CN101077899B - 乙烯基吡咯烷酮聚合物的制造方法 - Google Patents
乙烯基吡咯烷酮聚合物的制造方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims description 15
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F26/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F26/06—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
- C08F26/10—N-Vinyl-pyrrolidone
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/10—Aqueous solvent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
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Abstract
本发明提供可得到稳定性优异的乙烯基吡咯烷酮聚合物的制造方法。该方法是在溶液中使用自由基聚合引发剂使乙烯基吡咯烷酮单体进行聚合的乙烯基吡咯烷酮聚合物的制造方法,其中,使用2,2'-偶氮双(2-甲基丁腈)作为自由基引发剂进行聚合,乙烯基吡咯烷酮单体的聚合率达到99.80%以上后,通过添加作为选自柠檬酸、乳酸以及丙二酸的1种或2种以上的混合物的有机酸使pH为2~5而水解残留的单体,水解后添加碳酸胍以及三乙醇胺进行中和。
Description
技术领域
本发明涉及乙烯基吡咯烷酮聚合物的制造方法,特别涉及可得到保存稳定性优异的乙烯基吡咯烷酮聚合物的制造方法。
背景技术
已知乙烯基吡咯烷酮聚合物,无论是粉体还是溶液,与其形态无关,通常储藏稳定性存在问题。作为其对策,例如在特开2003-1 38087号公报中提出了通过添加胍类以及/或者双胍类、以使得即使在K值低的情况下也能抑制着色的进行了稳定化处理了的的乙烯基吡咯烷酮聚合物组合物,此处所谓的K值,是指德国的化学家费肯歇尔(Fikentscher)提出的表示聚合度的常数。
【专利文献1】特开2003-138087号公报
发明内容
但是,采用上述方法得到的乙烯基吡咯烷酮聚合物的稳定性提高效果不充分,存在因长期保存而产生着色、或需要添加大量的胍类或者双胍类的问题。
本发明鉴于上述问题而做出的发明,目的是提供可得到保存稳定性进一步提高的、长期维持良好色相的乙烯基吡咯烷酮聚合物的制造方法。
本发明的乙烯基吡咯烷酮聚合物的制造方法,是在溶液中使用自由基聚合引发剂使乙烯基吡咯烷酮单体进行聚合的乙烯基吡咯烷酮聚合物的制造方法,其中,使用2,2′-偶氮双(2-甲基丁腈)作为自由基引发剂进行聚合,乙烯基吡咯烷酮单体的聚合率达到99.80%以上后,通过添加选自柠檬酸、乳酸以及丙二酸的1种或2种以上的混合物这样的有机酸使pH达到2~5而水解残留的单体,水解后添加碳酸胍以及三乙醇胺进行中和。
在上述制造方法中,聚合时优选相对于乙烯基吡咯烷酮单体添加0.10~10重量%的异丙醇。
碳酸胍的添加量优选相对于乙烯基吡咯烷酮单体为100~5000重量ppm,三乙醇胺的添加量优选相对于乙烯基吡咯烷酮单体为100~5000重量ppm。
根据本发明,可特别得到K值为60~130、而且残留的单体量为100ppm以下的乙烯基吡咯烷酮聚合物。该乙烯基吡咯烷酮聚合物,保存稳定性进一步提高,即使长期保存色相也不变化。
具体实施方式
通过本发明制造的乙烯基吡咯烷酮聚合物,是乙烯基吡咯烷酮(N-乙烯基-2-吡咯烷酮,以下也记做VP)的均聚物或者VP和其它单体的共聚物。其它的单体只要是能和VP共聚就可以,不受特别限定,作为例子,有丙烯酸、甲基丙烯酸、丙烯酸的烷基酯(丙烯酸甲酯、丙烯酸乙酯等)、甲基丙烯酸的烷基酯(甲基丙烯酸甲酯、甲基丙烯酸乙酯等)、丙烯酸的氨基烷基酯(丙烯酸二乙氨基乙酯等)、甲基丙烯酸的氨基烷基酯、丙烯酸和二元醇的单酯、甲基丙烯酸和二元醇的单酯(甲基丙烯酸羟乙基酯等)、丙烯酸的碱金属盐、甲基丙烯酸的碱金属盐、丙烯酸的铵盐、甲基丙烯酸的铵盐、丙烯酸的氨基烷基酯的季铵衍生物、甲基丙烯酸的氨基烷基酯的季铵衍生物、丙烯酸二乙氨基乙酯和硫酸二甲酯的季铵化合物、乙烯基甲基醚、乙烯基乙基醚、乙烯基磺酸的碱金属盐、乙烯基磺酸的铵盐、苯乙烯磺酸、苯乙烯磺酸盐、烯丙基磺酸、烯丙基磺酸盐、甲代烯丙基磺酸、甲代烯丙基磺酸盐、乙酸乙烯酯、硬脂酸乙烯酯、N-乙烯基咪唑、N-乙烯基乙酰胺、N-乙烯基甲酰胺、N-乙烯基己内酰胺、N-乙烯基咔唑、丙烯酰胺、甲基丙烯酰胺、N-烷基丙烯酰胺、N-羟甲基丙烯酰胺、N,N-亚甲基双丙烯酰胺、二丙烯酸乙二酯、二甲基丙烯酸乙二酯、二乙烯基苯、乙二醇二烯丙基醚等。
