CN112538302A - 一种仿生型石油管道无氟涂层及其制备方法 - Google Patents

一种仿生型石油管道无氟涂层及其制备方法 Download PDF

Info

Publication number
CN112538302A
CN112538302A CN202011227330.6A CN202011227330A CN112538302A CN 112538302 A CN112538302 A CN 112538302A CN 202011227330 A CN202011227330 A CN 202011227330A CN 112538302 A CN112538302 A CN 112538302A
Authority
CN
China
Prior art keywords
coating
fluorine
petroleum pipeline
bis
bionic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202011227330.6A
Other languages
English (en)
Other versions
CN112538302B (zh
Inventor
赵杰
田丽梅
窦海旭
范勇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jilin University
Original Assignee
Jilin University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jilin University filed Critical Jilin University
Priority to CN202011227330.6A priority Critical patent/CN112538302B/zh
Publication of CN112538302A publication Critical patent/CN112538302A/zh
Application granted granted Critical
Publication of CN112538302B publication Critical patent/CN112538302B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D151/085—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds on to polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065—After-treatment
    • B05D3/067—Curing or cross-linking the coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
    • 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
    • C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • 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
    • C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/24—Homopolymers or copolymers of amides or imides
    • C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L58/00—Protection of pipes or pipe fittings against corrosion or incrustation
    • F16L58/02—Protection of pipes or pipe fittings against corrosion or incrustation by means of internal or external coatings
    • F16L58/04—Coatings characterised by the materials used
    • F16L58/10—Coatings characterised by the materials used by rubber or plastics
    • F16L58/1009—Coatings characterised by the materials used by rubber or plastics the coating being placed inside the pipe
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2201/00—Polymeric substrate or laminate
    • B05D2201/02—Polymeric substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/10—Metallic substrate based on Fe
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/10—Metallic substrate based on Fe
    • B05D2202/15—Stainless steel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/40—Metallic substrate based on other transition elements
    • B05D2202/45—Metallic substrate based on other transition elements based on Cu
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2502/00—Acrylic polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2518/00—Other type of polymers
    • B05D2518/10—Silicon-containing polymers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Paints Or Removers (AREA)

Abstract

本发明涉及一种仿生型石油管道无氟涂层及其制备方法，属于新型高分子表面涂层。该涂层以典物鲀鱼体表为基本研究模型，利用亲水性单体和PDMS以及二苯甲酮类光引发剂聚合而成。通过紫外光引发可以将涂层固定在各种基底材料表面，基底与涂层之间附着力较强。涂层改变了基底的表面性能，实现了对基底表面的亲水改性和对低表面张力液体如多种油类的防黏附性能。这类涂层可实现动态和静态环境下的优异亲水疏油性能。此发明重点实用于解决石油管道内衬管壁结蜡的共性难题，其具有节能、高效、长寿等特点，属于防止管壁结蜡的“治本”的技术，具有良好的应用前景和经济价值，是未来输油管道防蜡技术的发展必然趋势。

