CN105907077A - 无芳烃冷芯盒树脂粘结剂 - Google Patents
无芳烃冷芯盒树脂粘结剂 Download PDFInfo
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- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
- B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
- B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22C1/24—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of oily or fatty substances; of distillation residues therefrom
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及一种冷芯盒树脂粘结剂，特别涉及一种基于聚氨酯的无芳烃冷芯盒树脂粘结剂，包含酚醛树脂的组分a，和聚异氰酸酯的组分b，其中a和/或b包含一种或多种植物油作为溶剂。本发明的植物油价格低廉，容易获得。当使用植物油代替芳烃溶剂时，在配制粘结剂时可消除包括苯、甲苯、二甲苯、1,2,4三甲苯、萘的化合物和其它芳族化合物，在粘结剂系统中不存在挥发性有机化合物，VOC含量极低，同时减少或消除了浇注、冷却和振动脱砂过程中不希望的气体、烟雾和气味的形成。
Description
技术领域
本发明涉及一种冷芯盒树脂粘结剂，特别涉及一种基于聚氨酯的无芳烃冷芯盒树脂粘结剂。所述粘结剂用于制造型芯和铸模，特别用于铸造冷芯盒混合物。
背景技术
现有技术中，冷芯盒树脂粘结剂包括酚醛树脂组分和聚异氰酸酯组分，是基于聚氨酯的铸造粘结剂体系，粘结剂通常具有低的粘度和储存稳定性，通过将粘结剂与铸造集料混合而制备铸造混合料，借助于碱性催化剂来硬化。
现在使用的铸造冷芯盒粘结剂都包含有大量的芳烃溶剂，芳烃溶剂又可包含诸如苯、甲苯、二甲苯、1,2,4三甲苯、萘的化合物和其它芳族化合物以及相关部分。通常，酚醛树脂组分的溶剂是由高沸点的极性溶剂(如酯和酮)和高沸点的芳烃组成的混合物。聚异氰酸酯组分的溶剂是高沸点的芳烃。近年来，在铸造粘结剂中使用芳烃溶剂引起的环保问题受到人们的日益关注。
EP0771569描述了用一种或更多种具有12个碳原子碳链的脂肪酸的甲酯替代芳烃溶剂，虽然该粘结剂制得有用的型芯和模具，但已发现在浇注、冷却和振动脱砂过程中冒烟和发出刺鼻气味，并且用这些粘结剂制得的模具和型芯在用过后得到的砂更难再生和再用。因此，在实践中，趋向于将脂肪酸酯与传统芳烃溶剂组合用作供溶剂。
EP1057554披露了使用硅酸烷基酯，特别是硅酸四乙酯替代芳烃溶剂。该技术也存在一些缺点，例如在用于减少胺固化气体的酸性洗涤溶液中形成凝胶，并且形成的白色二氧化硅细粒可沉积在铸件上、积聚在用过的砂中或在空气中载带。
鉴于此背景，需要迫切开发出不包含芳烃溶剂，同时保持优异的性能，并且充分考虑环境、健康和安全问题的绿色铸造粘结剂。
发明内容
本发明涉及一种无芳烃冷芯盒树脂粘结剂，所述粘结剂包含
包含酚醛树脂的组分a，和
包含聚异氰酸酯的组分b，
其中a和/或b包含一种或多种植物油作为溶剂。
优选的，所述植物油选自可再生生物基材料。所述植物油选自干性油、半干性油和不干性油。所述干性油的碘值为130以上，优选自桐油、梓油、亚麻油、棉籽油中的一种或多种的混合物。所述半干性油的碘值为100-130，优选自包括豆油、糠油、向日葵油中的一种或多种的混合物；所述不干性油的碘值100以下，优选自橄榄油、蓖麻油中的一种或两种的混合物。
