WO2012055084A1 - 一种含氟的防腐涂料 - Google Patents

一种含氟的防腐涂料 Download PDF

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WO2012055084A1
WO2012055084A1 PCT/CN2010/002211 CN2010002211W WO2012055084A1 WO 2012055084 A1 WO2012055084 A1 WO 2012055084A1 CN 2010002211 W CN2010002211 W CN 2010002211W WO 2012055084 A1 WO2012055084 A1 WO 2012055084A1
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component
fluorine
agent
coupling agent
fluororubber
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PCT/CN2010/002211
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English (en)
French (fr)
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刘斌
邢华燕
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中昊晨光化工研究院
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Priority to EP10858813.8A priority Critical patent/EP2634227A4/en
Priority to US13/881,373 priority patent/US20130225747A1/en
Publication of WO2012055084A1 publication Critical patent/WO2012055084A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D115/00—Coating compositions based on rubber derivatives
    • C09D115/02—Rubber derivatives containing halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds

Definitions

  • the present invention relates to an anticorrosive coating, and more particularly to a fluorine-containing anticorrosive coating. Background technique
  • Fluoro Rubber is a synthetic polymeric elastomer containing fluorine atoms in the carbon chain of the main chain or side chain. Compared with other rubbers, fluororubber has excellent high temperature resistance, oil resistance and resistance to various chemicals. The characteristics of chemical corrosion, so it is widely used in aviation, chemical, petroleum, machinery and other industries. With the development of industry in recent years in China, the requirements for anti-corrosion performance of fluororubbers are becoming more and more demanding. The general anti-corrosion coatings are applied to pipes and equipment in the chemical industry and other industries, which cannot meet the requirements. For example, anti-corrosion coatings cannot be used for a long time. Application under harsh conditions such as strong acid and alkali will bring inconvenience to production and life.
  • An object of the present invention is to improve a conventional general coating material and to provide a fluorine-containing anticorrosive coating material having excellent weather resistance, durability, corrosion resistance, abrasion resistance, and tack resistance.
  • a fluorine-containing anticorrosive coating of the present invention is a fluororubber-based film-forming material, which is provided with an auxiliary agent, a reinforcing agent and an additive, and after being kneaded to obtain a fluorine-kneaded rubber,
  • the fluorine-containing coating obtained by dissolving in the organic solvent to obtain the component A glue, and using the component A glue and the component B silane coupling agent at a low temperature to cure.
  • the fluororubber is a F26 type fluororubber having a molecular weight of 30,000-50,000 and a molecular formula of -. - CH 2 -CF 2 -CF-CF 2 + n
  • the promoter of CF 3 is activated magnesium oxide and calcium hydroxide, the reinforcing agent is thermal black carbon MT N990, the additive is a release agent Rhein, and the silane coupling agent is KH550.
  • the A component glue liquid comprises the following raw materials by weight: F26 type fluororubber 100, active magnesium oxide 5-12, calcium hydroxide 4-8, thermal black carbon MT N990 20-30 , release agent Rheinland 1-2 and organic solvent 40-90.
  • the organic solvent is one or more of methyl isobutyl ketone, toluene, ketone and methyl ethyl ketone.
  • the fluorine-containing coating material has a fluorine content of from 10 to 60 w/w%.
  • the curing ratio of the A component glue to the B component silicon germanium coupling agent is 100: 3 to 5, and the curing ratio is preferably 20:1.
  • the curing temperature of the A component glue and the B component silicon germanium coupling agent is 30-80 °C. If the curing temperature is 80 ° C during the curing process, the curing time of the coating film can be shortened.
  • the fluorine-containing anticorrosive coating of the present invention is an improved and preferred component of the conventional general anticorrosive paint, which is a base material of a fluorine-containing rubber as a main film-forming material, and the fluorine-containing paint is composed of two groups of A and B.
  • the composition of the component is added to the component A glue during the construction.
  • the component B can be dried 24 hours after the film is applied, and the film is completely cured after 5 days.
  • the fluorine-containing paint of the invention is used for anti-corrosion, and is characterized in that the construction is easy, and the defects of high-temperature vulcanization of the fluororubber are required, and the construction is difficult, and the use of the harsh environment which cannot be satisfied by the general anti-corrosion coating is improved. It maintains the excellent weather resistance, durability, corrosion resistance, wear resistance and viscosity resistance of fluororubber. It is widely used as an anticorrosive coating with excellent performance in some specific heavy-duty anti-corrosion fields. It is especially suitable for the weathering and anti-corrosion coating coating of metal components of large buildings. It is especially suitable for corrosion resistant coatings with acid, alkali and oxidant under severe conditions.
  • the F26 type fluororubbers in the following examples were purchased from Zhonghao Chenguang Chemical Research Institute, active magnesia and ultrafine calcium hydroxide were purchased from Japan Concord, and thermal cracking carbon black MT N990 was purchased from Canadian cancarb company, release agent.
  • the Rheinland bulk was purchased from TÜV Rheinland, the silane coupling agent KH550 was purchased from Jiangsu Coupling Agents Co., Ltd., and the organic solvent was commercially available analytically pure.
  • the formulation of the fluorine compound in the A component glue is as follows:
  • the above raw materials are kneaded by an open mill to obtain a fluoro-kneaded rubber.
  • the obtained fluoro-kneaded rubber was dissolved in a mixed solution of 112.5 ml of methyl isobutyl ketone and 12.5 ml of toluene at a solid content of 10% until completely dissolved, to obtain a component A paste.
  • the A component glue and the B component silane coupling agent KH550 are mixed according to the mass ratio of 20:1, and then sprayed or brushed on the surface of the substrate such as pipeline, reaction kettle, external wall, stainless steel, etc. Carry out antiseptic.
  • the formulation of the fluorine compound in the A component glue is as follows:
  • the above raw materials are kneaded by an open mill to obtain a fluoro-kneaded rubber.
  • the obtained fluorine rubber compound was dissolved in 112.5 ml of methyl isobutyl ketone according to a solid content of 15%.
  • a component A paste was obtained in a mixed solution with 12.5 ml of toluene, until completely dissolved.
  • the A component glue and the B component silane coupling agent KH550 are mixed according to the mass ratio of 20:1, and then sprayed or brushed on the surface of the substrate such as pipeline, reaction kettle, external wall, stainless steel, etc. Carry out antiseptic.
  • the formula of the rubber compound in the A component glue is as follows:
  • the above raw materials are kneaded by an open mill to obtain a fluoro-kneaded rubber.
  • the obtained fluoro-kneaded rubber was dissolved in a mixed solution of 112.5 ml of methyl ethyl ketone and 12.5 ml of toluene according to a solid content of 20% until completely dissolved, to obtain a component A paste.
  • the A component glue and the B component silane coupling agent KH550 are mixed according to the mass ratio of 20:1, and then sprayed or brushed on the surface of the substrate such as pipeline, reaction kettle, external wall, stainless steel, etc. Carry out antiseptic.
  • the formulation of the fluorine compound in the A component glue is as follows:
  • the above raw materials are kneaded by an open mill to obtain a fluoro-kneaded rubber.
  • the obtained fluoro-kneaded rubber was dissolved in a mixed solution of U2.5 ml of ketone and 12.5 ml of toluene in an amount of 25% until completely dissolved, to obtain a component A paste.
  • a component A paste When constructing, take the A component
  • the glue and the B component silicon germanium coupling agent KH550 are mixed according to a mass ratio of 20:1, and then sprayed or brushed on the surface of the substrate such as a pipe, a reaction kettle, an outer wall, a stainless steel, etc., and the substrate is preserved.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Description

