CN1137927C - 一种受阻酚类聚烯烃抗氧剂的制备工艺 - Google Patents
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Abstract
本发明的β-晶型抗氧剂1010的制备工艺，通过C6烷烃和C1-2低级醇组成的混合溶剂做为结晶溶剂对抗氧剂1010混晶粗品进行精制，具有制品晶型单一、纯度高、工艺简单、易于后处理的特点。
Description
本发明涉及一种聚烯烃抗氧剂的制备工艺，特别是β-晶型抗氧剂1010的制备工艺。
抗氧剂1010是一种分子量较高的受阻酚类抗氧剂，由2，6-二叔丁基苯酚和丙烯酸甲酯先进行加成反应，生成β-(3，5-二叔丁基-4-羟基苯基)丙酸甲酯，然后再与季戊四醇进行酯交换反应制得，其化学名称为四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯，化学结构式如下：
该物质作为聚丙烯、线形低密度聚乙烯、聚酯、聚氯乙烯、聚苯乙烯、ABS、聚尿烷、聚乙醛以及动植物油、烃类、脂肪酸酯、润滑油等的抗氧剂，具有高效、低毒、无臭、不变色、不污染、不易挥发和耐热水萃取等多方面的优异性能。当它与其他辅助抗氧剂、稳定剂、紫外线吸收剂等配用时，呈现出明显的增效效应。目前在国内外，抗氧剂1010都被视为最理想的聚烯烃抗氧剂。
从晶体而言，抗氧剂1010具有多晶特性。尽管其化学结构完全相同，但存在多种不同的晶型结构，文献报道有α、β、δ、λ和γ等多种晶型，各种晶型结构产品，在性能上存在不同差异，特别是在熔点、流动性、堆密度等方面。专利Ep244,361提供了一种单一β一晶型抗氧剂1010制备方法。专利指出：在混合物A和水存在下，用乙醇、甲醇或其混合溶剂为结晶溶剂，可制得立方体型的β晶型抗氧剂1010。混合物A由10-90％的“3，5-甲酯”和90-10％“三酯”组成。三酯是指在酯交换反应中，季戊四醇的四个羟基中的三个羟基被取代后的不完全反应产物，因此该法要制备得到β-晶型抗氧剂1010，酯交换产物中须含有一定比例的混合物A这种特殊组成的物质。由于含有混合物A，增加了分离的一定难度，同时，造成结晶收率低，产品纯度差等问题，其应用受到一定的限制。
本发明的目的是为了克服上述专利方法的不足，提供一种工艺简单，产品纯度高，易于后处理的β-晶型抗氧剂1010制备工艺。
为实现本发明目的，采用以下方法：将抗氧剂1010混晶粗品，充分溶解于由C6烷烃和C1-2低级醇组成的混合溶剂中，在60-10℃温度范围加入β-型晶体做晶种，诱导结晶，析出物经洗涤，干燥、冷却即得制品。
例如可采取以下方法，效果最佳：先将抗氧剂1010混晶粗品加入至由C6烷烃和C1-2低级醇组成的混合溶剂中，升温至35-50℃，搅拌使之完全溶解，形成一透明溶液，降温至28-32℃，加入0.5-5％(wt)β-型晶体做晶种，诱导结晶，母液继续冷却至20℃以下，使抗氧剂1010完全析出；过滤去母液，析出物用C1-2低级醇洗涤后，干燥、冷却即可得性能较好的β-型抗氧剂1010。
最佳的质剂比范围1∶3-1∶4，最佳的溶剂组成配比为3∶2-2∶3(C6烷烃∶C1-2低级醇)。
抗氧剂1010在C6烷烃中的溶解度大。其配比对结晶产品结果影响较为明显。配比过低，混合溶剂的溶解能力降低，产品纯度低。配比高，则收率差。一般将结晶终温维持在20℃以下，恒温30min，以保证β-晶型抗氧剂1010完全析出，使产品有较高的收率。
本发明的β-晶型抗氧剂1010制备工艺的特点是工艺简单，易手后处理，制品晶型单一，纯度好。产品的晶型分别用经典的熔点法和粉末X-衍射法进行了分析确定。将透光率在425nm处小于90％，500nm处小于95％，熔点为110-116℃的抗氧剂1010混晶粗品，经本发明的方法精制后，可得到透光率在425nm处大于98％，500nm处大于99％，熔点为111-115℃，单一β-晶型抗氧剂1010产品。
实施例1：
