CN104130373A - 一种铸造用三乙胺法冷芯盒树脂的生产方法 - Google Patents

一种铸造用三乙胺法冷芯盒树脂的生产方法 Download PDF

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CN104130373A
CN104130373A CN201410378914.1A CN201410378914A CN104130373A CN 104130373 A CN104130373 A CN 104130373A CN 201410378914 A CN201410378914 A CN 201410378914A CN 104130373 A CN104130373 A CN 104130373A
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triethylamine
core box
resin
cold core
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韩文
杨洋
朱劲松
何龙
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Kocel Chemicals Co ltd
Shared New Materials Shandong Co ltd
Kocel Machinery Co Ltd
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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
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • 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
    • B22C1/2273—Polyurethanes; Polyisocyanates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C7/00—Patterns; Manufacture thereof so far as not provided for in other classes
    • B22C7/06—Core boxes
    • 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
    • C08G18/54—Polycondensates of aldehydes
    • C08G18/542—Polycondensates of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids

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Abstract

本发明涉及一种适用于高湿环境的三乙胺法冷芯盒树脂的生产方法，尤其是涉及一种铸造用三乙胺法冷芯盒树脂的生产方法，该方法为先分别合成组分Ⅰ和组分Ⅱ，然后将组分Ⅰ和组分Ⅱ混合即可；上述原料的重量百分含量为：组分Ⅰ中，苯醚型酚醛树脂：42%-65%，芳烃溶剂：16.2%-25%，柠檬酸酯增塑剂：6%-12%，脂肪酸族二元酸酯增塑剂：12%-24%，硅烷偶联剂0.4%-0.8%；组分Ⅱ中，多亚甲基多苯基多异氰酸酯PAPI：72.5%，合成植物酯：27%，磷酸酯类抑制剂：0.5%；本发明方法独特、抗湿性能好、环保性能高、改善铸造生产条件，实现“绿色铸造”，提高铸件表面质量和铸件尺寸精确度。

