the polyether content is 0.6-4.76 wt% of the total mass of the nano-metal oxides.

[0035] In this invention, there is no particular limitation on the type of nano-oxide. Any nano-oxide used as a coating can be used in this invention. According to a preferred embodiment of this invention, the nano-oxide is selected from one or more of nano-alumina, nano-zinc oxide, nano-titanium oxide and nano-magnesium oxide.

[0036] In this invention, there is no particular limitation on the preparation method of the polyether. This invention provides a method for preparing the polyether, comprising the following steps: (1) In the presence of a catalyst, under the conditions of the first polymerization reaction, the initiator and ethylene oxide are brought into contact to carry out the first polymerization reaction; (2) Under the conditions of the second polymerization reaction, the product obtained from the first polymerization reaction is subjected to a second polymerization reaction with propylene oxide; Wherein, the molar ratio of ethylene oxide to initiator is 30-200:1, and the molar ratio of ethylene oxide to propylene oxide is 0.3-3:1; The initiator has the structure shown in formula (3). Equation (3), In equation (3), R1, R2, R3, and R4 correspond to R1, R2, R3, and R4 in equation (1).

[0037] It should be noted that in the preparation method of the present invention, the order of the first polymerization reaction and the second polymerization reaction is significantly affected by the product structure and performance. In the first polymerization reaction, ethylene oxide can undergo ring-opening polymerization with the initiator to obtain a first block copolymer containing ethylene oxide blocks. Then, the first block copolymer is subjected to a second polymerization reaction with propylene oxide to obtain a polyether with a block polyether structure as shown in formula (1).

[0038] According to a preferred embodiment of the present invention, in formula (3), R1 is selected from -(CH2). x1 -、-CH2-CH(CH3)-(CH2) x2 -, -CH2-C(CH3)2-(CH2) x3 -、-CH(CH3)-(CH2) x4 -、-C(CH3)2-(CH2) x5 -、-C(CH3)(CH2CH3)-(CH2) x6 - or -C(CH3)(C3H7)-(CH2) x7 - where x1-x7 are each independently selected from 0, 1, 2, 3 or 4.

[0039] In this invention, in formula (3), R2, R3, and R4 are each independently selected from C1-C3 alkyl groups, wherein the alkyl group can be a straight-chain or branched alkyl group, including but not limited to methyl, ethyl, n-propyl, or isopropyl, and more preferably, R2, R3, and R4 are methyl.

[0040] According to a preferred embodiment of the present invention, the initiator is selected from at least one of 3,5,5-trimethyl-1-hexanol, 2,3,3-trimethyl-2-butanol, 2,2-dimethyl-1-propanol, 3,3-dimethyl-1-butanol, 2,3-dimethyl-3-pentanol, 2-methyl-2-butanol, and 3,3-dimethyl-1-pentanol, preferably 3,5,5-trimethyl-1-hexanol and / or 2,3,3-trimethyl-2-butanol.

[0041] According to a preferred embodiment of the present invention, the molar ratio of ethylene oxide to the initiator is 50-150:1, for example, it can be a typical but not limiting ratio such as 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, 110:1, 120:1, 130:1, 140:1, 150:1.

[0042] According to a preferred embodiment of the present invention, the molar ratio of ethylene oxide to propylene oxide is 0.5-2:1. It is understood that the amounts of each component are sufficient to ensure that the resulting polyether has the desired composition of its structural units.

[0043] In this invention, the selection range of the catalyst is relatively wide, as long as it can catalyze the ring-opening polymerization of ethylene oxide and propylene oxide. It can be selected from conventional alkali metal or alkaline earth metal catalysts well known to those skilled in the art. Preferably, the catalyst is selected from at least one of potassium hydroxide, sodium hydroxide, barium hydroxide, and calcium acetate, and more preferably potassium hydroxide and / or sodium hydroxide.

[0044] According to a preferred embodiment of the present invention, the amount of catalyst used is 2-6 wt% of the total amount of ethylene oxide and propylene oxide, preferably 2.5-4 wt%.

