CN107082887A - 一种超分散剂的制备方法及其应用 - Google Patents

一种超分散剂的制备方法及其应用 Download PDF

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CN107082887A
CN107082887A CN201710241397.7A CN201710241397A CN107082887A CN 107082887 A CN107082887 A CN 107082887A CN 201710241397 A CN201710241397 A CN 201710241397A CN 107082887 A CN107082887 A CN 107082887A
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陈君求
万红亮
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Hunan Better New Materials Co ltd
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Abstract

本发明提供一种超分散剂的制备方法,以苯乙烯‑马来酸酐共聚物为主链,聚乙烯亚胺和多乙烯多胺为支链,其主链在多种树脂中具有优异的相容性,支链可与各种涂料用的色粉的表面相结合,起到良好的锚定作用,其梳妆结构可以有很好的空间效应,用于制备分散液,使得色粉能很好的分散在体系中,具有很好的展色性。

Description

一种超分散剂的制备方法及其应用
技术领域
本发明涉及一种超分散剂的制备方法及其应用,尤其涉及一种改性的苯乙烯-马来酸酐共聚物分散剂的制备方法及其应用,属于分散剂加工技术领域。
背景技术
苯乙烯-马来酸酐共聚物(SMA)分子链中既有疏水性苯乙烯链段,又含有亲水性马来酸酐链段,其水解产物是一种常用的高分子产物。为了获得性能优异的高分子分散剂,可以对苯乙烯-马来酸酐共聚物进行改性。现有的改性苯乙烯-马来酸酐共聚物一般只能用于特定的树脂中,其酰胺化产物很少用作分散剂,原因是其没有好的锚定基团,可以很好的锚定到颜料表面。且现有产品对颜料的润湿、分散性不够强,只能分散特定种类的颜料,且现有产品大多含有有机溶剂,不利用环保。
发明内容
本发明的目的在于提供一种超分散剂的制备方法,以苯乙烯-马来酸酐为主链,聚乙烯亚胺和多乙烯多胺为支链,合成一种具有宽广的树脂相容性、良好分散性和展色性的超分散剂。
本发明的技术方案如下:
一种超分散剂的制备方法,具体包括以下步骤:
步骤(1):利用苯乙烯和马来酸酐共聚,获得苯乙烯-马来酸酐共聚物产品;
步骤(2):在氮气的保护下,加入苯乙烯-马来酸酐共聚物和多乙烯多胺,在50-70℃条件下反应4h以上;
步骤(3):在氮气的保护下,向步骤(2)反应物中加入聚乙烯亚胺,继续反应4h以上,降温,得到黄色液体。
所述超分散剂的制备方法,其中,所述步骤(1)可以利用现有方法制备苯乙烯-马来酸酐共聚物。优选按照以下步骤进行:
步骤a:称取苯乙烯、马来酸酐,用甲苯在反应瓶内加热溶解马来酸酐,在搅拌下先后将BPO(过氧化苯甲酰)及1/3的苯乙烯加入反应瓶;
步骤b:在60-90℃条件下,反应20-60分钟,有白色混浊出现时,用甲苯溶解余下的苯乙烯,慢慢滴入反应瓶中,1-5小时加完,再反应半小时,升温至80-100℃,反应0.5-2小时;
步骤c:反应完全后,即刻减压过滤,用少量甲苯洗沉淀三次,抽干,80℃烘干,得白色细粉状的苯乙烯-马来酸酐共聚物产品。
所述超分散剂的制备方法,步骤(1)所的苯乙烯-马来酸酐共聚物的分子量为1000-20000,马来酸酐的含量为10%-50%(摩尔比)。
所述超分散剂的制备方法,步骤(2)中,多乙烯多胺与马来酸酐的摩尔比为1:1,多乙烯多胺的分子量为100-1000。
所述超分散剂的制备方法,步骤(3)中,聚乙烯亚胺与马来酸酐的摩尔比为1:1,聚乙烯亚胺为非线性结构,其分子量为1000-10000。