一种含氟的防腐涂料 技术领域
本发明涉及一种防腐涂料，具体地说，涉及一种含氟的防腐涂料。 背景技术
氟橡胶（ Fluoro Rubber )是指主链或侧链的碳原子上含有氟原子 的一种合成高分子弹性体， 与其它橡胶相比， 氟橡胶具有优异的耐高 温、 耐油性及耐多种化学药品腐蚀的特性， 所以广泛应用于航空、 化 工、 石油、 机械等行业。 随着我国近年来工业的发展， 对于氟橡胶在 防腐蚀性能上的要求也日趋苛刻，一般的防腐涂层应用于化工等行业 管道、 设备中， 已经不能满足要求， 如防腐涂层不能长时间在强酸、 强碱等恶劣条件下应用， 将给生产和生活带来诸多不便， 频繁地更换 防腐产品及设备， 势必会影响到生产的正常进行， 增加企业的运营成 本。 然而， 目前国内生产的该类防腐涂料的巿场价格较高， 且施工性 较难。 因此， 研究和开发低成本的、 易于施工的、 高防腐的新型涂料 来代替传统的一般涂料， 成为亟待解决的问题。 发明内容
本发明的目的是对传统的一般涂料进行改进，提供一种具有优异 的耐候性、 耐久性、 耐腐蚀性、 耐磨性、 耐粘性等性能的含氟防腐涂 料。 '
为了实现本发明目的， 本发明的一种含氟的防腐涂料， 其是以氟 橡胶为基本的成膜物， 配以助剂、 补强剂和添加剂， 经过混炼得到氟 混炼胶后， 溶于有机溶剂得到 A组分胶液， 使用时将 A组分胶液与 B 组分硅烷偶联剂经低温固化得到的含氟涂料。
前述的涂料， 所述氟橡胶为 F26型氟橡胶， 其分子量为 3-5万， 分 子式为-. - CH2-CF2-CF-CF2+n
CF3 所述助剂为活性氧化镁和氢氧化钙， 所述补强剂为热裂法炭黑 MT N990, 所述添加剂为脱模剂莱茵散， 所述硅烷偶联剂为 KH550。
前述的涂料， 所述 A组分胶液中包括下述重量份的原料： F26型 氟橡胶 100、 活性氧化镁 5-12、 氢氧化钙 4-8、 热裂法炭黑 MT N990 20-30、 脱模剂莱茵散 1-2和有机溶剂 40-90。
前述的涂料， 所述有机溶剂为甲基异丁基甲酮、 甲苯、 甲酮和丁 酮中的一种或多种。
前述的涂料， 所述含氟涂料的含氟量为 10-60w/w%。
前述的涂料， 所述 A组分胶液与 B组分硅垸偶联剂的固化比为 100: 3〜5， 优选固化比为 20: 1。
前述的涂料， 所述 A组分胶液与 B组分硅垸偶联剂的固化温度为 30-80°C。 在固化过程中如果固化温度为 80°C， 可缩短涂膜固化时间。
本发明的含氟的防腐涂料是对原有一般的防腐涂料做了改进并 优选了组分，其是以氟橡胶为主要成膜物质的基料，该含氟涂料由 A、 B两个组分构成， 施工时向 A组分胶液中加入固化剂 B组分， 可在 涂膜后 24h表干， 5天后涂膜完全固化。 本发明的含氟涂料用于防腐 的特点在于， 施工容易， 且有效地改进了氟橡胶需要高温硫化， 施工 难度大等缺点， 改进了一般防腐涂层不能满足的较恶劣环境下的使 用， 同时保持了氟橡胶优异的耐候性、 耐久性、 耐腐蚀性、 耐磨性、 耐粘性等性能， 其作为性能极佳的防腐涂料品种， 在一些特定的重防 腐领域得到了广泛的应用和推广。尤其适用于各大型建筑金属构件的 耐候性和防腐性的成膜涂料， 特别适合苛刻条件下的耐酸、碱和氧化 剂的耐腐蚀涂层， 可广泛应用于石油、 化工、 机械、 制冷、 航空、 军 事、 航天、 电子等国民经济建设领域。 具体实施方式 以下实施例用于说明本发明， 但不用来限制本发明的范围。 以下各实施例中的 F26型氟橡胶购自中昊晨光化工研究院， 活性 氧化镁和超细氢氧化钙购自日本协和公司，热裂法炭黑 MT N990购自 加拿大 cancarb公司， 脱模剂莱茵散购自德国莱茵公司， 硅烷偶联剂 KH550购自江苏偶联剂公司， 有机溶剂为市售分析纯。
