CN108219641B - 一种木质素磺酸盐分散自愈合聚脲涂料及其制备方法和涂层与应用 - Google Patents
一种木质素磺酸盐分散自愈合聚脲涂料及其制备方法和涂层与应用 Download PDFInfo
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- CN108219641B CN108219641B CN201810004406.5A CN201810004406A CN108219641B CN 108219641 B CN108219641 B CN 108219641B CN 201810004406 A CN201810004406 A CN 201810004406A CN 108219641 B CN108219641 B CN 108219641B
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- lignosulfonates
- healing
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- coating
- carbamide paint
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- 125000001931 aliphatic group Chemical group 0.000 claims description 2
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- WNYIBZHOMJZDKN-UHFFFAOYSA-N n-(2-acetamidoethyl)acetamide Chemical compound CC(=O)NCCNC(C)=O WNYIBZHOMJZDKN-UHFFFAOYSA-N 0.000 claims description 2
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- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
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- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 1
- RWYKESRENLAKMN-UHFFFAOYSA-N 1-[4-[1-[4-[2-[4-[5-(1,2-dihydroxypropyl)-3-(hydroxymethyl)-7-methoxy-2,3-dihydro-1-benzofuran-2-yl]-2-methoxyphenoxy]-3-hydroxy-1-(4-hydroxy-3-methoxyphenyl)propoxy]-3-hydroxy-5-methoxyphenyl]-3-hydroxy-2-[4-[4-(4-hydroxy-3,5-dimethoxyphenyl)-1,3,3a,4,6, Chemical compound O1C=2C(OC)=CC(C(O)C(C)O)=CC=2C(CO)C1C(C=C1OC)=CC=C1OC(CO)C(C=1C=C(OC)C(O)=CC=1)OC(C(=C1)OC)=C(O)C=C1C(C(CO)OC=1C(=CC(=CC=1)C1C2COCC2C(O1)C=1C=C(OC)C(O)=C(OC)C=1)OC)OC(C(=C1)OC)=CC=C1C(O)C(CO)OC1=CC=C(C=CCO)C=C1OC RWYKESRENLAKMN-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
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- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/02—Polyureas
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- 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
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/40—High-molecular-weight compounds
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- C08G18/50—Polyethers having heteroatoms other than oxygen
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- 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
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- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
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- 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
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
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- 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
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- 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
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- 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
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- 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
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- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
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- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- 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
- C09D197/00—Coating compositions based on lignin-containing materials
- C09D197/005—Lignin
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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
- 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
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Abstract
本发明属于高分子材料技术领域,公开了一种木质素磺酸盐分散自愈合聚脲涂料及其制备方法和涂层与应用。本发明涂料由包括以下质量份组分反应得到:1~10份木质素磺酸盐包埋愈合剂的微胶囊;10~100份聚脲预聚体;20~120份端氨基聚醚和位阻型胺类扩链剂的混合液。本发明还提供上述涂料的制备方法及基于其的涂层。本发明通过在聚脲涂层中掺入木质素磺酸盐包埋愈合剂的微胶囊得到自愈合聚脲涂料,该自愈合聚脲涂料的制备拓展了木质素在高分子材料中的应用,同时克服了聚脲涂层应力破坏后难以修复的问题,能够更好的应用到钢结构防腐蚀中,可应用于材料表面防护领域中,作为海洋用钢结构材料的应用有着很好的前景。
Description
技术领域
本发明属于高分子材料技术领域,特别涉及一种木质素磺酸盐分散自愈合聚脲涂料及其制备方法和涂层与应用。
背景技术
钢结构在海洋设施建设中有大量应用,例如海洋采油平台、海底管线、隧道、以及舰船等水下部位。然而海洋大气环境中盐雾含量较高、湿度较大,易在钢铁表面形成有腐蚀性的水膜,腐蚀作用强烈,暴露在海雾长期饱和的空气中的钢的腐蚀速度是在普通大气的8倍。因此,海洋大气腐蚀造成钢结构使用寿命大大缩短,后期维护费用成倍增加,所以必须对钢结构予以保护。
聚脲是一种新型绿色的海洋用钢结构防腐材料,与传统的防腐涂层相比,具有对温度、湿度不敏感、耐化学腐蚀、耐磨、耐老化性、力学性能好等优势。聚脲的硬度和颜色可以根据需求随意调配,此外聚脲还具有不依附于基材的自身强度,也就是聚脲可以作为涂料同样也可作为衬里来进行使用。但是,受外力影响如海洋生物、海洋垃圾等挤压和摩擦时,聚脲涂层将会产生裂缝,继而海水渗透并侵蚀钢结构。目前对于聚脲涂层的改善方法是通过调整软硬段的比例或者是采用新型的组分以提高聚脲涂层的性能;另一种低成本且有效的方法是予以聚脲涂层自愈合性能,当涂层破损时,能够自动修复,防止钢结构与腐蚀介质接触,从而避免腐蚀。
自愈合材料在军工、人造卫星、飞机、电子等领域已经得到了广泛地应用。材料自愈合一般通过液芯纤维法、微胶囊法、动态化学键等形式实现,其中最常用的是微胶囊法。通过将包裹愈合剂的微胶囊分散到材料中,在外力作用下部分微胶囊破裂,修复剂流出并渗透到材料的裂纹中会与催化剂或者其他介质发生化学反应实现愈合。通过微胶囊化,可以改善愈合剂的物理性质,提高愈合剂的稳定性,控制释放等。目前,尚无自愈合聚脲自愈合涂层的报道,只有利用聚脲为壁材制备微胶囊与环氧树脂共混,制备自愈合环氧树脂自愈合涂层的尝试。Yang等利用异佛尔酮二异氰酸酯(IPDI)和预聚物作愈合剂,通过1,4-丁二醇引发界面聚合反应制备了不同聚脲微胶囊,并研究了转速对微胶囊粒径,壁厚和分子量等的影响(Macromolecules,2008,41,9650-9655)。进一步,Huang等将制备的聚脲微胶囊干燥后与环氧树脂混合得到自愈合涂层(J.mater.Chem.2011,21,11123-11130)。然而,环氧树脂柔韧性差,在外力撞击或者温度交替变化下极易出现开裂,而且环氧树脂低温柔韧性越差,使得环氧树脂在海洋用钢材抗侵蚀应用上受到很大的限制。因此,发展高性能的自愈合聚脲涂层十分必要。
木质素磺酸盐是天然的两亲高分子表面活性剂,同时含有酚羟基、醇羟基等活性反应基团。因此,本发明利用木质素磺酸盐制备聚脲自愈合涂层,木质素磺酸盐既可以乳化愈合剂,同时还能够与聚脲的异氰酸酯组分反应,得到具有微胶囊的改性异氰酸酯组分,进一步和端氨基聚醚、扩链剂反应制得具有自愈合功能的聚脲材料。
发明内容
为了克服上述现有技术的缺点与不足,本发明的首要目的在于提供一种木质素磺酸盐分散自愈合聚脲涂料。
本发明另一目的在于提供一种上述木质素磺酸盐分散自愈合聚脲涂料的制备方法。
本发明再一目的在于提供一种基于上述木质素磺酸盐分散自愈合聚脲涂料的涂层。
本发明再一目的在于提供上述木质素磺酸盐分散自愈合聚脲涂料在材料表面防护领域中的应用。
本发明的目的通过下述方案实现:
一种木质素磺酸盐分散自愈合聚脲涂料,由包括以下质量份组分反应得到:1~10份木质素磺酸盐包埋愈合剂的微胶囊;10~100份聚脲预聚体;20~120份端氨基聚醚和位阻型胺类扩链剂的混合液。
所述木质素磺酸盐包埋愈合剂的微胶囊由包括以下步骤方法制备得到:将10~100重量份的木质素磺酸盐水溶液与1~50重量份的由芳香族异氰酸酯和脂肪族异氰酸酯形成的微胶囊愈合剂混合,乳化,室温干燥得到。
所述芳香族异氰酸酯和脂肪族异氰酸酯的质量比优选为10:1~3:1。
所述的芳香族异氰酸酯为高反应活性的芳香族异氰酸酯。
所述的脂肪族异氰酸酯为低反应活性的脂肪族异氰酸酯。
为进一步更好地实现本发明目的,所用木质素磺酸盐水溶液与微胶囊愈合剂的重量比为10:1~1:0.4。
所述木质素磺酸盐水溶液的质量浓度优选为0.5~2%。
所述乳化在高速剪切下进行,高速剪切的速度优选为6000~11000rpm/min。
所述乳化的时间优选为30s~3min。
进一步的,所述木质素磺酸盐包埋愈合剂的微胶囊由包括以下步骤方法制备得到:将10~100重量份的木质素磺酸盐水溶液与1~50重量份的由芳香族异氰酸酯和脂肪族异氰酸酯形成的微胶囊愈合剂混合,在3000~25000rpm/min转速的高速剪切条件下乳化5s~10min得到O/W型pickering乳液,室温干燥,得到木质素磺酸盐包埋愈合剂的微胶囊。
所述聚脲预聚体由包括以下步骤方法制备得到:将摩尔比为0.5:1~2:1的端氨基聚醚与脂肪族异氰酸酯混合,升温到20℃~100℃下搅拌反应10min~24h得到。
所述端氨基聚醚与脂肪族异氰酸酯的摩尔比优选为1:1~1.5:1。
所述升温优选升温至35~75℃。
所述端氨基聚醚和位阻型胺类扩链剂的混合液中,端氨基聚醚和位阻型胺类扩链剂的摩尔比优选为0.5:0.1~2:0.1,更优选为0.5:0.1~1:0.1。
本发明涂料中,所述的木质素磺酸盐包括竹浆木质素磺酸盐、麦草浆木质素磺酸盐、芦苇木质素磺酸盐、蔗渣浆木质素磺酸盐、龙须草浆木质素磺酸盐、棉浆粕木质素磺酸盐等,工业木质素(包括碱木质素、溶剂型木质素、酶解木质素等)的磺化产物及工业木质素的磺甲基化产物中的一种或一种以上。
所述的芳香族异氰酸酯包括甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、聚合二苯基甲烷二异氰酸酯(PMDI)、多亚甲基多苯基多异氰酸酯(PAPI)等中的一种或一种以上。
所述的脂肪族异氰酸酯包括异佛尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)、HDI三聚体等中的一种或一种以上。
所述的端氨基聚醚包括聚醚胺D230、聚醚胺D400、聚醚胺D2000等中的一种或一种以上。
所述的位阻型胺类扩链剂包括3,5-二氨-4-氯苯甲酸异丁醇酯、二乙酰乙二胺、二乙酰间苯二胺、4,4-二乙酰氨基二苯甲烷、二乙基甲苯二胺等中的一种或一种以上。
本发明还提供一种上述木质素磺酸盐分散自愈合聚脲涂料的制备方法,包括以下步骤:室温下,将木质素磺酸盐包埋愈合剂的微胶囊、端氨基聚醚和位阻型胺类扩链剂的混合液加入聚脲预聚体中,室温反应10min~4h,得到木质素磺酸盐分散自愈合聚脲涂料。
所述反应时间优选为30min~2h。
本发明以端氨基聚醚作为氨基组分参与反应,利用由高反应活性的芳香族异氰酸酯和低反应活性的脂肪族异氰酸酯形成的微胶囊愈合剂与木质素磺酸盐反应,得到木质素磺酸盐包埋愈合剂的微胶囊。
本发明还提供一种基于上述木质素磺酸盐分散自愈合聚脲涂料的涂层,将本发明涂料按上述制备方法混合后,涂覆于基材表面,反应后,得到木质素磺酸盐分散自愈合聚脲涂层。本发明涂层中,木质素磺酸盐包埋愈合剂微胶囊的粒径为30~90μm,内部包裹为IPDI和PMDI,聚脲涂层厚度为230~500μm。
本发明木质素磺酸盐分散自愈合聚脲涂料克服了聚脲涂层应力破坏后难以修复的问题,能够更好的应用到钢结构防腐蚀中,可应用于材料表面防护领域中,作为海洋用钢结构材料的应用有着很好的前景。
本发明的机理为:
本发明涂料的自愈合机理是采用微胶囊法,以木质素磺酸盐为分散剂,包裹高反应活性的芳香族异氰酸酯和低反应活性的脂肪族异氰酸酯形成微胶囊愈合剂,表层的木质素磺酸盐与脂肪族异氰酸酯反应,形成含有木质素基愈合剂微胶囊的异氰酸酯组分,与氨基组分反应形成含有木质素基愈合剂微胶囊聚脲涂层。在外力作用下,微胶囊被划破或挤破,里面的愈合剂会与空气中的水或者聚脲涂层中过量的氨基组分反应,从而起到自愈合的作用。
木质素磺酸盐既含有磺酸基等亲水基团,同时存在酚羟基和醇羟基等活性反应位点,本发明将木质素磺酸盐分散溶解于水中,油相为高反应活性的芳香族异氰酸酯和低反应活性的脂肪族异氰酸酯形成微胶囊愈合剂,在高速剪切下,木质素磺酸盐分散油相形成O/W型Pickering乳液。包裹愈合剂的乳滴外层木质素磺酸钠分子中的酚羟基和醇羟基能够和脂肪族异氰酸酯反应形成异氰酸酯组分。异氰酸酯组分与氨基组分反应形成含有木质素基愈合剂微胶囊聚脲涂料。本发明通过在聚脲涂层中掺入木质素磺酸盐包埋愈合剂的微胶囊得到自愈合聚脲涂料,该自愈合聚脲涂料的制备拓展了木质素在高分子材料中的应用,同时克服了聚脲涂层应力破坏后难以修复的问题,能够更好的应用到钢结构防腐蚀中,可应用于材料表面防护领域中,作为海洋用钢结构材料的应用有着很好的前景。
本发明相对于现有技术,具有如下的优点及有益效果:
1、来源丰富、价格低廉的工业木质素直接作为原料,分散在水中,无需额外添加乳化剂和交联剂,采用一步法制得木质素磺酸盐包埋愈合剂微胶囊,制备过程简单,过程绿色环保、本发明以成本低廉。同时保留了木质素中具有紫外吸收的酚羟基结构。
2、本发明采用具有两亲性的木质素磺酸盐,其分散性较好,木质素中羟基的反应性有利于后续制备自愈合涂层。
3、本发明使用的木质素来源于植物,天然高分子的结构使其具有良好的光稳定性,作为壁材不但可以提高微胶囊的稳定性,而且应用到涂层中减少材料受阳光辐射降解。
4、本发明将包裹愈合剂的微胶囊掺到聚脲涂层中,相比没有添加微胶囊的聚脲涂层,具有明显的抗侵蚀性,显著延长钢片的使用寿命。在聚脲涂层本身具有柔韧性好、强度高、抗腐蚀、耐老化的特点的基础上,赋予了聚脲涂层自愈合性能,更好的发挥了聚脲涂层优势。因而在海洋用钢结构材料上有着很好的应用前景和市场潜力。
附图说明
图1是实施例1自愈合聚脲涂层的抗侵蚀照片。
图2是普通聚脲涂层的抗侵蚀照片。
图3和图4是实施例1自愈合聚脲涂层的扫描电镜图。
具体实施方式
下面结合实施例对本发明作进一步详细的描述,但本发明的实施方式不限于此。
下列实施例中涉及的物料均可从商业渠道获得。
实施例1
(1)将10g的2%的麦草浆木质素磺酸钠加入到30mL白色盖子玻璃样品后,在样品瓶中加入混合均匀的0.5g的PMDI和2.5g的IPDI,在11000rpm/min转速下机械乳化3min,得到O/W型pickering乳液,备用。
(2)在室温下,在150mL烧杯中加入0.01mol端氨基聚醚D-2000和0.012molHDI,水浴锅匀速升温到75℃(5℃/min)机械搅拌300rpm反应1h,得到粘稠透明的HDI预聚体,待预聚体室温冷却。
(3)室温下,在步骤(2)预聚体中加入步骤(1)乳液后,加入0.001mol溶于1mL甲苯的位阻型胺类扩链剂和0.05mol端氨基聚醚D-2000,机械搅拌300rpm反应1h。
(4)用砂纸打磨钢片,丙酮冲洗后干燥。用工字涂布器在钢片上涂覆步骤(3)的复合物,涂层500μm厚,室温放置24h后进行抗侵蚀测试。
(5)抗侵蚀测试:用剃须刀片在钢片表面划痕后放置到10%NaCl水溶液中48h。
测试后的涂层如图所示,图1为本发明添加微胶囊的自愈合聚脲涂层,图2为未添加微胶囊的聚脲涂层。可以看出,普通聚脲涂层在划痕处锈迹明显,而本发明自愈合聚脲涂层则没有这种迹象。另外图3、图4的自愈合涂层的扫描电镜图也表明微胶囊破裂后与水或者过量的端氨基聚醚反应,形成的新的涂层。
实施例2
(1)将6g的0.5%的麦草浆木质素磺酸钠加入到30mL白色盖子玻璃样品后,在样品瓶中加入混合均匀的1g的MDI和5g的IPDI,在11000rpm/min转速下机械乳化30s,得到O/W型pickering乳液。
(2)在室温下,在150mL烧杯中加入0.01mol端氨基聚醚D-2000和0.012molHDI,水浴锅匀速升温到45℃(5℃/min)机械搅拌200rpm反应1.5h,得到粘稠透明的HDI预聚体,待预聚体室温冷却。
(3)室温下,在步骤(2)预聚体中加入步骤(1)乳液后,加入0.001mol溶于1mL甲苯的位阻型胺类扩链剂和0.05mol端氨基聚醚D-2000,机械搅拌200rpm反应30min。
(4)用砂纸打磨钢片,丙酮冲洗后干燥。用工字涂布器在钢片上涂覆步骤(3)的复合物,涂层500μm厚,室温放置24h后进行抗侵蚀测试。
(5)抗侵蚀测试:用剃须刀片在钢片表面划痕后放置到10%NaCl水溶液中48h。观察,划痕处无明显锈迹。
实施例3
(1)将4g的1%的竹浆木质素磺酸钠加入到30mL白色盖子玻璃样品后,在样品瓶中加入混合均匀的0.5g的PMDI和0.5g的IPDI,在11000rpm/min转速下机械乳化30s,得到O/W型pickering乳液。
(2)在室温下,在150mL烧杯中加入0.01mol端氨基聚醚D-2000和0.012molHDI,水浴锅匀速升温到60℃(5℃/min)机械搅拌300rpm反应1h,得到粘稠透明的HDI预聚体,待预聚体室温冷却。
(3)室温下,在步骤(2)预聚体中加入步骤(1)乳液后,加入0.001mol溶于1mL甲苯的位阻型胺类扩链剂和0.05mol端氨基聚醚D-2000,机械搅拌300rpm反应40min。
(4)用砂纸打磨钢片,丙酮冲洗后干燥。用工字涂布器在钢片上涂覆步骤(3)的复合物,涂层500μm厚,室温放置24h后进行抗侵蚀测试。
(5)抗侵蚀测试:用剃须刀片在钢片表面划痕后放置到10%NaCl水溶液中48h。观察,划痕处无明显锈迹。
实施例4
(1)将6g的1%的竹浆木质素磺酸钠加入到30mL白色盖子玻璃样品后,在样品瓶中加入混合均匀的4g的PMDI和1g的IPDI,在11000rpm/min转速下机械乳化30s,得到O/W型pickering乳液。
(2)在室温下,在150mL烧杯中加入0.02mol端氨基聚醚D-400和0.03molHDI,水浴锅匀速升温到65℃(5℃/min)机械搅拌300rpm反应1h,得到粘稠透明的HDI预聚体,待预聚体室温冷却。
(3)室温下,在步骤(2)预聚体中加入步骤(1)乳液后,加入0.005mol溶于1mL甲苯的位阻型胺类扩链剂和0.01mol端氨基聚醚D-2000,机械搅拌300rpm反应40min。
(4)用砂纸打磨钢片,丙酮冲洗后干燥。用工字涂布器在钢片上涂覆步骤(3)的复合物,涂层500μm厚,室温放置24h后进行抗侵蚀测试。
(5)抗侵蚀测试:用剃须刀片在钢片表面划痕后放置到10%NaCl水溶液中48h。观察,划痕处无明显锈迹。
实施例5
(1)将5g的1%的芦苇木质素磺酸钠加入到30mL白色盖子玻璃样品后,在样品瓶中加入混合均匀的4g的PMDI和1g的IPDI,在11000rpm/min转速下机械乳化20s,得到O/W型pickering乳液。
(2)在室温下,在150mL烧杯中加入0.01mol端氨基聚醚D-2000和0.015molHDI,水浴锅匀速升温到70℃(5℃/min)机械搅拌300rpm反应1h,得到粘稠透明的HDI预聚体,待预聚体室温冷却。
(3)室温下,在步骤(2)预聚体中加入步骤(1)乳液后,加入0.005mol溶于1mL甲苯的位阻型胺类扩链剂和0.05mol端氨基聚醚D-2000,机械搅拌300rpm反应30min。
(4)用砂纸打磨钢片,丙酮冲洗后干燥。用工字涂布器在钢片上涂覆步骤(3)的复合物,涂层500μm厚,室温放置24h后进行抗侵蚀测试。
(5)抗侵蚀测试:用剃须刀片在钢片表面划痕后放置到10%NaCl水溶液中48h。观察,划痕处无明显锈迹。
实施例6
(1)将5g的1%的芦苇木质素磺酸钠加入到30mL白色盖子玻璃样品后,在样品瓶中加入混合均匀的4g的MDI和1g的IPDI,在11000rpm/min转速下机械乳化30s,得到O/W型pickering乳液。
(2)在室温下,在150mL烧杯中加入0.01mol端氨基聚醚D-2000和0.012molHDI,水浴锅匀速升温到70℃(5℃/min)机械搅拌300rpm反应1h,得到粘稠透明的HDI预聚体,待预聚体室温冷却。
(3)室温下,在步骤(2)预聚体中加入步骤(1)乳液反应30min后,加入0.001mol溶于1mL甲苯的位阻型胺类扩链剂和0.005mol端氨基聚醚D-2000,机械搅拌300rpm反应1h。
(4)用砂纸打磨钢片,丙酮冲洗后干燥。用工字涂布器在钢片上涂覆步骤(3)的复合物,涂层300μm厚,室温放置24h后进行抗侵蚀测试。
(5)抗侵蚀测试:用剃须刀片在钢片表面划痕后放置到10%NaCl水溶液中48h。观察,划痕处无明显锈迹。
实施例7
(1)将6g的1%蔗渣浆木质素磺酸钠加入到30mL白色盖子玻璃样品后,在样品瓶中加入混合均匀的3g的PMDI和1g的IPDI,在11000rpm/min转速下机械乳化30s,得到O/W型pickering乳液。
(2)在室温下,在150mL烧杯中加入0.01mol端氨基聚醚D-2000和0.012molHDI,水浴锅匀速升温到70℃(5℃/min)机械搅拌300rpm反应1h,得到粘稠透明的HDI预聚体,待预聚体室温冷却。
(3)室温下,在步骤(2)预聚体中加入步骤(1)乳液反应30min后,加入0.001mol溶于1mL甲苯的位阻型胺类扩链剂和0.002mol端氨基聚醚D-2000,机械搅拌300rpm反应1h。
(4)用砂纸打磨钢片,丙酮冲洗后干燥。用工字涂布器在钢片上涂覆步骤(3)的复合物,涂层300μm厚,室温放置24h后进行抗侵蚀测试。
(5)抗侵蚀测试:用剃须刀片在钢片表面划痕后放置到10%NaCl水溶液中48h。观察,划痕处无明显锈迹。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (9)
1.一种木质素磺酸盐分散自愈合聚脲涂料,其特征在于由包括以下质量份组分反应得到:1~10份木质素磺酸盐包埋愈合剂的微胶囊;10~100份聚脲预聚体;20~120份端氨基聚醚和位阻型胺类扩链剂的混合液;
所述木质素磺酸盐包埋愈合剂的微胶囊由包括以下步骤方法制备得到:将10~100重量份的木质素磺酸盐水溶液与1~50重量份的由芳香族异氰酸酯和脂肪族异氰酸酯形成的微胶囊愈合剂混合,乳化,室温干燥得到。
2.根据权利要求1所述的木质素磺酸盐分散自愈合聚脲涂料,其特征在于:所述芳香族异氰酸酯和脂肪族异氰酸酯的质量比为10:1~3:1;所用木质素磺酸盐水溶液与微胶囊愈合剂的重量比为10:1~1:0.4;所述木质素磺酸盐水溶液的质量浓度为0.5~2%;所述乳化在高速剪切下进行,高速剪切的速度为6000~11000rpm/min;所述乳化的时间为30s~3min。
3.根据权利要求1所述的木质素磺酸盐分散自愈合聚脲涂料,其特征在于:所述聚脲预聚体由包括以下步骤方法制备得到:将摩尔比为0.5:1~2:1的端氨基聚醚与脂肪族异氰酸酯混合,升温到20℃~100℃下搅拌反应10min~24h得到。
4.根据权利要求3所述的木质素磺酸盐分散自愈合聚脲涂料,其特征在于:所述端氨基聚醚与脂肪族异氰酸酯的摩尔比为1:1~1.5:1;所述升温为升温至35~75℃。
5.根据权利要求1所述的木质素磺酸盐分散自愈合聚脲涂料,其特征在于:所述端氨基聚醚和位阻型胺类扩链剂的混合液中,端氨基聚醚和位阻型胺类扩链剂的摩尔比为0.5:0.1~2:0.1。
6.根据权利要求1所述的木质素磺酸盐分散自愈合聚脲涂料,其特征在于:所述的木质素磺酸盐包括竹浆木质素磺酸盐、麦草浆木质素磺酸盐、芦苇木质素磺酸盐、蔗渣浆木质素磺酸盐、龙须草浆木质素磺酸盐、棉浆粕木质素磺酸盐、工业木质素磺化产物及工业木质素磺甲基化产物中的一种或一种以上;
所述的芳香族异氰酸酯包括甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、聚合二苯基甲烷二异氰酸酯、多亚甲基多苯基多异氰酸酯中的一种或一种以上;
所述的脂肪族异氰酸酯包括异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、六亚甲基二异氰酸酯三聚体中的一种或一种以上;
所述的端氨基聚醚包括聚醚胺D230、聚醚胺D400、聚醚胺D2000中的一种或一种以上;
所述的位阻型胺类扩链剂包括3,5-二氨-4-氯苯甲酸异丁醇酯、二乙酰乙二胺、二乙酰间苯二胺、4,4-二乙酰氨基二苯甲烷、二乙基甲苯二胺中的一种或一种以上。
7.一种权利要求1所述的木质素磺酸盐分散自愈合聚脲涂料的制备方法,其特征在于包括以下步骤:室温下,将木质素磺酸盐包埋愈合剂的微胶囊、端氨基聚醚和位阻型胺类扩链剂的混合液加入聚脲预聚体中,室温反应10min~4h,得到木质素磺酸盐分散自愈合聚脲涂料。
8.一种基于权利要求1所述的木质素磺酸盐分散自愈合聚脲涂料的涂层。
9.权利要求1所述的木质素磺酸盐分散自愈合聚脲涂料在材料表面防护领域中的应用。
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