按照上述制备方法制得的超分散剂,其结构式如下:
其中,x、y、m、n、p均为1-50之间的整数。
一种上述超分散剂在制备分散液中的应用,所述分散液中含有涂料、无机颜料、有机颜料、油墨或成膜树脂。
上述超分散剂在制备分散液中的应用,其中,所述成膜树脂为丙烯酸树脂、醇酸树脂、环氧树脂或聚氨树脂。
本发明的有益效果是:
1、以苯乙烯-马来酸酐共聚物为主链,聚乙烯亚胺和多乙烯多胺为支链,合成一种改性的超分散剂,其主链在多种树脂中具有优异的相容性,支链可与各种涂料用的色粉的表面相结合,起到良好的锚定作用。其梳妆结构可以有很好的空间效应,使得色粉能很好的分散在体系中,具有很好的展色性;
2、与现有产品相比,本发明所得超分散剂具有宽广的树脂相容性,在丙烯酸树脂、醇酸树脂、环氧树脂及聚氨树脂中对无机颜料和有机颜料有良好的分散效果;
3、制备方法简单,条件温和,所得产物中无有机溶剂,没有VOC排放,节是一种绿色环保的溶剂型分散剂。
附图说明
图1为本发明实施例1所得产物的红外光谱图。
具体实施方式
为使本发明的目的、技术方案及效果更加清楚、明确,以下举实例对本发明进一步详细说明。应当理解,此处所描述的具体实施例仅用于解释本发明,并不用于限定本发明。
实施例1
按照以下步骤合成超分散剂:
步骤(1):利用苯乙烯和马来酸酐共聚,获得苯乙烯-马来酸酐共聚物产品;
步骤(2):在氮气的保护下,按照马来酸酐与多乙烯多胺为1:1的摩尔比加入苯乙烯-马来酸酐共聚物和多乙烯多胺(重均分子量约为400),在60℃条件下反应;
步骤(3):在氮气的保护下,按照马来酸酐与聚乙烯亚胺为1:1的摩尔比向步骤(2)反应物中加入非线性聚乙烯亚胺(重均分子量约为1800),继续反应4h,降温,得到黄色液体即为本发明所述超分散剂。
本实施例中,所述超分散剂的制备方法,其中,所述步骤(1)所得苯乙烯-马来酸酐共聚物的重均分子量约为2000,其中,且步骤(1)优选按照以下步骤进行:
步骤a:按照1:1的摩尔比称取苯乙烯和马来酸酐,用甲苯在反应瓶内加热溶解马来酸酐,在搅拌下先后将BPO(过氧化苯甲酰)及1/3的苯乙烯加入反应瓶;
步骤b:在80℃条件下,反应30分钟,有白色混浊出现时,用甲苯溶解余下的苯乙烯,慢慢滴入反应瓶中,3小时加完,再反应半小时,升温至90℃,反应1.5小时;
步骤c:反应完全后,即刻减压过滤,用少量甲苯洗沉淀三次,抽干,80℃烘干,得白色细粉状的苯乙烯-马来酸酐共聚物产品。
本实施例所得超分散剂的红外光谱图如图1所示,其中,1602.86cm-1、1454.33cm-1处的吸收峰为芳烃的特征吸收峰,证明苯乙烯在主链上;1697.36cm-1为酰胺键的特征吸收峰,1768cm-1处为C=O的特征吸收峰,3000cm-1-3100cm-1处为仲胺的特征吸收峰,3500cm-1-3600cm-1处为伯胺的特征吸收峰,从图中可看出,本产品的胺通过形成酰胺的形式连接在含有芳烃的主链上。其反应方程式如下:
其中,x、y、m、n、p均为1-50之间的整数。
实施例2
按照以下步骤合成超分散剂:
步骤(1):利用苯乙烯和马来酸酐共聚,获得苯乙烯-马来酸酐共聚物产品;
步骤(2):在氮气的保护下,按照马来酸酐与多乙烯多胺为1:1的摩尔比加入苯乙烯-马来酸酐共聚物和多乙烯多胺(重均分子量约为900),在60℃条件下反应;
步骤(3):在氮气的保护下,按照马来酸酐与聚乙烯亚胺为1:1的摩尔比向步骤(2)反应物中加入非线性聚乙烯亚胺(重均分子量约为6000),继续反应4h,降温,得到黄色液体即为本发明所述超分散剂。
本实施例中,所述超分散剂的制备方法,其中,所述步骤(1)所得苯乙烯-马来酸酐共聚物的重均分子量约为10000,其中,且步骤(1)优选按照以下步骤进行:
步骤a:按照3:1的摩尔比称取苯乙烯和马来酸酐,用甲苯在反应瓶内加热溶解马来酸酐,在搅拌下先后将BPO(过氧化苯甲酰)及1/3的苯乙烯加入反应瓶;
步骤b:在60℃条件下,反应60分钟,有白色混浊出现时,用甲苯溶解余下的苯乙烯,慢慢滴入反应瓶中,1.1小时加完,再反应半小时,升温至100℃,反应0.5小时;