Description

一种仿生型石油管道无氟涂层及其制备方法
技术领域
本发明属于新型高分子表面涂层，高分子仿生材料技术领域。具体涉及一种仿生型石油 管道涂层及其制备方法。
背景技术
仿生型亲水疏油表面：海洋工程用热塑性玻纤增强柔性管是山东冠通管业有限公司联合 国内众多高校科研院所，在国家工信部《高技术船舶科研项目》的支持下，研制出的一种轻 质高强的非金属原有输送管道，它具有耐腐蚀、抗疲劳，抗降解、使用寿命长等特点，是继 荷兰Airborne公司、法国Technip公司及美国Deepflex公司后，国内首家掌握该产品制造工 艺核心技术的高新技术企业，打破了国外在该领域的垄断，填补了石油管道国内空白。
该型管道在实际应用过程中，仍然存在未能解决的管道内衬管壁结蜡的共性难题。该问 题属于世界性难题。针对上述难题，国内外采用的防蜡原理及发展现状如下：
1.机械清蜡技术
主要借助机械工具去除油管壁上附着的石蜡，并借助液体冲刷清理干净即可。采用的是 机械外力剥离法，该方法及技术原理简单，是防蜡技术应用中最为常见的一种方法，然后， 由于该技术治标不治本，且需要停止输送作业才能进行，具有成本高、效率低的弊端。
2.热力保温技术
通过对油井内原油温度的加热，保证其温度在石蜡析蜡点之上的一种应用方法，其原理 是利用温度，维持析蜡点温度，防止其结晶，使其保持熔融状态的一种技术。通过加热、表 面管线保温的方法，使得热力保温技术成为管道防蜡方法成为最为有效的方法之一，然而加 热或是管线保温，需要额外的动力作为热源，则会大大提高原油输送成本，也是成为其广泛 使用的一个重要原因。
3.化学药剂防蜡技术
其原理是利用参混的化学药剂改变管壁的吸附性能或是使蜡晶无法按规整状态长大，无 法形成蜡晶，最终导致石蜡结晶体与管壁的结合强度大大降低。化学药剂防蜡技术由于成本 低、效果好，目前应用十分广泛。
以上的方法虽然能够解决石蜡结晶的问题，但是不同程度的存在需要增加石油输送成本 的问题和无法长效解决的问题。
发明内容
为了解决上述问题，受典型生物鲀鱼特殊的体表结构亲水疏油机制启发，本发明提出了 一种仿生型石油管道涂层，该涂层的制备步骤具体如下：
1)制备具有PDMS链的光引发剂预聚物：以二苯甲酮类光引发剂、亲水性单体、PDMS-M 为原料，将上述原料溶于溶剂中，加入引发剂偶氮二异丁腈(AIBN)，在55～90℃的温度条 件下加热3～18h制备得到具有含氟长链的光引发剂预聚物；所用溶剂为二甲基甲酰胺、乙醇、 丙酮、异丙醇、丁醇、四氢呋喃和甲苯中的一种或多种的组合；
二苯甲酮类光引发剂是一类以二苯甲酮为主体，其中一个苯基的对位上带有修饰基团， 修饰基团上至少含有一个位于端头的双键的化合物；优选4-丙烯酰氧基二苯甲酮、2-羟基 -4-(甲基丙烯酰氧基)二苯甲酮、4,4'-二[2-(1-丙烯基)苯氧基]二苯甲酮、4-甲基丙烯酰氧基二苯 甲酮和4-丙烯酰氧基-2-羟基二苯甲酮中的一种或多种的组合；
亲水性单体为丙烯酸或其衍生物，如丙烯酸酯类、丙烯酰胺类；优选丙烯酸(AAc)、甲 基丙烯酸羟乙酯(HEMA)、为丙烯酰胺(AAm)、N-羟乙基丙烯酰胺(HEAA)、丙烯酸羟乙 酯(HEA)、甲基丙烯酸丙磺酸(AMPS)中的一种或多种；
