JP2018536063A - 高耐熱性スチレン−アクリロニトリル樹脂及びその製造方法 - Google Patents
高耐熱性スチレン−アクリロニトリル樹脂及びその製造方法 Download PDFInfo
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- JP2018536063A JP2018536063A JP2018524404A JP2018524404A JP2018536063A JP 2018536063 A JP2018536063 A JP 2018536063A JP 2018524404 A JP2018524404 A JP 2018524404A JP 2018524404 A JP2018524404 A JP 2018524404A JP 2018536063 A JP2018536063 A JP 2018536063A
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Abstract
Description
本出願は、2016年11月1日付韓国特許出願第10-2016-0144510号に基づいた優先権の利益を主張し、当該韓国特許出願の文献に開示されている全ての内容は本明細書の一部として含まれる。
本発明が解決しようとする課題は、重合溶液の準備段階で、特定の温度でN-置換マレイミド単量体と不飽和ニトリル単量体の混合溶液を準備及び貯蔵することにより、N-置換マレイミド単量体と不飽和ニトリル単量体の副反応を抑制し、前記混合溶液を重合反応器にスチレン系単量体と分離して投入することにより、N-置換マレイミド単量体とスチレン系単量体の接触を防止し、PMI副産物を抑制してオリゴマーの含量を低減させることができるSAN樹脂の製造方法を提供することである。
1)N-置換マレイミド単量体及び不飽和ニトリル単量体の混合溶液を準備する段階;2)前記混合溶液及びスチレン系単量体を含む重合溶液を準備する段階;3)前記重合溶液を第1重合反応器及び第2重合反応器に順次投入して重合反応を行なう段階;及び、4)前記重合反応後、重合生成物を脱揮発槽に移送させる段階を含み、前記重合溶液は、混合溶液及びスチレン系単量体を第1重合反応器前端の撹拌槽に分離し投入して製造することを特徴とするSAN樹脂の製造方法を提供する。
1)N-置換マレイミド単量体及び不飽和ニトリル単量体の混合溶液を準備する段階;2)前記混合溶液及びスチレン系単量体を含む重合溶液を準備する段階;3)前記重合溶液を第1重合反応器及び第2重合反応器に順次投入して重合反応を行なう段階;及び、4)前記重合反応後、重合生成物を脱揮発槽に移送させる段階を含み、
前記重合溶液は、混合溶液及びスチレン系単量体を第1重合反応器前端の撹拌槽に分離し投入して製造することを特徴とする。
本発明の一実施形態に係る前記段階1)は、N-置換マレイミド単量体及び不飽和ニトリル単量体の混合溶液を準備するための段階であって、液状の不飽和ニトリル単量体に固相のN-置換マレイミド単量体を溶解させて製造することを特徴とする。
本発明の一実施形態に係る前記段階2)は、混合溶液及びスチレン系単量体を含む重合溶液を準備するための段階であって、段階1)で準備したN-置換マレイミド単量体及び不飽和ニトリル単量体の混合溶液とスチレン系単量体を混合して製造することができる。
本発明の一実施形態に係る前記段階3)は、重合生成物を製造するためのものであって、前記重合溶液を第1重合反応器及び第2重合反応器に順次投入して重合反応を行なうことを特徴とする。
本発明の一実施形態に係る前記段階4)は、重合反応後、重合生成物を脱揮発槽に移送させる段階であって、未反応単量体と反応溶媒を回収及び除去してペレット形態のSAN樹脂を製造することを特徴とする。
N-フェニルマレイミド(PMI)及びアクリロニトリル(AN)の混合溶液の総重量に対してN-フェニルマレイミド55重量部をアクリロニトリル45重量部に溶解し、PMI+AN 混合溶液を準備して61℃の温度で準備した。
下記表1でみるところのように前記実施例1の各条件を異にして、実施例2から5、比較例1から4のSAN樹脂を製造した。
前記実施例1から5、比較例1から4で製造した各樹脂の特性を比較分析するため、各樹脂に対して下記の分析を実施し、その結果を下記表1に示した。
各樹脂内のオリゴマーの含量はゲルクロマトグラフィーで分析した。
2)ガラス転移温度(℃)
ガラス転移温度(Tg)は、TA社のQ20示差走査型熱量計(DSC)を用いて各樹脂の10mgを昇温速度10/min、窒素フロー50cc/minの条件で測定した。
より具体的に、PMI+AN混合溶液を本発明の温度範囲で製造した実施例1または2の樹脂の場合、他の全ての条件は同一で、本発明より高い温度でPMI+AN混合溶液を製造した比較例1の樹脂に比べてオリゴマーの含量が大幅に減少し、ガラス転移温度が増加して耐熱性が改善されたことが分かる。
PMI+AN混合溶液及びスチレン系単量体を重合反応器に投入する前、反応器前端の撹拌槽(Static mixer)を通過させて均一に混合した重合溶液を投入した実施例1の樹脂の場合、撹拌槽を通過させていない比較例2の樹脂に比べてオリゴマーの含量が大幅に減少し、ガラス転移温度が増加して耐熱性が改善されたことが分かる。
第1及び第2重合反応器の温度を本発明の温度範囲に維持した実施例1または2の樹脂の場合、第1及び第2重合反応器の温度が本発明より高い比較例3または4の樹脂に比べてオリゴマーの含量が大幅に減少し、ガラス転移温度が増加して耐熱性が改善されたことが分かる。
Claims (14)
2)前記混合溶液及びスチレン系単量体を含む重合溶液を準備する段階;
3)前記重合溶液を第1重合反応器及び第2重合反応器に順次投入して重合反応を行なう段階;及び、
4)前記重合反応後、重合生成物を脱揮発槽に移送させる段階
を含み、
前記重合溶液は、混合溶液及びスチレン系単量体を前記第1重合反応器前端の撹拌槽に分離し投入して準備することを特徴とするSAN樹脂の製造方法。
前記SAN樹脂の100重量部に対してオリゴマーの含量が0.1から0.5重量部であるSAN樹脂。
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