乙烯基吡咯烷酮和其它的单体的比例不受特别限定,但是如果VP的比例太小,与本发明的目的相违背,因此作为目标,VP的比例为20重量%以上。
VP的聚合或者VP和其它的单体的共聚,可通过溶液聚合进行。作为溶剂,优选水或者水系溶剂。所谓的水系溶剂,意思是指能和水相互混合的化合物的1种或者2种以上的混合溶剂、或者在这样化合物中以水为主要成分进行混合了的混合溶剂。作为能和水相互混合的化合物,可例举例如甲醇、乙醇、1-丙醇等的醇,乙二醇等的二醇,丙三醇等的三醇类等的多元醇等。
作为溶液的浓度,以VP的浓度表示优选10~45重量%,更优选15~30重量%。如果浓度变低,生产率差、有导致成本增加的倾向,如果浓度变高,聚合中,随着时间的增加粘度变高,搅拌变得困难,容易对反应产生障碍。
在本发明的制造方法中,为了得到保存稳定性优异的乙烯基吡咯烷酮聚合物,在使用2,2′-偶氮双(2-甲基丁腈)作为引发剂聚合了的乙烯基吡咯烷酮聚合物中,添加有机酸、碳酸胍以及三乙醇胺。
特别优选以下的方法,即在溶液中使用2,2′-偶氮双(2-甲基丁腈)作为自由基聚合引发剂聚合后,用有机酸使pH为2~5,水解残留的单体,用碳酸胍以及三乙醇胺进行中和。这是因为如果先添加碳酸胍以及三乙醇胺、水溶液变成碱性,会引起着色。
2,2′-偶氮双(2-甲基丁腈)相对于乙烯基吡咯烷酮单体,优选添加0.01~1.0重量%。如果不到0.01重量%,稳定性下降,如果超过1.0重量%,难以透明地溶解在水中。
另外,优选分2次以上添加2,2′-偶氮双(2-甲基丁腈)。通过增加添加的次数可减少引发剂的量。
予以说明的是,可以直接添加2,2′-偶氮双(2-甲基丁腈),也可以将其溶解于甲醇、乙醇、异丙醇等的有机溶剂中添加。其中,优选异丙醇,根据的理由如下。
即、在本发明中,通过添加相对于单体为0.10~10重量%的异丙醇,可进一步改善色相。如果添加不到0.10重量%,得不到所希望的效果,如果添加超过10.0重量%,产生聚合速度变慢这样的问题。
进行聚合后,在乙烯基吡咯烷酮单体的聚合率达到99.00%以上、优选99.80%以上时,添加有机酸使反应液的pH为2~5,水解残留的单体。
作为有机酸,可使用柠檬酸、乳酸、丙二酸、甲酸、乙酸、苹果酸等,从特别提高稳定性方面考虑,优选使用柠檬酸、乳酸以及丙二酸中的任意1种或者2种以上的混合物。
水解后,通过同时使用碳酸胍以及三乙醇胺对反应液进行中和,乙烯基吡咯烷酮聚合物的稳定性和色相变得良好。
碳酸胍的使用量,相对于乙烯基吡咯烷酮单体优选为100~5000重量ppm,更优选200~2000重量ppm。如果不到100重量ppm,稳定性下降,如果超过5000重量ppm,随着时间变得难以透明地溶于水中。
三乙醇胺的使用量,相对于乙烯基吡咯烷酮单体优选为100~5000重量ppm,更优选200~3500重量ppm。如果不到100重量ppm,稳定性下降,如果超过5000重量ppm,随着时间色相变差。
实施例
以下对本发明的实施例进行说明,但本发明并不受以下的实施例的限定。
[实施例1]
将VP400kg、水1600kg加入到容量约2.5m3的带夹套的釜中。一边进行氮气清洗(purge)一边加热至70℃,将相对于VP为0.10重量%(400g)的V-59(化合物名:2,2′-偶氮双(2-甲基丁腈)、和光纯药工业(株)制)(第一次)形成10%异丙醇溶液后添加,开始聚合。1小时后,反应液因反应热达到90℃。之后,在聚合结束前在夹套中使温水流动以使得反应液达到90~99℃。从反应开始计2小时后,进一步将相对于VP为0.1重量%(400g)的V-59(第二次)形成10%的异丙醇溶液添加,确认聚合率为99.81%,添加相对于VP为2000重量ppm(800g)的90%乳酸,使反应液的pH为4.2,保持2小时加热。然后,添加1500重量ppm(600g)的碳酸胍和3000重量ppm(1200g)的三乙醇胺。结果,得到残留的VP为3ppm、K值为90、10%APHA(固形分浓度为10%的水溶液APHA,以下同样)为10的乙烯基吡咯烷酮聚合物。
