CN109679486A - 一种饮用水容器用快速喷涂改性聚氨酯涂层材料及其制备方法 - Google Patents
一种饮用水容器用快速喷涂改性聚氨酯涂层材料及其制备方法 Download PDFInfo
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- CN109679486A CN109679486A CN201811620509.0A CN201811620509A CN109679486A CN 109679486 A CN109679486 A CN 109679486A CN 201811620509 A CN201811620509 A CN 201811620509A CN 109679486 A CN109679486 A CN 109679486A
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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
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3237—Polyamines aromatic
- C08G18/324—Polyamines aromatic containing only one aromatic ring
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
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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
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- Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
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Abstract
本发明提供一种环保无毒、快速反应、低吸水率聚氨酯弹性体组合物,由植物油多元醇与多异氰酸酯反应得到的预聚物为一个组分;植物油多元醇、扩链剂、色浆及多种功能性助剂的混合为另一组分。采用喷涂快速固化型的方式,达到施工简单、提高施工效率的目的,得到的制品具有较高强度、很低的吸水率、安全环保,适用于大规模的饮用水管道和储罐的内衬施工。
Description
技术领域
本发明属于聚氨酯弹性体涂层及其制备方法,具体涉及一种饮用水容器用快速喷涂改性聚氨酯涂层材料及其制备方法。
背景技术
随着生活水平的日益提高和保健意识的增强,人们对直接影响人类健康的饮用水接触涂层的要求也越来越高。随着新型材料的应用,目前可应用于饮用水接触涂层的材质品种非常繁多。从材质上主要有金属材质、非金属材质,从成品来分主要是容器和管道,大口径管道主要包括钢管、球墨铸铁管,中小口径的管材常用薄壁不锈钢、聚乙烯管等。钢管和球墨铸铁管若不进行任何处理会很容易产生腐蚀。管道腐蚀后不仅降低了输水能力、增加的电耗,主要的是对供水水质产生了严重的影响,对饮用者的健康产生威胁。因此钢管和铸铁管必须内衬涂防腐涂层才能应用于供水管道中。现有的内衬主要有水泥砂浆衬里、环氧树脂、聚氨酯涂层、PE膜涂层等产品。传统的水泥砂浆衬里易开裂,且涂层较厚,大大降低了输送效率,且衬里呈碱性,与水接触后会增大水中的pH值,对水质有碱性劣化现象。环氧树脂固化慢,且温度对其固化速度有很大的影响,冬天、寒冷地区无法正常施工,涂装后需要几天时间才能完全固化投入使用。PE膜涂层工艺复杂,接口需 要热熔接容易产生裂缝,对于形状复杂的弯头等部位施工复杂。