Description

一种铸造用三乙胺法冷芯盒树脂的生产方法
技术领域
本发明涉及一种适用于高湿环境的三乙胺法冷芯盒树脂的生产方法，尤其是涉及一种铸造用三乙胺法冷芯盒树脂的生产方法。
背景技术
三乙胺冷芯盒工艺是目前铸造生产中应用最多的冷芯盒制芯工艺。经过近20年推广，我国也已广泛采用。随着铸造企业高精技术及绿色生产的发展步伐，冷芯盒造型工艺暴漏出的抗湿性能差、高温性能差、环保性能低等缺陷，阻碍了现代铸造企业向着精细化、“绿色铸造”方向发展的进程。
目前还没有克服上述缺陷的方法。
发明内容
本发明的目的是克服现有技术的缺陷，提供一种方法独特、抗湿性能好、环保性能高、改善铸造生产条件，实现“绿色铸造”，提高铸件表面质量和铸件尺寸精确度的一种铸造用三乙胺法冷芯盒树脂的生产方法。
本发明通过如下方式实现：
一种铸造用三乙胺法冷芯盒树脂的生产方法，其特征在于：该方法为先分别合成组分Ⅰ和组分Ⅱ，然后将组分Ⅰ和组分Ⅱ混合即可；上述原料的重量百分含量为：组分Ⅰ中，苯醚型酚醛树脂：42%-65%，芳烃溶剂：16.2%-25%，柠檬酸酯增塑剂：6%-12%，脂肪酸族二元酸酯增塑剂：12%-24%，硅烷偶联剂0.4%-0.8%；组分Ⅱ中，多亚甲基多苯基多异氰酸酯PAPI：72.5%，合成植物酯：27%，磷酸酯类抑制剂：0.5%；
所述组分Ⅰ合成方法如下：
Ⅰ.将苯醚型酚醛树脂：42%-65%投入反应釜中，开启搅拌，加入柠檬酸酯增塑剂：6%-12%，通蒸汽加热至50-60℃，搅拌20分钟；
Ⅱ.加入脂肪酸族二元酸酯增塑剂：12%-24%，芳烃溶剂：16.2%-25%，搅拌30分钟；
Ⅲ.降温至40℃以下，硅烷偶联剂0.4%-0.8%，搅拌20分钟，检测、包装；
所述组分Ⅱ合成方法为将多亚甲基多苯基多异氰酸酯PAPI、合成植物酯、磷酸酯类抑制剂，按照72.5%:27%:0.5%的比例加入反应釜中，搅拌30分钟、检测、包装；
所述苯醚型酚醛树脂为固体多聚甲醛与工业苯酚在乙醇、醋酸锌催化下，加成、缩聚、脱水所得，柠檬酸酯增塑剂为柠檬酸三丁酯，脂肪酸酯增塑剂为己二酸二辛酯，合成植物酯为二甘醇二苯甲酸酯，芳烃溶剂为S—200、硅烷偶联剂为KH—602型。
本发明有如下效果：
1）该工艺树脂组分Ⅰ中采用柠檬酸酯、脂肪酸酯两种无毒环保增塑剂，有效改善了作业环境，提高了树脂的抗湿性能及型砂的强度，砂型在相对湿度80%的高湿条件下，存放72小时，强度仍然可达到24小时强度的85%以上；
2）工艺树脂组分Ⅰ中加入了芳烃溶剂，与柠檬酸酯、脂肪酸酯作为苯醚型酚醛树脂的混合溶剂，很大程度上延长了型砂的可使用时间，工艺放大样品在某大型铸造厂试用，现场型砂可使用时间达到了180分钟，较某国外进口冷芯盒树脂还长30分钟；
3）工艺树脂组分Ⅱ采用合成植物酯、磷酸酯类抑制剂作为异氰酸酯的溶剂，有效抑制了异氰酸酯的反应活性，使组分Ⅱ树脂的保存期延长了2-3倍。且材料无毒、环保性能高，价格相对便宜，利于推广应用。
4）.组分Ⅰ中加入了柠檬酸酯及脂肪酸族二元酸酯类环保型增塑剂，有效提高了树脂的环保性能；
5）柠檬酸酯、脂肪酸族二元酸酯增塑剂的加入，提高了树脂砂强度及抗湿性能；
6）组分Ⅱ中加入合成植物酯，很好的与异氰酸酯溶解，降低了组分Ⅱ的粘度，型砂流动性好，强度高；
7）组分Ⅱ中加入磷酸酯类抑制剂，便于异氰酸酯长时间使用、储存，并有效延长了型砂的可使用时间，便于铸造生产。
具体实施方式
实施例一：一种铸造用三乙胺法冷芯盒树脂的生产方法，该方法为：
Ⅰ.将苯醚型酚醛树脂：42%投入反应釜中，开启搅拌，加入柠檬酸酯增塑剂： 12%，通蒸汽加热至50-60℃，搅拌20分钟；
Ⅱ.加入脂肪酸族二元酸酯增塑剂： 24%，芳烃溶剂：21.6%，搅拌30分钟；
Ⅲ.降温至40℃以下，硅烷偶联剂0.4%，搅拌20分钟，检测、包装。
说明：此配方为高抗湿型三乙胺冷芯盒树脂。
实施例二：一种铸造用三乙胺法冷芯盒树脂的生产方法，该方法为：
Ⅰ.将苯醚型酚醛树脂：65%投入反应釜中，开启搅拌，加入柠檬酸酯增塑剂： 6%，通蒸汽加热至50-60℃，搅拌20分钟；
Ⅱ.加入脂肪酸族二元酸酯增塑剂： 12%，芳烃溶剂：16.2%，搅拌30分钟；
Ⅲ.降温至40℃以下，硅烷偶联剂0.8%，搅拌20分钟，检测、包装。
说明：此配方为高强度型三乙胺冷芯盒树脂。
实施例三：一种铸造用三乙胺法冷芯盒树脂的生产方法，该方法为：
Ⅰ.将苯醚型酚醛树脂：50.4%投入反应釜中，开启搅拌，加入柠檬酸酯增塑剂： 6%，通蒸汽加热至50-60℃，搅拌20分钟；
Ⅱ.加入脂肪酸族二元酸酯增塑剂： 18%，芳烃溶剂：25%，搅拌30分钟；
Ⅲ.降温至40℃以下，硅烷偶联剂0.6%，搅拌20分钟，检测、包装。
说明：此配方为均衡型三乙胺冷芯盒树脂。

