Industrial coupling agent and preparation method thereof

Abstract

The invention relates to the technical field of coupling agent preparation, in particular to an industrial coupling agent and a preparation method thereof. The coupling agent comprises the following components in parts by weight: 70-80 parts of perfluoropolyether base oil, 5-15 parts of a composite additive and 10-20 parts of filler, wherein the perfluoropolyether base oil is composed of perfluoropolyether with the kinematic viscosity of 5-30 cst, 45-300 cst and 420-650 cst at the temperature of 40 DEG C according to the mass ratio of (3-12): (5-12): (2-9). The industrial coupling agent is prepared by taking perfluoropolyether oil as base oil and mixing the base oil with the composite additive and the filler, the characteristics of good low-temperature performance, low surface tension, high chemical stability and the like of the perfluoropolyether base oil are utilized, traditional silicone oil and mineral oil are replaced to prepare the coupling agent with a wide temperature range, and the industrial coupling agent can meet high and low temperature use scenes at the same time.

Description

Technical Field

[0001] The present invention relates to the technical field of couplant preparation, and particularly relates to an industrial couplant and a preparation method thereof. Background Art

[0002] Ultrasonic testing is a non-destructive testing method that uses ultrasonic waves to inspect internal defects of components (generally metal components). An ultrasonic wave is emitted from a transmitting probe to the surface of the component through a couplant. When the ultrasonic wave propagates inside the component and encounters different interfaces, different reflection signals (echoes) will occur. By using the time difference of different reflection signals propagating to the probe, defects inside the component can be detected. Ultrasonic testing is widely used in many fields such as special equipment, energy and power, aerospace, petroleum and petrochemical, transportation, iron and steel heavy industry, etc., and can accurately and quickly complete the detection, positioning, evaluation and diagnosis of various defects (such as cracks, inclusions, pores, etc.) inside the workpiece.

[0003] Industrial couplants are used to expel the air between the probe and the object to be measured, so that ultrasonic waves can effectively penetrate into the workpiece to achieve the detection purpose. If the type or usage method is not selected properly, errors or couplant marks will flash and measurement cannot be performed. Commonly used industrial couplants include machine oil, transformer oil, grease, water, glycerol, alcohol, water glass, industrial glue, chemical paste, etc.

[0004] With the continuous development of advanced manufacturing in China, the production conditions for special processes are gradually becoming more stringent. The reaction device will involve many extreme high-temperature and low-temperature working conditions. At this time, the monitoring of equipment reliability is particularly important. However, existing low-temperature couplants will agglomerate and solidify under extremely low-temperature conditions, and the high-temperature resistance of existing high-temperature couplants is not ideal. After the temperature is higher than 180°C, coking and smoking are likely to occur. Moreover, the existing couplants also have the following problems: Generally, different couplants are used for low-temperature workpieces and high-temperature workpieces. For example, the patent with the application number 201510627802.X discloses a high-temperature couplant, which is prepared by mixing silicone oil, grease, antioxidant, anti-coking agent, and filler. This couplant has a relatively high heat-resistant temperature and can ensure the thickness measurement accuracy under high-temperature conditions. Another example is the patent with the application number 201711012098.2, which discloses an industrial couplant for rail flaw detection, including ethylene glycol, water, glycerol, rust inhibitor, and trimethylolpropane. This couplant has excellent sound transmission effect, rust and corrosion prevention performance, and low-temperature resistance. Existing couplants cannot meet both high- and low-temperature working conditions at the same time. Therefore, an industrial couplant with a wide temperature range is needed. Summary of the Invention

[0005] To solve the above problems, the present invention provides an industrial coupling agent, which is prepared by mixing a perfluoropolyether base oil composed of perfluoropolyethers with low, medium and high viscosity ranges, a composite additive and a filler. The industrial coupling agent of the present invention has good stability in a wide temperature range and can meet the requirements of high and low temperature working conditions simultaneously.

[0006] An industrial coupling agent, by weight, comprises the following components: 70 - 80 parts of perfluoropolyether base oil, 5 - 15 parts of composite additive, and 10 - 20 parts of filler;

[0007] Among them, the perfluoropolyether base oil is composed of perfluoropolyethers with kinematic viscosities of 5 - 30 cst, 45 - 300 cst, and 420 - 650 cst at 40°C in a mass ratio of 3 - 12:5 - 12:2 - 9.

[0008] In some preferred embodiments, the perfluoropolyether base oil is composed of perfluoropolyethers with kinematic viscosities of 5 - 10 cst, 13 - 18 cst, 19 - 30 cst, 45 - 100 cst, 120 - 180 cst, 200 - 300 cst, 420 - 480 cst, 485 - 560 cst, and 565 - 650 cst at 40°C in a mass ratio of 1 - 4:1 - 4:1 - 4:2 - 4:2 - 4:1 - 4:1 - 3:1 - 3:1 - 3.

[0009] In some more preferred embodiments, the perfluoropolyether base oil is composed of perfluoropolyethers with kinematic viscosities of 8 cst, 15 cst, 22 cst, 60 cst, 150 cst, 260 cst, 460 cst, 510 cst, and 570 cst at 40°C in a mass ratio of 1 - 4:1 - 4:1 - 4:2 - 4:2 - 4:1 - 4:1 - 3:1 - 3:1 - 3.

[0010] In some embodiments, the perfluoropolyether is K - type perfluoropolyether. Specifically, the K - type perfluoropolyether has the following structure:

[0011]

[0012] Among them, n = 5 - 60.

[0013] In some embodiments, the composite additive is composed of N - cyclohexylthiophthalimide, 4,4' - bis(phenylisopropyl)diphenylamine, and perfluoropolyether - modified aniline in a mass ratio of 3 - 5:3 - 6:1 - 2.

[0014] In some embodiments, the perfluoropolyether - modified aniline has the following structure:

[0015]

[0016] wherein, Rf is C3F7O(CF(CF3)CF2) m CF(CF3), and m is an integer between 10 and 100.

[0017] In some embodiments, the filler is selected from at least three of titanium dioxide powder, kaolin powder, graphite powder, and silica powder.

[0018] In some preferred embodiments, the filler is composed of titanium dioxide powder, kaolin powder, graphite powder, and silica powder in a mass ratio of 2-4:5-7:3-5:1-3.

