WO2013026331A1 - 一种rtv防污闪涂料及其制备方法 - Google Patents

一种rtv防污闪涂料及其制备方法 Download PDF

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Publication number
WO2013026331A1
WO2013026331A1 PCT/CN2012/078286 CN2012078286W WO2013026331A1 WO 2013026331 A1 WO2013026331 A1 WO 2013026331A1 CN 2012078286 W CN2012078286 W CN 2012078286W WO 2013026331 A1 WO2013026331 A1 WO 2013026331A1
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Prior art keywords
parts
rtv
formula
test
water repellent
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PCT/CN2012/078286
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English (en)
French (fr)
Inventor
王生明
黄荣华
张栋
闫晓宏
康心亮
焦广旭
于闽英
李新宝
修伟
梁静
马建国
常雷雷
Original Assignee
山西省电力公司晋城供电分公司
太原市中天兴电力技术有限公司
武汉大学
国家电网公司
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Application filed by 山西省电力公司晋城供电分公司, 太原市中天兴电力技术有限公司, 武汉大学, 国家电网公司 filed Critical 山西省电力公司晋城供电分公司
Priority to BR112013025013A priority Critical patent/BR112013025013B8/pt
Publication of WO2013026331A1 publication Critical patent/WO2013026331A1/zh
Priority to US14/021,675 priority patent/US9058920B2/en

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/46Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes silicones
    • H01B3/465Silicone oils
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/06Ethers; Acetals; Ketals; Ortho-esters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/54Silicon-containing compounds
    • C08K5/541Silicon-containing compounds containing oxygen
    • C08K5/5415Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/63Additives non-macromolecular organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/65Additives macromolecular
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/045Polysiloxanes containing less than 25 silicon atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/22Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2265Oxides; Hydroxides of metals of iron

Definitions

  • the invention relates to an RTV anti-pollution flash paint and a preparation method thereof, and belongs to the technical field of coatings for power transmission and transformation equipment of electric power systems. Background technique
  • the object of the present invention is to provide a long-life RTV anti-fouling flash coating for the short service life of the coating agent caused by the rapid release rate of the water repellent in the RTV anti-smudge flash coating.
  • the present invention provides an RTV anti-soil flash coating comprising the following components by weight: 100 parts of polydimethylsiloxane, 4-10 parts of reinforcing filler, 0.1-1 part of catalyst, crosslinking agent 1-5 parts, 3-6 parts of water repellent, 1-2 parts of pigment, 1-2 parts of decabromodiphenyl ether, 30-40 parts of toluene;
  • the water repellent is a mixture of a substance having the structure shown in Formula 1 and one or more of a small molecular weight silicone oil, dihydroxydiphenylsilane, fluorine-containing silicone oil, and white oil:
  • R'-Si is a polysiloxane group or a fluorine-containing siloxane group, and its structure is as shown in Formula 2:
  • the reinforcing filler is fumed silica or precipitated silica or the like.
  • the catalyst is one or a combination of an organotin compound, an organotin chelate compound, an organotitanium compound, and an organotitanium chelate compound.
  • the pigment is any one of iron red or an inert pigment.
  • the RTV antifouling flash coating provided by the present invention has the following structure:
  • the substance having the structure represented by Formula 1 preferably, in the water repellent, the substance having the structure represented by Formula 1 and a small molecular weight silicone oil, dihydroxydiphenylsilane, fluorine-containing silicone oil and white oil
  • the mass ratio of the substance of the formula 1 to the other components of the mixture of one or more of the compounds is from 1:1 to 1:4 (preferably from 1:1 to 1:2).
  • the invention also provides a preparation method of the above RTV anti-soil flash coating, which comprises the following steps:
  • control test may also be carried out in accordance with the steps included in the above preparation method, except that the water repellent may be changed or not added depending on the test.
  • the RTV anti-smudge flash coating provided by the invention has the following beneficial effects compared with the prior art: 1.
  • the curing test, the performance test test and the hydrophobic migration aging test show that the mechanical properties, electrical properties, water repellency, water loss and recovery, hydrophobic migration characteristics, etc. of the coating of the RTV anti-smudge flash coating provided by the present invention are all Meet current industry standards.
  • the water repellent in the RTV anti-smudge flash coating provided by the present invention is linked to the vulcanized coating of the RTV coating by a temporary chemical bond during the preparation process, and the temporary chemical bond can be broken under the environmental factor during use, and the water repellent is released.
  • the specific control release mechanism is as follows:
  • the dotted line indicates a dissociable chemical bond, including an ester bond, a Schiff base, and the like.
