TWI457353B - 高分子、高分子混摻物、與阻燃材料 - Google Patents

高分子、高分子混摻物、與阻燃材料 Download PDF

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TWI457353B
TWI457353B TW101116310A TW101116310A TWI457353B TW I457353 B TWI457353 B TW I457353B TW 101116310 A TW101116310 A TW 101116310A TW 101116310 A TW101116310 A TW 101116310A TW I457353 B TWI457353 B TW I457353B
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monomer
nitrogen
phosphorus
based monomer
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Lung Chang Liu
Po Jen Yang
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Description

高分子、高分子混摻物、與阻燃材料
本發明係關於耐燃材料，更特別關於其包含之耐燃劑結構。
阻燃劑(Flame retarder)是指添加於可燃性材料(如塑膠、橡膠、纖維、紙、木材等)中使其難以燃燒或是火燄不擴展的藥劑。近幾十年來應用阻燃劑的領域廣泛，舉凡各種民生化工與電子產品皆可見其應用。常見阻燃劑皆以鹵素為主，然而2006年7月1日歐盟頒布了RoHS(有害物質限用)指令規定在3C產業的用途上(如電腦、電視等產品中的基板與塑膠外殼等)禁用鹵素阻燃劑。開發高性能無鹵阻燃劑，以便未來法規趨嚴時能有所因應並保持競爭力，成為一重要課題。
本發明一實施例提供一種高分子，包括磷系單體聚合而成之聚合物、氮系單體聚合而成之聚合物、或磷系單體與氮系單體共聚而成之聚合物；其中磷系單體之結構如下：；R1 係氫、苯基、C1-12 之烷苯基、C1-12 之烷基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷基；R2 係苯撐基、C1-12 之烷苯撐基、C1-12 之烷撐基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷撐基；其中氮系單體之結構如下：；R3 係氫、苯基、C1-12 之烷苯基、C1-12 之烷基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷基；R4 係苯撐基、C1-12 之烷苯撐基、C1-12 之烷撐基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷撐基。
本發明一實施例提供一種高分子混摻物，係磷系單體聚合而成之聚合物、氮系單體聚合而成之聚合物、與該磷系單體與該氮系單體共聚而成之聚合物中至少二者之混摻物，其中該磷系單體之結構如下：
R1 係氫、苯基、C1-12 之烷苯基、C1-12 之烷基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷基；R2 係苯撐基、C1-12 之烷苯撐基、C1-12 之烷撐基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷撐基；其中該氮系單體之結構如下：
R3 係氫、苯基、C1-12 之烷苯基、C1-12 之烷基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷基；R4 係苯撐基、C1-12 之烷苯撐基、C1-12 之烷撐基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷撐基。
本發明一實施例提供一種阻燃材料，包括：磷系單體聚合而成之聚合物、氮系單體聚合而成之聚合物、磷系單體與氮系單體共聚而成之聚合物、或上述至少二者之混掺物；其中磷系單體之結構如下：；R1 係氫、苯基、C1-12 之烷苯基、C1-12 之烷基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷基；R2 係苯撐基、C1-12 之烷苯撐基、C1-12 之烷撐基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷撐基；其中氮系單體之結構如下：；R3 係氫、苯基、C1-12 之烷苯基、C1-12 之烷基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷基；R4 係苯撐基、C1-12 之烷苯撐基、C1-12 之烷撐基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷撐基；以及熱固性樹脂，其中無鹵阻燃劑與熱固性樹脂之重量比約介於1:1至1:200之間。