所述的PDMS-M的烷基端的端头为丙烯基的PDMS树脂，优选双-3-甲基丙烯基氧丙基 化四甲基二硅氧烷、甲基丙烯酰氧基五甲基二硅氧烷、(丙烯酰氧丙基)甲基-二甲基共聚硅氧 烷、1,3-双(3-甲基丙烯酰氧丙基)四(三甲基硅氧基)二硅氧烷、1,3-双(3-甲基丙烯酰胺丙基)四 甲基二硅氧烷、1,3-双(3-甲基丙烯酰氧基-2-羟丙基氧基丙基)四甲基二硅氧烷、1,3-双(3-甲基 丙烯基氧丙基)-1,1,3,3-四甲基二硅氧烷、1,3-双(4-丙烯酰氧丁基)四甲基二硅氧烷中的一种或 多种的组合。
二苯甲酮类光引发剂与亲水性单体的质量比为1:5～100，PDMS-M与亲水性单体的质量 比为1:2～50；原料与溶剂的比例为5～50g/mL。
2)光引发制备涂层：步骤1)得到的预聚物是分散在溶剂中的，将其涂覆在含有碳氢键 的基底表面，将基底薄片进行紫外光照射处理，然后用乙醇清洗基底上的未反应预聚物，然 后将涂层样品置于真空烘箱干燥，将乙醇溶液挥发掉。
步骤2)涂覆的方法可以采用旋涂、刷涂或浸涂的方法。
基底可为金属和非金属，金属包括铁、铜、不锈钢材质，非金属包括：环氧类树脂、聚 氨酯类树脂，上述基底表面具有碳氢键用于参加光引发。
紫外光波长290-400nm，优选365nm，紫外光下照射时间为0.5h以上。
本发明与现有技术相比具有以下优点:
本发明首次公开一种仿生防蜡涂层材料及其制备方法，本涂层能够形成一种亲水疏油仿 生功能表面，阻隔石蜡直接在固壁表面结晶，开展的仿生防蜡技术体系，其具有节能、高效、 长寿等特点，并且该发明不使用含氟物，避免了氟化物对环境的污染；此发明利用仿生原理 从本质上解决了黏附问题，属于防止管壁结蜡的“治本”的技术，是未来输油管道防蜡技术 的发展必然趋势。
本发明的防蜡原理在于利用构筑的亲水疏油仿生功能表面，吸附原油中的水分子，在管 壁表面形成水膜，防止石蜡直接在管道固壁表面结晶，同时防止原油中的油分子在表面上的 黏附，可以有效的降低管壁石蜡结晶，或者即便有结晶发育成石蜡层，由于管壁表面上水膜 层的存在，其剪切力很低，在原油流动剪切力的作用下脱落。
附图说明
图1为水和十六烷接触角测定；
图2为将十六烷滴在实施例1制备的玻璃片上的展示图；
图3为实施例1中将预聚物分别刷涂到玻璃片、铝片、铁片上并紫外光照射后的成品图；
图4为十六烷滴在实施例1中的玻璃片、铝片、铁片上，液滴滑动的序列图。
图5在普通玻璃片表面和亲水疏油涂层表面均滴加石蜡液滴，石蜡凝固黏附后用水流冲 刷固体石蜡，石蜡没有从普通玻璃片表面脱离而从亲水疏油涂层表面脱离
具体实施方式
以下采用具体实施例的形式结合附图对本发明所采用的技术方案做进一步的解释和说明。
实施例1
本实施例所采用的合成路线如下：
Figure BDA0002764000370000031
制备具有PDMS链的光引发剂预聚物
将4-丙烯酰氧基二苯甲酮(0.60g，2.4mmol)、丙烯酸(8.40g，116.6mmol)、(丙烯酰氧丙基)甲基-二甲基共聚硅氧烷(1g，3.6mmol)、引发剂偶氮二异丁腈(16.4mg,0.10mmol)溶解在盛有乙醇(30mL)的圆底烧瓶中，在75℃的油浴中反应8h。
光引发制备涂层
