CN114507331A - 一种高柔韧性电泳树脂及其制备方法 - Google Patents
一种高柔韧性电泳树脂及其制备方法 Download PDFInfo
- Publication number
- CN114507331A CN114507331A CN202210106238.7A CN202210106238A CN114507331A CN 114507331 A CN114507331 A CN 114507331A CN 202210106238 A CN202210106238 A CN 202210106238A CN 114507331 A CN114507331 A CN 114507331A
- Authority
- CN
- China
- Prior art keywords
- parts
- flexibility
- epoxy
- resin
- electrophoretic
- 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.)
- Pending
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 64
- 239000011347 resin Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 30
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003822 epoxy resin Substances 0.000 claims abstract description 22
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 22
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 21
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 19
- 229920000570 polyether Polymers 0.000 claims abstract description 19
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004593 Epoxy Substances 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 230000035484 reaction time Effects 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical group CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002981 blocking agent Substances 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- 238000001962 electrophoresis Methods 0.000 claims description 2
- 230000003247 decreasing effect Effects 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 20
- 238000000576 coating method Methods 0.000 abstract description 20
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 4
- 229910000831 Steel Inorganic materials 0.000 abstract description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000010959 steel Substances 0.000 abstract description 3
- 238000007259 addition reaction Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000005662 electromechanics Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 229920006334 epoxy coating Polymers 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/4465—Polyurethanes