[0045] According to a preferred embodiment of the present invention, the first polymerization reaction conditions include: a reaction temperature of 110-160°C, preferably 120-150°C; a reaction pressure of 0-0.4 MPa, preferably 0.2-0.4 MPa; and a reaction time of 10-60 min, preferably 30-40 min.

[0046] According to a preferred embodiment of the present invention, the second polymerization reaction conditions include: a reaction temperature of 110-160°C, preferably 130-150°C; a reaction pressure of 0-0.4 MPa, preferably 0.2-0.4 MPa; and a reaction time of 10-60 min, preferably 20-30 min.

[0047] In this invention, it is understood that during the first or second polymerization reaction, as the reaction proceeds, the pressure in the reaction system gradually decreases, and the temperature in the reaction system increases due to the exothermic reaction, as long as the pressure and temperature during the reaction process meet the above-mentioned pressure and temperature range.

[0048] In this invention, the first polymerization reaction and the second polymerization reaction can be carried out using conventional operating methods and reactors in the art, and this invention does not have any particular limitations. Preferably, the first polymerization reaction and the second polymerization reaction are carried out in a high-temperature and high-pressure reactor.

[0049] According to a preferred embodiment of the present invention, the first polymerization reaction includes: first, adding a catalyst and an initiator into a reactor, removing oxygen and drawing a vacuum, then adjusting to the first polymerization reaction conditions, and then adding ethylene oxide to carry out the first polymerization reaction.

[0050] According to a preferred embodiment of the present invention, the deoxygenation operation can be carried out using conventional methods in the art, such as introducing an inert gas into the reactor for displacement. Preferably, the inert gas is nitrogen.

[0051] In this invention, the deoxygenation and vacuuming steps can optionally be repeated. Preferably, the deoxygenation and vacuuming steps are repeated at least twice.

[0052] According to a preferred embodiment of the present invention, the first polymerization reaction and the second polymerization reaction are each carried out independently under stirring conditions, wherein the stirring rate is each independently 1500-3000 rpm, preferably 1800-2500 rpm.

[0053] According to a preferred embodiment of the present invention, the preparation method further includes: sequentially subjecting the product of the second polymerization reaction to impurity removal, neutralization, adsorption, and filtration to obtain the polyether. The impurity removal, neutralization, adsorption, and filtration can be performed using conventional operations in the art, and the present invention does not have any special requirements for them. For example, unreacted monomers and small molecules in the system can be removed by vacuuming.

[0054] A second aspect of the present invention provides a method for preparing the modified oxide filler of the present invention, the method comprising: mixing nano-oxide, polyether and solvent, and drying; According to a preferred embodiment of the present invention, the method for preparing the modified oxide filler includes: mixing 2-5 parts of nano-oxide, 0.03-0.1 parts of polyether and 40-50 parts of solvent, and drying.

[0055] According to a preferred embodiment of the present invention, the method for preparing the modified oxide filler includes: (1) Mix 2-5 parts of nano-oxide, 0.03-0.1 parts of polyether and 40-50 parts of solvent; (2) The mixture is ultrasonically treated for 30-120 minutes and then dried.

[0056] According to a preferred embodiment of the present invention, the solvent is water; According to a preferred embodiment of the present invention, the drying method is freeze drying.

[0057] A third aspect of the present invention provides the application of the modified oxide filler described herein in a heat-dissipating coating.

[0058] To further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, and not for limiting the scope of the claims of the present invention.

[0059] In the following examples, the dispersibility test of the modified oxide filler was performed using a stratification sedimentation test.

[0060] Preparation Example 1 (1) Add 1 g of (CH3)3CCH2CH(CH3)CH2CHOH and 2 g of potassium hydroxide to a high-temperature and high-pressure reactor and seal the reactor. Before heating, purge and replace with nitrogen gas, then evacuate. Repeat the nitrogen purging and evacuation process at least twice. Start stirring and heat to 125 °C. Add 40 g of ethylene oxide to carry out the first polymerization reaction. Control the reaction temperature at 140-150 °C and the reaction pressure at 0.3-0.4 MPa. Continue stirring for 40 min until the pressure drops to 0 MPa.