步骤c:反应完全后,即刻减压过滤,用少量甲苯洗沉淀三次,抽干,80℃烘干,得白色细粉状的苯乙烯-马来酸酐共聚物产品。其化学反应方程式及所得产物的红外光谱图与实施例1基本相同。
实施例3
按照以下步骤合成超分散剂:
步骤(1):利用苯乙烯和马来酸酐共聚,获得苯乙烯-马来酸酐共聚物产品;
步骤(2):在氮气的保护下,按照马来酸酐与多乙烯多胺为1:1的摩尔比加入苯乙烯-马来酸酐共聚物和多乙烯多胺(重均分子量约为400),在60℃条件下反应;
步骤(3):在氮气的保护下,按照马来酸酐与聚乙烯亚胺为1:1的摩尔比向步骤(2)反应物中加入非线性聚乙烯亚胺(重均分子量约为10000),继续反应4h,降温,得到黄色液体即为本发明所述超分散剂。
本实施例中,所述超分散剂的制备方法,其中,所述步骤(1)所得苯乙烯-马来酸酐共聚物的重均分子量约为20000,其中,且步骤(1)优选按照以下步骤进行:
步骤a:按照9:1的摩尔比称取苯乙烯和马来酸酐,用甲苯在反应瓶内加热溶解马来酸酐,在搅拌下先后将BPO(过氧化苯甲酰)及1/3的苯乙烯加入反应瓶;
步骤b:在90℃条件下,反应20分钟,有白色混浊出现时,用甲苯溶解余下的苯乙烯,慢慢滴入反应瓶中,5小时加完,再反应半小时,升温至80℃,反应2小时;
步骤c:反应完全后,即刻减压过滤,用少量甲苯洗沉淀三次,抽干,80℃烘干,得白色细粉状的苯乙烯-马来酸酐共聚物产品。其化学反应方程式及所得产物的红外光谱图与实施例1基本相同。
实施例4相容性、分散性、稳定性、着色力、展色性和颜色性能测试
为了证明本发明所得超分散剂的有益效果,本实施例采用正十六烷基胺将苯乙烯-马来酸酐共聚物酰胺化(酰胺化过程与本发明上述方法基本相同,区别仅在于用正十六烷基胺替代多乙烯多胺和聚乙烯亚胺)后制得的超分散剂作为对照品,进行对比试验,测试方法如下:
相容性:将实施例1-3制得的超分散剂以及对照品与多种成膜物质按1:10的比例混合均匀,同时利用隔夜观察分散体系是否清澈透明,结果见表1。
分散性:按先按配方研磨黑浆和黄浆,研磨介质:φ1-1.2mm玻璃珠10000rpm*60min。测量色浆细度、粒径分布、粘度。
配方:醇酸树脂46%
二甲苯13%
PMA 9%
分散剂14%
黑浆或黄浆18%
着色力和颜色数据:研磨得到的色浆分别在深色测试基础漆里按照10%和浅色测试基础漆里按照2%的比例加入各只色浆,静置消泡后用100μ涂布器在黑白卡上刮板。测量样板光泽,以国外竞品4310样板为标准,对比色差。
展色性:分别用热贮存前后的色浆按照上一试验的方法配成色漆,分散均匀后静置过夜,观察湿样浮色情况,在白色铜版纸上200μ刮板指研,测试色差。
稳定性:色浆和配好的色漆50℃贮存30天,检测有无返粗、增稠、分层、沉淀等问题。
实验结果如下:
表1:各组分散剂相容性测试结果
成膜物质 实施例1 实施例2 实施例3 对照品
丙烯酸树脂 清澈 清澈 清澈 清澈
醇酸树脂 清澈 清澈 清澈 轻微浑浊
聚酰胺 清澈 清澈 清澈 轻微浑浊
聚氨树脂 清澈 清澈 轻微浑浊 清澈
环氧树脂 轻微浑浊 清澈 清澈 清澈
纤维素 清澈 清澈 清澈 清澈
由表1可知,按照本发明所述方法制得的分别以多乙烯多胺、聚乙烯亚胺为支链的超分散剂,其与丙烯酸树脂、醇酸树脂、聚酰胺、聚氨树脂、环氧树脂、纤维素等成膜物质具有良好的相容性,优于以正十六烷基胺为支链的苯乙烯-马来酸酐共聚物。
表2:分散性、稳定性,着色力和颜色数据
由表2可知,按照本发明所述方法制得的分别以多乙烯多胺、聚乙烯亚胺为支链的超分散剂,其分散性、着色能力及稳定性与4310相当,而以正十六烷基胺为支链的超分散剂对照品的性能欠佳。
表3展色性测试结果
由表2可知,按照本发明所述方法制得的分别以多乙烯多胺、聚乙烯亚胺为支链的超分散剂,其展色性显著优于4310和以正十六烷基胺为支链的超分散剂对照品。
以上对本发明进行了详细的介绍,对本领域普通技术人员来说,可以根据上述说明加以改进或变换,而所有这些改进和变换都应属于本发明所附权利要求的保护范围。