[实施例2]
和实施例1同样开始聚合,确认聚合率为99.90%后,添加相对于VP为1000重量ppm(400g)的丙二酸,使反应液的pH为3.6,保持2小时加热。然后,添加1000重量ppm(400g)的碳酸胍和1500重量ppm(600g)的三乙醇胺。结果,得到残留的VP为4ppm、K值为92、10%APHA为10的乙烯基吡咯烷酮聚合物。
[实施例3]
和实施例1同样开始聚合,确认聚合率为99.95%后,添加相对于VP为500重量ppm(200g)的柠檬酸,使反应液的pH为4.9,保持2小时加热。然后,添加200重量ppm(80g)的碳酸胍和200重量ppm(80g)的三乙醇胺。结果,得到残留的VP为8ppm、K值为94、10%APHA为10的乙烯基吡咯烷酮聚合物。
[实施例4]
用鼓式干燥器对实施例1得到的乙烯基吡咯烷酮聚合物(液体产品)进行干燥,用粉碎机粉末化,粉末化了的乙烯基吡咯烷酮聚合物的K值为94。
[比较例1]
将实施例1的V-59(第一次)改成苯甲酰基过氧化物(benzoylperoxide)、添加相对于VP的0.30重量%(1200g),开始聚合。1小时后,反应液因反应热达到93℃。之后,在聚合结束前在夹套中使温水流动以使得反应液为90~99℃。从反应开始计2小时后,将实施例1的V-59(第二次)改成苯甲酰过氧化物、添加相对于VP的0.30重量%(1200g)。其结果,得到残留的VP为4ppm、K值为82、10%APHA为10的乙烯基吡咯烷酮聚合物。
[比较例2]
除了用三乙醇胺全部代替碳酸胍以外,进行和实施例1同样的操作,其结果得到残留的VP为6ppm、K值为91、10%APHA为10的乙烯基吡咯烷酮聚合物。
[比较例3]
除了用碳酸胍全部代替三乙醇胺以外,进行和实施例1同样的操作,其结果得到残留的VP为3ppm、K值为90、10%APHA为10的乙烯基吡咯烷酮聚合物。
[评价]
在氮气气流下在60℃下保管3周,测定保管后的K值以及色相(固形分浓度为10%的水溶液APHA),对比保管前后的变化,结果示于表1中。
予以说明的是,K值通过以下的测定方法求出。即、在K值不到20的情况下测定固形分浓度为5%(g/100ml)溶液的粘度,在K值为20以上的情况下测定固形分浓度为1%(g/100ml)溶液的粘度。K值在20以上的情况精密地测定1.0g的试样,加入到100ml的容量瓶中,在室温下加入蒸馏水,一边振荡一边使其完全溶解,加入蒸馏水准确至100ml。在恒温槽中(2 5±0.2℃)中放置该试样溶液30分钟后,使用乌波劳德(Ubbelohde)型粘度计测定使试样溶液流过2个印线之间的时间(流动时间),测定数次,取平均值。为了转化成相对粘度,即使对于蒸馏水也进行同样的测定。根据Hagenbach-Couette的修正值对2个得到的流动时间进行修正。
【数1】
上述式中,C表示试样的浓度(%:g/100ml),Z表示浓度C的溶液的相对粘度(ηrel)。相对粘度ηrel通过下式得到。
ηrel=(溶液的流动时间)÷(水的流动时间)
另外,色相是调制固形分浓度为10%的水溶液,测定黑氏色值(Hazen color number)。
固形分,是使用通过在140℃下减压1小时求出的减少量(wt%)、根据下式求出;
固形分(%)=100-减少量(%)
表1
通过本发明得到的乙烯基吡咯烷酮聚合物即使经过长期保存色相也不变化,因此可以在化妆品用途等重视色相的领域中使用。
Claims (2)
1.一种乙烯基吡咯烷酮聚合物的制造方法,其是在溶液中使用自由基聚合引发剂使乙烯基吡咯烷酮单体进行聚合的乙烯基吡咯烷酮聚合物的制造方法,其特征在于,作为自由基聚合引发剂使用2,2′-偶氮双(2-甲基丁腈)进行聚合,乙烯基吡咯烷酮单体的聚合率达到99.80%以上后,通过添加作为选自柠檬酸、乳酸以及丙二酸的1种或2种以上的混合物的有机酸使pH达到2~5而水解残留的单体,水解后添加碳酸胍以及三乙醇胺进行中和,上述碳酸胍的添加量相对于乙烯基吡咯烷酮单体为100~5000重量ppm,三乙醇胺的添加量相对于乙烯基吡咯烷酮单体为100~5000重量ppm。
2.如权利要求1所述的乙烯基吡咯烷酮聚合物的制造方法,其特征在于,在上述聚合时,添加相对于乙烯基吡咯烷酮单体为0.10~10重量%的异丙醇。
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