-
- 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
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4488—Cathodic paints
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Molecular Biology (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
本发明公开了一种高柔韧性电泳树脂及其制备方法,属于涂装材料技术领域。其主要包括以下重量份的原料,聚醚环氧乙烷14~16份、双酚A 15~20份、环氧树脂5~10份、封闭型一乙醇胺10~20份和异佛尔酮二异氰酸酯5~15份。本发明通过在高柔韧性电泳树脂主链中引入高柔韧性的基团,提高了树脂的柔软性能,使用于汽车涂料的阴极电泳涂料中,涂装后的涂膜具有优秀的抗形变能力,涂膜附着力加强,汽车钢材的防腐蚀、防锈能力提升,具有广泛推广的价值。
Description
技术领域
本发明涉及涂装材料技术领域,具体涉及一种高柔韧性电泳树脂及其制备方法。
背景技术
电泳涂料树脂作为一类新型的低污染、省能源、省资源、起作保护和防腐蚀性的涂料,具有涂膜平整,耐水性和耐化学性好等特点,容易实现涂装工业的机械化和自动化,适合形状复杂,有边缘棱角、孔穴工件涂装,被大量应用于汽车、自动车、机电、家电等五金件的涂装。由于阳极电泳涂料存在阳极工件易氧化、抗腐蚀性能很难有较大幅度提高等问题的存在,电泳涂料已经逐渐向阴极电泳转变。
阴极电泳涂料使用的树脂是阳离子型树脂,为了使树脂提供更好的涂膜性能,使树脂阳离子化的方法也越来越多样化。阴极电泳涂料体系常用的树脂种类有环氧树脂、丙烯酸树脂、聚丁二烯和聚氨酯等,其中应用最多的类型是环氧树脂和丙烯酸树脂。
目前环氧树脂类阳离子型树脂主要是环氧胺加成物,环氧树脂的阳离子化方法通常是将环氧树脂与多元胺开环反应引入氨基成盐基团,生成环氧树脂的胺加成物,然后用有机酸或无机酸中和,或者是先扩链,再用胺中和、酸化。这类阳离子型环氧树脂在成膜后也存在很多实际问题,如环氧涂膜脆性大,在钢材变形时,容易被剥离。同样也有采用聚酰胺基团改性树脂柔韧性,这带来的涂膜成本增高。
发明内容
本发明的目的是提供一种高柔韧性电泳树脂及其制备方法,以解决现有电泳树脂存在脆性大,容易被剥离的问题。
本发明解决上述技术问题的技术方案如下:
一种高柔韧性电泳树脂,主要包括以下重量份的原料,聚醚环氧乙烷14~16份、双酚A 15~20份、环氧树脂5~10份、封闭型一乙醇胺10~20份和异佛尔酮二异氰酸酯5~15份。
在本发明中,采用的聚醚环氧乙烷分子式为OH-(CHOH-CH2-O-)nCH2CHOCH3。
进一步地,在所述的高柔韧性电泳树脂中,主要包括以下重量份的原料,聚醚环氧乙烷14~16份、双酚A 16~18份、环氧树脂7~9份、封闭型一乙醇胺12~18份和异佛尔酮二异氰酸酯7~12份。
进一步地,在所述的高柔韧性电泳树脂中,所述封闭型一乙醇胺的封闭剂为甲基异丁基酮。
在本发明中,封闭型一乙醇胺具有良好的水溶性,使得树脂具备电泳能力。封闭型一乙醇胺,水解之后,末端支链较少,分子位阻力小,更加便于树脂的中和乳化
进一步地,在所述的高柔韧性电泳树脂中,所述异佛尔酮二异氰酸酯为半封闭异佛尔酮二异氰酸酯。
在本发明中,异佛尔酮二异氰酸酯具有良好的固化交联能力,给与树脂良好的成膜性能,最终的涂膜具备良好的附着力。半封闭的异佛尔酮二异氰酸酯较常规使用的TDI毒性小,同时具有更有的耐候性能,耐黄变性能。
本发明还提供上述的高柔韧性电泳树脂的制备方法,包括以下步骤:
(1)将聚醚环氧乙烷和双酚A混合后加热并进行反应,在搅拌的状态下加入催化剂封闭型一乙醇胺后开始计时,跟踪检测环氧合格值;在本发明中分别在90min、120min、135min、150min跟踪检测环氧合格值。
(2)检测到环氧合格值后,将环氧树脂和催化剂封闭型一乙醇胺加入到步骤(1)中开始计时,继续升温进行反应,时检测粘度合格值和环氧合格值;在本发明中分别在60min,90min,120min,150min时检测粘度合格值和环氧合格值。
(3)检测到粘度合格值和环氧合格值后,向步骤(2)中再加入催化剂封闭型一乙醇胺继续反应并开始计时,检测粘度合格值和环氧合格值;在本发明中分别于180min,210min,240min后检测粘度合格值和环氧合格值
(4)降温处理,并向步骤(3)中加入异佛尔酮二异氰酸酯继续反应,得到所述高柔韧性电泳树脂。
