TW201722978A - 含磷化合物及其應用與製法 - Google Patents

含磷化合物及其應用與製法 Download PDF

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TW201722978A
TW201722978A TW104144142A TW104144142A TW201722978A TW 201722978 A TW201722978 A TW 201722978A TW 104144142 A TW104144142 A TW 104144142A TW 104144142 A TW104144142 A TW 104144142A TW 201722978 A TW201722978 A TW 201722978A
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phosphorus
resin
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劉英麟
許智淵
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國立清華大學
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    • C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
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    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
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    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
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Abstract

一種含磷化合物，如下式(Ⅲ)所示：□式(Ⅲ) 在式(Ⅲ)中，n及R1~R3的定義如說明書所述。本發明含磷化合物可有效提升樹脂的難燃性質，且可確保樹脂的熱穩定性。本發明亦提供該含磷化合物的應用及一種該含磷化合物的製法。

Description

含磷化合物及其應用與製法
本發明是有關於一種含磷化合物，特別是指一種核心結構為1個具有反應基團的苯環帶有2個DOPO的含磷化合物及其應用與製法。
為使高分子材料(如環氧樹脂、酚醛樹脂)具備高的難燃性質，傳統上多使用鹵素化合物作為難燃劑，但因應環保要求，無鹵(halogen-free)的難燃劑已成為開發難燃高分子材料的必要條件，因此，市面上的產品多採用磷酸酯(phosphate)與膦酸酯(phosphonate)為主的磷系難燃劑。但使用上述磷系難燃劑時往往會面臨耐熱性(熱穩定性)及耐水解性不良的問題，因此，可避免上述問題的9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide，以下簡稱DOPO)的衍生物成為主要的發展對象。
另一方面，為了能使用於熱固性樹脂之電子材料，難燃劑需要具有可以和熱固性樹脂反應的化學基團，即反應型(reactive type)難燃劑。
TW 572954公開一種可作為反應型難燃劑的含磷化合物，其化學結構如下所示：
然而，其核心結構為2個具有反應基團的苯環帶有2個DOPO，且其磷含量僅為9.86 wt%，難燃劑的磷含量對於其難燃效果呈正相關。
TW 201302771 A公開二種可作為反應型難燃劑的含磷化合物，其化學結構分別如下所示：
其磷含量分別為11.25 wt%及10.86 wt%，但合成該二化合物之反應物不易取得，又其DOPO是位在酚基(反應基團)的鄰位，會對於酚基的後續反應造成立體障礙，降低其作為反應型難燃劑時的反應性。
TW 201136984 A公開一種可作為反應型難燃劑的含磷寡聚物，其化學結構如下所示：
然而，其為n個具有反應基團的苯環帶有(n+1)個DOPO之寡聚物的混合物，並非純化合物，且其是分別在120℃及180℃下分段反應而得。
因此，本發明之第一目的，即在提供一種含磷化合物，可提升樹脂的難燃性及確保樹脂的熱穩定性。
於是，本發明含磷化合物如下式(Ⅲ)所示： 【化學式1】式(Ⅲ)
在式(Ⅲ)中，n 為1~4；R1 表示氫或C1 ~C4 直鏈或支鏈烷基，當n ≧2時，多個R1 可為相同或不同；R2 表示氫、或透過連接的環氧樹脂；或表示，其中，Ar 表示C1 ~C12 直鏈或支鏈烷基或C6 ~C12 芳基；及R3 表示氫或甲基。
本發明之第二目的，即在提供一種難燃樹脂組成物，包含如上所述的含磷化合物及一樹脂。
本發明之第三目的，即在提供一種經硬化的難燃樹脂，包含由如上所述的難燃樹脂組成物進行硬化而得的難燃樹脂。