[0019] The present invention also provides a preparation method of the above industrial coupling agent, comprising the following steps:

[0020] (1) Prepare perfluoropolyether base oil, composite additive, and filler respectively;

[0021] (2) Mix the perfluoropolyether base oil, composite additive, and filler evenly at 40-70°C to obtain the industrial coupling agent.

[0022] In some preferred embodiments, the filler is added in multiple times.

[0023] In some more preferred embodiments, the filler is added in three times, 20% by weight of the filler is added for the first time, 40% by weight of the filler is added for the second time, and 40% by weight of the filler is added for the third time.

[0024] Compared with the prior art, the beneficial effects of the present invention are:

[0025] (1) The present invention provides an industrial coupling agent, which is prepared by mixing perfluoropolyether oil as the base oil with a composite additive and a filler. The present invention utilizes the good low-temperature performance, low surface tension, high chemical stability and other characteristics of perfluoropolyether base oil to replace traditional silicone oil and mineral oil to prepare a coupling agent with a wide temperature range, which can simultaneously meet high- and low-temperature usage scenarios.

[0026] (2) For the industrial coupling agent of the present invention, the perfluoropolyether base oil is composed of three different viscosity ranges of perfluoropolyether, namely low, medium, and high. The low-viscosity perfluoropolyether is used to lower the overall freezing point of the coupling agent, the medium-viscosity perfluoropolyether is used to enable the coupling agent to meet the usage under normal working conditions, and the high-viscosity perfluoropolyether is used to improve the high-temperature stability of the coupling agent. Through the cooperation of the three viscosity ranges, the effect of the coupling agent being applicable in a wide temperature range is achieved.

[0027] (3) The industrial coupling agent of the present invention further refines the composition of the perfluoropolyether base oil. Nine perfluoropolyethers with low, medium, and high viscosity distributions are used to prepare the perfluoropolyether base oil. The perfluoropolyether has a relatively small viscosity span, which further improves the low-temperature and high-temperature performance of the prepared coupling agent, and the applicable temperature range covers different temperatures, making it more continuous and stable.

[0028] (4) The industrial coupling agent of the present invention further optimizes the composition of the composite additive. 4,4'-bis(phenylisopropyl)diphenylamine is used as an antioxidant, and perfluoropolyether-modified aniline is added as an anti-corrosion agent, further improving the high-temperature stability of the coupling agent and its protective performance against metals. Detailed implementation manners

[0029] The technical solutions of the present invention will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of them. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0030] The perfluoropolyether in the present invention can be synthesized by those skilled in the art through well-known preparation methods or obtained by purchasing conventional commercially available products. The well-known preparation methods of perfluoropolyether by those skilled in the art include photocatalytic polymerization method, anion catalytic polymerization method, etc. Perfluoropolyethers with different viscosities can be obtained by controlling the feeding amount of reaction raw materials. Commercially available perfluoropolyether products, such as those produced by Sanming Haisifu Chemical Co., Ltd., usually correspond to different models or batches of perfluoropolyether products for perfluoropolyethers with different viscosities. It should be noted that since perfluoropolyether is a polymer prepared through a polymerization reaction, and the polymerization reaction process is difficult to precisely control, the viscosities of different batches of perfluoropolyether obtained by the same method usually fluctuate within a certain range, that is, for a specific model of perfluoropolyether product, its viscosity usually varies within a certain range; however, for a specific specific product, it still has a specific viscosity value. At the same time, it should be further noted that the viscosity fluctuations of the same model of product due to the polymerization reaction characteristics will not affect the effects of the present invention.

[0031] The perfluoropolyethers in the specific implementation manners of the present invention are all produced by Sanming Haisifu Chemical Co., Ltd. The general structural formula of the perfluoropolyether is as follows:

[0032] Among them, n = 5 - 60.

[0033] Among them, the corresponding relationship between the product model and viscosity of the perfluoropolyether is as follows:

[0034] Model Kinematic viscosity at 40°C, cst FBO-101 5-10 FBO-102 13-18 FBO-103 19-30 FBO-104 45-100 FBO-105 120-180 FBO-106 200-300 FBO-107 420-480 FBO-108 485-560 FBO-109 565-650

[0035] The perfluoropolyether-modified aniline in the specific implementation manner of the present invention has the following structure:

[0036]

[0037] wherein, Rf is C3F7O(CF(CF3)CF2) m CF(CF3), and m is an integer between 10 and 100. Specifically, in Examples 1-3, m is 10, 20, and 50 respectively; in Examples 4-11 and Comparative Examples 1-9, m is 20.

[0038] Example 1

[0039] An industrial coupling agent is composed of the following raw materials in parts by weight: 70 parts of perfluoropolyether base oil, 15 parts of compound additive, and 15 parts of filler. The perfluoropolyether base oil is composed of perfluoropolyethers with kinematic viscosities of 5 cst (FBO-101), 45 cst (FBO-104), and 420 cst (FBO-107) at 40 °C in a mass ratio of 3:5:2; the compound additive is composed of N-cyclohexylthiophthalimide, 4,4'-bis(phenylisopropyl)diphenylamine, and perfluoropolyether-modified aniline in a mass ratio of 2:2:1; the filler is composed of titanium dioxide powder, kaolin powder, and graphite powder in a mass ratio of 2:5:3.

[0040] The preparation method of the industrial coupling agent includes the following steps:

[0041] (1) Prepare the perfluoropolyether base oil, compound additive, and filler respectively according to the ratio;

[0042] (2) Put the perfluoropolyether base oil, compound additive, and filler weighed by parts by weight into a container at 40-70 °C, stir and mix evenly to obtain the industrial coupling agent.

[0043] Example 2

[0044] An industrial coupling agent is composed of the following raw materials in parts by weight: 75 parts of perfluoropolyether base oil, 10 parts of compound additive, and 15 parts of filler. The perfluoropolyether base oil is composed of perfluoropolyethers with kinematic viscosities of 15 cst (FBO-102), 150 cst (FBO-105), and 510 cst (FBO-108) at 40 °C in a mass ratio of 4:3:3; the compound additive is composed of N-cyclohexylthiophthalimide, 4,4'-bis(phenylisopropyl)diphenylamine, and perfluoropolyether-modified aniline in a mass ratio of 4:5:1; the filler is composed of titanium dioxide powder, kaolin powder, graphite powder, and silica powder in a mass ratio of 2:5:3:1.