进一步地,在所述的高柔韧性电泳树脂的制备方法中,步骤(1)中加热的温度范围为100~120℃,检测环氧值的合格范围为0.3~0.5,反应的时间为2~3.5h。
进一步地,在所述的高柔韧性电泳树脂的制备方法中,步骤(2)中升温至140~160℃,粘度合格范围为E~L,环氧值合格范围为0.6~0.7,反应的时间为2~3.5h。
进一步地,在所述的高柔韧性电泳树脂的制备方法中,步骤(3)检测时体系的温度在130~150℃,粘度合格范围为Q~Z,环氧值合格范围为0.5~1.5,反应的时间为3~5h。
在本发明中,对步骤(3)继续测试粘度和环氧值,是随着反应的进行,环氧链不断扩增,环氧值逐渐增大,粘度逐渐增大,通过测试判定反应的进行程度。
进一步地,在所述的高柔韧性电泳树脂的制备方法中,步骤(4)中降温至110℃以下。
进一步地,在所述的高柔韧性电泳树脂的制备方法中,所述制备方法还包括:采用稀释剂与高柔韧性电泳树脂进行搅拌混合,再过滤。
向制得的高柔韧性电泳树脂中加入5~10%的二乙醇丁醚溶液搅拌稀释,降低其粘度,方便包装使用。
本发明具有以下有益效果:
本发明以聚醚环氧乙烷作为柔韧剂通过在高柔韧性电泳树脂主链中引入高柔韧性的基团,提高了树脂的柔软性能,使用于汽车涂料的阴极电泳涂料中,涂装后的涂膜具有优秀的抗形变能力,涂膜附着力加强,汽车钢材的防腐蚀、防锈能力提升,具有广泛推广的价值。
具体实施方式
以下结合实施例对本发明的原理和特征进行描述,所举实例只用于解释本发明,并非用于限定本发明的范围。实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。、
需要说明的是,本发明下面实施例具体采用环氧树脂828;PP-300P聚醚环氧乙烷。
实施例1:
本实施例的高柔韧性电泳树脂,主要包括以下重量份的原料,聚醚环氧乙烷14份、双酚A 15份、环氧树脂5份、封闭封闭型一乙醇胺10份和半封闭异佛尔酮二异氰酸酯5份。
本实施例的高柔韧性电泳树脂的制备方法包括以下步骤:
(1)向反应釜依次投料柔韧剂聚醚环氧丙烷和双酚A,升温到100℃,30%搅拌开度,从催化剂斗加入封闭型一乙醇胺至反应釜后开始计时,分别于90min,120min,135min,150min后跟踪检测环氧值,环氧值范围为0.3~0.5,反应时间为2h;
(2)向计量槽添加环氧树脂和和封闭型一乙醇胺并放料至反应釜完成主链加成反应,升温到140℃后开始计时并反应跟踪,分别于60min,90min,120min,150min时检测粘度和环氧值,粘度范围为E~L,环氧值范围为0.6~0.7,反应时间为2h;
(3)向计量槽添加封闭型一乙醇胺并放料至反应釜进行加成反应并开始计时,130℃跟踪检测,分别于180min,210min,240min后检测粘度和环氧值,粘度范围为Q~Z,环氧值范围为0.5~1.5,反应的时间为3h;
(4)反应釜降温至110℃,向反应釜添加异佛尔酮二异氰酸酯,反应1h;
(5)向反应釜加入乙二醇丁醚并搅拌,均匀后开始过滤和包装。
实施例2:
本实施例的高柔韧性电泳树脂,主要包括以下重量份的原料,聚醚环氧乙烷14.5份、双酚A 16份、环氧树脂7份、封闭一乙醇胺12份和半封闭异佛尔酮二异氰酸酯7份。
本实施例的高柔韧性电泳树脂的制备方法包括以下步骤:
(1)向反应釜依次投料柔韧剂聚醚环氧丙烷和双酚A,升温到110℃,30%搅拌开度,从催化剂斗加入封闭型一乙醇胺至反应釜后开始计时,分别于90min,120min,135min,150min后跟踪检测环氧值,环氧值范围为0.3~0.5,反应时间为3h;
(2)向计量槽添加环氧树脂和和封闭型一乙醇胺并放料至反应釜完成主链加成反应,升温到150℃后开始计时并反应跟踪,分别于60min,90min,120min,150min时检测粘度和环氧值,粘度范围为E~L,环氧值范围为0.6~0.7,反应时间为2.5h;
(3)向计量槽添加封闭型一乙醇胺并放料至反应釜进行加成反应并开始计时,130~150℃跟踪检测,分别于180min,210min,240min后检测粘度和环氧值,粘度范围为Q~Z,环氧值范围为0.5~1.5,反应的时间为4h;
(4)反应釜降温至95℃,向反应釜添加异佛尔酮二异氰酸酯,反应1h;
(5)向反应釜加入乙二醇丁醚并搅拌,均匀后开始过滤和包装。
实施例3:
本实施例的高柔韧性电泳树脂,主要包括以下重量份的原料,聚醚环氧乙烷15份、双酚A 17份、环氧树脂8份、封闭一乙醇胺14份和半封闭异佛尔酮二异氰酸酯9份。
本实施例的高柔韧性电泳树脂的制备方法包括以下步骤:
(1)向反应釜依次投料柔韧剂聚醚环氧丙烷和双酚A,升温到120℃,30%搅拌开度,从催化剂斗加入封闭型一乙醇胺至反应釜后开始计时,分别于90min,120min,135min,150min后跟踪检测环氧值,环氧值范围为0.3~0.5,反应时间为3.5h;