本發明之第四目的，即在提供一種如上所述的含磷化合物的製法，包含：使如下式(Ⅰ)所示的對-羥基苯甲醯基衍生物與如下式(Ⅱ)所示的氧雜磷雜菲氧化物在190~250℃且無溶劑的環境下進行反應； 【化學式2】式(Ⅰ) 【化學式3】式(Ⅱ)
在式(Ⅰ)中，n 、R1 及R3 的定義如上所述，且該對-羥基苯甲醯基衍生物與該氧雜磷雜菲氧化物的莫耳數比範圍為1：2~1：5.5。
本發明含磷化合物之功效在於：藉由其核心結構及較高的磷含量，可有效提升樹脂的難燃性，並確保樹脂的熱穩定性。
以下將就本發明內容進行詳細說明：
較佳地，在本發明的含磷化合物中，R2 表示氫。
較佳地，在本發明的含磷化合物中，R1 表示氫。
較佳地，在本發明的含磷化合物中，R3 表示氫。
較佳地，在本發明的含磷化合物中，Ar 表示苯基。
較佳地，該環氧樹脂是選自於環氧改性(甲)酚醛樹脂、雙酚A環氧樹脂、雙酚F環氧樹脂、脂肪族環氧樹脂或縮水甘油胺樹脂。在本發明的具體實施例中，該環氧樹脂是環氧改性甲酚醛樹脂(cresol-novolac epoxy)。
較佳地，在本發明的難燃樹脂組成物中，該樹脂為熱固性樹脂。
較佳地，在本發明的含磷化合物的製法中，該反應的溫度範圍為200~220℃。以利於一步合成核心結構為1個具有反應基團的苯環帶有2個DOPO的含磷化合物。
本發明將就以下實施例來作進一步說明，但應瞭解的是，該實施例僅為例示說明之用，而不應被解釋為本發明實施之限制。
＜ 實施例 ＞
[ 含磷化合物 P1~P4 的合成 ]
合成例 1
將630 g (2.92 mol) DOPO以150℃加熱除水1小時，再加入70 g (0.57 mol) 4-羥基苯甲醛，在氮氣環境下以200℃反應3小時，得到合成例1的含磷化合物P1。合成反應如下所示： 【化學式4】
含磷化合物P1的結構顯示其核心結構為1個具有反應基團(羥基)的苯環帶有2個DOPO，且其磷含量為11.55 wt%。含磷化合物P1的1 H NMR鑑定結果如圖1所示，質譜鑑定結果[m/z 559.0842 (M+23)]如圖2所示。
合成例 2
將53.6 g (0.1 mol)上述含磷化合物P1及170 g (1.8 mol)環氧氯丙烷(epichlorohydrin)置於反應瓶中，回流反應6小時，回收過量之環氧氯丙烷，加入甲苯後，進行水洗，乾燥後得到合成例2的含磷化合物P2。合成反應如下所示： 【化學式5】
含磷化合物P2的結構顯示其核心結構為1個具有反應基團(環氧基)的苯環帶有2個DOPO。
合成例 3
將53.6 g (0.1 mol)上述含磷化合物P1、9.3 g (0.1 mol)苯胺及3.0 g (0.1 mol)聚甲醛(paraformaldehyde)置於反應瓶中，在110℃下反應3小時，加入500 mL氯仿，以1 N 氫氧化鈉水溶液和純水潤洗後收集有機相，去除溶劑後得到合成例3的含磷化合物P3。合成反應如下所示： 【化學式6】
含磷化合物P3的結構顯示其核心結構為1個苯并 (benzoxazine)帶有2個DOPO。
合成例 4
將53.6 g (0.1 mol)上述含磷化合物P1及34 g環氧改性甲酚醛樹脂(cresol-novolac epoxy)溶於800 mL甲基異丁基酮之中，加入0.6 g三苯基膦，回流反應3小時，除去溶劑後得到合成例4的含磷化合物P4。合成反應如下所示： 【化學式7】
含磷化合物P4的結構顯示其核心結構為1個連接有環氧樹脂的苯環帶有2個DOPO。
[ 難燃樹脂組成物及難燃樹脂 ]
應用例 1~4 及比較應用例
將雙酚A環氧樹脂(diglycidyl of bisphenol, DGEBA，環氧當量為188 g/mol)、二氰二胺(dicyanodiamide, DICY)及上述含磷化合物P1分別以下表1的比例配製並溶於甲基乙基酮(溶劑)中，分別得到應用例1~4的難燃樹脂組成物及比較應用例1的樹脂組成物。以160℃加熱1小時、190℃加熱2小時及200℃加熱2小時接續加熱硬化上述難燃樹脂組成物及樹脂組成物，分別得到應用例1~4的難燃樹脂E1~E4及比較應用例的樹脂CE。以元素分析法分別測試上述難燃樹脂E1~E4及樹脂CE的磷含量，以熱重分析儀(TGA)分別測試其在空氣中的5%熱重損失溫度(Td )，並以UL 94垂直測試標準分別測試其難燃等級，結果分別如下表1所示： 【表1】
由上表1可以得知，本發明的含磷化合物可有效提升難燃樹脂E1~E4的難燃等級(V0)，且可確保難燃樹脂E1~E4的熱穩定性(Td 可達到312~321℃)。
綜上所述，本發明含磷化合物藉由1個具有反應基團的苯環帶有2個DOPO的核心結構及較高的磷含量，可有效提升所製得之樹脂的難燃性質及確保樹脂的熱穩定性，且其製程簡單，故確實能達成本發明之目的。
惟以上所述者，僅為本發明之實施例而已，當不能以此限定本發明實施之範圍，凡是依本發明申請專利範圍及專利說明書內容所作之簡單的等效變化與修飾，皆仍屬本發明專利涵蓋之範圍內。
本發明之其他的特徵及功效，將於參照圖式的實施方式中清楚地呈現，其中： ［圖1］是本發明含磷化合物P1的1 H NMR圖譜；及 ［圖2］是該含磷化合物P1的質譜圖。