  • crosslinking agent has the following structure:
  • the above water repellent is a mixture of a substance having the following structure and a small molecular weight silicone oil in a weight ratio of 1:1:
  • R is acetoxy CH 3 COO-
  • crosslinking agent has the following structure:
  • R is methoxy CH 3 0- ; is ethyl CH 3 CH 2 -.
  • the above water repellent is a mixture obtained by mixing a substance having the following structure with dihydroxydiphenylsilane in a weight ratio of 1:1.5:
  • R is a methoxy CH 3 0- ;
  • -Si is a polysiloxane group or a fluorine-containing siloxane group, and the structure is as follows:
  • R 2 is CF 3 -.
  • crosslinking agent has the following structure:
  • R is a ketoximino MeEtCNO-; is ethyl CH 3 CH 2 -.
  • the water repellent is a mixture of a substance having the following structure and a fluorine-containing silicone oil in a weight ratio of 1:2:
  • R is a ketoximino group MeEtCNO-;
  • W-Si is a polysiloxane group or a fluorine-containing siloxane group, and the structure is as follows:
  • n 3 and R 2 is CH 3 -.
  • crosslinking agent has the following structure:
  • R is an amide group AcMeN-; is ethyl CH 3 CH :
  • R is an amide group AcMeN-; -Si is a polysiloxane group or a fluorosilicone group, and the structure is as follows:
  • the water repellent is a mixture of a substance having the following structure and a small molecular weight silicone oil and dihydroxydiphenylsilane in a weight ratio of 1:
  • R is an amino group C 6 H u NH- ;
  • -Si is a polysiloxane group or a fluorine-containing siloxane group, and the structure is as follows:
  • crosslinking agent has the following structure:
  • the water repellent is a mixture of a substance having the following structure and a small molecular weight silicone oil, dihydroxydiphenylsilane, and fluorine-containing silicone oil in a weight ratio of 1: 1:2:1:
  • the RTV antifouling coatings provided in Examples 1-5 can all be prepared in accordance with the preparation methods provided herein.
  • the present invention provides an RTV anti-smudge flash coating without a water repellent, an RTV anti-smudge flash coating added to the market existing water repellent, and a different amount of the present invention.
  • the RTV anti-fouling flash coatings of the water repellent were respectively subjected to five groups of controlled tests.
  • the components of the coating provided in the Control Test 1 include:
  • the crosslinking agent has the following structure:
  • R is acetoxy CH 3 COO- ; is methyl CH 3 -.
  • Curing test Pour the RTV anti-soil flashing paint provided in this control test into a Teflon mold (slot depth 2mm), flatten it, and place the mold in a constant temperature and humidity chamber for vulcanization, wherein the vulcanization temperature is 25 °C. The vulcanization relative humidity is 50%. During the vulcanization process, the dry time and complete curing time of the coating were observed. The thickness after vulcanization was 1.5 mm. The results were as follows: The surface drying time was 45 min (45 min), and the complete curing time was 24 h ( ⁇ 72 h), where the brackets were standard. Requirements, the results show that the test determines that all indicators meet the requirements.
  • test piece After the sample is vulcanized, the test piece is obtained. The test piece is tested for appearance, electrical properties, mechanical properties, water repellency (including water repellency, water loss and recovery, and hydrophobic migration) according to standard DL/T627-2004. The results are as follows, with standard requirements in parentheses:
  • the cured film of this RTV coating has a smooth, smooth appearance, no bubbles, no skin, no cracking; tear strength is 8.21kN/m (>3kN/m), and shear strength is 2MPa ( >0.8MPa ) ;
  • the dielectric strength is 21.26kV/mm ( > 18kV/mm);
  • the hydrophobic HC classification value is Grade 1 (Level 1-2); the hydrophobic loss grade value is Grade 4-5 (Level 1-2), which is difficult to recover, and the hydrophobic migration HC classification value is Grade 4-5 (2- Level 3);
  • the standardization of the hydration migration aging experiment is not as standard, but it is critical for the life evaluation of RTV coatings.
  • the hydration migration aging experiment is carried out by artificial high temperature accelerated experiment, multiple hydration migration aging, and the migration rate of hydrophobic migration agent is evaluated by the number of hydration migration aging experiments and the recovery time of each HC grading value.
  • Test procedure According to the hydrophobicity migration test procedure, the diatomaceous earth was uniformly coated on the surface of the test piece with a gray density of 1.0 mg/cm 2 , and after standing at a constant temperature of 80 ° C for 2 hours, the surface water repellency was tested by a spray method. , determine the HC grading value, if it is difficult to recover within 2h, extend the test time until the final recovery HC value is 1-2, the time is extended no more than 8h ; after each water repellency recovery, the test piece is taken out, the surface of the diatomaceous earth is cleaned After drying, re-paint diatomaceous earth, repeat the above test process until the test piece is water-repellent (HC recovery to 1-2). It is difficult to recover at 8h, the number of test times is the final test number, and the time of each recovery. .