(2)向计量槽添加环氧树脂和和封闭型一乙醇胺并放料至反应釜完成主链加成反应,升温到160℃后开始计时并反应跟踪,分别于60min,90min,120min,150min时检测粘度和环氧值,粘度范围为E~L,环氧值范围为0.6~0.7,反应时间为3.5h;
(3)向计量槽添加封闭型一乙醇胺并放料至反应釜进行加成反应并开始计时,130~150℃跟踪检测,分别于180min,210min,240min后检测粘度和环氧值,粘度范围为Q~Z,环氧值范围为0.5~1.5,反应的时间为5h;
(4)反应釜降温至100℃,向反应釜添加异佛尔酮二异氰酸酯,反应1h;
(5)向反应釜加入乙二醇丁醚并搅拌,均匀后开始过滤和包装。
实施例4:
本实施例的高柔韧性电泳树脂,主要包括以下重量份的原料,聚醚环氧乙烷15.5份、双酚A 18份、环氧树脂9份、封闭型一乙醇胺18份和半封闭异佛尔酮二异氰酸酯12份。
本实施例的高柔韧性电泳树脂的制备方法与实施例1的制备方法一致。
实施例5:
本实施例的高柔韧性电泳树脂,主要包括以下重量份的原料,聚醚环氧乙烷16份、双酚A 20份、环氧树脂10份、封闭一乙醇胺120份和半封闭异佛尔酮二异氰酸酯15份。
本实施例的高柔韧性电泳树脂的制备方法与实施例2的制备方法一致。
实施例1-5制得的高柔韧性电泳树脂外观为透明的,在130℃下,2.2g原料反应3h的固体份为77.5%~79.5%,在20℃下,加德纳粘度为UV~YZ,TN胺值为41~49。满足涂装要求。
根据本实施例1制作的高柔韧性电泳树脂进行电泳涂装检测,满足以下性能:
可以看出,本发明的高柔韧性电泳树脂通过十字花格测试,说明电泳涂层的附着力强,盐雾性能和抗折弯性能同样表明具有很好的抗防腐抗锈以及抗形变能力。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种高柔韧性电泳树脂,其特征在于,主要包括以下重量份的原料,聚醚环氧乙烷14~16份、双酚A 15~20份、环氧树脂5~10份、封闭型一乙醇胺10~20份和异佛尔酮二异氰酸酯5~15份。
2.根据权利要求1所述的高柔韧性电泳树脂,其特征在于,主要包括以下重量份的原料,聚醚环氧乙烷14~16份、双酚A16~18份、环氧树脂7~9份、封闭型一乙醇胺12~18份和异佛尔酮二异氰酸酯7~12份。
3.根据权利要求1或2所述的高柔韧性电泳树脂,其特征在于,所述封闭型一乙醇胺的封闭剂为甲基异丁基酮。
4.根据权利要求1或2所述的高柔韧性电泳树脂,其特征在于,所述异佛尔酮二异氰酸酯为半封闭异佛尔酮二异氰酸酯。
5.一种如权利要求1-4任一项所述的高柔韧性电泳树脂的制备方法,其特征在于,包括以下步骤:
(1)将聚醚环氧乙烷和双酚A混合后加热并进行反应,在搅拌的状态下加入催化剂封闭型一乙醇胺后开始计时,跟踪检测环氧合格值;
(2)检测到环氧合格值后,将环氧树脂和催化剂封闭型一乙醇胺加入到步骤(1)中开始计时,继续升温进行反应,检测粘度合格值和环氧合格值;
(3)检测到粘度合格值和环氧合格值后,向步骤(2)中再加入催化剂封闭型一乙醇胺继续反应并开始计时,检测粘度合格值和环氧合格值;
(4)降温处理,并向步骤(3)中加入异佛尔酮二异氰酸酯继续反应,得到所述高柔韧性电泳树脂。
6.根据权利要求5所述的高柔韧性电泳树脂的制备方法,其特征在于,步骤(1)中加热的温度范围为100~120℃,检测环氧值的合格范围为0.3~0.5,反应的时间为2~3.5h。
7.根据权利要求5所述的高柔韧性电泳树脂的制备方法,其特征在于,步骤(2)中升温至140~160℃,粘度合格范围为E~L,环氧值合格范围为0.6~0.7,反应的时间为2~3.5h。
8.根据权利要求5-7任一项所述的高柔韧性电泳树脂的制备方法,其特征在于,步骤(3)检测时体系的温度在130~150℃,粘度合格范围为Q~Z,环氧值合格范围为0.5~1.5,反应的时间为3~5h。
9.根据权利要求8所述的高柔韧性电泳树脂的制备方法,其特征在于,步骤(4)中降温至110℃以下。
10.根据权利要求8所述的高柔韧性电泳树脂的制备方法,其特征在于,所述制备方法还包括:采用稀释剂与得到的高柔韧性电泳树脂进行搅拌混合,再过滤。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210106238.7A CN114507331A (zh) | 2022-01-28 | 2022-01-28 | 一种高柔韧性电泳树脂及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210106238.7A CN114507331A (zh) | 2022-01-28 | 2022-01-28 | 一种高柔韧性电泳树脂及其制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN114507331A true CN114507331A (zh) | 2022-05-17 |