中国专利号89105340.9公开了一种无毒无溶剂环氧涂料,以环氧树脂为主要原料(分子量为900以下),加入胺类固化剂、颜料、增塑剂,即邻苯二甲酸 酯类、活性剂,即苯甲醇,按一定比例和工艺混合后机械喷涂,用于食品饮料 加工罐、槽的防腐。缺点是在实际使用过程中,涂料对施工操作条件要求苛刻,喷涂设备清洗困难,不适合大型设备的挤涂。同时该专利中应用的增塑剂-邻苯二甲酸酯类和活性剂苯甲醇类可能从涂层中迁移并在水中富集。作为养料提供给微生物,而恶臭假单胞菌生存在苯甲醇高度聚集以吸引不动杆菌的地方,从而使微生物中恶臭假单胞菌数量增多,管道中的水质具有恶臭味。
中国专利公开号CN1137950c公开了一种饮用水管道、容器内防腐涂料。A 组分以改性环氧树脂为主要原料,添加助剂(气相二氧化硅)和填料(钛白粉、云母粉、重晶石粉、硫酸钡),B组分以改性聚酰胺为主,含有溶剂醋酸乙酯和丁醇。该专利称选用的助剂和填料无毒,但是,有机溶剂的存在却是一大问题。固化后产品中残留的有机溶剂很难挥发完全,与水接触后被人体吸收,对人体存在着健康的威胁。且环氧树脂反应速度很慢,需要长时间固化后才能投入使用,大大影响了施工效率。
传统聚氨酯涂层包含的多元醇组分多采用聚醚聚乙二醇醚、聚丙二醇醚、聚四氢呋喃醚二醇、聚己内酯二醇等石油基聚合物多元醇。原料来源少、成本高,属于不可再生资源。制品的生物降解性差,对环境不友好,耐水(解)性能较差,长时间浸水环境下体积膨胀,强度变低,对管道壁的附着力变差。
发明内容
本发明提供了一种饮用水容器用快速喷涂改性聚氨酯涂层材料及其制备方法,该材料具有施工效率高,涂层均匀,易于施工的特点。植物油多元醇的使用大大降低了对石油基原料的依赖,使材料更加绿色环保,同时制品的耐水(解)型更高,大大提高了制品的寿命和强度,对金属底材以及混凝土基材的附着力。可用于饮用水管道、容器及储罐的防护衬里。
为解决其技术问题,本发明提供如下技术方案。
一种饮用水容器用快速喷涂改性聚氨酯涂料,包括A、B两种组分,其特征在于:所述A 组分多异氰酸酯和植物油聚醚多元醇合成的异氰酸酯封端的半预聚物;所述B组分包括植物油聚醚多元醇、扩链剂、颜料、助剂的混合;按照A组分与B组分的当量比,也就是异氰酸酯指数在0.9-1.2之间进行 配合,所述A组分与所述B组分按体积比1∶1配合。
本发明称谓A、B组分只是为了表述上的方便。
进一步的:
上述组分的制备方法,所述A组分的合成方法是:以重量份计,将55-85份的多异氰酸酯加入到有氮气保护的反应釜中,匀速搅拌,加热至50~60℃,向反应釜中缓慢加入15-50份的植物油聚醚多元醇,在60~90℃下,保温反应0.5-1.5h小时,加入0.1-1份的催化剂,继续在此温度搅拌反应1.5-2.5h后冷却出料。
所述B组分的制备方法是:以重量份计,将25-75份的植物油多元醇、15-30份扩链剂、5-10份的色浆、5-15份助剂常温混合,利用高剪切分散设备高速搅拌 20~40分钟后出料;
其上所述A组分中的多异氰酸酯为官能度在2.0~2.7之间, 2,4’-二苯基甲烷二异氰酸酯,4,4’-二苯基甲烷二异氰酸酯,碳 化二亚胺-脲酮亚胺改性的4,4’-二苯基甲烷二异氰酸酯、2,4’-二苯基甲 烷二异氰酸酯,多次甲基多苯基异氰酸酯,4,4’-二环己基甲烷二异氰酸酯或 异佛尔酮二异氰酸酯中的一种或几种。
所述A组份和B组份中的植物油多元醇为分子量200-4000,官能度在2-4之间的为蓖麻油、蓖麻油衍生物多元醇、大豆油多元醇、棕榈油多元醇、脂肪酸二聚体二醇、二聚体聚酯二醇中的一种或几种的混合。
所述扩链剂包括二甲硫基甲苯二胺(DMTDA),二乙基甲苯二胺(DETDA),3,3′-二氯-4,4′-二苯基甲烷二胺(MOCA),1,4-环己基二胺,异佛尔酮二胺,4,4’-二环己基甲烷二胺,1,4-二胺乙基甲烷,1,4-丁二醇、1,3-丁二醇、三羟甲基丙烷、丙三醇中的一种或几种。
所述色浆为蓖麻油分散的颜料或染料。
所述助剂包括促进体系反应的催化剂:二月桂酸二丁基锡、辛酸亚锡、异辛酸铅、异辛酸铋的一种或几种,除水剂,偶联剂,消泡剂润湿剂等。
本发明的改性聚氨酯喷涂材料,不含溶剂,所用颜料及助剂均通过FDA认证。产品经检测完全通过了BS6920标准,完全可以安全的应用于饮用水管道及容器内衬。同时,本发明材料固化速度快、施工便捷、一次成膜厚,非常适合于大规模的饮用水管道、容器和储罐的内衬施工。
具体实施方式
下面结合实施例对本发明进一步详细描述,但发明的方式不限于此。此外应理解为在阅读本发明介绍的内容之后,本领域技术人员可以对本发明做各种改动或修改,这些等价形式同样属于本申请所附权利要求书所限定的范围。
以下实施例所用材料如下:未作特别说明,各百分数均指的是质量百分数。
MDI-50 4,4′-二苯基甲烷二异氰酸酯(50%)、2,4′-二苯基甲烷二异氰酸酯(50%)
MDI-100 4,4′-二苯基甲烷二异氰酸酯(>99%)
蓖麻油 羟值163-164 mg KOH/g 植物油多元醇
棕榈油 羟值58-65 mg KOH/g 棕榈油多元醇
E100 二乙基甲苯二胺 扩链剂
A3 分子筛干燥剂
T-12 二月桂酸二丁基锡 有机锡催化剂
8118 异辛酸铋 有机铋催化剂
BYK-530 有机硅类消泡剂
中络黄色浆
实施例一:
A组分:以重量份计,将70份的MDI-50加入到有氮气保护的反应釜中,匀速搅拌,加热至50℃,向反应釜中缓慢加入35份蓖麻油,15份棕榈油,在80℃左右保温反应1小时,加入0.3份T-12继续保温反应2h后冷却出料;
B组分:以重量份计,将45份蓖麻油,30份棕榈油,10份E100、5份的色浆、5份A3、0.03份BYK-530、0.5份8118常温混合,利用高剪切分散设备高速搅拌 30钟后出料;
实施例二:
A组分:以重量份计,将40份的MDI-50、30份MDI-100加入到有氮气保护的反应釜中,匀速搅拌,加热至50℃,向反应釜中缓慢加入25份的蓖麻油,25份棕榈油,在80℃左右保温反应1小时,加入0.1份T-12继续保温反应2h后冷却出料;
B组分:以重量份计,将40份蓖麻油,35份棕榈油,15份E100、5份的色浆、5份A3、0.03份BYK-530、0.4份8118常温混合,利用高剪切分散设备高速搅拌 30钟后出料;
实施例三:
A组分:以重量份计,将70份的MDI-50加入到有氮气保护的反应釜中,匀速搅拌,加热至50℃,向反应釜中缓慢加入15份的蓖麻油,35份棕榈油,在80℃左右保温反应1小时,加入0.3份T-12继续保温反应2h后冷却出料;
B组分:以重量份计,将30份的蓖麻油、45份棕榈油,18份E100、4份的色浆、5份A3、0.03份BYK-530、0.2份8118常温混合,利用高剪切分散设备高速搅拌 30钟后出料;
实施例四:
A组分:以重量份计,将70份的多异氰酸酯加入到有氮气保护的反应釜中,匀速搅拌,加热至50℃,向反应釜中缓慢加入5份的蓖麻油,45份棕榈油,在80℃左右保温反应1小时,加入0.3份T-12继续保温反应2h后冷却出料;
B组分:以重量份计,将20份蓖麻油、55份棕榈油,22份E100、4份的色浆、5份A3、0.03份BYK-530、0.2份8118常温混合,利用高剪切分散设备高速搅拌 30钟后出料;
实施例五:
A组分:以重量份计,将将45份的MDI-50、25份MDI-100加入到有氮气保护的反应釜中,匀速搅拌,加热至50℃,向反应釜中缓慢加入50份的棕榈油,在80℃左右保温反应1小时,加入0.3份T-12继续保温反应2h后冷却出料;
B组分:以重量份计,将75份的蓖麻油、25份E100、4份的色浆、5份A3、0.03份BYK-530、0.15份8118常温混合,利用高剪切分散设备高速搅拌 30钟后出料。
以上实施例得到的A组分和B组分以体积比1:1的比例系数,使用专业聚脲喷涂机喷涂固化成型。
下表为各实施例得到制品的性能数据
材料性能 | 实施例一 | 实施例二 | 实施例三 | 实施例四 | 实施例五 |
拉伸强度/Mpa | 24.5 | 28.2 | 28.8 | 26.7 | 29.4 |
伸长率/% | 75 | 80 | 72 | 68 | 89 |
硬度/shore D | 62 | 75 | 65 | 60 | 65 |
吸水率/% | 0.9 | 0.5 | 0.8 | 1.2 | 0.8 |
与钢材附着力/Mpa(拉拔法) | 15.6 | 18.7 | 19.2 | 18.2 | 19.6 |
经检验,本发明具有以下优点和积极效果:
1. 涂膜干燥后漆膜无毒。化学检验完全符合英国标准BS6920的要求。因此,该材料完全可以作为饮用水管道、容器内防腐蚀材料,不会对水质造成污染,不会产生对人体有害的物质;
2. 材料可生物降解,对环境污染小,满足材料的环保要求;
2.快速固化。体系可在几秒到几十秒之间快速固化,大大提高了施工效率;
4.可厚涂层施工,一次施工即可达到要求,克服了以往多次施工的弊病;
5.优良的化学稳定性能和耐水、抗老化性能,使用寿命长;
6.材料附着力好。对钢、铸铁、铝、混凝土等各类底材均具有优良的附着力;
7.涂层表面光滑,降低了摩擦阻力,加大了水流速度,节省了输送能量。
以上所述,仅是本发明的较佳实施例而已,并非是对本发明作其它形式的 限制,任何熟悉本专业的技术人员可能利用上述揭示的技术内容加以变更或改 型为等同变化的等效实施例。但是凡是未脱离本发明技术方案内容,依据本发 明的技术实质对以上实施例所作的任何简单修改、等同变化与改型,仍属于本 发明技术方案的保护范围。
Claims (10)
1.饮用水容器用快速喷涂改性聚氨酯涂层材料,其特征在于两种组分构成组合物:A组分:异氰酸酯封端预聚体的合成及B组分植物油聚醚多元醇、扩链剂、颜料、助剂的混合。
2.根据权利1所述的A组分异氰酸酯封端预聚体的合成方法:以重量份计,将55-85份的多异氰酸酯加入到有氮气保护的反应釜中,匀速搅拌,加热至50~60℃,向反应釜中缓慢加入15-50份的植物油聚醚多元醇,在60~90℃下,保温反应0.5-1.5h小时,加入0.1-1份的催化剂,继续在此温度搅拌反应1.5-2.5h后冷却出料。
3.根据权利1所述B组分的制备方法是:以重量份计,25-75份的植物油多元醇、15-30份扩链剂、5-10份的色浆、5-15份助剂常温混合,利用高剪切分散设备高速搅拌 20~40分钟后出料。
4.根据权利1所述组合物,其特征在于:所述A组分与B组分的当量比,也就是异氰酸酯指数在0.9-1.2之间进行 配合,所述A组分与所述B组分按体积比1∶1配合。
5.根据权利1-4任意项所述组合物,其特征在于:所述A组分中的多异氰酸酯为官能度在2.0~2.7之间, 2,4’-二苯基甲烷二异氰酸酯,4,4’-二苯基甲烷二异氰酸酯,碳 化二亚胺-脲酮亚胺改性的4,4’-二苯基甲烷二异氰酸酯、2,4’-二苯基甲 烷二异氰酸酯,多次甲基多苯基异氰酸酯,4,4’-二环己基甲烷二异氰酸酯或 异佛尔酮二异氰酸酯中的一种或几种。
6.根据权利1-4任意项所述组合物,其特征在于所述A组份和B组份中的植物油聚醚多元醇为分子量200-5000,官能度在2-4之间,植物油聚醚多元醇为蓖麻油、蓖麻油衍生物多元醇、大豆油多元醇、棕榈油多元醇、脂肪酸二聚体二醇、二聚体聚酯二醇中的一种或几种的混合。
7.根据权利1-4任意项所述组合物,其特征在于所述扩链剂包括二甲硫基甲苯二胺(DMTDA),二乙基甲苯二胺(DETDA),3,3′-二氯-4,4′-二苯基甲烷二胺(MOCA),1,4-环己基二胺,异佛尔酮二胺,4,4’-二环己基甲烷二胺,1,4-二胺乙基甲烷,1,4-丁二醇、1,3-丁二醇、三羟甲基丙烷、丙三醇中的一种或几种。
8.根据权利要求1所述的组合物,其特征在于:A组分和B组分采用专业喷涂机混合喷涂成型,混合温度为55-65℃,凝胶及表干时间小于5min,常温固化24h后可得到聚氨酯制品。
9.根据权利要求8所述的聚氨酯改性材料,其特征在于:所述材料的拉伸强度10-25Mpa,拉断伸长率在50-200%,硬度在40-70shoreD,吸水率<1.5%。
10.根据权利要求1-8所述制备方法所得的制品主要用于饮用水管道、容器和储罐等饮用水环境的内衬防护涂层。
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