[0061] (2) Heat the high-temperature and high-pressure reactor to 125°C, add 40g of propylene oxide to carry out the second polymerization reaction, control the reaction temperature to 140-150°C, and control the reaction pressure to 0.3-0.4 MPa. Stir for 30 min to reduce the pressure to 0 MPa.

[0062] (3) Turn on the vacuum pump and maintain it for 20 min to remove unreacted monomers and small molecules from the system. After the temperature of the reactor drops to below 50°C, remove potassium hydroxide through neutralization, adsorption, and filtration to obtain polyether A1.

[0063] The obtained polyether A1 was analyzed by carbon NMR and hydrogen NMR spectra and determined to be a block polyether containing the following structural composition. The hydrogen NMR spectrum of polyether A1 is shown below. Figure 1 As shown, the carbon NMR spectrum of polyether A1 is as follows: Figure 2 As shown; like Figure 3The two-dimensional carbon-hydrogen correlation spectrum of the nuclear magnetic resonance HMBC shown can be seen to have three carbon signals related to the hydrogen of the terminal hydroxyl group, proving that the terminal hydroxyl group comes from the propylene oxide block.

[0064]

[0065] Where m=3, n=3, m:n=1, the total particle flow chromatogram of polyether A1 is as follows: Figure 4 As shown, the measured molecular weight of the polyether is 480 g / mol, the HLB value is 15.6, and the viscosity at 25°C is 567 centipoise.

[0066] The polyether was mixed with water to obtain an aqueous solution of the polyether, the mass concentration of which was 0.1%, and the static surface tension of the aqueous solution of the polyether was 28.93 mN / m and the dynamic surface tension was 35.06 mN / m.

[0067] Preparation Example 2 (1) Add 1 g of CH3(CH2CH2CH3)(CH2CH3)COH and 2 g of potassium hydroxide to a high-temperature and high-pressure reactor and seal the reactor. Before heating, purge and replace with nitrogen gas, then evacuate. Repeat the nitrogen purging and evacuation process at least twice. Start stirring and heat to 125 °C. Add 40 g of ethylene oxide to carry out the first polymerization reaction. Control the reaction temperature at 130-140 °C and the reaction pressure at 0.3-0.4 MPa. Continue stirring for 30 min until the pressure drops to 0 MPa.

[0068] (2) Heat the high-temperature and high-pressure reactor to 125°C, add 80g of propylene oxide to carry out the second polymerization reaction, control the reaction temperature to 140-150°C, and control the reaction pressure to 0.3-0.4 MPa. Stir for 30 min to reduce the pressure to 0 MPa.

[0069] (3) Turn on the vacuum pump and keep it for 20 min to remove unreacted monomers and small molecules from the system. After the temperature of the reactor drops to below 50℃, potassium hydroxide is removed by neutralization, adsorption and filtration to obtain polyether A2, the structure of which is shown in formula (1), where R is CH3(CH2CH2CH3)(CH2CH3)C-, m:n=0.5:1, m=3, n=6, M=596g / mol, HLB value is 16.1, and viscosity at 25℃ is 859 centipoise.

[0070] The polyether was mixed with water to obtain an aqueous solution of the polyether, the mass concentration of which was 0.1%, and the static surface tension of the aqueous solution of the polyether was 29.46 mN / m and the dynamic surface tension was 38.59 mN / m.

[0071] Preparation Example 3 (1) Add 1 g of CH3CH2C(CH3)2CH2CH2OH and 2 g of potassium hydroxide to a high-temperature and high-pressure reactor and seal the reactor. Before heating, purge and replace with nitrogen gas, then evacuate. Repeat the nitrogen purging and evacuation process at least twice. Start stirring and heat to 125 °C. Add 80 g of ethylene oxide to carry out the first polymerization reaction. Control the reaction temperature at 140-150 °C and the reaction pressure at 0.3-0.4 MPa. Continue stirring for 40 min until the pressure drops to 0 MPa.