本發明一實施例提供一種阻燃材料，包括:磷系單體聚合而成之聚合物、氮系單體聚合而成之聚合物、磷系單體與氮系單體共聚而成之聚合物、或上述至少二者之混掺物；其中磷系單體之結構如下：；R1 係氫、苯基、C1-12 之烷苯基、C1-12 之烷基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷基；R2 係苯撐基、C1-12 之烷苯撐基、C1-12 之烷撐基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷撐基；其中氮系單體之結構如下：；R3 係氫、苯基、C1-12 之烷苯基、C1-12 之烷基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷基；R4 係苯撐基、C1-12 之烷苯撐基、C1-12 之烷撐基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷撐基；以及熱塑性樹脂，其中無鹵阻燃劑與熱塑性樹脂之重量比約介於1:1至1:200之間。
本發明一實施例中，取磷系單體如式1聚合形成的高分子作為無鹵阻燃劑。
在式1中，R1 係氫、苯基、C1-12 之烷苯基、C1-12 之烷基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷基；R2 係苯撐基、C1-12 之烷苯撐基、C1-12 之烷撐基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷撐基。
本發明一實施例中，取氮系單體如式2聚合形成的高分子作為無鹵耐燃劑。
在式2中，R3 係氫、苯基、C1-12 之烷苯基、C1-12 之烷基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷基；R4 係苯撐基、C1-12 之烷苯撐基、C1-12 之烷撐基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷撐基。
在本發明一實施例中，取氮系單體與磷系單體共聚形成之高分子作為無鹵阻燃劑。在此實施例中，氮系單體與磷系單體之莫耳比約介於1:1至1:10之間。上述聚合物之阻燃效果，優於氮系單體之聚合物與磷系單體之聚合物。若聚合物中氮系單體之莫耳比例過低，則聚合物之阻燃效果將與磷系單體之聚合物類似。若聚合物中磷系單體之莫耳比例過低，則聚合物之阻燃效果將與氮系單體之聚合物類似。
本發明一實施例中，混合氮系單體之聚合物與磷系單體之聚合物，以作為無鹵阻燃劑；其中氮系單體之聚合物與磷系單體之聚合物的重量比約為1:1~1:5。
在本發明一實施例中，混合氮系單體之聚合物、磷系單體之聚合物、與氮系單體與磷系單體之聚合物中至少兩者，以作為無鹵阻燃劑。
上述之聚合物之重量平均分子量約介於1,000至1,000,000之間或約介於5,000至15,000之間。若聚合物或聚合物之重量平均分子量過高，則缺乏加工性。若聚合物或聚合物之重量平均分子量過低，則缺乏阻燃性與耐熱性。
在本發明一實施例中，上述之磷系單體之結構如式3所示：
在本發明一實施例中，上述之氮系單體之結構如式4所示：
上述之無鹵阻燃劑可進一步與熱塑性樹脂或熱固性樹脂混合，以形成阻燃材料。熱塑性樹脂可為聚醯胺、聚烯烴(如C2~C6的聚烯烴)、或苯乙烯-乙烯-丁二烯-苯乙烯共聚物。熱固性樹脂可為環氧樹脂。當阻燃材料包含熱固性樹脂與無鹵阻燃劑時，無鹵阻燃劑與該熱固性樹脂之重量比介約於1:1至1:200之間或約介於1:1至1:10。當阻燃材料包含熱塑性樹脂與無鹵阻燃劑時，無鹵阻燃劑與該熱塑性樹脂之重量比約介於1:1至1:200之間或約介於1:1至1:10。若無鹵阻燃劑之比例過高，則固含量過多而無法加工。若無鹵阻燃劑之比例過低，則無法使阻燃材料具有足夠的阻燃效果。值得注意的是，上述無鹵阻燃劑與熱固性樹脂(或熱塑性樹脂)彼此混合，兩者之間並未產生交聯或具有共價鍵結。
在本發明一實施例中，上述之阻燃材料可進一步含有其他添加劑，比如加工助劑、顏料、其他市售阻燃劑、或其他常見添加劑。
為了讓本發明之上述和其他目的、特徵、和優點能更明顯易懂，下文特舉數實施例配合所附圖示，作詳細說明如下：
【實施例】
合成例1
將9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(100.0克，0.46莫耳(Aldrich Co.))置於2公升圓底瓶內，加入600毫升的乙醇中攪拌溶解，再加入300毫升的雙氧水溶液，加熱迴流反應12小時，運用薄層色層分析法，點片追蹤確定反應完全。冷卻至室溫，利用真空旋轉濃縮機移除溶劑，用異丙醇和水(3比1體積比)再結晶，過濾取固體；將過濾物放入真空乾燥箱乾燥，得到白色固體，產率為95%。上述反應如式5，而產物之氫譜如下：1 H NMR(400 MHz,DMSO-d 6 ,ppm): 4.41(s,1H),7.23-7.31(m,2H),7.41-7.56(m,2H),7.72-7.83(m,2H),8.11-8.15(m,2H).