[0045] The preparation method of the industrial coupling agent comprises the following steps:

[0046] (1) Prepare perfluoropolyether base oil, compound additive, and filler respectively according to the ratio.

[0047] (2) Put the perfluoropolyether base oil and the compound additive weighed by weight into a container, and stir and mix evenly at a temperature of 40 - 70 °C to obtain mixture A.

[0048] (3) Add the filler to mixture A in three portions while stirring at a temperature of 40 - 70 °C. Add 20% by weight of the filler for the first time, 40% by weight of the filler for the second time, and 40% by weight of the filler for the third time. After the addition is completed, continue to stir and mix evenly to obtain the industrial coupling agent.

[0049] Example 3

[0050] An industrial coupling agent is composed of the following raw materials by weight: 80 parts of perfluoropolyether base oil, 10 parts of compound additive, and 10 parts of filler. The perfluoropolyether base oil is composed of perfluoropolyethers with kinematic viscosities of 30 cst (FBO - 103), 300 cst (FBO - 106), and 650 cst (FBO - 109) at 40 °C in a mass ratio of 5:3:2; the compound additive is composed of N - cyclohexylthiophthalimide, 4,4' - bis(phenylisopropyl)diphenylamine, and perfluoropolyether - modified aniline in a mass ratio of 5:3:2; the filler is composed of titanium dioxide powder, kaolin powder, and silica powder in a mass ratio of 2:5:3.

[0051] The preparation method of the industrial coupling agent comprises the following steps:

[0052] (1) Prepare perfluoropolyether base oil, compound additive, and filler respectively according to the ratio.

[0053] (2) Put the perfluoropolyether base oil and the compound additive weighed by weight into a container, and stir and mix evenly at a temperature of 40 - 70 °C to obtain mixture A.

[0054] (3) Add the filler to mixture A in three portions while stirring at a temperature of 40 - 70 °C. Add 20% by weight of the filler for the first time, 40% by weight of the filler for the second time, and 40% by weight of the filler for the third time. After the addition is completed, continue to stir and mix evenly to obtain the industrial coupling agent.

[0055] Example 4

[0056] An industrial coupling agent is composed of the following raw materials in parts by weight: 75 parts of perfluoropolyether base oil, 10 parts of composite additive, and 15 parts of filler. The perfluoropolyether base oil is composed of perfluoropolyethers with kinematic viscosities of 5 cst (FBO-101), 13 cst (FBO-102), 19 cst (FBO-103), 45 cst (FBO-104), 120 cst (FBO-105), 200 cst (FBO-106), 420 cst (FBO-107), 485 cst (FBO-108), and 565 cst (FBO-109) at 40 °C in a mass ratio of 2:2:2:4:4:2:2:1:1; the composite additive is composed of N-cyclohexylthiophthalimide, 4,4'-bis(phenylisopropyl)diphenylamine, and perfluoropolyether-modified aniline in a mass ratio of 4:5:1; the filler is composed of titanium dioxide powder, kaolin powder, graphite powder, and silica powder in a mass ratio of 3:6:4:2.

[0057] The preparation method of the industrial coupling agent includes the following steps:

[0058] (1) Prepare the perfluoropolyether base oil, composite additive, and filler respectively according to the ratio.

[0059] (2) Put the perfluoropolyether base oil and the composite additive weighed by parts by weight into a container, and stir and mix evenly at a temperature of 40-70 °C to obtain mixture A.

[0060] (3) Add the filler to mixture A in three portions while stirring at a temperature of 40-70 °C. Add 20% by weight of the filler for the first time, 40% by weight of the filler for the second time, and 40% by weight of the filler for the third time. After the addition is completed, continue to stir and mix evenly to obtain the industrial coupling agent.

[0061] Example 5

[0062] An industrial coupling agent is composed of the following raw materials in parts by weight: 75 parts of perfluoropolyether base oil, 10 parts of compound additive, and 15 parts of filler. The perfluoropolyether base oil is composed of perfluoropolyethers with kinematic viscosities of 8 cst (FBO-101), 15 cst (FBO-102), 22 cst (FBO-103), 60 cst (FBO-104), 150 cst (FBO-105), 260 cst (FBO-106), 460 cst (FBO-107), 510 cst (FBO-108), and 570 cst (FBO-109) at 40 °C in a mass ratio of 4:4:4:2:2:1:1:1:1; the compound additive is composed of N-cyclohexylthiophthalimide, 4,4'-bis(phenylisopropyl)diphenylamine, and perfluoropolyether-modified aniline in a mass ratio of 4:5:1; the filler is composed of titanium dioxide powder, kaolin powder, graphite powder, and silica powder in a mass ratio of 3:6:4:2.

[0063] The preparation method of the industrial coupling agent includes the following steps:

[0064] (1) Prepare the perfluoropolyether base oil, compound additive, and filler respectively according to the ratio.

[0065] (2) Put the perfluoropolyether base oil and the composite additive weighed by parts by weight into a container, and stir and mix evenly at a temperature of 40-70 °C to obtain mixture A.

[0066] (3) Add the filler to mixture A in three portions while stirring at a temperature of 40-70 °C. Add 20% by weight of the filler for the first time, 40% by weight of the filler for the second time, and 40% by weight of the filler for the third time. After the addition is completed, continue to stir and mix evenly to obtain the industrial coupling agent.

[0067] Example 6

[0068] An industrial coupling agent is composed of the following raw materials in parts by weight: 75 parts of perfluoropolyether base oil, 10 parts of compound additive, and 15 parts of filler. The perfluoropolyether base oil is composed of perfluoropolyethers with kinematic viscosities at 40°C of 10 cst (FBO-101), 18 cst (FBO-102), 30 cst (FBO-103), 100 cst (FBO-104), 180 cst (FBO-105), 300 cst (FBO-106), 480 cst (FBO-107), 560 cst (FBO-108), and 650 cst (FBO-109) in a mass ratio of 4:4:4:2:2:1:1:1:1; the compound additive is composed of N-cyclohexylthiophthalimide, 4,4'-bis(phenylisopropyl)diphenylamine, and perfluoropolyether-modified aniline in a mass ratio of 4:5:1; the filler is composed of titanium dioxide powder, kaolin powder, graphite powder, and silica powder in a mass ratio of 3:6:4:2.