[0072] (2) Heat the high-temperature and high-pressure reactor to 130°C, add 40g of propylene oxide to carry out the second polymerization reaction, control the reaction temperature to 140-150°C, and control the reaction pressure to 0.3-0.4 MPa. Stir for 25 min to reduce the pressure to 0 MPa.

[0073] (3) Turn on the vacuum pump and keep it for 20 min to remove unreacted monomers and small molecules in the system. After the temperature of the reactor drops to below 50℃, potassium hydroxide is removed by neutralization, adsorption and filtration to obtain polyether A3, with the structure shown in formula (1), where R is CH3CH2C(CH3)2CH2CH2-, m:n=2:1, m=8, n=4, M=700g / mol, HLB value is 12, and the viscosity at 25℃ is 758 centipoise.

[0074] The polyether was mixed with water to obtain an aqueous solution of the polyether, the mass concentration of which was 0.1%, and the static surface tension of the aqueous solution of the polyether was 28.56 mN / m and the dynamic surface tension was 36.72 mN / m.

[0075] Preparation Example 4 (1) Add 1 g of CH3CH2(CH3)2COH and 2 g of potassium hydroxide to a high-temperature and high-pressure reactor and seal the reactor. Before heating, purge and replace with nitrogen gas, then evacuate. Repeat the nitrogen purging and evacuation process at least twice. Start stirring and heat to 125 °C. Add 80 g of ethylene oxide to carry out the first polymerization reaction. Control the reaction temperature at 120-130 °C and the reaction pressure at 0.4-0.5 MPa. Continue stirring for 60 min until the pressure drops to 0 MPa.

[0076] (2) Heat the high-temperature and high-pressure reactor to 130°C, add 100g of propylene oxide to carry out the second polymerization reaction, control the reaction temperature to 140-150°C, and control the reaction pressure to 0.3-0.4 MPa. Stir for 20 min to reduce the pressure to 0 MPa.

[0077] (3) Turn on the vacuum pump and keep it for 20 min to remove unreacted monomers and small molecules from the system. After the temperature of the reactor drops to below 50℃, potassium hydroxide is removed by neutralization, adsorption and filtration to obtain polyether A4, with the structure shown in formula (1), where R is CH3CH2(CH3)2C-, m:n=1:2, m=4, n=8, M=728 / mol, HLB value is 5.62, and the viscosity at 25℃ is 865 centipoise.

[0078] The polyether is mixed with water to obtain an aqueous solution of the polyether, wherein the mass concentration of the polyether is 0.1%, and the static surface tension of the aqueous solution of the polyether is 28.98 mN / m and the dynamic surface tension is 36.74 mN / m.

[0079] Preparation Example 5 Following the method of Preparation Example 1, except that an equal amount of 1-pentanol was used to replace 3,5,5-trimethyl-1-hexanol, and the other conditions were the same as in Preparation Example 1, polyether D1 was prepared.

[0080] Example 1 Two grams of nano-alumina powder were weighed and placed in a mixing container, followed by 0.06 grams of polyether A1 and 50 ml of deionized water. Ultrasonic treatment was initiated and set for 60 minutes. The ultrasonically treated mixture was then freeze-dried to obtain the modified alumina filler, with a polyether content of 2.91 wt% of the total mass of the nano-metal oxides.

[0081] Ten parts of A1-modified alumina filler were mixed with 20 parts of acrylic acid. After mechanical stirring, the mixture was transferred to a three-roll mill and mixed at 120 rpm for 30 minutes. The mixture was allowed to stand at 25°C for 3 months without aggregation.

[0082] Example 2 Two grams of nano-alumina powder were weighed and placed in a mixing container, followed by 0.06 grams of polyether A2 and 60 ml of deionized water. Ultrasonic treatment was initiated and set for 50 minutes. The ultrasonically treated mixture was then freeze-dried to obtain the modified alumina filler, with a polyether content of 2.91 wt% of the total mass of the nano-metal oxides.