取式5產物(50.0克，0.22莫耳)置於500毫升雙頸瓶內，在氮氣系統下先加入300毫升的無水四氫呋喃混合攪拌溶解，隨後加入甲基丙烯酸缩水甘油酯(39.8克，0.28莫耳(Adrich Co.))攪拌均勻，再打入液狀催化劑N,N-二甲基苄胺(0.87克，6.5毫莫耳)，加熱至70℃後反應一天。運用薄層色層分析法，點片追蹤確定反應完全。冷卻至室溫，利用真空旋轉濃縮機移除溶劑，以正己烷洗滌，用真空抽器乾燥，得到半透明黏稠液體，產率85%。上述反應如式6，而產物之氫譜如下：1 H NMR(400 MHz,CDCl3 ,ppm): 1.90(s,3H),1.96(s,1H),3.45-3.50(m,2H),4.10-4.19(m,3H),5.55(s,1H),6.07(s,1H),7.23-7.30(m,2H),7.40-7.53(m,2H),7.74-8.00(m,4H).
取式6之化合物(50.0克，0.13莫耳)和催化劑2,2'-二氰基-2,2'-偶氮丙烷(1.2克，6.7毫莫耳)置於1公升圓底瓶內，在氮氣系統下，加入500毫升的無水四氫呋喃混合攪拌溶解，加熱至65℃後反應一天。將反應後之混合物冷卻至室溫，再倒入到乙醚中並析出大量白色固體。將乙醚懸浮液過濾後，取濾餅放入真空乾燥箱乾燥，得到白色固體，產率為80%。上述反應如式7，而產物重量平均分子量為8,600，其氫譜如下：1 H NMR(400 MHz,DMSO-d 6 ,ppm): 0.67(br,5H),3.80-3.97(br,m,4H),5.28-5.40(br,m,1H),7.21-7.34(br,m,3H),7.49(br,1H),7.69(br,1H),7.85(br,1H),8.19(br,2H).
合成例2
將4-羥基苯甲腈(50.0克，0.42莫耳(Adrich Co.))、碳酸鉀(116.0克，0.84莫耳)和碘化鉀(5.0克，30毫莫耳)置於1公升圓底瓶內，加入600毫升的丙酮混合攪拌，然後慢慢滴入4-氯甲基苯乙烯(78.3克，0.51莫耳(Adrich Co.))加熱迴流48小時，運用薄層色層分析法，點片追蹤確定反應完全。冷卻至室溫，過濾並用丙酮洗滌取濾液，真空旋轉濃縮移除溶劑，再利用真空旋轉濃縮機移除溶劑，最後以正己烷再結晶，過濾取固體。將過濾物放入真空乾燥箱乾燥，得到白色固體，產率為93%。上述反應如式8，而產物之氫譜如下：1 H NMR(400 MHz,CDCl3 ,ppm): 5.10(s,2H),5.28(d,J =14.5 Hz,1H),5.77(d,J =23.4 Hz,1H),6.73(dd,J 1 =14.5 Hz,J 2 =23.4 Hz,3H),7.02(d,J =9.1 Hz,2H),7.37(d,J =10.9 Hz,2H),7.44(d,J =10.9 Hz,2H),7.59(d,J =9.1 Hz,2H).
將式8之產物(40.0克，0.17莫耳)和氫氧化鉀(38.1克，0.68莫耳)置於500毫升圓底瓶內，加入160毫升的乙二醇甲醚混合攪拌，然後慢慢加入氰基胍(78.3克，0.51莫耳)加熱至90℃後反應8小時，運用薄層色層分析法，點片追蹤確定反應完全。冷卻至室溫，倒入到冰水中，此時大量白色固體析出，過濾並用水洗滌取固體，在用異丙醇和水(5比1體積比)再結晶，過濾取固體；將過濾物放入真空乾燥箱乾燥，得到白色固體，產率為88%。上述反應如式9，而產物之氫譜如下：1 H NMR(400 MHz,DMSO-d 6 ,ppm): 5.14(s,2H),5.26(d,J =10.9 Hz,1H),5.84(d,J =17.7 Hz,1H),6.66(s,4H),6.73(dd,J 1 =10.9 Hz,J 2 =17.7 Hz,1H),7.07(d,J =8.8 Hz,2H),7.43(d,J =8.1 Hz,2H),7.49(d,J =8.1 Hz,2H),8.19(d,J =8.8 Hz,2H).