用水和酒精清洗玻璃薄片，风干十分钟后放在载玻片上。利用刷涂的方法将玻璃薄片涂 覆上光引发剂预聚物涂层。将玻璃薄片暴露在紫外光(365nm)下0.5h，用乙醇溶液清洗基 底上未反应的预聚物。然后将涂层样品置于真空烘箱干燥，将乙醇溶液挥发掉。
实施例2
制备具有PDMS链的光引发剂预聚物
将4-丙烯氧基-2-羟基二苯甲酮(0.60g，2.4mmol)、丙烯酰胺(7.68g，108.2mmol)、1,3-双(3-甲基丙烯酰胺丙基)四甲基二硅氧烷(1.72g，4.5mmol)、引发剂偶氮二异丁腈(16.4 mg,0.10mmol)溶解在盛有二甲基甲酰胺(30mL)的圆底烧瓶中，在80℃的油浴中反应15h。
光引发制备涂层
用水和酒精清洗玻璃薄片，风干十分钟后放在载玻片上。利用喷涂的方法将玻璃薄片涂 覆上光引发剂预聚物涂层。将玻璃薄片暴露在紫外光(365nm)下0.5h，后用乙醇溶液清洗 基底上的未反应预聚物。然后将涂层样品置于真空烘箱干燥，将乙醇溶液挥发掉。
实施例3
制备具有PDMS链的光引发剂预聚物
将4-甲基丙烯酰氧基二苯甲酮(0.64g，2.4mmol)、丙烯酸羟乙酯(8.08g，69.6mmol)、 1,3-双(3-甲基丙烯基氧丙基)-1,1,3,3-四甲基二硅氧烷(1.28g，3.3mmol)、引发剂偶氮二异丁 腈(16.4mg,0.10mmol)溶解在盛有二甲基甲酰胺(30mL)的圆底烧瓶中，在75℃的油浴 中反应10h。
光引发制备涂层
用水和酒精清洗玻璃薄片，风干十分钟后放在载玻片上。利用刷涂的方法将玻璃薄片涂 覆上光引发剂预聚物涂层。将玻璃薄片暴露在紫外光(365nm)下0.5h，后用乙醇溶液清洗 基底上的未反应预聚物。然后将涂层样品置于真空烘箱干燥，将乙醇溶液挥发掉。
如图5所示，玻璃薄片表面的石蜡，在滴水后由于管壁表面上水膜层的存在，其剪切力 很低，在原油流动剪切力的作用下脱落，实现了防蜡的效果。
本发明中的所用溶剂可以是二甲基甲酰胺、乙醇、丙酮、异丙醇、丁醇、四氢呋喃和甲 苯中的一种或多种的组合；
二苯甲酮类光引发剂是一类以二苯甲酮为主体，其中一个苯基的对位上带有修饰基团， 修饰基团上至少含有一个位于端头的双键的化合物；优选4-丙烯酰氧基二苯甲酮、2-羟基 -4-(甲基丙烯酰氧基)二苯甲酮、4,4'-二[2-(1-丙烯基)苯氧基]二苯甲酮、4-甲基丙烯酰氧基二苯 甲酮和4-丙烯酰氧基-2-羟基二苯甲酮中的一种或多种的组合；
亲水性单体为丙烯酸或其衍生物，如丙烯酸酯类、丙烯酰胺类等；优选丙烯酸(AAc)、 甲基丙烯酸羟乙酯(HEMA)、为丙烯酰胺(AAm)、N-羟乙基丙烯酰胺(HEAA)、丙烯酸羟乙酯(HEA)、甲基丙烯酸丙磺酸(AMPS)中的一种或多种；
所述的PDMS-M的烷基端的端头为丙烯基的PDMS树脂，优选双-3-甲基丙烯基氧丙基 化四甲基二硅氧烷、甲基丙烯酰氧基五甲基二硅氧烷、(丙烯酰氧丙基)甲基-二甲基共聚硅氧 烷、1,3-双(3-甲基丙烯酰氧丙基)四(三甲基硅氧基)二硅氧烷、1,3-双(3-甲基丙烯酰胺丙基)四 甲基二硅氧烷、1,3-双(3-甲基丙烯酰氧基-2-羟丙基氧基丙基)四甲基二硅氧烷、1,3-双(3-甲基 丙烯基氧丙基)-1,1,3,3-四甲基二硅氧烷、1,3-双(4-丙烯酰氧丁基)四甲基二硅氧烷中的一种或 多种的组合。