实验装置由500ml带有搅拌装置、测温装置、回流冷凝装置的三口烧瓶组成，三口烧瓶外部用恒温水浴装置控温。将80g抗氧剂1010粗品置于三口烧瓶中，再将4 00ml由1∶1环己烷和乙醇组成的混合溶液加入其中，升温至36℃，使抗氧剂1010粗品和杂质完全溶解，在30℃左右加入1％(wt)β-型晶体做晶种，冷却结晶。母液继续冷却至20℃，结晶析出抗氧剂1010；过滤去母液，析出物经乙醇洗涤、干燥后，得65gβ-晶型抗氧剂1010。堆密度0.38g/cm3，熔点111-114℃，X-衍射为β-晶型，如图1所示。
图1为实施例1所得制品的粉末X-衍射图。
实施例2：
采用与实施例1相同的装置，将107g抗氧剂1010粗品溶于400ml由1∶1配比的己烷和乙醇组成的混合溶液，升温至47℃使抗氧剂1010粗品和杂质完全溶解，冷却结晶，在35℃左右加入3％(wt)β-型晶体做晶种，诱导结晶，母液继续冷却至20℃，恒温30min，析出抗氧剂1010；过滤去母液，析出物经乙醇洗涤、干燥，即得82gβ-型抗氧剂1010。堆密度0.39g/cm3，熔点113-115℃，X-衍射为β-晶型，如图2所示。
实施例3：
采用与实施例1相同的装置，将90g抗氧剂1010粗品溶于400ml由2∶3配比的苯和甲醇组成的混合溶液，升温至43℃使抗氧剂1010粗品和杂质完全溶解，冷却结晶，在32℃左右加入3％(wt)β-型晶体做晶种，诱导结晶，母液继续冷却至20℃，恒温30min，析出抗氧剂1010；过滤去母液，析出物经甲醇洗涤、干燥，即得82gβ-型抗氧剂1010。堆密度0.38g/cm3，熔点113-114℃，X-衍射为β-晶型，如图3所示。
Claims (4)
1.一种β-晶型四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯的制备工艺，其特点在于将四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯混晶粗品，充分溶解于由C6烷烃和C1～2低级醇组成的混合溶剂中，升温至35～50℃，搅拌使之完全溶解，形成一透明溶液，降温至28～32℃，加入0.5～5 wt％β-型晶体做晶种，诱导结晶，母液继续冷却至20℃以下，使四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯完全析出；过滤去母液，析出物经洗涤，干燥、冷却即得制品。
2.根据权利要求1所述的β-晶型四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯的制备工艺，其特点为析出物用C1-2低级醇洗涤。
3.根据权利要求2所述的β-晶型四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯的制备工艺，其特点在于质剂比1∶3～1∶4。
4.根据权利要求1或2或3所述的β-晶型四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯的制备工艺，其特点在于溶剂中C6烷烃：C1-2低级醇为3∶2～2∶3。
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| CN105542285A (zh) * | 2016-02-17 | 2016-05-04 | 黄秀茹 | 一种用于聚合物的添加剂及其制备方法以及由其组成的聚合物组合物 |
| CN105713231A (zh) * | 2016-02-17 | 2016-06-29 | 黄秀茹 | 一种用于聚合物的添加剂及其制备方法以及由其组成的聚合物组合物 |
| CN105601993A (zh) * | 2016-02-17 | 2016-05-25 | 黄秀茹 | 一种用于聚合物的添加剂及其制备方法以及由其组成的聚合物组合物 |
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