取式4之化合物(50.0克，0.15莫耳)和催化劑2,2'-二氰基-2,2'-偶氮丙烷(AIBN,1.3克，7.6毫莫耳)置於1公升圓底瓶內，在氮氣系統下，加入500毫升的無水二甲基甲醯胺混合攪拌溶解，加熱至65℃後反應一天。冷卻至室溫，倒入到甲醇中大量白色析出，過濾取固體。將過濾物放入真空乾燥箱乾燥，得到白色固體，產率為75%。上述反應如式10，而產物重量平均分子量為11,500，其氫譜如下：1 H NMR(400 MHz,DMSO-d 6 ,ppm): 1.65(br,2H),4.93(br,2H),6.63(br,6H),6.92(br,m,4H),8.18(br,2H).
合成例3
取式3之化合物(25.0克，66毫莫耳)、式4之化合物(21.3克，66毫莫耳)、和催化劑2,2'-二氰基-2,2'-偶氮丙烷(1.1克，6.8毫莫耳)置於1公升圓底瓶內，在氮氣系統下，加入460毫升的無水二甲基甲醯胺混合攪拌溶解，加熱於65度下反應一天。冷卻至室溫，倒入到甲醇和乙醚(4/1體積比)中大量白色析出，過濾取固體。將過濾物放入真空乾燥箱乾燥，得到白色固體，產率為60%。上述反應如式11，而產物重量平均分子量為12,500，其氫譜如下：1 H NMR(400 MHz,DMSO-d 6 ,ppm): 0.66-1.60(br,m,8H),3.74-3.96(br,m,4H),4.93-5.27(br,m,3H),6.48-7.62(br,m,12H),7.83-7.94(br,m,4H),8.11-8.18(br,4H).
在式11中，m與n的比例為1:1，且式11之產物為無規聚合物。
實施例1
取50重量份之聚丙烯(購自李長榮化工之PT100)、50重量份之苯乙烯-乙烯-丁二烯-苯乙烯共聚物(SEBS，購自台化之3151)、不同重量份之式7的產物、不同重量份之式10的產物、不同重量份之式11的產物、不同重量份之DOPO、不同重量份之三聚氰胺、不同重量份之聚磷酸銨(恆橋APP-1)，混合後以熱壓成型法(190℃，5~10分鐘)製成12.5 cm×1.3 cm×0.3 cm之試片，上述試片組成如第1表所示。
接著測量試片的分解溫度(Td ，熱重損失5%的溫度)、800℃下的成碳量、氧極限指數(LOI)、UL-94-V、以及加熱至190℃後的試片外觀、及加熱至90℃下兩天後的試片外觀，如第2表所示。
在第1表中，批次a至e採用合成例1-3的產物作為阻燃劑，而批次f至h採用DOPO、三聚氰胺、或聚磷酸銨作為阻燃劑。由第2表之比對可知，本發明之阻燃劑在高溫下的外觀不會有出油(blooming)的現象，且均具有250℃之熱分解溫度(Td )。
雖然本發明已以數個較佳實施例揭露如上，然其並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之精神和範圍內，當可作任意之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。

Claims (10)

  1. 一種高分子，包括一氮系單體聚合而成之聚合物、或一磷系單體與該氮系單體共聚而成之聚合物；其中該磷系單體之結構如下： R1 係氫、苯基、C1-12 之烷苯基、C1-12 之烷基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷基；R2 係苯撐基、C1-12 之烷苯撐基、C1-12 之烷撐基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷撐基；其中該氮系單體之結構如下： R3 係氫、苯基、C1-12 之烷苯基、C1-12 之烷基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷基；R4 係苯撐基、C1-12 之烷苯撐基、C1-12 之烷撐基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷撐基，其中該磷系單體與該氮系單體共聚而成之聚合物之中，該磷系單體與該氮系單體之莫耳比介於1：1至10：1之間。
  2. 如申請專利範圍第1項所述之高分子，其中該磷系 單體之結構如下：
  3. 如申請專利範圍第1項所述之高分子，其中該氮系單體之結構如下：