[0083] Ten parts of A2-modified alumina filler were mixed with 20 parts of acrylic acid. After mechanical stirring, the mixture was transferred to a three-roll mill and mixed at 120 rpm for 30 minutes. The mixture was allowed to stand at 25°C for two months without aggregation.

[0084] Example 3 Two grams of nano-alumina powder were weighed and placed in a mixing container, followed by 0.03 grams of polyether A3 and 60 ml of deionized water. Ultrasonic treatment was initiated and set for 50 minutes. The ultrasonically treated mixture was then freeze-dried to obtain the modified alumina filler, with a polyether content of 1.48 wt% of the total mass of the nano-metal oxides.

[0085] Ten parts of A2-modified alumina filler were mixed with 20 parts of acrylic acid. After mechanical stirring, the mixture was transferred to a three-roll mill and mixed at 120 rpm for 30 minutes. The mixture was allowed to stand at 25°C for 40 days without aggregation.

[0086] Example 4 Two grams of nano-alumina powder were weighed and placed in a mixing container, followed by 0.09 grams of polyether A3 and 50 ml of deionized water. Ultrasonic treatment was initiated and set for 80 minutes. The ultrasonically treated mixture was then freeze-dried to obtain the modified alumina filler, with a polyether content of 4.31 wt% of the total mass of the nano-metal oxides.

[0087] Ten parts of A2-modified alumina filler were mixed with 20 parts of acrylic acid. After mechanical stirring, the mixture was transferred to a three-roll mill and mixed at 120 rpm for 30 minutes. The mixture was allowed to stand at 25°C for 50 days without aggregation.

[0088] Comparative Example 1 Two grams of nano-alumina powder were weighed and placed in a mixing container, followed by 50 ml of deionized water. Ultrasonic treatment was initiated and set to 80 minutes. The ultrasonically treated mixture was then freeze-dried to obtain alumina filler, free of polyether.

[0089] Ten parts of alumina filler were mixed with 20 parts of acrylic acid, mechanically stirred, and then transferred to a three-roll mill. The mixture was stirred at 120 rpm for 30 minutes. No aggregation was observed within 5 days of standing at 25°C.

[0090] Comparative Example 2 Two grams of nano-alumina powder were weighed and placed in a mixing container, followed by 0.06 grams of polyether D1 prepared in Preparation Example 5 and 50 ml of deionized water. Ultrasonication was initiated and set for 60 min. The ultrasonically treated mixture was then freeze-dried to obtain the modified alumina filler, with a polyether content of 2.91 wt% of the total mass of the nano-metal oxides.

[0091] Ten parts of modified alumina filler were mixed with 20 parts of acrylic acid, mechanically stirred, and then transferred to a three-roll mill at 120 rpm for 30 minutes. No aggregation was observed within 8 days of standing at 25°C.

[0092] Application Example 1 (1) Take 5 parts of polyisobutylene (viscosity average molecular weight (M) v The value is 2321×10 3 Add the powdered graphene (median particle size of 18 μm) into the internal mixer, set the mixing temperature to 130℃, and after the rotor speed stabilizes, add 30 parts of powdered graphene (median particle size of 18 μm) and 15 parts of modified alumina (modified filler prepared according to the method of Example 1), control the rotor speed to 90 rpm, and discharge the material after mixing for 20 minutes.

[0093] (2) Take 20 parts of acrylic acid and add it to the mixture obtained in step (1). After mechanical stirring, transfer it into a three-roll mill and mix for 30 minutes at a speed of 120 rpm.

[0094] (3) Add 15 parts of matrix resin (10 parts of acrylic resin, brand name LR-7647, 5 parts of polyurethane resin, brand name BR-167), 6 parts of solvent (n-butyl acetate), 2 parts of barium sulfate, 5 parts of flake glass, 1 part of mica iron oxide and 1 part of carbon black to the mixture obtained in step (2). After shearing and stirring at 1000 rpm for 15 min, transfer it into a sand mill and grind it to a fineness of ≤25 μm.