实施例 1
A组分胶液中氟混炼胶的配方如下：
F26型氟橡胶 100kg
活性氧化镁 8kg
超细氢氧化钙 5kg
补强剂炭黑 20kg
脱模剂 （莱茵散） 1kg
上述原料经过开炼机混炼得到氟混炼胶。
将得到的氟混炼胶按照固含量 10%溶于 112.5ml甲基异丁基甲酮 和 12.5ml甲苯的混合溶液中， 直至完全溶解， 得到 A组分胶浆。 施工 时， 取 A组分胶浆与 B组分硅烷偶联剂 KH550按照质量比 20: 1混合， 然后喷涂或者刷涂于管道、 反应釜、 外墙、 不锈钢等基材表面上， 对 基材进行防腐。
实施例 2
A组分胶液中氟混炼胶的配方如下：
F26型氟橡胶 100kg
活性氧化镁 10kg
超细氢氧化钙 7kg
补强剂炭黑 25kg
脱模剂 （莱茵散） 1.5kg
上述原料经过开炼机混炼得到氟混炼胶。
将得到的氟混炼胶按照固含量 15%溶于 112.5ml甲基异丁基甲酮 和 12.5ml甲苯的混合溶液中， 直至完全溶解， 得到 A组分胶浆。 施工 时， 取 A组分胶浆与 B组分硅烷偶联剂 KH550按照质量比 20: 1混合， 然后喷涂或者刷涂于管道、 反应釜、 外墙、 不锈钢等基材表面上， 对 基材进行防腐。
实施例 3
A组分胶液中 混炼胶的配方如下:
F26型氟橡胶 100kg
活性氧化镁 12kg
超细氢氧化钙 8kg
补强剂炭黑 30kg
脱模剂 （莱茵散） 2kg
上述原料经过开炼机混炼得到氟混炼胶。
将得到的氟混炼胶按照固含量 20%溶于 112.5ml丁酮和 12.5ml甲 苯的混合溶液中， 直至完全溶解， 得到 A组分胶浆。 施工时， 取 A组 分胶浆与 B组分硅烷偶联剂 KH550按照质量比 20: 1混合， 然后喷涂或 者刷涂于管道、 反应釜、 外墙、 不锈钢等基材表面上， 对基材进行防 腐。
实施例 4
A组分胶液中氟混炼胶的配方如下：
F26型氟橡胶 100kg
活性氧化镁 12kg
超细氢氧化钙 8kg
补强剂炭黑 30kg
脱模剂 （莱茵散） 2kg
上述原料经过开炼机混炼得到氟混炼胶。
将得到的氟混炼胶按照含量 25%溶于 U2.5ml甲酮和 12.5ml甲苯 的混合溶液中， 直至完全溶解， 得到 A组分胶浆。 施工时， 取 A组分 胶浆与 B组分硅垸偶联剂 KH550按照质量比 20: 1混合， 然后喷涂或者 刷涂于管道、反应釜、外墙、不锈钢等基材表面上，对基材进行防腐。
本发明含氟的防腐涂料的稳定性及漆膜的强度， 如表 1所示。
表 1 本发明含氟的防腐涂料的稳定性及漆膜的强度
Figure imgf000006_0001
虽然，上文中已经用一般性说明及具体实施方案对本发明作了详 尽的描述， 但在本发明基础上， 可以对之作一些修改或改进， 这对本 领域技术人员而言是显而易见的。 因此， 在不偏离本发明精神的基础 上所做的这些修改或改进， 均属于本发明要求保护的范围。 工业实用性 本发明的含
电子等国民经济建设领域。