  • composition of the coating provided in this comparative test was based on the coating provided in Comparative Test 1, and 3 kg of a small molecular weight silicone oil (viscosity 20-100 cp) was added as a water repellent.
  • the hydrophobic HC classification value is Grade 1 (Level 1-2); the hydrophobic loss classification value is 1-2 grade (Level 1-2), which is difficult to recover, and the hydrophobic migration HC classification value is 1-2 (2- Grade 3), the results show that the experimental determination of all indicators meet the requirements; ⁇ water migration aging test results: the number of hydration migration aging test is 5 times, the recovery time is 2.5 hours.
  • the components of the coating provided in this control test were based on the components of the coating provided in Control Test 1, and a hydrophobic agent having a structure of less than 3 kg was added:
  • R is acetoxy CH 3 COO.
  • R l -Si is
  • n 1 and R 2 is CH 3 -.
  • the grading value of drowning HC is 1 (1-2); the grading value of drowning is 1-2 (1-2), which is difficult to recover.
  • the grading value of hydrophobic HC is 1-2 (2- Level 3);
  • Tear strength 8.21kN/m (>3kN/m), shear strength 2MPa (>0.8MPa); dielectric strength 21.26kV/mm (> 18kV/mm);
  • Drowning migration aging test results The number of hydration migration aging tests is 3 times, and the recovery time is infinite.
  • composition of the coating provided in this control test is based on the composition of the coating provided in Comparative Test 1, and the addition of 1.5 kg of a small-molecular weight methyl silicone oil (viscosity 20-100 C) and a structure of less than 1.5 kg of water repellent:
  • R is acetoxy CH 3 COO.
  • R -Si is
  • the hydrophobic HC classification value is Grade 1 (Level 1-2); the hydrophobic loss classification value is 1-2 grade (Level 1-2), the recovery time is 12h ( ⁇ 24h), and the hydrophobic migration HC grade is 2- Level 3 (Level 2-3); The results show that all indicators meet the requirements.
  • the results of the hydration migration aging test The number of sample tests was 9 and the recovery time was 10 hours.
  • composition of the coating provided in this control test is based on the coating composition provided in Control Test 1, adding 0.75 kg of small molecular weight methyl silicone oil (viscosity 20-100 Cp), 0.75 kg of diphenyldihydroxysilane and 1.5 kg or less.
  • Water repellent :
  • R is acetoxy CH 3 COO.
  • R -Si is
  • Tear strength 10.45kN/m (>3kN/m), shear strength 2MPa (>0.8MPa); dielectric strength 19.58kV/mm (> 18kV/mm);
  • the hydrophobic HC classification value is Grade 1 (Level 1-2); the hydrophobic loss grade is 1-2 grade (Level 1-2), the recovery time is 12h ( ⁇ 24h), and the hydrophobic migration HC grade is 1- Level 2 (Level 2-3); The results show that all indicators meet the requirements.
  • the results of the hydration migration aging test The number of sample tests was 12 and the recovery time was 4.5 hours.
  • the RTV anti-soil flash coating has the best performance, which is better than the long-acting water-repellent agent, and is also superior to the commonly used water repellent.

