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研究生:謝宛融
研究生(外文):Wan-Jung Hsieh
論文名稱:新穎非鹵型難燃劑之合成與性質探討
論文名稱(外文):Study on Synthesis and Properties of Novel Non-halogen Flame Retardants
指導教授:王春山
指導教授(外文):Chun-Shan Wang
學位類別:碩士
校院名稱:國立成功大學
系所名稱:化學工程學系碩博士班
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2004
畢業學年度:92
語文別:中文
論文頁數:103
中文關鍵詞:非鹵素難燃劑氮磷共乘氰酸酯
外文關鍵詞:Non-halogenFlame retardantSynergistic effectCyanate ester
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非鹵型難燃電子材料為現今研發重點之一,目前逐漸採用磷酸酯難燃劑,因其在燃燒時不放出有毒氣體且具良好難燃性。本實驗乃針對非鹵素型難燃劑,合成反應型和添加型兩種不同類型,並藉由氮-磷共乘效應,以期較少量之難燃劑就賦與高分子材料難燃性質。

反應型難燃劑是將常用的硬化劑(六官能Phenol Novolac,PN)和Diphenyl chlorophosphate(DPCP)以不同比例反應,形成帶有含磷的基團的硬化劑,以含磷硬化劑與PN來硬化環氧樹脂,當含磷量達4.36%時即可達到UL-94燃燒測試V-0級,但Tg卻下降至96.53℃。為了減少磷的用量,將PN改成含有氮的硬化劑(Diphenyl diaminomethane, DDM),利用DDM中的氮和含磷PN的磷產生氮磷共乘阻燃效果,可使磷用量下降至3.68%,氮含量0.83%即可達V-0級,而Tg也上升至139.83℃。再將含磷的PN改質為氰酸酯,則磷含量只需2.98%、氮含量2.69%可達V-0級且Tg提升至169.73℃。
再者,考慮經濟因素,將含磷的PN系列中添加無機難燃劑氫氧化鋁,則摻入Al(OH)3佔主體之20%,磷含量只需1.10%、氮含量1.49%,可達V-0級且Tg達168.74℃。

另外針對添加型難燃劑,由於磷酸酯分子量小,欲達UL-94 V-0難燃級大約需2 ~ 4 % 以上的磷,磷酸酯一多,難免影響高分子材料的物性。將Diphenyl diaminomethane(DDM)和Diphenyl chlorophosphate(DPCP)反應,合成氮•磷共乘難燃劑(BDPAM),將所合成的BDPAM分別以5%、10%、15%混摻於工程塑膠(PET、PC)中並作熱性質測試。在難燃效果方面,PET添加難燃劑的量需15%,磷含量為1.40%、氮含量為0.63%;而耐熱性高的PC添加量只要10%,磷含量為0.94%、氮含量為0.42%,可達UL-94V燃燒測試的V-0難燃級;亦針對難燃劑對工程塑膠之玻璃轉移溫度(Tg)和modulus的影響作探討。
另外,由TGA的數據顯示,當有磷或氮磷成分存在時,由於難燃劑發揮阻燃效果,char yield會升高,表示難燃劑造成物質碳化且減少燃燒後放出的有害氣體,可降低對環境的污染。
Recently, research efforts have been focused on the non-halogen flame retardants for electronic applications. Presently organophosphates have been developed to replace traditional flame-retardants, since they do not release toxic gases during combustion and have an excellent flame resistancy. The main purpose of this study is to synthesize non-halogen flame retardants which are reactive and additive types. The nitrogen-phosphorus synergistic effect was also evaluated to achieve the required flame retardancy of polymer.

Reactive flame-retardants were synthesized by Phenol Novolac(PN) and Diphenyl chlorophosphate (DPCP) in various ratios. The resulted phosphorus -containing PN was used as curing agents for epoxy resins, such as the epoxy resin(PNE) was cured with Phenol Novolac(PN) and the phosphorus -containing curing agent. The Underwriters Laboratory 94(UL-94) V-0 rating could be achieved with a phosphorus content of 4.36% for PN type of polymer. But the glass-transition temperature of the polymer decreased to 96℃. When the cuing agent, PN was replaced by diphenyldiaminomethane (DDM), the V-0 rating could be achieved with the least content (3.68 wt% P and 0.83 wt% N) and Tg was increased to 139℃. The cyanate ester- containing PN was synthesized by phosphorus-containing PN and cyanogen bromide (BrCN). The use of cyanate ester-containing PN as a curing agent has further increased Tg to 169℃ and the content of phosphorus could be reduce to 2.98 % with V-0 rating.
Considering economical factors, the inorganic flame-retardant, aluminum hydroxide was added to the phosphorus-containing polymers in twenty weight percentage. UL-94 V-0 rating could be achieved with very low nitrogen and phosphorus contents (1.10 wt% P and 1.49 wt% N) and maintained Tg at 168℃.

The additive type flame-retardant, Bis(diphenyl -phosphorylamino -phenyl)methane (BDPAM) was synthesized by diphenyldiaminomethane (DDM) and Diphenyl chlorophosphate(DPCP). The nitrogen- phosphorus synergistic flame retardant, BDPAM was added to engineering plastics (PET、PC) in various weight ratios and tested for their thermal properties. For flame retardancy, UL-94 V-0 rating could be achieved with phosphorus and nitrogen contents of 1.40% and 0.63% respectively for PET, while 0.94% and 0.42% respectively for PC.
Thermal stabilities of polymers were examined by thermogravimetric (TGA). The polymers which contain flame-retardants have a high char yield because of the nitrogen-phosphorus synergistic effect. Flame-retardants have caused polymers to char and hence reduced toxic gas emission, that could minimize environmental pollutions.
第一章 緒 論.......................1

第二章 原理與文獻回顧...............7

第三章 實驗部份....................22

第四章 反應型難燃劑之性質探討......37

第五章 添加型難燃劑之性質探討......64

第六章 結論........................72
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