[0069] The preparation method of the industrial coupling agent includes the following steps:

[0070] (1) Prepare the perfluoropolyether base oil, compound additive, and filler respectively according to the ratio.

[0071] (2) Put the perfluoropolyether base oil and the compound additive weighed by weight into a container, and stir and mix evenly at a temperature of 40-70°C to obtain mixture A.

[0072] (3) At a temperature of 40-70°C, add the filler to mixture A in three portions while stirring. Add 20% by weight of the filler for the first time, 40% by weight of the filler for the second time, and 40% by weight of the filler for the third time. After the addition is completed, continue to stir and mix evenly to obtain the industrial coupling agent.

[0073] Example 7

[0074] An industrial coupling agent is composed of the following raw materials in parts by weight: 75 parts of perfluoropolyether base oil, 10 parts of compound additive, and 15 parts of filler. The perfluoropolyether base oil is composed of perfluoropolyethers with kinematic viscosities at 40 °C of 8 cst (FBO-101), 15 cst (FBO-102), 22 cst (FBO-103), 60 cst (FBO-104), 150 cst (FBO-105), 260 cst (FBO-106), 460 cst (FBO-107), 510 cst (FBO-108), and 570 cst (FBO-109) in a mass ratio of 3:3:3:4:3:1:1:1:1; the compound additive is composed of N-cyclohexylthiophthalimide, 4,4'-bis(phenylisopropyl)diphenylamine, and perfluoropolyether-modified aniline in a mass ratio of 4:5:1; the filler is composed of titanium dioxide powder, kaolin powder, graphite powder, and silica powder in a mass ratio of 3:6:4:2.

[0075] The preparation method of the industrial coupling agent includes the following steps:

[0076] (1) Prepare the perfluoropolyether base oil, compound additive, and filler respectively according to the ratio.

[0077] (2) Put the perfluoropolyether base oil and the composite additive weighed by parts by weight into a container, and stir and mix evenly at a temperature of 40 - 70 °C to obtain mixture A.

[0078] (3) While stirring, add the filler to mixture A in three portions at a temperature of 40 - 70 °C. Add 20% by weight of the filler for the first time, 40% by weight of the filler for the second time, and 40% by weight of the filler for the third time. After the addition is completed, continue to stir and mix evenly to obtain the industrial coupling agent.

[0079] Example 8

[0080] An industrial coupling agent is composed of the following raw materials in parts by weight: 75 parts of perfluoropolyether base oil, 10 parts of composite additive, and 15 parts of filler. The perfluoropolyether base oil is composed of perfluoropolyethers with kinematic viscosities of 8 cst (FBO-101), 15 cst (FBO-102), 22 cst (FBO-103), 60 cst (FBO-104), 150 cst (FBO-105), 260 cst (FBO-106), 460 cst (FBO-107), 510 cst (FBO-108), and 570 cst (FBO-109) at 40 °C in a mass ratio of 1:1:1:2:1:1:1:1:1; the composite additive is composed of N-cyclohexylthiophthalimide, 4,4'-bis(phenylisopropyl)diphenylamine, and perfluoropolyether-modified aniline in a mass ratio of 4:5:1; the filler is composed of titanium dioxide powder, kaolin powder, graphite powder, and silica powder in a mass ratio of 3:6:4:2.

[0081] The preparation method of the industrial coupling agent includes the following steps:

[0082] (1) Prepare the perfluoropolyether base oil, composite additive, and filler respectively according to the ratio.

[0083] (2) Put the perfluoropolyether base oil and the composite additive weighed by parts by weight into a container, and stir and mix evenly at a temperature of 40-70 °C to obtain mixture A.

[0084] (3) While stirring, add the filler to mixture A in three portions at a temperature of 40-70 °C. Add 20% by weight of the filler for the first time, 40% by weight of the filler for the second time, and 40% by weight of the filler for the third time. After the addition is completed, continue to stir and mix evenly to obtain the industrial coupling agent.

[0085] Example 9

[0086] An industrial coupling agent is composed of the following raw materials in parts by weight: 75 parts of perfluoropolyether base oil, 10 parts of composite additive, and 15 parts of filler. The perfluoropolyether base oil is composed of perfluoropolyethers with kinematic viscosities of 8 cst (FBO-101), 15 cst (FBO-102), 22 cst (FBO-103), 60 cst (FBO-104), 150 cst (FBO-105), 260 cst (FBO-106), 460 cst (FBO-107), 510 cst (FBO-108), and 570 cst (FBO-109) at 40 °C in a mass ratio of 1:1:1:4:3:4:3:2:1; the composite additive is composed of N-cyclohexylthiophthalimide, 4,4'-bis(phenylisopropyl)diphenylamine, and perfluoropolyether-modified aniline in a mass ratio of 4:5:1; the filler is composed of titanium dioxide powder, kaolin powder, graphite powder, and silica powder in a mass ratio of 3:6:4:2.

[0087] The preparation method of the industrial coupling agent comprises the following steps:

[0088] (1) Prepare the perfluoropolyether base oil, composite additive, and filler respectively according to the ratio.

[0089] (2) Put the perfluoropolyether base oil and the composite additive weighed by parts by weight into a container, and stir and mix evenly at a temperature of 40-70 °C to obtain mixture A.

[0090] (3) While stirring, add the filler to mixture A in three portions at a temperature of 40-70 °C. Add 20% by weight of the filler for the first time, 40% by weight of the filler for the second time, and 40% by weight of the filler for the third time. After the addition is completed, continue to stir and mix evenly to obtain the industrial coupling agent.

[0091] Example 10

[0092] An industrial coupling agent is composed of the following raw materials in parts by weight: 75 parts of perfluoropolyether base oil, 10 parts of compound additive, and 15 parts of filler. The perfluoropolyether base oil is composed of perfluoropolyethers with kinematic viscosities of 8 cst (FBO-101), 15 cst (FBO-102), 22 cst (FBO-103), 60 cst (FBO-104), 150 cst (FBO-105), 260 cst (FBO-106), 460 cst (FBO-107), 510 cst (FBO-108), and 570 cst (FBO-109) at 40 °C in a mass ratio of 1:1:2:4:4:4:2:1:1; the compound additive is composed of N-cyclohexylthiophthalimide, 4,4'-bis(phenylisopropyl)diphenylamine, and perfluoropolyether-modified aniline in a mass ratio of 4:5:1; the filler is composed of titanium dioxide powder, kaolin powder, graphite powder, and silica powder in a mass ratio of 3:6:4:2.