Family
ID=81551216
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210106238.7A Pending CN114507331A (zh) | 2022-01-28 | 2022-01-28 | 一种高柔韧性电泳树脂及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114507331A (zh) |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1836016A (zh) * | 2003-06-16 | 2006-09-20 | 杰富意钢铁株式会社 | 高耐蚀性表面处理钢板及其制造方法 |
CN101054487A (zh) * | 2007-04-30 | 2007-10-17 | 袁兴 | 低温固化环保型阴极电泳涂料的制备方法 |
CN102533044A (zh) * | 2010-12-10 | 2012-07-04 | 比亚迪股份有限公司 | 一种阴极电泳涂料及其制备方法和阴极电泳涂装方法 |
CN102838846A (zh) * | 2012-09-26 | 2012-12-26 | 中国海洋石油总公司 | 一种高泳透力阴极电泳涂料用树脂乳液及其制备方法 |
CN106232750A (zh) * | 2014-04-28 | 2016-12-14 | 日东化成株式会社 | 电沉积涂料组合物、电沉积涂料组合物用催化剂 |
CN109251482A (zh) * | 2018-08-28 | 2019-01-22 | 广东科德环保科技股份有限公司 | 改性环氧树脂及其制备方法和应用、阴极电泳涂料及其制备方法和应用 |
CN109627951A (zh) * | 2018-12-18 | 2019-04-16 | 广东科德环保科技股份有限公司 | 一种改性环氧树脂及其制备方法和高泳透力阴极电泳涂料 |
-
2022
- 2022-01-28 CN CN202210106238.7A patent/CN114507331A/zh active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1836016A (zh) * | 2003-06-16 | 2006-09-20 | 杰富意钢铁株式会社 | 高耐蚀性表面处理钢板及其制造方法 |
CN101054487A (zh) * | 2007-04-30 | 2007-10-17 | 袁兴 | 低温固化环保型阴极电泳涂料的制备方法 |
CN102533044A (zh) * | 2010-12-10 | 2012-07-04 | 比亚迪股份有限公司 | 一种阴极电泳涂料及其制备方法和阴极电泳涂装方法 |
CN102838846A (zh) * | 2012-09-26 | 2012-12-26 | 中国海洋石油总公司 | 一种高泳透力阴极电泳涂料用树脂乳液及其制备方法 |
CN106232750A (zh) * | 2014-04-28 | 2016-12-14 | 日东化成株式会社 | 电沉积涂料组合物、电沉积涂料组合物用催化剂 |
CN109251482A (zh) * | 2018-08-28 | 2019-01-22 | 广东科德环保科技股份有限公司 | 改性环氧树脂及其制备方法和应用、阴极电泳涂料及其制备方法和应用 |
CN109627951A (zh) * | 2018-12-18 | 2019-04-16 | 广东科德环保科技股份有限公司 | 一种改性环氧树脂及其制备方法和高泳透力阴极电泳涂料 |
Non-Patent Citations (1)
Title |
---|
孙超;吴金鹏;: "低温固化阴极电泳涂料的合成与涂装研究", 电镀与精饰, no. 01, pages 29 - 31 * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0200397B1 (en) | Amine-epoxide reaction products and aqueous dispersions thereof useful in coating compositions suitable for electrodeposition | |
EP0119769B1 (en) | Heat-curable resin coating composition | |
US4810535A (en) | Glycidol-modified polyepoxide-polyoxyalkylenepolyamine adducts | |
CA3119870A1 (en) | Ionic aqueous epoxy curing agent, preparation method therefor and use thereof | |
JPS6079072A (ja) | 基板を電着塗装する方法 | |
EP2994507A1 (en) | Epoxy resin compositions | |
US4310646A (en) | Self-crosslinking cationic binders and their preparation | |
CN111793192A (zh) | 一种新型防腐的水性环氧改性固化剂及其制备方法 | |
CN101631839A (zh) | 含有硅烷的成膜物质,交联剂和涂料组合物,制备涂料组合物和经涂覆的基材的方法 | |
CN112680105A (zh) | 一种环保防腐涂料、超支化环氧树脂及其制备方法 | |
JPS61200117A (ja) | 陰極電着可能ペイントバインダーの製造方法 | |
US4711937A (en) | Self-crosslinking paint binders and process for their manufacture | |
CN114605616B (zh) | 快干型非离子水性环氧固化剂及其制备方法和应用 | |
US4596844A (en) | Self-hardenable resin composition | |
CN112341604B (zh) | 一种乳液型环氧固化剂及其制备方法 | |
US5618893A (en) | Process for the preparation of cationic binders for coatings, the binders produced, and their use | |
CN114507331A (zh) | 一种高柔韧性电泳树脂及其制备方法 | |
CN112795278A (zh) | 一种聚氨酯改性环氧树脂乳液及其制备方法 | |
JPS6178826A (ja) | 溶剤系用ノボラツク型エポキシ樹脂硬化剤 | |
US4321305A (en) | Beta-diketone-epoxy resin reaction products useful for providing corrosion resistance | |
US8524808B2 (en) | Radiation curable compositions | |
US4435529A (en) | Tannin-epoxy reaction products and compositions thereof | |
KR20010101313A (ko) | 음극 전기피복 코팅 조성물 | |
US4321304A (en) | Beta-diketone-epoxy resin reaction products blended with monomeric or polymeric phosphonium salts useful for providing corrosion resistance | |
JPH05295318A (ja) | 水性塗料用樹脂組成物 |
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 | ||
CB02 | Change of applicant information | ||
CB02 | Change of applicant information |
Country or region after: China Address after: No. 1, Huananzhong 1st Road, Changshou District, Chongqing, 401220 Applicant after: Chongqing HUYUN Technology Co.,Ltd. Address before: 401220 room 5-2, No. 20, Qixin Avenue, Yanjia street, Changshou District, Chongqing Applicant before: Chongqing HUYUN Technology Co.,Ltd. Country or region before: China |