Claims (10)

  1. 一種如下式(Ⅲ)所示的含磷化合物： 【化學式1】式(Ⅲ) 在式(Ⅲ)中，n 為1~4；R1 表示氫或C1 ~C4 直鏈或支鏈烷基，當n ≧2時，多個R1 可為相同或不同；R2 表示氫、或透過連接的環氧樹脂； 或表示，其中，Ar 表示C1 ~C12 直鏈或支鏈烷基或C6 ~C12 芳基；及R3 表示氫或甲基。
  2. 如請求項1所述的含磷化合物，其中，R2 表示氫。
  3. 如請求項1所述的含磷化合物，其中，R1 表示氫。
  4. 如請求項1所述的含磷化合物，其中，R3 表示氫。
  5. 如請求項1所述的含磷化合物，其中，Ar 表示苯基。
  6. 如請求項1所述的含磷化合物，其中，該環氧樹脂是選自於環氧改性(甲)酚醛樹脂、雙酚A環氧樹脂、雙酚F環氧樹脂、脂肪族環氧樹脂或縮水甘油胺樹脂。
  7. 一種難燃樹脂組成物，包含如請求項1至6中任一項所述的含磷化合物及一樹脂。
  8. 一種經硬化的難燃樹脂，包含由如請求項7所述的難燃樹脂組成物進行硬化而得的難燃樹脂。
  9. 一種如請求項1所述的含磷化合物的製法，包含：使如下式(Ⅰ)所示的對-羥基苯甲醯基衍生物與如下式(Ⅱ)所示的氧雜磷雜菲氧化物在190~250℃且無溶劑的環境下進行反應； 【化學式2】式(Ⅰ) 【化學式3】式(Ⅱ) 在式(Ⅰ)中，n 、R1 及R3 的定義如請求項1所述，且該對-羥基苯甲醯基衍生物與該氧雜磷雜菲氧化物的莫耳數比範圍為1：2~1：5.5。
  10. 如請求項9所述的含磷化合物的製法，其中，該反應的溫度範圍為200~220℃。
TW104144142A 2015-12-29 2015-12-29 含磷化合物及其應用與製法 TWI547498B (zh)

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US15/135,802 US9695299B1 (en) 2015-12-29 2016-04-22 Phosphorous-containing compound, application thereof, and method for preparing the same

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