  4. 如申請專利範圍第1項所述之高分子，其中該磷系單體聚合而成之聚合物、該氮系單體聚合而成之聚合物、或該磷系單體與該氮系單體共聚而成之聚合物的重均分子量介於1,000至1,000,000之間。
  5. 一種高分子混摻物，係一磷系單體聚合而成之聚合物、一氮系單體聚合而成之聚合物、與該磷系單體與該氮系單體共聚而成之聚合物中至少二者之混摻物，其中該磷系單體之結構如下： R1 係氫、苯基、C1-12 之烷苯基、C1-12 之烷基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷基；R2 係苯撐基、C1-12 之烷苯撐基、C1-12 之烷撐基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷撐基；其中該氮系單體之結構如下： R3 係氫、苯基、C1-12 之烷苯基、C1-12 之烷基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷基；R4 係苯撐基、C1-12 之烷苯撐基、C1-12 之烷撐基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷撐基，其中該磷系單體與該氮系單體共聚而成之聚合物之中，該磷系單體與該氮系單體之莫耳比介於1：1至10：1之間。
  6. 如申請專利範圍第5項所述之高分子混摻物，係1重量份之該氮系單體聚合而成之聚合物與1至5重量份之該磷系單體聚合而成之聚合物之混摻物。
  7. 一種阻燃材料，包括：一磷系單體聚合而成之聚合物、一氮系單體聚合而成之聚合物、該磷系單體與該氮系單體共聚而成之聚合物、或上述至少二者之混掺物；其中該磷系單體之結構如下： R1 係氫、苯基、C1-12 之烷苯基、C1-12 之烷基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷基；R2 係苯撐基、C1-12 之烷苯撐基、C1-12 之烷撐基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷撐基；其中該氮系單體之結構如下： R3 係氫、苯基、C1-12 之烷苯基、C1-12 之烷基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷基；R4 係苯撐基、C1-12 之烷苯撐基、C1-12 之烷撐基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷撐基；以及一熱固性樹脂，其中該無鹵阻燃劑與該熱固性樹脂之重量比介於1：1至1：200之間，其中該磷系單體與該氮系單體共聚而成之聚合物之中，該磷系單體與該氮系單體之莫耳比介於1：1至10：1之間。
  8. 如申請專利範圍第7項所述之阻燃材料，其中該熱 固性樹脂包括環氧樹脂。
  9. 一種阻燃材料，包括：一磷系單體聚合而成之聚合物、一氮系單體聚合而成之聚合物、該磷系單體與該氮系單體共聚而成之聚合物、或上述至少二者之混掺物；其中該磷系單體之結構如下： R1 係氫、苯基、C1-12 之烷苯基、C1-12 之烷基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷基；R2 係苯撐基、C1-12 之烷苯撐基、C1-12 之烷撐基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷撐基；其中該氮系單體之結構如下： R3 係氫、苯基、C1-12 之烷苯基、C1-12 之烷基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷基；R4 係苯撐基、C1-12 之烷苯撐基、C1-12 之烷撐基、C1-12 之醚基、C1-12 之烷醇基、或C1-12 之羥基烷撐基；以及一熱塑性樹脂， 其中該無鹵阻燃劑與該熱塑性樹脂之重量比介於1：1至1：200之間，其中該磷系單體與該氮系單體共聚而成之聚合物之中，該磷系單體與該氮系單體之莫耳比介於1：1至10：1之間。
  10. 如申請專利範圍第9項所述之阻燃材料，其中該熱塑性樹脂包括聚醯胺、聚烯烃、或苯乙烯-乙烯-丁二烯-苯乙烯聚合物。
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