Claims (8)

1.一种仿生型石油管道无氟涂层的制备方法，其特征在于，其步骤具体如下：
1)制备具有PDMS链的光引发剂预聚物：以二苯甲酮类光引发剂、亲水性单体、PDMS-M为原料，将上述原料溶于溶剂中，加入偶氮二异丁腈，在55～90℃的温度条件下加热3～18h制备得到具有含氟长链的光引发剂预聚物；所用溶剂为二甲基甲酰胺、乙醇、丙酮、异丙醇、丁醇、四氢呋喃和甲苯中的一种或多种的组合；
其中，二苯甲酮类光引发剂是一类以二苯甲酮为主体，其中一个苯基的对位上带有修饰基团，修饰基团上至少含有一个位于端头的双键的化合物；亲水性单体为丙烯酸或其衍生物，所述的PDMS-M的烷基端的端头为丙烯基的PDMS树脂；
二苯甲酮类光引发剂与亲水性单体的质量比为1:5～100，含氟表面活性剂与亲水性单体的质量比为1:2～50；原料与溶剂的比例为5～50g/mL。
2)光引发制备涂层：步骤1)得到的预聚物是分散在溶剂中的，将其涂覆在含有碳氢键的基底表面，将基底薄片进行紫外光照射处理，然后用乙醇清洗基底上的未反应预聚物，然后将涂层样品置于真空烘箱干燥，将乙醇溶液挥发掉。
2.根据权利要求1所述的仿生型石油管道无氟涂层的制备方法，其特征在于，二苯甲酮类光引发剂为4-丙烯酰氧基二苯甲酮、2-羟基-4-(甲基丙烯酰氧基)二苯甲酮、4,4'-二[2-(1-丙烯基)苯氧基]二苯甲酮、4-甲基丙烯酰氧基二苯甲酮和4-丙烯酰氧基-2-羟基二苯甲酮中的一种或多种的组合。
3.根据权利要求1所述的仿生型石油管道无氟无氟涂层的制备方法，其特征在于，亲水性单体为丙烯酸、甲基丙烯酸羟乙酯、为丙烯酰胺、N-羟乙基丙烯酰胺、丙烯酸羟乙酯、甲基丙烯酸丙磺酸中的一种或多种。
4.根据权利要求1所述的仿生型石油管道无氟涂层的制备方法，其特征在于，PDMS-M为双-3-甲基丙烯基氧丙基化四甲基二硅氧烷、甲基丙烯酰氧基五甲基二硅氧烷、(丙烯酰氧丙基)甲基-二甲基共聚硅氧烷、1,3-双(3-甲基丙烯酰氧丙基)四(三甲基硅氧基)二硅氧烷、1,3-双(3-甲基丙烯酰胺丙基)四甲基二硅氧烷、1,3-双(3-甲基丙烯酰氧基-2-羟丙基氧基丙基)四甲基二硅氧烷、1,3-双(3-甲基丙烯基氧丙基)-1,1,3,3-四甲基二硅氧烷、1,3-双(4-丙烯酰氧丁基)四甲基二硅氧烷中的一种或多种的组合。
5.根据权利要求1所述的仿生型石油管道无氟涂层的制备方法，其特征在于，步骤2)涂覆的方法可以采用旋涂、刷涂或浸涂的方法。
6.根据权利要求1所述的仿生型石油管道无氟涂层的制备方法，其特征在于，基底为金属和非金属，金属包括铁、铜、不锈钢材质，非金属包括：环氧类树脂、聚氨酯类树脂。
7.根据权利要求1所述的仿生型石油管道无氟涂层的制备方法，其特征在于，步骤2)中紫外光照射处理紫外光波长为290-400nm，紫外光下照射时间为0.5h以上。
8.一种按照权利要求1～7中任意一项所述方法制备的仿生型石油管道无氟涂层。
CN202011227330.6A 2020-11-06 2020-11-06 一种仿生型石油管道无氟涂层及其制备方法 Active CN112538302B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011227330.6A CN112538302B (zh) 2020-11-06 2020-11-06 一种仿生型石油管道无氟涂层及其制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011227330.6A CN112538302B (zh) 2020-11-06 2020-11-06 一种仿生型石油管道无氟涂层及其制备方法

Publications (2)

Publication Number Publication Date
CN112538302A true CN112538302A (zh) 2021-03-23
CN112538302B CN112538302B (zh) 2021-12-28

Family

ID=75013995

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011227330.6A Active CN112538302B (zh) 2020-11-06 2020-11-06 一种仿生型石油管道无氟涂层及其制备方法

Country Status (1)

Country Link
CN (1) CN112538302B (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113249097A (zh) * 2021-05-20 2021-08-13 浙江传化功能新材料有限公司 一种聚丙烯酸酯相变微胶囊及其制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0475149A2 (en) * 1990-09-10 1992-03-18 Nippon Arc Co., Ltd. Coating composition and resin article coated thereby
US20100296049A1 (en) * 2009-05-22 2010-11-25 Justyna Justynska Actinically-crosslinkable siloxane-containing copolymers
CN106716182A (zh) * 2014-09-26 2017-05-24 诺华股份有限公司 具有亲水性取代基的可聚合聚硅氧烷
CN110669243A (zh) * 2019-10-14 2020-01-10 中国科学院长春应用化学研究所 一种具有pH监测功能的抗菌涂层、具有pH监测功能的抗菌涂层的功能材料及其制备方法
CN111303717A (zh) * 2020-02-18 2020-06-19 吉林大学 一种光引发交联的防雾涂层的制备方法
CN111440519A (zh) * 2020-03-31 2020-07-24 东华大学 一种基于贻贝仿生的长期稳定两亲性防污涂层的制备方法
CN111499811A (zh) * 2020-06-05 2020-08-07 中国科学院兰州化学物理研究所 一种耐磨防雾树脂及其制备方法以及一种防雾涂层