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Abstract

一种RTV防污闪涂料及其制备方法。该RTV防污闪涂料由以下重量份数的组分组成:聚二甲基硅氧烷100份、增强填料4-10份、催化剂0.1-1份、交联剂1-5份、憎水剂3-6份、颜料1-2份、十溴联苯醚1-2份、甲苯30-40份;其中所述的憎水剂为具有式I所示的结构的物质与小分子量硅油、二羟基二苯基硅烷、含氟硅油、白油中任意一种或者几种的混合物。式I中,R为乙酰氧基CH3COO—、甲氧基CH3O—、酮肟基MeEtCNO—、酰胺基AcMeN—、氨基C6H11NH—或者丙酮基H2C=CMeO—中的任意一种;R1—Si为聚硅氧烷基团或含氟硅氧烷基团,其结构式如式II所示。式II中n=1〜4,R2为CH3—或CF3—中的任意一种。

Description

种 RTV防污闪涂料及其制备方法
Figure imgf000003_0001
本发明涉及一种 RTV防污闪涂料及其制备方法, 属于电力系统输变电设备用涂料 技术领域。 背景技术
变电设备在长期的使用过程中, 表面会覆盖很多灰尘等固体颗粒, 使变电设备表面 具有一定的导电能力, 因此在使用过程中会漏电, 即浪费了资源又带来了一定的安全隐 患。 为了解决此类问题, 人们常在变电设备的表面涂刷 RTV防污闪涂料, 该涂料赋予 变电设备表面很强的憎水性, 即使其表面被固体颗粒物覆盖, 依然保持疏水特性, 从而 限制其表面泄漏电流, 提高闪络电压。
TV防污闪涂料常用的憎水剂包括小分子量硅油 (Mw=300-500)、 二羟基二苯基 硅烷、小分子量含氟硅油、 3#白油等,这些憎水剂是在涂料捏合加工过程中添加进去的, 硫化时通过物理包埋的方式存在于 RTV涂层之中, 使用过程中, 憎水剂受浓度差导致 的扩散力驱动向表面迁移, 其释放速率和憎水剂的扩散系数、 扩散面积等有关, 消耗速 度很快, 因此人们常采用增加憎水剂的浓度的方法来提高 RTV防污闪涂料的使用寿命, 但是文献报道, 单纯提高憎水剂含量到一定程度后, 对 RTV防污闪涂料的寿命基本上 没有影响, 因此必须寻找其它的方法来有效降低憎水剂的释放速率。 发明内容
本发明的目的是针对 RTV防污闪涂料中憎水剂释放速度快引起的涂料使用寿命短, 工作人员需要不断重复涂刷的问题, 而提供一种使用寿命长的 RTV防污闪涂料。
本发明的目的还在于提供该 RTV防污闪涂料的制备方法。
为达到上述目的, 本发明提供了一种 RTV防污闪涂料, 其包括以下重量份组成: 聚二甲基硅氧烷 100份、 增强填料 4-10份、 催化剂 0.1-1份、 交联剂 1-5份、 憎水 剂 3-6份、 颜料 1-2份、 十溴联苯醚 1-2份、 甲苯 30-40份;
其中, 所述憎水剂为具有式 1所示的结构的物质与小分子量硅油、 二羟基二苯基硅 烷、 含氟硅油和白油中的一种或者几种的混合物:
Figure imgf000003_0002
其中, R为乙酰氧基 CH3COO-、甲氧基 CH30-、酮肟基 MeEtCNO-、酰胺基 AcMeN -、 氨基 C6HuNH-和丙酮基 H2C=CMeO-中的任意一种;
R'-Si为聚硅氧烷基团或含氟硅氧烷基团, 其结构如式 2所示:
(CH3)3SiO― (Si(CH3)0)-—— SiCH30—— Si(CH3)32 其中, n=i -4, R2为 CH3-或 CF3-中的任意一种。
在本发明提供的 RTV防污闪涂料中, 优选地, 所述增强填料为气相白炭黑或者沉 淀白炭黑等。
在本发明提供的 RTV防污闪涂料中, 优选地, 所述催化剂为有机锡化合物、 有机 锡螯合物、 有机钛化合物和有机钛螯合物等中的一种或几种的组合。
在本发明提供的 RTV防污闪涂料中, 优选地, 所述颜料为铁红或惰性颜料等中的 任意一种。
在本发明提供的 RTV防污闪涂 所述交联剂具有以下结构:
Figure imgf000004_0001
其中, R为乙酰氧基 CH3COO-、甲氧基 CH30-、酮肟基 MeEtCNO-、酰胺基 AcMeN -、 氨基 C6HuNH-或者丙酮基 H2C=CMeO-中的任意一种; 为甲基 CH3-或乙基 CH3CH2- 中的任意一种。
在本发明提供的 RTV防污闪涂料中, 优选地, 在憎水剂中, 所述具有式 1所示的 结构的物质与小分子量硅油、 二羟基二苯基硅烷、 含氟硅油和白油中的一种或者几种的 混合物的式 1所示物质和其他组分质量比为 1 : 1 - 1: 4 (优选为 1 : 1 - 1: 2)。