[0093] The preparation method of the industrial coupling agent includes the following steps:

[0094] (1) Prepare the perfluoropolyether base oil, compound additive, and filler respectively according to the ratio.

[0095] (2) Put the perfluoropolyether base oil and the composite additive weighed by parts by weight into a container, and stir and mix evenly at a temperature of 40-70 °C to obtain mixture A.

[0096] (3) Add the filler to mixture A in three portions while stirring at a temperature of 40-70 °C. Add 20% by weight of the filler for the first time, 40% by weight of the filler for the second time, and 40% by weight of the filler for the third time. After the addition is completed, continue to stir and mix evenly to obtain the industrial coupling agent.

[0097] Example 11

[0098] An industrial coupling agent is composed of the following raw materials in parts by weight: 75 parts of perfluoropolyether base oil, 10 parts of compound additive, and 15 parts of filler. The perfluoropolyether base oil is composed of perfluoropolyethers with kinematic viscosities of 8 cst (FBO-101), 15 cst (FBO-102), 22 cst (FBO-103), 60 cst (FBO-104), 150 cst (FBO-105), 260 cst (FBO-106), 460 cst (FBO-107), 510 cst (FBO-108), and 570 cst (FBO-109) at 40 °C in a mass ratio of 1:1:1:2:3:3:3:3:3; the compound additive is composed of N-cyclohexylthiophthalimide, 4,4'-bis(phenylisopropyl)diphenylamine, and perfluoropolyether-modified aniline in a mass ratio of 4:5:1; the filler is composed of titanium dioxide powder, kaolin powder, graphite powder, and silica powder in a mass ratio of 3:6:4:2.

[0099] The preparation method of the industrial coupling agent includes the following steps:

[0100] (1) Prepare the perfluoropolyether base oil, compound additive, and filler respectively according to the ratio.

[0101] (2) Put the perfluoropolyether base oil and the composite additive weighed by parts by weight into a container, and stir and mix evenly at a temperature of 40-70 °C to obtain mixture A.

[0102] (3) Add the filler to mixture A in three portions while stirring at a temperature of 40-70 °C. Add 20% by weight of the filler for the first time, 40% by weight of the filler for the second time, and 40% by weight of the filler for the third time. After the addition is completed, continue to stir and mix evenly to obtain the industrial coupling agent.

[0103] Example 12

[0104] An industrial coupling agent is composed of the following raw materials in parts by weight: 75 parts of perfluoropolyether base oil, 10 parts of compound additive, and 15 parts of filler. The perfluoropolyether base oil is composed of perfluoropolyethers with kinematic viscosities of 8 cst (FBO-101), 15 cst (FBO-102), 22 cst (FBO-103), 60 cst (FBO-104), 150 cst (FBO-105), 260 cst (FBO-106), 460 cst (FBO-107), 510 cst (FBO-108), and 570 cst (FBO-109) at 40 °C in a mass ratio of 4:4:4:2:2:1:1:1:1; the compound additive is composed of N-cyclohexylthiophthalimide and 4,4'-bis(phenylisopropyl)diphenylamine in a mass ratio of 4:5; the filler is composed of titanium dioxide powder, kaolin powder, graphite powder, and silica powder in a mass ratio of 3:6:4:2.

[0105] The preparation method of the industrial coupling agent includes the following steps:

[0106] (1) Prepare the perfluoropolyether base oil, compound additive, and filler respectively according to the ratio.

[0107] (2) Put the perfluoropolyether base oil and the composite additive weighed by parts by weight into a container, and stir and mix evenly at a temperature of 40-70 °C to obtain mixture A.

[0108] (3) Add the filler to mixture A in three portions while stirring at a temperature of 40-70 °C. Add 20% by weight of the filler for the first time, 40% by weight of the filler for the second time, and 40% by weight of the filler for the third time. After the addition is completed, continue to stir and mix evenly to obtain the industrial coupling agent.

[0109] Comparative Example 1

[0110] An industrial coupling agent is composed of the following raw materials in parts by weight: 75 parts of methyl silicone oil, 10 parts of compound additive, and 15 parts of filler. The compound additive is composed of N-cyclohexylthiophthalimide, 4,4'-bis(phenylisopropyl)diphenylamine, and perfluoropolyether-modified aniline in a mass ratio of 4:5:1; the filler is composed of titanium dioxide powder, kaolin powder, graphite powder, and silica powder in a mass ratio of 3:6:4:2.

[0111] The preparation method of the industrial coupling agent includes the following steps:

[0112] (1) Prepare the methyl silicone oil, compound additive, and filler respectively according to the ratio.

[0113] (2) Weigh methyl silicone oil and the composite additive by weight parts, put them into a container, and stir and mix evenly at a temperature of 40 - 70 °C to obtain mixture A;

[0114] (3) At a temperature of 40 - 70 °C, add the filler to mixture A in three portions while stirring. Add 20% by weight of the filler for the first time, 40% by weight of the filler for the second time, and 40% by weight of the filler for the third time. After the addition is complete, continue to stir and mix evenly to obtain the industrial coupling agent.

[0115] Comparative Example 2

[0116] An industrial coupling agent is composed of the following raw materials by weight parts: 75 parts of ethyl silicone oil, 10 parts of composite additive, and 15 parts of filler. The composite additive is composed of N - cyclohexylthiophthalimide, 4,4' - bis(phenylisopropyl)diphenylamine, and perfluoropolyether - modified aniline in a mass ratio of 4:5:1; the filler is composed of titanium dioxide powder, kaolin powder, graphite powder, and silica powder in a mass ratio of 3:6:4:2.

[0117] The preparation method of the industrial coupling agent includes the following steps:

[0118] (1) Prepare ethyl silicone oil, composite additive, and filler respectively according to the ratio;

[0119] (2) Weigh ethyl silicone oil and the composite additive by weight parts, put them into a container, and stir and mix evenly at a temperature of 40 - 70 °C to obtain mixture A;

[0120] (3) At a temperature of 40 - 70 °C, add the filler to mixture A in three portions while stirring. Add 20% by weight of the filler for the first time, 40% by weight of the filler for the second time, and 40% by weight of the filler for the third time. After the addition is complete, continue to stir and mix evenly to obtain the industrial coupling agent.