Claims (4)

1. 一种铸造用三乙胺法冷芯盒树脂的生产方法，其特征在于：该方法为先分别合成组分Ⅰ和组分Ⅱ，然后将组分Ⅰ和组分Ⅱ混合即可；上述原料的重量百分含量为：组分Ⅰ中，苯醚型酚醛树脂：42%-65%，芳烃溶剂：16.2%-25%，柠檬酸酯增塑剂：6%-12%，脂肪酸族二元酸酯增塑剂：12%-24%，硅烷偶联剂0.4%-0.8%；组分Ⅱ中，多亚甲基多苯基多异氰酸酯PAPI：72.5%，合成植物酯：27%，磷酸酯类抑制剂：0.5%。
2. 如权利要求1所述的一种铸造用三乙胺法冷芯盒树脂的生产方法，其特征在于： 所述组分Ⅰ合成方法如下：
Ⅰ.将苯醚型酚醛树脂：42%-65%投入反应釜中，开启搅拌，加入柠檬酸酯增塑剂：6%-12%，通蒸汽加热至50-60℃，搅拌20分钟；
Ⅱ.加入脂肪酸族二元酸酯增塑剂：12%-24%，芳烃溶剂：16.2%-25%，搅拌30分钟；
Ⅲ.降温至40℃以下，硅烷偶联剂0.4%-0.8%，搅拌20分钟，检测、包装。
3. 如权利要求1所述的一种铸造用三乙胺法冷芯盒树脂的生产方法，其特征在于： 所述组分Ⅱ合成方法为将多亚甲基多苯基多异氰酸酯PAPI、合成植物酯、磷酸酯类抑制剂，按照72.5%:27%:0.5%的比例加入反应釜中，搅拌30分钟、检测、包装。
4. 如权利要求1所述的一种铸造用三乙胺法冷芯盒树脂的生产方法，其特征在于： 所述苯醚型酚醛树脂为固体多聚甲醛与工业苯酚在乙醇、醋酸锌催化下，加成、缩聚、脱水所得，柠檬酸酯增塑剂为柠檬酸三丁酯，脂肪酸酯增塑剂为己二酸二辛酯，合成植物酯为二甘醇二苯甲酸酯，芳烃溶剂为S—200、硅烷偶联剂为KH—602型。
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104923713A (zh) * 2015-04-30 2015-09-23 宁夏共享化工有限公司 一种长保存期三乙胺法冷芯盒固化剂及其生产方法
CN110834065A (zh) * 2019-11-28 2020-02-25 苏州兴业材料科技股份有限公司 环氧植物油改性三乙胺法冷芯盒树脂ⅰ组分及其制备方法
CN112548023A (zh) * 2020-12-08 2021-03-26 四川东树新材料有限公司 一种高溃散铸铝发动机缸体用冷芯盒树脂及其制备方法

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CN101058112A (zh) * 2007-05-30 2007-10-24 苏州市兴业铸造材料有限公司 采用钝化与活化技术的三乙胺法冷芯盒树脂

Patent Citations (1)

* Cited by examiner, † Cited by third party
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CN101058112A (zh) * 2007-05-30 2007-10-24 苏州市兴业铸造材料有限公司 采用钝化与活化技术的三乙胺法冷芯盒树脂

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104923713A (zh) * 2015-04-30 2015-09-23 宁夏共享化工有限公司 一种长保存期三乙胺法冷芯盒固化剂及其生产方法
CN110834065A (zh) * 2019-11-28 2020-02-25 苏州兴业材料科技股份有限公司 环氧植物油改性三乙胺法冷芯盒树脂ⅰ组分及其制备方法
CN112548023A (zh) * 2020-12-08 2021-03-26 四川东树新材料有限公司 一种高溃散铸铝发动机缸体用冷芯盒树脂及其制备方法

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