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0475149A2 (en) * 1990-09-10 1992-03-18 Nippon Arc Co., Ltd. Coating composition and resin article coated thereby
US20100296049A1 (en) * 2009-05-22 2010-11-25 Justyna Justynska Actinically-crosslinkable siloxane-containing copolymers
CN106716182A (zh) * 2014-09-26 2017-05-24 诺华股份有限公司 具有亲水性取代基的可聚合聚硅氧烷
CN110669243A (zh) * 2019-10-14 2020-01-10 中国科学院长春应用化学研究所 一种具有pH监测功能的抗菌涂层、具有pH监测功能的抗菌涂层的功能材料及其制备方法
CN111303717A (zh) * 2020-02-18 2020-06-19 吉林大学 一种光引发交联的防雾涂层的制备方法
CN111440519A (zh) * 2020-03-31 2020-07-24 东华大学 一种基于贻贝仿生的长期稳定两亲性防污涂层的制备方法
CN111499811A (zh) * 2020-06-05 2020-08-07 中国科学院兰州化学物理研究所 一种耐磨防雾树脂及其制备方法以及一种防雾涂层

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHADRON MARK FRIESEN ET AL: "Outstanding telechelic perfluoropolyalkylethers and applications therefrom", 《PROGRESS IN POLYMER SCIENCE》 *
JIAHUI SU ET AL: "Photoinitiability of triblock copolymer PDMS-b-(PMAEBB-co-PDMAEMA)2 as a macro-photoinitiatorprepared via RAFT polymerization", 《PROGRESS IN ORGANIC COATINGS》 *
李桂林: "UV固化涂料", 《涂料工业》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113249097A (zh) * 2021-05-20 2021-08-13 浙江传化功能新材料有限公司 一种聚丙烯酸酯相变微胶囊及其制备方法

Also Published As

Publication number Publication date
CN112538302B (zh) 2021-12-28

Similar Documents

Publication Publication Date Title
Zhong et al. Facile fabrication of durable superhydrophobic silica/epoxy resin coatings with compatible transparency and stability
US8513342B2 (en) Durable superhydrophobic coatings
Qin et al. Fast healable superhydrophobic material
Cheng et al. Improving the durability of a drag-reducing nanocoating by enhancing its mechanical stability
Xu et al. Rapid fabrication of large-area, corrosion-resistant superhydrophobic Mg alloy surfaces
CN102241939B (zh) 一种有机-无机杂化的超亲水涂料及其制备方法与应用
CN102504701B (zh) 可紫外固化的有机/无机纳米复合耐磨透明涂层材料及制备方法
CN112538302B (zh) 一种仿生型石油管道无氟涂层及其制备方法
Yang et al. Superhydrophobic coating derived from the spontaneous orientation of janus particles
Gao et al. Rational design of durable anti-fouling coatings with high transparency, hardness, and flexibility
CN110218519B (zh) 一种静态抗污自分层有机硅涂料及其制备方法与应用
CN101982560A (zh) 一种低成本的铝合金超疏水表面处理方法
Luo et al. Fabrication of robust, anti-reflective, transparent superhydrophobic coatings with a micropatterned multilayer structure
CN113502129B (zh) 一种透明防污贴片及其制备方法和应用
CN1807530A (zh) 陶瓷隔热防腐涂料
CN109593390A (zh) 一种具有高透光率持久超亲水性的二氧化钛-有机复合自清洁涂层及其温和制备方法
CN112521813B (zh) 一种仿生型石油管道涂层及其制备方法
CN113527977B (zh) 一种硅丙树脂涂料及其制备方法和应用
Dong et al. Hydrogel antifouling coating with highly adhesive ability via lipophilic monomer
CN113880996A (zh) 一种多功能海洋防污涂料树脂及其制备方法
Jiang et al. Anti-wetting surfaces with self-healing property: Fabrication strategy and application
CN116656248B (zh) 一种无底纸不干胶标签纸
CN109135485A (zh) 一种氟硅共聚改性两亲性丙烯酸酯聚合物防腐蚀涂料及其制备方法
CN114525050B (zh) 疏水防雾涂料、其制备方法及防雾制品
CN112409889A (zh) 一种uv纳米防腐涂料、所得电路板及制备方法和应用

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant