CN111808248B - 乙酸乙烯酯和环状烯酮缩醛单体的共聚物粒子的水性分散液 - Google Patents
乙酸乙烯酯和环状烯酮缩醛单体的共聚物粒子的水性分散液 Download PDFInfo
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Abstract
本发明涉及一种包含共聚物粒子的水性分散液的组合物,所述共聚物粒子包含乙酸乙烯酯、环状烯酮缩醛单体和单烯系不饱和酸单体或其盐的结构单元;其中所述环状烯酮缩醛单体的特征在于以下结构:
Description
背景技术
本发明涉及一种聚合物粒子的水性分散液,所述聚合物粒子包含乙酸乙烯酯和环状烯酮缩醛单体的结构单元。
乙酸乙烯酯(VA)和环状烯酮缩醛(CKA)单体(如2-亚甲基-1,3-二氧杂环庚烷(MDO))的共聚物尤其适用于需要聚合物主链降解(如可降解包装)或聚合物类薄膜和表面涂层的物理腐蚀的应用。如例如在《高分子杂志(Polym.J.)》2009,41,650-660;《高分子化学(Polym.Chem.)》2012,3,1260-1266;《高分子化学》2015,6,7447-7454;和US 1996/5541275中所公开的,这些共聚物被描述为在有机溶剂存在下制备。
因为已知CKA水解不稳定,所以使用有机溶剂制备含CKA的聚合物。举例来说,MDO在水中水解形成乙酸4-羟丁酯,从而降低MDO的结构单元掺入到共聚物主链中的效率。因此,MDO的水解不稳定性要求使用不起反应的有机溶剂;不利的是,这些溶剂由于其较高成本(其去除、回收和再循环的成本)以及其促成最终分离产物中的残余挥发性有机溶剂而不合需要。
因此,找到一种以显著减少非所需水解副产物形成的方式来制备水基VA-CKA共聚物的方法将是有利的。
发明内容
本发明通过提供一种组合物来解决本领域中的需要,所述组合物包含具有在50nm到500nm范围内的z平均粒度的共聚物粒子的水性分散液,按所述共聚物粒子的重量计,聚合物粒子包含:a)75重量%到98.5重量%乙酸乙烯酯的结构单元;b)1重量%到20重量%环状烯酮缩醛单体的结构单元;和c)0.05重量%到5重量%单烯系不饱和酸单体或其盐的结构单元;其中所述环状烯酮缩醛单体的特征在于以下结构:
其中n为0、1或2;
R为H或C1-C6烷基;
R1和R2各自独立地是H、C1-C12烷基、苯基或乙烯基;或R1和R2与其所连接的碳原子一起形成稠合苯环或稠合C3-C7环脂族环;和
R1'和R2'各自独立地是H或C1-C12烷基;或R1和R1'和/或R2和R2'形成环外双键;
其条件是当n为1时:
R3和R3'各自独立地是H、C1-C12烷基、苯基,或R3和R3'形成环外双键或螺环脂族基团或螺-2-亚甲基-1,3-二氧杂环庚烷基团;
其进一步的条件是当n为2时:
每一R3为H、C1-C12烷基,或与其所连接的碳原子一起形成双键、稠合苯环或稠合C3-C7环脂族环。
本发明的组合物提供一种水性分散液,其基本上不含挥发性有机溶剂并且提供适用于例如制造可生物降解包装产品的易降解聚合物。
具体实施方式
本发明涉及一种组合物,其包含具有通过动态光散射测得的在50nm到500nm范围内的z平均粒度的共聚物粒子的水性分散液,按聚合物粒子的重量计,所述共聚物粒子包含:a)75重量%到98.5重量%乙酸乙烯酯的结构单元;b)1重量%到20重量%环状烯酮缩醛单体的结构单元;和c)0.05重量%到5重量%单烯系不饱和酸单体或其盐的结构单元;其中所述环状烯酮缩醛单体的特征在于以下结构:
其中n为0、1或2;
R为H或C1-C6烷基;
R1和R2各自独立地是H、C1-C12烷基、苯基或乙烯基;或R1和R2与其所连接的碳原子一起形成稠合苯环或稠合C3-C7环脂族环;和
R1'和R2'各自独立地是H或C1-C12烷基;或R1和R1'和/或R2和R2'形成环外双键;
其条件是当n为1时:
R3和R3'各自独立地是H、C1-C12烷基、苯基,或R3和R3'形成环外双键或螺环脂族基团,或螺-2-亚甲基-1,3-二氧杂环庚烷基团;