本发明还提供了上述 RTV防污闪涂料的制备方法, 其包括以下步骤:
将聚二甲基硅氧烷、增强填料、颜料和憎水剂加入行星搅拌器中,升温到 110- 13CTC 混炼 2-4小时后抽真空 2-3小时(使真空度低于 -0.09MPa), 再加入交联剂混炼, 再抽真 空 0.5小时(使真空度低于 -0.09MPa), 加入催化剂、 十溴联苯醚和溶剂甲苯稀释后取出 成品, 密封包装, 得到所述 RTV防污闪涂料。
在本发明中, 对照试验也可以按照上述制备方法所包括的步骤进行, 只是根据不同 的试验, 憎水剂可以有所改变或者不加入。
本发明所提供的 RTV防污闪涂料与现有技术相比具有以下有益效果: 1、 固化试验、 性能测试试验和憎水迁移老化试验显示, 本发明提供的 RTV防污闪 涂料的涂层的机械性能、 电性能、 憎水性、 憎水丧失和恢复、 憎水迁移特性等均符合现 行行业标准。
2、本发明提供的 RTV防污闪涂料中的憎水剂在制备过程中通过临时化学键链接到 RTV涂料的硫化涂层中, 使用时在环境因素下临时化学键可以断裂, 释放出憎水剂, 通 过化学力控制和降低憎水剂的释放速度, 具体控制释放机理如下:
Figure imgf000005_0001
其中: 虚线所示为可离解的化学键, 包括酯键、 希夫碱基等。 具体实施方式
实施例 1
本实施例提供了一种 RTV防污闪涂料, 其包括以下组分:
聚二甲基硅氧烷 100千克、 气相白炭黑 4千克、 二丁基二月桂酸锡 0.1千克、 交联 剂 1千克、 憎水剂 3千克、 铁红 1千克、 十溴联苯醚 1千克、 甲苯 30千克。
其中, 上述交联剂具有以下结构:
RD
RO— Si—— 其中, R为乙酰氧基 CH3COO-; 为甲基 CH3-。
上述憎水剂为具有以下结构的物质与小分子量硅油按照 1 : 1 的重量比混合得到的 混合物:
Figure imgf000005_0002
其中, R为乙酰氧基 CH3COO-、 -Si为聚硅氧烷基团或含氟硅氧烷基团, 其结构 如下: 其中, n=l, R2为 CH3-。
实施例 2
本实施例提供了一种 RTV防污闪涂料, 其包括以下组分:
聚二甲基硅氧烷 100千克、 沉淀白炭黑 5千克、 二丁基二辛基锡 0.3千克、 交联剂 2千克、 憎水剂 4千克、 铁红 1.5千克、 十溴联苯醚 1.5千克、 甲苯 35千克。
其中, 上述交联剂具有以下结构:
Figure imgf000006_0001
其中, R为甲氧基 CH30-; 为乙基 CH3CH2-。
上述憎水剂为具有以下结构的物质与二羟基二苯基硅烷按照 1 : 1.5的重量比混合得 到的混合物:
Figure imgf000006_0002
其中, R为甲氧基 CH30-; -Si为聚硅氧烷基团或含氟硅氧烷基团, 结构如下:
: 、 : : :: ¾ .¾-:';'■' ¾—:: - ϊ"^一 其中, n=2, R2为 CF3-。
实施例 3
本实施例提供了一种 RTV防污闪涂料, 其包括以下组分:
聚二甲基硅氧烷 100千克、 气相白炭黑 6千克、 二丁基锡二乙酰丙酮螯合物 0.5千 克、 交联剂 3千克、 憎水剂 5千克、 铁红 2千克、 十溴联苯醚 2千克、 甲苯 38千克。
其中, 上述交联剂具有以下结构:
Figure imgf000006_0003
其中, R为酮肟基 MeEtCNO-; 为乙基 CH3CH2-。
上述憎水剂为具有以下结构的物质与含氟硅油按照 1 : 2的重量比混合得到的混合 物:
Figure imgf000007_0001
其中, R为酮肟基 MeEtCNO-; W-Si为聚硅氧烷基团或含氟硅氧烷基团,结构如下:
R2
\
(CH3)3SiO— (Si(CH3)0); SiCH30— Si(CH3)
其中, n=3 , R2为 CH3-。
实施例 4
本实施例提供了一种 RTV防污闪涂料, 其包括以下组分:
聚二甲基硅氧烷 100千克、 沉淀白炭黑 7千克、 钛酸正丁酯 0.7千克、 交联剂 4千 克、 憎水剂 6千克、 铁红 1.2千克、 十溴联苯醚 1.2千克、 甲苯 40千克。
其中, 上述交联剂具有以下结构:
Figure imgf000007_0002
其中, R为酰胺基 AcMeN-; 为乙基 CH3CH:
Figure imgf000007_0003
其中, R为酰胺基 AcMeN-; -Si为聚硅氧烷基团或含氟硅氧烷基团, 结构如下:
(CH3)3SiO― (Si(CH3)O)-—— SiCH3O—— Si(CH3)3 其中, n=4, R2为 CF3-。
实施例 5
本实施例提供了一种 RTV防污闪涂料, 其包括以下组分:
聚二甲基硅氧烷 100千克、 气相白炭黑 8千克、 二丙氧基钛二乙酰丙酮螯合物 1千 克、 交联剂 5千克、 憎水剂 6千克、 铁红 2千克、 十溴联苯醚 1.4千克、 甲苯 36千克。
其中, 上述交联剂具有以下结构: RD
\
RD— Sr
RD / 其中, R为氨基 C6HuNH-; R 为甲基 CH3-。
上述憎水剂为具有以下结构的物质与小分子量硅油、 二羟基二苯基硅烷按照 1 : 重量比混合得到的混合物:
Figure imgf000008_0001
其中, R为氨基 C6HuNH-; -Si为聚硅氧烷基团或含氟硅氧烷基团, 结构如下:
(CH3)3SiO― (Si(CH3)O)-—— SiCH3O—— Si(CH3)3 其中, n=l, R2为 CH3-。
实施例 6
本实施例提供了一种 RTV防污闪涂料, 其包括以下组分:
聚二甲基硅氧烷 100千克、沉淀白炭黑 10千克、 二丁基二辛基锡 0.8千克、交联剂 4千克、 憎水剂 5千克、 铁红 1.6千克、 十溴联苯醚 1.8千克、 甲苯 40千克。
其中, 上述交联剂具有以下结构:
RD
\
RD— Si—— 其中, R为丙酮基 H2C=CMeO-; R 为甲基 CH3-。
上述憎水剂为具有以下结构的物质与小分子量硅油、 二羟基二苯基硅烷、 含氟硅油 按照 1 : 1: 2: 1的重量比混合得到的混合物:
Figure imgf000008_0002
其中, R为丙酮基 H2C=CMeO-; -Si为聚硅氧烷基团或含氟硅氧烷基团, 其结构 如下: (CH3)3SiO― (Si(CH3)O)-—— SiCH3O—— Si(CH3)3 其中, n=3, R2为 CH3-。
实施例 1-5提供的 RTV防污闪涂料均可以按照本发明所提供的制备方法制备得到。 为进一步表明本发明提供的 RTV防污闪涂料的效果, 本发明对未加憎水剂的 RTV 防污闪涂料、 加入市场现有憎水剂的 RTV防污闪涂料、 加入不同量本发明提供的憎水 剂的 RTV防污闪涂料分别进五组对照试验。
对照试验 1- (未加憎水剂)
该对照试验 1提供的涂料的组分包括:
聚二甲基硅氧烷 100千克、 气相白炭黑 4千克、 二月桂酸二丁基锡 0.1千克、 交联 剂 1千克、 铁红 1千克、 十溴联苯醚 1.5千克、 甲苯 30千克;
其中, 交联剂具有以下结构:
RD
\
RD— Si——
R为乙酰氧基 CH3COO-; 为甲基 CH3-。
固化试验: 将本对照试验提供的 RTV 防污闪涂料倒入聚四氟乙烯模具中 (槽深 2mm), 铺平, 将模具放入恒温恒湿箱中硫化, 其中硫化温度为 25°C, 硫化相对湿度为 50%。 在硫化的过程中观察记录涂料表干时间和完全固化时间, 硫化后厚度为 1.5mm, 结果如下: 表干时间为 45min ( 45min), 完全固化时间为 24h ( <72h), 其中括号内 为标准要求, 结果表明试验测定各项指标均符合要求。
性能测试试验: 样品硫化后, 得到试片, 按标准 DL/T627-2004对试片进行外观、 电性能、 力学性能、 憎水性 (包括憎水性、 憎水丧失和恢复、 憎水迁移)测试, 结果如 下, 括号内为标准要求:
外观: 该 RTV涂料固化后的涂膜外观平整、 光滑, 无气泡, 不起皮, 不龟裂; 撕裂强度为 8.21kN/m ( >3kN/m), 剪切强度为 2MPa ( >0.8MPa);
介电强度为 21.26kV/mm ( > 18kV/mm);
憎水性 HC分级值为 1级( 1-2级); 憎水丧失分级值为 4-5级( 1-2级), 难以恢复, 憎水迁移性 HC分级值为 4-5级 (2-3级);
上述试验结果表明实验测定该涂料的各项指标均符合要求。
憎水迁移老化实验未见标准规定, 但其对 RTV涂料的寿命评价至关重要, 本试验 的憎水迁移老化实验是通过人工高温加速实验, 多次进行憎水迁移老化, 通过憎水迁移 老化实验的次数和每次的 HC分级值恢复时间来评价憎水迁移剂迁移速率的大小。
试验过程: 按憎水迁移性测试过程操作, 将硅藻土按灰密 1.0 mg/cm2均匀地涂刷在 试片表面上, 恒温 80°C放置 2h后, 利用喷雾法测试其表面憎水性, 测定 HC分级值, 如果 2h内难以恢复, 则延长测试时间直至最终恢复 HC值为 1-2, 时间延长不超过 8h; 每次憎水性恢复后, 将试片取出, 清洗表面的硅藻土, 晾干后再重新涂刷硅藻土, 重复 上述测试过程, 直到试片的憎水性 (HC恢复至 1-2) 在 8h难以恢复, 记录测试次数为 最终测试次数, 以及每次恢复的时间。
结果显示: 本对照试验提供的试片未表现出憎水迁移性能, 憎水迁移老化测试次数 为 0次, 恢复时间无限长。
对照试验 2- (采用市场现有憎水剂)
本对照试验提供的涂料的组分是在对照试验 1提供的涂料的基础上加入了 3千克小 分子量硅油 (粘度 20-lOOcp) 作为憎水剂。
固化试验、 性能测试试验、 憎水迁移老化试验过程和条件与对照试验 1相同, 结果 如下:
固化试验结果: 表干时间 45min ( 45min), 完全固化时间 24h ( <72h), 结果显 示各项指标均符合要求。
性能测试试验结果:
外观: RTV涂料固化后的涂膜外观平整, 光滑, 无气泡, 不起皮, 不龟裂; 撕裂强度 8.21kN/m ( >3kN/m), 剪切强度 2MPa ( >0.8MPa);
介电强度 21.26kV/mm ( > 18kV/mm);
憎水性 HC分级值为 1级(1-2级); 憎水丧失分级值为 1-2级(1-2级), 难以恢复, 憎水迁移性 HC分级值为 1-2级 (2-3级), 结果表明实验测定各项指标均符合要求; 憎水迁移老化试验结果: 憎水迁移老化测试次数为 5次, 恢复时间 2.5小时。
结果表明: 本对照试验提供的涂料表现出一定的憎水迁移性能。
对照试验 3
本对照试验提供的涂料的组分是在对照试验 1提供的涂料的组分基础上加入了 3千 克以下结构的憎水剂:
Figure imgf000011_0001
其中, R为乙酰氧基 CH3COO. Rl-Si为
(CH3)3SiO—— (Si(CH3)0),
Figure imgf000011_0002
其中, n=l, R2为 CH3-。
固化试验、 性能测试试验、 憎水迁移老化试验过程和条件与对照试验 1相同, 结果 如下:
固化试验结果: 表干时间 45min ( 45min), 完全固化时间 24h ( <72h), 结果显 示各项指标均符合要求。
性能测试试验结果: 外观: RTV涂料固化后的涂膜外观平整, 光滑, 无气泡, 不起 皮, 不龟裂;
憎水 HC分级值为 1级 (1-2级); 憎水丧失分级值为 1-2级 (1-2级), 难以恢复, 憎水迁移性 HC分级值为 1-2级 (2-3级);
撕裂强度 8.21kN/m( >3kN/m),剪切强度 2MPa( >0.8MPa);介电强度 21.26kV/mm ( > 18kV/mm);
憎水迁移老化试验结果: 憎水迁移老化测试次数为 3次, 恢复时间无限长。
结果表明: 本对照试验提供的涂料未表现出憎水迁移性能, 说明憎水剂的加入赋予 涂层一定的憎水迁移性能, 但迁移速率慢。
对照试验 4
本对照试验提供的涂料的组分是在对照试验 1 提供的涂料的组分基础上同时加入 1.5千克小分子量甲基硅油 (粘度 20-lOOC ) 和 1.5千克以下结构的憎水剂:
Figure imgf000011_0003
其中, R为乙酰氧基 CH3COO. R -Si为
R2
(CH3)3SiO— (Si(CH3)O), SiCH3O— Si(CH3) 其中, n=l, R2为 CH3-。
固化试验、 性能测试试验、 憎水迁移老化试验过程和条件与对照组 1相同, 结果如 下:
固化试验结果: 表干时间 45min ( 45min), 完全固化时间 24h ( <72h), 结果显 示各项指标均符合要求。
性能测试试验结果: 外观: RTV涂料固化后涂膜外观平整, 光滑, 无气泡, 不起皮, 不龟裂;
撕裂强度 9.05kN/m( >3kN/m),剪切强度 2MPa( >0.8MPa);介电强度 19.35kV/mm ( > 18kV/mm);
憎水性 HC分级值为 1级 (1-2级); 憎水丧失分级值为 1-2级 (1-2级), 恢复时间 12h ( <24h), 憎水迁移性 HC分级值为 2-3级 (2-3级); 结果显示各项指标均符合要 求。
憎水迁移老化试验结果: 样品测试次数为 9次, 恢复时间为 10小时。
结果表明本对照试验与对照组 3相比,表现出较好的憎水迁移性能和迁移老化性能。 对照试验 5
本对照试验提供的涂料的组分是在对照试验 1提供的涂料组分基础上同时加入 0.75 千克小分子量甲基硅油 (粘度 20-100Cp)、 0.75千克二苯基二羟基硅烷和 1.5千克以下 结构的憎水剂:
Figure imgf000012_0001
其中, R为乙酰氧基 CH3COO. R -Si为
(CH3)3SiO— (Si(CH3)O);j ~ SiCH3O—— Si(CH3)3 其中, n=l, R2为 CH3-。
固化试验、 性能测试试验、 憎水迁移老化试验过程和条件与对照试验 1相同, 结果 如下:
固化试验结果: 表干时间 45min ( 45min), 完全固化时间 24h ( <72h), 结果显 示各项指标均符合要求。 外观: RTV涂料固化后的涂膜外观平整, 光滑, 无气泡, 不起皮, 不龟裂, 耐化学 品性能良好;
撕裂强度 10.45kN/m( >3kN/m),剪切强度 2MPa( >0.8MPa);介电强度 19.58kV/mm ( > 18kV/mm);
憎水性 HC分级值为 1级 (1-2级); 憎水丧失分级值为 1-2级 (1-2级), 恢复时间 12h ( <24h), 憎水迁移性 HC分级值为 1-2级 (2-3级); 结果显示各项指标均符合要 求。
憎水迁移老化试验结果: 样品测试次数为 12次, 恢复时间为 4.5小时。
结果表明: 本对照试验提供的涂料与对照试验 1-4提供的涂料相比表现出较快的憎 水迁移速率和较多的迁移次数,说明采用小分子量硅油和二羟基二苯基硅烷复配的 RTV 防污闪涂料的性能最优, 优于单纯使用长效憎水剂, 也优于市场常用憎水剂。

Claims

权利要求书
1、 一种 RTV防污闪涂料, 其包括以下重量份组成:
聚二甲基硅氧烷 100份、 增强填料 4-10份、 催化剂 0.1-1份、 交联剂 1-5份、 憎水 剂 3-6份、 颜料 1-2份、 十溴联苯醚 1-2份、 甲苯 30-40份;
其中, 所述憎水剂为具有式 1所示的结构的物质与小分子量硅油、 二羟基二苯基硅 烷、 含氟硅油和白油中的一种或者几种的混合物:
Figure imgf000014_0001
式 1 其中, R为乙酰氧基 CH3COO-、甲氧基 CH30-、酮肟基 MeEtCNO-、酰胺基 AcMeN -、 氨基 C6HuNH-和丙酮基 H2C=CMeO-中的任意一种;
R'-Si为聚硅氧烷基团或含氟硅氧烷基团, 其结构如式 2所示:
(CH3)3SiO— (Si(CH3)0)5 ~ SiCH30― Si(CH3)32 其中, n=i-4, R2为 CH3-或 CF3-中的任意一种。
2、 根据权利要求 1所述的 RTV防污闪涂料, 其中, 所述增强填料为气相白炭黑或 者沉淀白炭黑。
3、 根据权利要求 1所述的 RTV防污闪涂料, 其中, 所述催化剂为有机锡化合物、 有机锡螯合物、 有机钛化合物和有机钛螯合物中的一种或几种的组合。
4、 根据权利要求 1所述的 RTV防污闪涂料, 其中, 所述颜料为铁红或惰性颜料中 的任意一种。
5、 根据权利要求 1所述的 RT 中, 所述交联剂具有以下结构:
Figure imgf000014_0002
其中, R为乙酰氧基 CH3COO-、甲氧基 CH30-、酮肟基 MeEtCNO-、酰胺基 AcMeN -、 氨基 C6HuNH-或者丙酮基 H2C=CMeO-中的任意一种; 为甲基 CH3-或乙基 CH3CH2- 中的任意一种。
6、 根据权利要求 1所述的 RTV防污闪涂料, 其中, 在所述憎水剂中, 所述具有式 1所示的结构的物质与小分子量硅油、 二羟基二苯基硅烷、 含氟硅油和白油中的一种或 者几种的混合物的式 1所示物质和其他组分质量比为 1 : 1-1: 4。
7、 权利要求 1-6任一项所述的 RTV防污闪涂料的制备方法, 其包括以下步骤: 将聚二甲基硅氧烷、增强填料、颜料和憎水剂加入行星搅拌器中,升温到 110-13CTC 混炼 2-4小时后抽真空 2-3小时, 再加入交联剂混炼, 再抽真空 0.5小时, 加入催化剂、 十溴联苯醚和溶剂甲苯稀释后取出成品, 得到所述 RTV防污闪涂料。
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