本发明使用的酚醛树脂是本领域技术人员已知的那些，这些树脂是固体的或液体的。
本发明所使用的多异氰酸酯也是本领域技术人员已知的那些，所述多异氰酸酯成分包括一种多异氰酸酯、种多异氰酸酯溶剂以及多种任选的组分。该多异氰酸酯具有两个或更多个、优选从2至5个的官能度。它可以是脂肪族的、脂环族的或芳香族的、或一种混合的多异氰酸酯。这些多异氰酸酯还可以是受保护的多异氰酸酯、多异氰酸酯预聚合物和多异氰酸酯准预聚合物。本发明还包括多种多异氰酸酯的混合物。在本发明中使用的多异氰酸酯类的代表性实例是脂肪族的多异氰酸酯类例如二异氰酸六亚甲酯，脂环族的多异氰酸酯类例如4，4’-二环己基甲烷二异氰酸酯，以及芳香族多异氰酸酯类例如2，4-和2，6甲苯二异氰酸酯、二苯甲烷二异氰酸酯，和它们的二甲基衍生物。多异氰酸酯类的其他实例是1，5-萘二异氰酸酯、三苯基甲烷三异氰酸酯、苯二甲基、和它们的甲基衍生物、聚亚甲基聚苯基异氰酸酯类、氯亚苯基2，4-二异氰酸酯，等。
优选的，所述冷芯盒粘结剂中包含一种或多种选自直链烃溶剂、二元酯溶剂、脂肪酸酯溶剂及其混合物的溶剂；优选的，所述溶剂可配入粘结剂的组分a或组分b、或同时加入组分a和组分b二者中。
优选的，所述溶剂的加入量为每100重量份粘结剂，加入溶剂10-80重量份；优选的，所述溶剂的加入量为每100重量份粘结剂，加入溶剂15-60重量份；更优选的，所述溶剂的加入量为每100重量份粘结剂，加入溶剂20-50重量份
优选的，所述植物油的加入量为每100重量份粘结剂，加入植物油1-40重量份；优选的，所述植物油的加入量为每100重量份粘结剂，加入植物油5-30重量份；最优选的，所述植物油的加入量为每100重量份粘结剂，加入植物油2-20重量份。
更优选的，所述植物油在组分a中的加入量为每100重量份的组分a中，加入植物油0-30重量份；优选的，所述植物油在组分a中的加入量为每100重量份的组分a中，加入植物油5-25重量份；更优选的，所述植物油在组分a中的加入量为每100重量份的组分a中，加入植物油5-20重量份。
更优选的，所述植物油在组分b中的加入量为每100重量份的组分b中，加入植物油0-15重量份；优选的，所述植物油在组分b中的加入量为每100重量份的组分b中，加入植物油0-10重量份；更优选的，所述植物油在组分b中的加入量为每100重量份的组分b中，加入植物油0-5重量份。
另一方面，本发明涉及一种所述树脂粘结剂的用途，其用于铸造冷芯盒混合物。该粘结剂与铸造骨料混合形成铸造树脂砂混合料，所述铸造树脂砂混合料用于制造铸造金属铸件的型芯模。
另一方面，本发明涉及一种包含所述树脂粘结剂的冷芯盒混合物。所述混合物中包含酚醛树脂、聚异氰酸酯、抑烟剂、阻燃助剂、气态胺催化剂。
所述气态胺催化剂选自三乙胺、二甲基乙胺或二甲基异丙胺，优选为三乙胺。所述的聚异氰酸酯是二苯基甲烷-4，4’-二异氰酸酯(简称为“MDI”)、粗二苯基甲烷-4，4’-二异氰酸酯(简称为粗“MDI”)、或多亚甲基多苯基多异氰酸脂(简称为“PAPI”)。
所述的抑烟剂为氢氧化铝、氢氧化镁、氧化锌的一种或其组合。
所述的阻燃助剂为有机硅烷偶联剂A-1100、有机硅烷偶联剂A-560、有机硅烷偶联剂A-1120中的一种或其组合。
上述的各组成可以是单独的组分，或者与其它所述的组分进行混合，但苄基醚酚醛树脂与聚异氰酸酯不能直接混合。优选地，该粘结剂由组分I和组分II构成；组分I包括所有重量份的苄基醚酚醛树脂、磷系阻燃增塑剂和抑烟剂；组分II包括所有重量份的聚异氰酸酯。更优选地，粘结剂体系以双组分体系包装和使用。组分I包括苄基醚酚醛树脂、磷系阻燃增塑剂、抑烟剂、阻燃助剂、高沸点酯或烃溶剂。组分II包括聚异氰酸酯硼、阻燃助剂、高沸点酯或烃溶剂。