[0095] (5) The graphene-containing high thermal conductivity anti-corrosion coating is sprayed onto the pre-treated carbon steel substrate by spraying (spraying pressure 0.6MPa). In all embodiments of the present invention, the paint film is applied by a two-coat spraying process with an interval of 2 hours between the two sprays and a paint film thickness of 200 μm.

[0096] According to GB / T1771-2007, GB / T4157-2006, and GB / T 5210-1985, the coating's resistance to neutral salt spray, hydrogen sulfide, and film adhesion were tested. Test results showed that after 800 hours of immersion in hydrogen sulfide solution, the substrate surface showed no blistering or peeling. After 1440 hours of neutral salt spray testing, only the scribing lines showed corrosion marks, and the corrosion did not spread to either side, meeting the requirements. The adhesion of the above-mentioned graphene-containing high thermal conductivity anti-corrosion coating was 8 MPa.

[0097] The thermal conductivity of the coating was tested according to GB / T 22588-2008, and the thermal conductivity of Example 1 was 3.81 W / (m·K).

[0098] Application Comparative Example 1 (1) Take 5 parts of polyisobutylene (viscosity average molecular weight (M) v The value is 2321×10 3 Add the powdered graphene (median particle size of 18μm) into the internal mixer, set the mixing temperature to 130℃, and after the rotor speed stabilizes, add 30 parts of powdered graphene (median particle size of 18μm) and 15 parts of unmodified alumina. Control the rotor speed to 90rpm and mix for 20 minutes before discharging.

[0099] (2) Take 20 parts of acrylic acid and add it to the mixture obtained in step (1). After mechanical stirring, transfer it into a three-roll mill and mix for 30 minutes at a speed of 120 rpm.

[0100] (3) Add 15 parts of matrix resin (10 parts of acrylic resin, brand name LR-7647, 5 parts of polyurethane resin, brand name BR-167), 6 parts of solvent (n-butyl acetate), 2 parts of barium sulfate, 5 parts of flake glass, 1 part of mica iron oxide and 1 part of carbon black to the mixture obtained in step (2). After shearing and stirring at 1000 rpm for 15 min, transfer it into a sand mill and grind it to a fineness of ≤25 μm.

[0101] (5) The graphene-containing high thermal conductivity anti-corrosion coating is sprayed onto the pre-treated carbon steel substrate by spraying (spraying pressure 0.6MPa). In all embodiments of the present invention, the paint film is applied by a two-coat spraying process with an interval of 2 hours between the two sprays and a paint film thickness of 200 μm.

[0102] According to GB / T1771-2007, GB / T4157-2006, and GB / T 5210-1985, the coating's resistance to neutral salt spray, hydrogen sulfide, and film adhesion were tested. Test results showed that after immersion in hydrogen sulfide solution for 500 hours, the substrate surface showed no blistering or peeling. After 1000 hours of neutral salt spray testing, only the scribing lines showed corrosion marks, and the corrosion did not spread to either side, meeting the requirements. The adhesion of the above-mentioned graphene-containing high thermal conductivity anti-corrosion coating was 5 MPa.

[0103] The thermal conductivity of the coating was tested according to GB / T 22588-2008, and the thermal conductivity was 2.12 W / (m·K).

[0104] As can be seen from Application Example 1 and Application Comparative Example 1, the modified filler described in this invention can significantly improve the performance of the coating.

[0105] Application Comparative Example 2 The method is the same as in Application Example 1, except that the modified alumina prepared according to Comparative Example 2 is used in equal proportions instead of the modified alumina prepared according to Example 1. All other conditions are the same as in Application Example 1.

[0106] According to GB / T1771-2007, GB / T4157-2006, and GB / T 5210-1985, the coating's resistance to neutral salt spray, hydrogen sulfide, and film adhesion were tested. Test results showed that after immersion in hydrogen sulfide solution for 530 hours, the graphene coating exhibited no blistering or peeling on the substrate surface. After 900 hours of neutral salt spray testing, corrosion marks were only observed at the scribing lines, and the corrosion did not spread to either side, meeting the requirements. The adhesion of the aforementioned graphene-containing high thermal conductivity anti-corrosion coating was 5.4 MPa.