[0121] Comparative Example 3

[0122] An industrial coupling agent is composed of the following raw materials by weight parts: 75 parts of phenyl silicone oil, 10 parts of composite additive, and 15 parts of filler. The composite additive is composed of N - cyclohexylthiophthalimide, 4,4' - bis(phenylisopropyl)diphenylamine, and perfluoropolyether - modified aniline in a mass ratio of 4:5:1; the filler is composed of titanium dioxide powder, kaolin powder, graphite powder, and silica powder in a mass ratio of 3:6:4:2.

[0123] The preparation method of the industrial coupling agent includes the following steps:

[0124] (1) Prepare phenyl silicone oil, composite additive, and filler respectively according to the ratio;

[0125] (2) Weigh the phenyl silicone oil and the composite additive by weight parts and put them into a container. Stir and mix them evenly at a temperature of 40 - 70 °C to obtain mixture A;

[0126] (3) At a temperature of 40 - 70 °C, add the filler to mixture A in three portions while stirring. Add 20% by weight of the filler for the first time, 40% by weight of the filler for the second time, and 40% by weight of the filler for the third time. After the addition is complete, continue to stir and mix evenly to obtain the industrial coupling agent.

[0127] Comparative Example 4

[0128] An industrial coupling agent is composed of the following raw materials by weight parts: 75 parts of perfluoropolyether base oil, 10 parts of composite additive, and 15 parts of filler. The perfluoropolyether base oil is composed of perfluoropolyethers with kinematic viscosities of 15 cst (FBO - 102) and 150 cst (FBO - 105) at 40 °C in a mass ratio of 4:3; the composite additive is composed of N - cyclohexylthiophthalimide, 4,4' - bis(phenylisopropyl)diphenylamine, and perfluoropolyether - modified aniline in a mass ratio of 4:5:1; the filler is composed of titanium dioxide powder, kaolin powder, graphite powder, and silica powder in a mass ratio of 2:5:3:1.

[0129] The preparation method of the industrial coupling agent includes the following steps:

[0130] (1) Prepare the perfluoropolyether base oil, composite additive, and filler respectively according to the ratio;

[0131] (2) Weigh the perfluoropolyether base oil and the composite additive by weight parts and put them into a container. Stir and mix them evenly at a temperature of 40 - 70 °C to obtain mixture A;

[0132] (3) At a temperature of 40 - 70 °C, add the filler to mixture A in three portions while stirring. Add 20% by weight of the filler for the first time, 40% by weight of the filler for the second time, and 40% by weight of the filler for the third time. After the addition is complete, continue to stir and mix evenly to obtain the industrial coupling agent.

[0133] Comparative Example 5

[0134] An industrial coupling agent is composed of the following raw materials in parts by weight: 75 parts of perfluoropolyether base oil, 10 parts of composite additive, and 15 parts of filler. The perfluoropolyether base oil is composed of perfluoropolyethers with kinematic viscosities of 15 cst (FBO-102) and 510 cst (FBO-108) at 40 °C in a mass ratio of 4:3; the composite additive is composed of N-cyclohexylthiophthalimide, 4,4'-bis(phenylisopropyl)diphenylamine, and perfluoropolyether-modified aniline in a mass ratio of 4:5:1; the filler is composed of titanium dioxide powder, kaolin powder, graphite powder, and silica powder in a mass ratio of 2:5:3:1.

[0135] The preparation method of the industrial coupling agent includes the following steps:

[0136] (1) Prepare the perfluoropolyether base oil, composite additive, and filler respectively according to the ratio;

[0137] (2) Put the perfluoropolyether base oil and the composite additive weighed by weight into a container, and stir and mix evenly at a temperature of 40-70 °C to obtain mixture A;

[0138] (3) Add the filler to mixture A in three portions while stirring at a temperature of 40-70 °C. Add 20% by weight of the filler for the first time, 40% by weight of the filler for the second time, and 40% by weight of the filler for the third time. After the addition is completed, continue to stir and mix evenly to obtain the industrial coupling agent.

[0139] Comparative Example 6

[0140] An industrial coupling agent is composed of the following raw materials in parts by weight: 75 parts of perfluoropolyether base oil, 10 parts of composite additive, and 15 parts of filler. The perfluoropolyether base oil is composed of perfluoropolyethers with kinematic viscosities of 150 cst (FBO-105) and 510 cst (FBO-108) at 40 °C in a mass ratio of 4:3; the composite additive is composed of N-cyclohexylthiophthalimide, 4,4'-bis(phenylisopropyl)diphenylamine, and perfluoropolyether-modified aniline in a mass ratio of 4:5:1; the filler is composed of titanium dioxide powder, kaolin powder, graphite powder, and silica powder in a mass ratio of 2:5:3:1.

[0141] The preparation method of the industrial coupling agent includes the following steps:

[0142] (1) Prepare the perfluoropolyether base oil, composite additive, and filler respectively according to the ratio;

[0143] (2) Put the perfluoropolyether base oil and the composite additive weighed by weight into a container, and stir and mix evenly at a temperature of 40-70 °C to obtain mixture A;

[0144] (3) At a temperature of 40 - 70 °C, while stirring, add the filler to mixture A in three portions. The first addition is 20% by weight of the filler, the second addition is 40% by weight of the filler, and the third addition is 40% by weight of the filler. After the addition is complete, continue to stir and mix evenly to obtain the industrial coupling agent.

[0145] Comparative Example 7

[0146] An industrial coupling agent is composed of the following raw materials in parts by weight: 75 parts of perfluoropolyether base oil, 10 parts of compound additive, and 15 parts of filler. Among them, the perfluoropolyether base oil is composed of perfluoropolyethers with kinematic viscosities of 8 cst (FBO - 101), 15 cst (FBO - 102), 22 cst (FBO - 103), 60 cst (FBO - 104), 150 cst (FBO - 105), and 260 cst (FBO - 106) at 40 °C in a mass ratio of 4:4:4:2:2:1; the compound additive is composed of N - cyclohexylthiophthalimide, 4,4' - bis(phenylisopropyl)diphenylamine, and perfluoropolyether - modified aniline in a mass ratio of 4:5:1; the filler is composed of titanium dioxide powder, kaolin powder, graphite powder, and silica powder in a mass ratio of 2:5:3:1.

[0147] The preparation method of the industrial coupling agent includes the following steps:

[0148] (1) Prepare the perfluoropolyether base oil, compound additive, and filler respectively according to the ratio.