本发明的冷芯盒粘结剂树脂中的树脂优选采用高邻位苄基醚酚醛树脂。所述的苄基醚酚醛树脂是数均分子量为800～1200的高邻位苄基醚酚醛树脂。
所述的高邻位苄基醚酚醛树脂通过以下方法制得：
A.将熔化好的苯酚、双酚A、甲醛和氧化钙投入反应釜中，用pH调节剂在30～40℃下调混合液PH值为4～7；
B.将反应釜冷凝器调整为回流状态，在搅拌下通蒸汽升温，在60分钟内使温度升至95℃，并在95～105℃保温反应90分钟；
C.将反应釜调整为分馏状态，在60分钟内使釜内温度升至115℃，并在115～120℃保温反应60分钟；
D.保温完毕，冷却降温至100℃以下，然后抽真空，使真空度达300～600mmHg，抽空时间30分钟既得高邻位苄基醚酚醛树脂。
本发明的植物油价格低廉，容易获得。当使用植物油代替芳烃溶剂时，在配制粘结剂时可消除包括苯、甲苯、二甲苯、1,2,4三甲苯、萘的化合物和其它芳族化合物，在粘结剂系统中不存在挥发性有机化合物，VOC含量极低，同时减少或消除了浇注、冷却和振动脱砂过程中不希望的气体、烟雾和气味的形成。
具体实施方式
通过参见本申请具体实施方式的内容可以更易于理解本发明，但是本发明并不限于本文所述和/或所示的具体方法、条件或参数，并且本文中所用的术语仅是为了以举例的方式描述具体实施方式，并不能限制本申请权利要求要求保护的技术方案。在下文中，将描述根据本发明的无芳烃冷芯盒树脂粘结剂及包含所述粘结剂的冷芯盒树脂。
树脂砂的强度检测参照GB2684《铸造用原砂及混合料试验方法》。
树脂砂VOC的测试方法：
取室温放置24小时的砂样抗弯试块称重，放入恒温110度的烘箱中90分钟，取出冷却至室温后称重。
将放置前抗弯试块重量减去放置后抗弯试块重量后除放置前抗弯试块重量，VOC以百分比来表示。
所述粘结剂为两组份体系，酚醛树脂组合物为组份a，而聚异氰酸酯组合物为组份b。
实施例1-3和对比例1-3：
按照100重量份大林标准砂、0.8重量份组分a、0.8重量份组分b比例配成树脂砂。首先加入组分a与砂混合1分钟，再加入组分b混合2分钟，然后将该树脂砂通过MLA1制芯机吹气压制成抗弯试块。其制芯工艺参数为：射砂压力0.3MPa，吹胺压力0.2MPa，洗涤压力0.2MPa，吹胺时间3.0秒，洗涤时间5.0秒。实施例1-3以及对比例1-3中加入的各组分含量以及最终的效果测试数据见下表。
实施例1-3和对比例1-3的具体组分和测试数据如下表所示：
实施例4-6和对比例4-6：
按照100重量份大林标准砂、0.88重量份组分a、0.72重量份组分b比例配成树脂砂。首先加入组分a与砂混合1分钟，再加入组分b混合2分钟，然后将该树脂砂通过MLA1制芯机吹气压制成抗弯试块。其制芯工艺参数为：射砂压力0.3MPa，吹胺压力0.2MPa，洗涤压力0.2MPa，吹胺时间3.0秒，洗涤时间5.0秒。实施例4-6以及对比例4-6中加入的各组分含量以及最终的效果测试数据见下表。
实施例4-5和对比例4-5的具体组分和测试数据如下表所示：
实施例7-9和对比例7-9：
按照100重量份大林标准砂、0.96重量份组分a、0.64重量份组分b比例配成树脂砂。首先加入组分a与砂混合1分钟，再加入组分b混合2分钟，然后将该树脂砂通过MLA1制芯机吹气压制成抗弯试块。其制芯工艺参数为：射砂压力0.3MPa，吹胺压力0.2MPa，洗涤压力0.2MPa，吹胺时间3.0秒，洗涤时间5.0秒。实施例7-9以及对比例7-9中加入的各组分含量以及最终的效果测试数据见下表。
实施例7-9和对比例7-9的具体组分和测试数据如下表所示：
从上述实施例1-9和对比例1-9的实验数据可以看出，采用植物油作为溶剂，相对于采用芳烃类的溶剂，在保持了优异的抗弯强度性能的同时，还大大地减少了树脂VOC排放，对环境更加友好。