其进一步的条件是当n为2时:
每一R3为H、C1-C12烷基,或与其所连接的碳原子一起形成内部双键、稠合苯环或稠合C3-C7环脂族环。
如本文所使用,术语“乙酸乙烯酯的结构单元”是指含有以下重复单元的聚合物主链:
其中虚线表示与聚合物主链中的其它结构单元的连接点。
术语“环状烯酮缩醛单体的结构单元”用于指含有以下重复单元的聚合物主链:
其中R、R1、R2、R3、R1'、R2'、R3'和n如先前所定义。
环状烯酮缩醛单体的实例包括:
优选的环状烯酮缩醛单体为2-亚甲基-1,3-二氧杂环庚烷(MDO)。
MDO的结构单元图解如下:
烯系不饱和酸单体可以是含羧酸的单体、含磷酸的单体或含硫酸的单体,或其盐。适合的含羧酸的单体的实例包括丙烯酸、甲基丙烯酸、衣康酸、丁烯酸、顺丁烯二酸和反丁烯二酸;适合的含磷酸的单体的实例包括甲基丙烯酸磷酸乙酯和膦酸2-(甲基丙烯酰氧基)乙酯;适合的含硫酸的单体的实例包括2-丙烯酰胺基-2-甲基-1-丙磺酸(AMPS)、乙烯基磺酸、丙烯酸2-磺乙酯、甲基丙烯酸2-磺乙酯、丙烯酸3-磺丙酯、甲基丙烯酸3-磺丙酯和2-丙烯-1-磺酸。烯系不饱和酸单体优选地是含磺酸的单体,优选地含磺酸的单体的盐,其中2-丙烯酰胺基-2-甲基丙烷磺酸的盐是尤其优选的。
优选地,聚合物粒子具有在从80nm、更优选从100nm到优选300nm、更优选到200nm并且最优选到150nm的范围内的z平均粒度。
优选地,按聚合物粒子的重量计,聚合物粒子包含从80重量%、更优选从85重量%到96.5重量%、更优选到95重量%乙酸乙烯酯的结构单元;从3重量%到15重量%、更优选到12重量%,并且最优选到8重量%CKA的结构单元,并且优选从0.1重量%到1重量%单烯系不饱和酸单体的结构单元。
此外,组合物包含基本上不存在的CKA和VA的水解副产物。更确切地说,在CKA为MDO的情况下,按聚合物粒子中MDO的结构单元的重量计,组合物优选包含小于20重量%,更优选小于10重量%,更优选小于5重量%,更优选小于2重量%,并且最优选小于1重量%的非所需酯乙酸4-羟丁酯(图解如下)。
组合物优选地进一步包含小于3000ppm,更优选地小于2000ppm的乙酸,其为VA水解的非所需副产物。
共聚物粒子的水性分散液宜在乳液聚合条件下通过使VA、CKA(优选MDO)和单烯系不饱和酸单体(优选含硫酸的单体的盐、更优选AMPS的盐)接触来制备。优选地,将VA和CKA组合在一起,然后在乳液聚合条件下与表面活性剂和单烯系不饱和酸单体的水溶液混合。反应宜控制在30℃,优选地35℃到小于60℃,优选到55℃,更优选到50℃,并且最优选到45℃范围内的温度下,并且在6.0,优选6.5,更优选7.0,并且最优选7.5到9.0,更优选到8.5范围内的pH下。在聚合完成之后,获得固体含量优选在20重量%、更优选25重量%并且最优选30重量%,到50重量%并且更优选到40重量%范围内的共聚物分散液。
出人意料地,已发现在不使用有机溶剂的情况下,可有效地制备VA和CKA的共聚物水性分散液,且CKA和VA的非所需水解副产物最少。
测量粒度的方法
使用Malvern Zetasizer Nano ZS90测量粒度,其使用Zetasizer软件7.11版,以90°的散射角使用动态光散射(dynamic light scattering,DLS)测量Z平均粒度(Dz)。使用MilliQ水(在25℃下18.2MΩ.cm)的水溶液来稀释样品分散液的液滴,获得200-400千次/秒(Kcps)范围内的粒子计数。使用仪器的粒子尺寸测量方法进行粒度测量,并且通过软件运算Dz。Dz也被称作基于强度的调和平均粒度,且表达为;
此处,Si为来自具有直径Di的粒子i的散射强度。在ISO 22412:2017(《粒度分析——动态光散射(DLS)(Particle size analysis-Dynamic light scattering(DLS))》)中描述了详细的Dz计算。
乙酸测定方法
使用安捷伦(Agilent)1100系列高效液相色谱系统对乙酸进行分析,所述系统配备有Phenomenex Rezex ROA-Organic Acid H+(8%)(250×4.6)mm柱(零件号码00G-0138-E0)、Phenomenex Security Guard Carbo-H4元件、在210nm的波长下操作的UV检测器和自动取样器。柱箱温度设定为35℃,且流动相是含2.5mM磷酸的MilliQ水。仪器以0.4mL/min(等度)的流动速率操作,并且样品注入体积为5μL。使用安捷伦化学化学工作站(AgilentChemStation)软件(版本B.04.03)进行数据获取和分析。制备样品用于通过在MilliQ水(1:100)中稀释,随后在水平往复振荡器上搅拌10分钟来分析。在25℃下以100 000rpm离心样品10分钟,并且通过0.45μm一次性注射器过滤器过滤上清液以用于注入。
实例1——制备VA/MDO聚合物粒子的水性分散液
在容器中通过将乙酸乙烯酯(VA,205.95g)和2-亚甲基-1,3-二氧杂环庚烷(MDO,10.88g)组合来制备单体混合物。分别地,在容器中通过将去离子水(46.18g)、2-丙烯酰胺基-2-甲基-1-丙磺酸钠盐(AMPS盐,1.40g,水中50%活性)、Tergitol-15-S-40二级醇乙氧基化物(15-S-40,1.51g,水中70%活性)和FES-32,月桂基醚磺酸钠(FES-32,6.15g,水中31%活性)来制备水性混合物。分别地,将去离子水(285.0g)添加到装备有顶置式搅拌器、冷凝器和热电偶的4颈、1L圆底反应器中。将反应器加热到40℃,之后借助于额外去离子水(51.6g),将FES-32(16.4g,水中31%活性)、AMPS盐(3.95g,水中50%活性)、FeSO4·7H2O(16.2g,水中0.15活性)和乙二胺四乙酸(EDTA,3.45g,1.0重量%于水中)添加到反应器中。将单体混合物和水性混合物经60分钟同时馈入反应器中,同时将反应器温度维持在40℃。同时,在70分钟内将分别制备的过硫酸铵/叔丁基过氧化氢(1.38g APS和0.58g t-BHP于37.0g水中)和Bruggolite FF6(2.62g于37.6g水中)的溶液馈入到反应器中。在整个馈入过程中,反应物测量为pH=6.5到7。在添加馈料完成后,反应器温度维持在40℃下15分钟,并且然后冷却到30℃。在添加氢氧化铵(水中28%活性)的情况下,将所得分散液调节到pH=7,并且通过38μm筛过滤。分析滤液的固体百分比(32.9%),并且如使用动态光散射(DLS)所测量的,测定z平均粒度为116nm。通过扩散编辑的1H NMR光谱法(diffusion-edited 1H NMR spectroscopy)测量2-亚甲基-1,3-二氧杂环庚烷(MDO)的掺入率为(84.3±4.3)%。在所有整合值中假设5%的误差,且所述误差通过计算MDO的掺入传递。
实例2
重复实例1,但通过逐滴添加氢氧化铵(水中28%活性)使反应物在整个馈入中维持在pH=8。分析滤液的固体百分比(31.3%),并且如DLS所测量的,测定z平均粒度为122nm。通过扩散编辑的1H NMR光谱法测量MDO的掺入率几乎为定量的(约100%)。
实例3
重复实例2,但通过组合VA(183.95g)和MDO(32.88g)制备单体混合物。分析滤液的固体百分比(29.7%),并且如DLS所测量的,测定z平均粒度为92nm。通过扩散编辑的1H NMR光谱法测量MDO的掺入率为97.8±6.6%。
比较实例1
重复实例1,但在整个馈入中反应温度维持在60℃。分析滤液的固体百分比(29.8%),并且如DLS所测量的,测定z平均粒度为177nm。通过扩散编辑的1H NMR光谱法测量MDO的掺入率为55.1±3.9%。
比较实例2
重复实例1,但在整个馈入中反应温度维持在80℃。分析滤液的固体百分比(29.4%),并且如DLS所测量的,测定z平均粒度为217nm。通过扩散编辑的1H NMR光谱法测量MDO的掺入率为37.8±2.7%。
比较实例3