[0149] (2) Put the perfluoropolyether base oil and the composite additive weighed by parts by weight into a container, and stir and mix evenly at a temperature of 40 - 70 °C to obtain mixture A.

[0150] (3) At a temperature of 40 - 70 °C, while stirring, add the filler to mixture A in three portions. The first addition is 20% by weight of the filler, the second addition is 40% by weight of the filler, and the third addition is 40% by weight of the filler. After the addition is complete, continue to stir and mix evenly to obtain the industrial coupling agent.

[0151] Comparative Example 8

[0152] An industrial coupling agent is composed of the following raw materials in parts by weight: 75 parts of perfluoropolyether base oil, 10 parts of compound additive, and 15 parts of filler. The perfluoropolyether base oil is composed of perfluoropolyethers with kinematic viscosities of 60 cst (FBO-104), 150 cst (FBO-105), 260 cst (FBO-106), 460 cst (FBO-107), 510 cst (FBO-108), and 570 cst (FBO-109) at 40 °C in a mass ratio of 4:4:4:1:1:1; the compound additive is composed of N-cyclohexylthiophthalimide, 4,4'-bis(phenylisopropyl)diphenylamine, and perfluoropolyether-modified aniline in a mass ratio of 4:5:1; the filler is composed of titanium dioxide powder, kaolin powder, graphite powder, and silica powder in a mass ratio of 2:5:3:1.

[0153] The preparation method of the industrial coupling agent includes the following steps:

[0154] (1) Prepare the perfluoropolyether base oil, compound additive, and filler respectively according to the ratio.

[0155] (2) Put the perfluoropolyether base oil and the composite additive weighed by parts by weight into a container, and stir and mix evenly at a temperature of 40-70 °C to obtain a mixture A.

[0156] (3) Add the filler to the mixture A in three portions while stirring at a temperature of 40-70 °C. Add 20% by weight of the filler for the first time, 40% by weight of the filler for the second time, and 40% by weight of the filler for the third time. After the addition is completed, continue to stir and mix evenly to obtain the industrial coupling agent.

[0157] Comparative Example 9

[0158] An industrial coupling agent is composed of the following raw materials in parts by weight: 75 parts of perfluoropolyether base oil, 10 parts of compound additive, and 15 parts of filler. The perfluoropolyether base oil is composed of perfluoropolyethers with kinematic viscosities of 8 cst (FBO-101), 15 cst (FBO-102), 22 cst (FBO-103), 460 cst (FBO-107), 510 cst (FBO-108), and 570 cst (FBO-109) at 40 °C in a mass ratio of 2:2:1:1:1:1; the compound additive is composed of N-cyclohexylthiophthalimide, 4,4'-bis(phenylisopropyl)diphenylamine, and perfluoropolyether-modified aniline in a mass ratio of 4:5:1; the filler is composed of titanium dioxide powder, kaolin powder, graphite powder, and silica powder in a mass ratio of 2:5:3:1.

[0159] The preparation method of the industrial coupling agent includes the following steps:

[0160] (1) Prepare perfluoropolyether base oil, compound additive, and filler respectively according to the ratio.

[0161] (2) Put the perfluoropolyether base oil and the composite additive weighed by weight into a container, and stir and mix evenly at a temperature of 40 - 70 °C to obtain mixture A.

[0162] (3) Add the filler to mixture A in three portions while stirring at a temperature of 40 - 70 °C. Add 20% by weight of the filler for the first time, 40% by weight of the filler for the second time, and 40% by weight of the filler for the third time. After the addition is completed, continue to stir and mix evenly to obtain the industrial coupling agent.

[0163] Perform performance tests on the industrial coupling agents prepared in Examples 1 - 12 and Comparative Examples 1 - 9. The test methods are as follows:

[0164] I. Detection in the full temperature range:

[0165] 1) Sampling: Take 10 grams each of the industrial coupling agents in Examples 1 - 12 and the coupling agent 1 in Comparative Examples 1 - 8 as samples. After labeling, place them in the same container for cooling and heating.

[0166] 2) Cool from 20 °C to -60 °C at a rate of 1 °C every 3 seconds, and observe the morphological changes of the coupling agent samples in Examples 1 - 12 and Comparative Examples 1 - 8 at low temperatures.

[0167] 3) Continuously heat from 20 °C at a rate of 1 °C every 3 seconds, and detect the maximum heat-resistant temperature of the coupling agent samples in Examples 1 - 12 and Comparative Examples 1 - 8. Visually observe the temperature before smoking or deformation occurs, which is the maximum heat-resistant temperature. The test results are shown in Table 1.

[0168] Table 1

[0169]

[0170]

[0171]

[0172] It can be seen from Table 1 that the industrial coupling agents with a wide temperature range in Examples 7 - 10 all have a low cold-resistant temperature and have excellent cold resistance, heat resistance, and high- and low-temperature deformation resistance when working under the conditions of (-60) - 250 °C.

[0173] In Examples 1-3, the perfluoropolyether base oil simultaneously contains three perfluoropolyethers with low, medium, and high viscosities. Among them, the perfluoropolyether with low viscosity (kinematic viscosity at 40 °C is 5-30 cst) can lower the overall freezing point of the coupling agent and improve its low-temperature performance; the perfluoropolyether with medium viscosity (kinematic viscosity at 40 °C is 45-300 cst) can ensure the normal operation of the coupling agent under normal working conditions; the perfluoropolyether with high viscosity (kinematic viscosity at 40 °C is 420-600 cst) can improve the high-temperature stability of the coupling agent. As can be seen from Table 1, the coupling agents prepared in Examples 1-3 can withstand a minimum temperature of -70 °C and a maximum temperature of 281 °C. By mixing perfluoropolyethers in three viscosity ranges, the present invention obtains a coupling agent applicable to a wide temperature range.

[0174] The inventors of the present application found in actual applications that the coupling agents prepared using three perfluoropolyethers with different viscosities in Examples 1-3 have a wider applicable temperature range, but there is a problem of unstable state. This is because the viscosity span of the mixed perfluoropolyethers is large and there is no continuous connection, resulting in an unstable change trend of performance with temperature changes; therefore, through further research, the inventors proposed a more preferred solution for Examples 4-11. In Examples 4-11, the perfluoropolyether simultaneously contains 9 perfluoropolyethers with different viscosities. The coupling agents prepared can withstand a minimum temperature of -70 °C and a maximum temperature of 291 °C, and are in a stable state in each temperature range. The overall applicable range covers different temperatures, and is more continuous and stable, and the performance is more excellent.