基于以上实施例应该明确的是，在不脱离本发明的精神或范围的情况下，可以对本发明进行各种改进和变变型。因此，本发明意在涵盖基于本发明的改进和变型，只要这些改进和变型落在所附的权利要求及其等同替代技术手段的范围内。
Claims (10)
1.一种无芳烃冷芯盒树脂粘结剂，所述粘结剂包含
包含酚醛树脂的组分a，和
包含聚异氰酸酯的组分b，
其中a和/或b包含一种或多种植物油作为溶剂。
2.根据权利要求1所述的无芳烃冷芯盒树脂粘结剂，所述植物油选自可再生生物基材料,
所述植物油选自干性油、半干性油和不干性油,
所述干性油的碘值为130以上，优选自桐油、梓油、亚麻油、棉籽油中的一种或多种的混合物,
所述半干性油的碘值为100-130，优选自包括豆油、糠油、向日葵油中的一种或多种的混合物；所述不干性油的碘值100以下，优选自橄榄油、蓖麻油中的一种或两种的混合物。
3.根据权利要求1或2所述的无芳烃冷芯盒树脂粘结剂，所述冷芯盒粘结剂中包含一种或多种选自直链烃溶剂、二元酯溶剂、脂肪酸酯溶剂及其混合物的溶剂；优选的，所述溶剂可配入粘结剂的组分a或组分b、或同时加入组分a和组分b二者中。
4.根据权利要求3所述的无芳烃冷芯盒树脂粘结剂，所述溶剂的加入量为每100重量份粘结剂，加入溶剂10-80重量份；优选的，所述溶剂的加入量为每100重量份粘结剂，加入溶剂15-60重量份；更优选的，所述溶剂的加入量为每100重量份粘结剂，加入溶剂20-50重量份。
5.根据权利要求1-4任一项所述的无芳烃冷芯盒树脂粘结剂，所述植物油的加入量为每100重量份粘结剂，加入植物油1-40重量份；优选的，所述植物油的加入量为每100重量份粘结剂，加入植物油5-30重量份；最优选的，所述植物油的加入量为每100重量份粘结剂，加入植物油2-20重量份。
6.根据权利要求3-5任一项所述的无芳烃冷芯盒树脂粘结剂，所述植物油在组分a中的加入量为每100重量份的组分a中，加入植物油0-30重量份；优选的，所述植物油在组分a中的加入量为每100重量份的组分a中，加入植物油5-25重量份；更优选的，所述植物油在组分a中的加入量为每100重量份的组分a中，加入植物油5-20重量份。
7.根据权利要求3-6任一项所述的无芳烃冷芯盒树脂粘结剂，所述植物油在组分b中的加入量为每100重量份的组分b中，加入植物油0-15重量份；优选的，所述植物油在组分b中的加入量为每100重量份的组分b中，加入植物油0-10重量份；更优选的，所述植物油在组分b中的加入量为每100重量份的组分b中，加入植物油0-5重量份。
8.一种如权利要求1-3任一项所述无芳烃冷芯盒树脂粘结剂的用途，其用于铸造冷芯盒混合物,
优选的，该粘结剂与铸造骨料混合形成铸造树脂砂混合料，所述铸造树脂砂混合料用于制造铸造金属铸件的型芯模。
9.一种包含如权利要求1-3任一项所述无芳烃冷芯盒树脂粘结剂的冷芯盒混合物,
所述混合物中包含酚醛树脂、聚异氰酸酯、抑烟剂、阻燃助剂、气态胺催化剂。
10.根据权利要求5所述的冷芯盒混合物，采用高邻位苄基醚酚醛树脂,
所述的苄基醚酚醛树脂是数均分子量为800～1200的高邻位苄基醚酚醛树脂。
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110139722A (zh) * | 2016-12-23 | 2019-08-16 | Ask化学品股份有限公司 | 制造型芯和模具的组分体系 |
| CN110139722B (zh) * | 2016-12-23 | 2021-10-26 | Ask化学品股份有限公司 | 制造型芯和模具的组分体系 |
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