[0107] The thermal conductivity of the coating was tested according to GB / T 22588-2008, and the thermal conductivity was 2.23 W / (m·K).

[0108] As can be seen from Application Example 1 and Application Comparative Example 2, the modified filler described in this invention can significantly improve the performance of the coating.

[0109] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A modified oxide filler, characterized in that, The modified oxide filler comprises nano-metal oxides and polyether, wherein the polyether has the structure shown in formula (1): Equation (1), Where the ratio of m to n is 0.3-3:1; R has the structure shown in equation (2), Equation (2), Wherein, R1 is a C0-C10 alkylene group, and R2, R3, and R4 are each independently selected from C1-C3 alkyl groups.

2. The modified oxide filler according to claim 1, wherein, R1 is selected from -(CH2) x1 -、-CH2-CH(CH3)-(CH2) x2 -, -CH2-C(CH3)2-(CH2) x3 -、-CH(CH3)-(CH2) x4 -、-C(CH3)2-(CH2) x5 -、-C(CH3)(CH2CH3)-(CH2) x6 -or -C(CH3)(C3H7)-(CH2) x7 - where x1-x7 are each independently selected from 0, 1, 2, 3 or 4; and / or R2, R3, and R4 are each independently selected from methyl, ethyl, n-propyl, or isopropyl.

3. The modified oxide filler according to claim 1 or 2, wherein, The ratio of m to n is 0.5-2:1; and / or m is 1-14, preferably 3-9; n is 1-14, preferably 3-9.

4. The modified oxide filler according to claim 1 or 2, wherein, R is selected from -CH2CH2CH(CH3)CH2C(CH3)2CH3, -C(CH2CH3)(CH2CH2CH3)CH3, -CH2CH2C(CH3)2CH2CH3 or -C(CH3)2CH2CH3; preferably -CH2CH2CH(CH3)CH2C(CH3)2CH3.

5. The modified oxide filler according to claim 1 or 2, wherein, The weight-average molecular weight of the polyether does not exceed 2000 g / mol, preferably 450-1500 g / mol; The polyether has a viscosity of 50 to 1000 centipoise at 25°C, preferably 500 to 1000 centipoise.

6. The modified oxide filler according to claim 1 or 2, wherein, The hydrophilic-lipophilic balance of the polyether is 5 to 18; and / or The dynamic surface tension of the 0.1 wt% aqueous solution of the polyether is 20-45 mN / m; and / or the static surface tension is 23-40 mN / m, preferably 25-30 mN / m.

7. The modified oxide filler according to claim 1 or 2, wherein, The polyether is selected from at least one of (CH3)3CCH2CH(CH3)CH2CH2O(C2H4O)3(C3H6O)3H, CH3(CH2CH2CH3)(CH2CH3)CO(C2H4O)3(C3H6O)6H, CH3CH2C(CH3)2CH2CH2O(C2H4O)8(C3H6O)4H, and CH3CH2(CH3)2CO(C2H4O)4(C3H6O)8H, preferably (CH3)3CCH2CH(CH3)CH2CH2O(C2H4O)3(C3H6O)3H.

8. The modified oxide filler according to any one of claims 1-7, wherein, The polyether content is 0.6-4.76 wt% of the total mass of the nano-metal oxides; and / or The nano-oxide is selected from one or more of nano-alumina, nano-zinc oxide, nano-titanium oxide, and nano-magnesium oxide.

9. The method for preparing the modified oxide filler according to any one of claims 1-8, characterized in that, The method includes: The nano-oxides, polyethers, and solvents are mixed and then dried. Preferably, Mix 2-5 parts of nano-oxide, 0.03-0.1 parts of polyether and 40-50 parts of solvent, and dry. Preferably, the solvent is water; The preferred drying method is freeze drying.

10. The application of the modified oxide filler according to any one of claims 1-8 in a heat-dissipating coating.

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