[0175] Comparing Example 5 and Example 12, Example 12 does not contain the anti-corrosion agent perfluoropolyether-modified aniline. The purpose of using this additive is to improve the compatibility of the coupling agent with the metal surface at high temperatures and protect the metal surface. For the coupling agent without this additive, after a long-term high-temperature test, the state of the coupling agent changes and an abnormal smell is emitted.

[0176] Comparing Example 5 with Comparative Examples 1-3, Comparative Examples 1-3 use methyl silicone oil, ethyl silicone oil, and phenyl silicone oil as the base oil respectively. Such coupling agents harden and solidify at low temperatures, and emit a smoky smell at high temperatures, seriously affecting the performance of the coupling agent.

[0177] Comparing Examples 1-3 and Examples 4-6, Examples 4-6 respectively select perfluoropolyethers with two viscosities to prepare the perfluoropolyether base oil. Compared with Examples 1-3, they lack the perfluoropolyether with high viscosity, medium viscosity, and low viscosity respectively. The lack of the perfluoropolyether with low viscosity reduces the low-temperature performance of the coupling agent, and the coupling agent is prone to hardening at low temperatures; the lack of the perfluoropolyether with high viscosity reduces the high-temperature resistance of the coupling agent, and smoking and a sharp decrease in viscosity will occur at high temperatures, ultimately resulting in a lack of stability in the performance of the prepared industrial coupling agent with temperature changes.

[0178] Comparing Example 5 with Comparative Examples 7 - 9, Comparative Examples 7 - 9 further refined the composition of the perfluoropolyether base oil on the basis of Examples 4 - 6. Six different viscosities of perfluoropolyether were selected and formulated respectively. However, overall, the perfluoropolyether base oil composition still lacked high-viscosity, medium-viscosity, and low-viscosity perfluoropolyethers respectively, and there was still the problem of unstable physical state with temperature change, resulting in poor stability of the prepared industrial coupling agent.

[0179] II. Practical Application Tests

[0180] Take the industrial coupling agents with a wide temperature range obtained in Examples 7 - 10 and the existing imported coupling agents, and conduct thickness measurement experiments under the same conditions. Each test is repeated three times, and the thickness measurement data is entered into Table 2.

[0181] Table 2

[0182]

[0183]

[0184] It can be seen from Table 2 that during the test, there is no obvious difference in the physical state stability of the industrial coupling agent with a wide temperature range of the present invention compared with the imported coupling agent. The stability of the thickness measurement data of the industrial coupling agent with a wide temperature range of the present invention is significantly better than that of the imported coupling agent, and its measurement results are more accurate and reliable. Moreover, the cost of the industrial coupling agent with a wide temperature range of the present invention is 20 - 40% of the price of the imported coupling agent, achieving outstanding technical effects in reducing the detection cost.

[0185] In summary, the industrial coupling agent of the present invention has excellent high and low temperature resistance performance, is suitable for pipelines with a large temperature span, can ensure the thickness measurement accuracy within the full working temperature range, simplifies the measurement steps, one coupling agent can meet both high and low temperature working conditions at the same time, has good application effects, and is suitable for popularization and application.

[0186] The above further describes the present invention with the aid of specific embodiments. However, it should be understood that this specific description should not be construed as a limitation on the essence and scope of the present invention. Various modifications made by those of ordinary skill in the art to the above embodiments after reading this specification all fall within the scope protected by the present invention.

Claims

1. An industrial coupling agent, characterized in that, By weight, it comprises the following components: 70-80 parts of perfluoropolyether base oil, 5-15 parts of compound additive, and 10-20 parts of filler; Among them, the perfluoropolyether base oil is composed of perfluoropolyethers with kinematic viscosities at 40 °C of 5-30 cst, 45-300 cst, and 420-650 cst in a mass ratio of 3-12:5-12:2-9.

2. The industrial coupling agent according to claim 1, characterized in that, The perfluoropolyether base oil is composed of perfluoropolyethers with kinematic viscosities at 40 °C of 5-10 cst, 13-18 cst, 19-30 cst, 45-100 cst, 120-180 cst, 200-300 cst, 420-480 cst, 485-560 cst, and 565-650 cst in a mass ratio of 1-4:1-4:1-4:2-4:2-4:1-4:1-3:1-3:1-3.

3. The industrial coupling agent according to claim 1 or 2, characterized in that, The perfluoropolyether base oil is composed of perfluoropolyethers with kinematic viscosities at 40 °C of 8 cst, 15 cst, 22 cst, 60 cst, 150 cst, 260 cst, 460 cst, 510 cst, and 570 cst in a mass ratio of 1-4:1-4:1-4:2-4:2-4:1-4:1-3:1-3:1-3.

4. The industrial coupling agent according to claim 1, wherein The perfluoropolyether is a K-type perfluoropolyether.

5. The industrial coupling agent according to claim 1, wherein The compound additive is composed of N-cyclohexylthiophthalimide, 4,4'-bis(phenylisopropyl)diphenylamine, and perfluoropolyether-modified aniline in a mass ratio of 3-5:3-6:1-2.

6. The industrial coupling agent according to claim 5, wherein The perfluoropolyether-modified aniline has the following structure: wherein, Rf is C3F7O(CF(CF3)CF2) m CF(CF3), and m is an integer between 10 and 100.

7. The industrial coupling agent according to claim 1, wherein The filler is selected from at least three of titanium dioxide powder, kaolin powder, graphite powder, and silica powder.

8. The industrial coupling agent according to claim 7, wherein The filler is composed of titanium dioxide powder, kaolin powder, graphite powder, and silica powder in a mass ratio of 2-4:5-7:3-5:1-3.

9. The preparation method of the industrial coupling agent according to any one of claims 1-8, characterized in that, It includes the following steps: (1) Prepare the perfluoropolyether base oil, compound additive, and filler respectively; (2) Mix the perfluoropolyether base oil, compound additive, and filler evenly at 40-70 °C to obtain the industrial coupling agent.

10. The preparation method of the industrial coupling agent according to claim 9, characterized in that, The filler is added in multiple times.

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