Claims

权 利 要 求 书
1. 一种含氟的防腐涂料， 其特征在于， 其是以氟橡胶为基本的 成膜物， 配以助剂、 补强剂和添加剂， 经过混炼得到氟混炼胶后， 溶 于有机溶剂得到 A组分胶液，使用时，将 A组分胶液与 B组分硅烷偶联 剂混合经低温固化得到的含氟涂料。
2. 根据杈利要求 1所述的涂料， 其特征在于， 所述氟橡胶为 F26 型氟橡胶， 其分子量为 3-5万， 分子式为. -
+CH CF2- CF-CF2+n
CF3 所述助剂为活性氧化镁和氢氧化钙， 所述补强剂为热裂法炭黑 MT N990, 所述添加剂为脱模剂莱茵散， 所述硅垸偶联剂为 KH550。
3. 根据权利要求 2所述的涂料， 其特征在于， 所述 A组分胶液中 包括下述重量份的原料： F26型氟橡胶 100、 活性氧化镁 5-12、 氢氧化 钙 4-8、 热裂法炭黑 MT N990 20-30、 脱模剂莱茵散 1-2和有机溶剂 40-90。
4. 根据权利要求 1-3任一项所述的涂料， 其特征在于， 所述有机 溶剂为甲基异丁基甲酮、 甲苯、 甲酮和丁酮中的一种或多种。
5. 根据权利要求 1-3任一项所述的涂料， 其特征在于， 所述含氟 涂料的含氟量为 10-60w/w%。
6. 根据权利要求 1-3任一项所述的涂料， 其特征在于， 所述 A组 分胶液与 B组分硅烷偶联剂的固化比为 100: 3-5。
7. 根据权利要求 6所述的涂料，其特征在于，所述 A组分胶液与 B 组分硅烷偶联剂的固化比为 20: 1。
8. 据权利要求 1-3任一项所述的涂料， 其特征在于， 所述 A组 分胶液与 B组分硅垸偶联剂的固化温度为 30-80 'C。
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EP2634227A4 (en) 2014-05-28

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