重复实例1,但在整个馈入中通过逐滴添加乙酸(水中10%活性)将反应物维持在pH=5。分析滤液的固体百分比(31.0%),并且如DLS所测量的,测定z平均粒度为248nm。通过扩散编辑的1H NMR光谱法测量MDO的掺入率为29.0±2.0%。
比较实例4
重复实例1,但在整个馈入中通过逐滴添加氢氧化铵(水中28%活性)将反应物维持在pH=9.5。分析滤液的固体百分比(29.6%),并且如DLS所测量的,测定z平均粒度为283nm。通过扩散编辑的1H NMR光谱法测量MDO的掺入率为90.3±6.3%;然而,样品显示出较差的胶体稳定性并且获得7850ppm的凝胶。样品在静置时变成深棕色,且观察到异常高的浓度的乙酸和乙醛。
实例展现温度和pH在优化水敏性单体掺入到聚合物主链中的掺入率和在减少由这些单体所致的非所需水解产物的产生方面的作用的重要性。
Claims (9)
1.一种包含具有在50nm到500nm范围内的z平均粒度的共聚物粒子的水性分散液的组合物,按所述共聚物粒子的重量计,聚合物粒子包含:a)75重量%到98.5重量%乙酸乙烯酯的结构单元;b)1重量%到20重量%环状烯酮缩醛单体的结构单元;和c)0.05重量%到5重量%单烯系不饱和酸单体或其盐的结构单元;其中所述环状烯酮缩醛单体选自下组:
2.根据权利要求1所述的组合物,其中按所述聚合物粒子的重量计,所述聚合物粒子包含:a)85重量%到96.5重量%乙酸乙烯酯的结构单元;b)3重量%到15重量%所述环状烯酮缩醛单体的结构单元;和c)0.1重量%到1重量%所述单烯系不饱和酸单体的结构单元。
3.根据权利要求2所述的组合物,其中所述环状烯酮缩醛单体为2-亚甲基-1,3-二氧杂环庚烷,并且所述酸单体为含硫酸的单体或其盐。
4.根据权利要求3所述的组合物,其中所述含硫酸的单体或其盐选自由以下组成的组:2-丙烯酰胺基-2-甲基-1-丙磺酸、2-丙烯酰胺基-2-甲基-1-丙磺酸的盐、乙烯基磺酸、乙烯基磺酸的盐、丙烯酸2-磺乙酯、甲基丙烯酸2-磺乙酯、丙烯酸3-磺丙酯、甲基丙烯酸3-磺丙酯、2-丙烯-1-磺酸和2-丙烯-1-磺酸的盐。
5.根据权利要求4所述的组合物,其中所述含硫酸的单体或其盐为2-丙烯酰胺基-2-甲基-1-丙磺酸的盐。
6.根据权利要求1所述的组合物,其中所述共聚物粒子的z平均粒度在80nm到300nm范围内。
7.根据权利要求4所述的组合物,按所述聚合物粒子中2-亚甲基-1,3-二氧杂环庚烷的结构单元的重量计,所述组合物包含小于20重量%的乙酸4-羟丁酯。
8.根据权利要求7所述的组合物,按所述聚合物粒子中2-亚甲基-1,3-二氧杂环庚烷的结构单元的重量计,所述组合物包含小于10重量%的乙酸4-羟丁酯。
9.根据权利要求8所述的组合物,按所述聚合物粒子中2-亚甲基-1,3-二氧杂环庚烷的结构单元的重量计,所述组合物包含小于2重量%的乙酸4-羟丁酯。
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Publication number | Priority date | Publication date | Assignee | Title |
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US4812510A (en) * | 1986-04-17 | 1989-03-14 | The Glidden Company | Small particle size latex based on vinyl acetate polymers |
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CN104350091A (zh) * | 2012-06-06 | 2015-02-11 | 巴斯夫欧洲公司 | 水性聚阴离子-聚乙烯亚胺溶液用于制备具有氧气阻隔性能的聚合物膜的用途 |
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