Claims (8)

1.一种超分散剂的制备方法,其特征在于,具体包括以下步骤:
步骤(1):利用苯乙烯和马来酸酐共聚,获得苯乙烯-马来酸酐共聚物产品;
步骤(2):在氮气的保护下,加入苯乙烯-马来酸酐共聚物和多乙烯多胺,在50-70℃条件下反应4h以上;
步骤(3):在氮气的保护下,向步骤(2)反应物中加入聚乙烯亚胺,继续反应4h以上,降温,得到黄色液体。
2.根据权利要求1所述的超分散剂的制备方法,其特征在于,所述步骤(1)按照以下步骤进行:
步骤a:称取苯乙烯、马来酸酐,用甲苯在反应瓶内加热溶解马来酸酐,在搅拌下先后将BPO(过氧化苯甲酰)及1/3的苯乙烯加入反应瓶;
步骤b:在60-90℃条件下,反应20-60分钟,有白色混浊出现时,用甲苯溶解余下的苯乙烯,慢慢滴入反应瓶中,1-5小时加完,再反应半小时,升温至80-100℃,反应0.5-2小时;
步骤c:反应完全后,即刻减压过滤,用少量甲苯洗沉淀三次,抽干,80℃烘干,得白色细粉状的苯乙烯-马来酸酐共聚物产品。
3.根据权利要求1所述的超分散剂的制备方法,其特征在于,步骤(1)所的苯乙烯-马来酸酐共聚物的分子量为1000-20000,马来酸酐的含量为10%-50%。
4.根据权利要求1所述的超分散剂的制备方法,其特征在于,步骤(2)中,所述多乙烯多胺与马来酸酐的摩尔比为1:1,多乙烯多胺的分子量为100-1000。
5.根据权利要求1所述的超分散剂的制备方法,其特征在于,步骤(3)中,所述聚乙烯亚胺与马来酸酐的摩尔比为1:1,聚乙烯亚胺为非线性结构,其分子量为1000-10000。
6.按照权利要求1-5中任一项所述的制备方法制得的超分散剂,其结构式如下:
其中,x、y、m、n、p均为1-50之间的整数。
7.一种权利要求6所述的超分散剂在制备分散液中的应用,其特征在于,所述分散液中含有涂料、无机颜料、有机颜料、油墨或成膜树脂。
8.根据权利要求7所述的超分散剂在制备分散液中的应用,其特征在于,所述成膜树脂为丙烯酸树脂、醇酸树脂、环氧树脂或聚氨树脂。
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