TWI501974B - Novel phosphinated diamines and novel phosphinated polyimides and preparation method thereof - Google Patents

Novel phosphinated diamines and novel phosphinated polyimides and preparation method thereof Download PDF

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TWI501974B
TWI501974B TW102124770A TW102124770A TWI501974B TW I501974 B TWI501974 B TW I501974B TW 102124770 A TW102124770 A TW 102124770A TW 102124770 A TW102124770 A TW 102124770A TW I501974 B TWI501974 B TW I501974B
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phosphorus
bisamine
polyimine
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TW201502133A (en
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Ching Hsuan Lin
Chin Kuang Hsu
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Nat Univ Chung Hsing
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新穎磷系雙胺化合物及新穎磷系聚醯亞胺及其製造方法Novel phosphorus-based bisamine compound and novel phosphorus-based polyimine and preparation method thereof

本發明係關於磷系化合物及其製造方法，特別係關於一種具有不對稱結構之磷系雙胺、其聚醯亞胺及其製造方法。The present invention relates to a phosphorus-based compound and a process for producing the same, and, in particular, to a phosphorus-based bisamine having an asymmetric structure, a polyimine thereof, and a process for producing the same.

自古以來，火災一直都是危害人類的生命財產的最大意外之一，因此各種建築或建設都需要防火難燃材料作為建材以降低火災意外發生時的損失。傳統的防火難燃材料多是添加含鹵素的化合物，以形成耐熱性高的組成物。傳統的防火難燃材料雖對抑燃有相當的效果，但會產生具有腐蝕性及毒性物質，如戴奧辛(Dioxin)，可能引起人體新陳代謝失常而造成緊張、睡眠失常、頭痛、眼疾、動脈硬化、肝臟腫瘤等病症，而經由動物實驗更發現會導致癌症。Since ancient times, fires have always been one of the biggest accidents that endanger human life and property. Therefore, various buildings or constructions need fire-resistant and flame-retardant materials as building materials to reduce the losses in the event of fire accidents. Conventional fire-retardant materials are mostly added with a halogen-containing compound to form a composition having high heat resistance. Although traditional fire-retardant materials have a considerable effect on fire suppression, they can produce corrosive and toxic substances, such as Dioxin, which may cause abnormal metabolism and cause nervousness, sleep disorders, headache, eye diseases, arteriosclerosis, Diseases such as liver tumors, and more through animal experiments, can lead to cancer.

近年研究顯示，有機磷的化合物能提升高分子聚合物之難燃性質。與含鹵素難燃劑相比，有機磷的化合物不會產生煙霧(即有毒氣體)，且另外具有加工性佳、添加量少及發煙量低等優點，尤其是將有機磷反應基團導入高分子的主要結構時將使得聚合物更具有難燃效果。Recent studies have shown that organophosphorus compounds can enhance the flame retardant properties of high molecular polymers. Compared with halogen-containing flame retardants, organophosphorus compounds do not produce smoke (ie, toxic gases), and have the advantages of good processability, low added amount, and low smoke generation, especially the introduction of organophosphorus reactive groups. The main structure of the polymer will make the polymer more flame retardant.

在含磷衍生物中，具反應性的9,10-二氫-9-氧雜-10-磷菲-10-氧化物(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,DOPO)深受 矚目，因其可與如苯二酮(benzoquinone)[1] 、環氧乙烷(oxirane)[2] 、馬來酸(maleic acid)[3] 、雙馬來亞醯胺(bismaleimide)[4] 、二胺基二苯甲酮(diaminobenzophenone)[5-6] 及對苯二甲醛(terephthaldicarboxaldehyde)[7] 等缺電子性化合物進行親核加成反應。DOPO衍生的化合物可做為環氧樹脂、聚醯亞胺及聚醯胺等高分子材料的原料。由於雙酚A會在酸催化下裂解成酚及不安定的4-異丙烯基酚(4-isopropenylphenol)[7] ，故使DOPO與雙酚A在酸催化下進行反應，則會形成單官能酚類化合物。Reactive 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) in phosphorus-containing derivatives , DOPO) is highly regarded because it can be combined with, for example, benzoquinone [1] , ethylene oxide (oxirane) [2] , maleic acid [3] , bimaleimide (bismaleimide) [4] , diaminobenzophenone [5-6] and phthalic acid (terephthaldicarboxaldehyde) [7] and other electron-deficient compounds for nucleophilic addition reaction. The DOPO-derived compound can be used as a raw material for a polymer material such as an epoxy resin, a polyimide, or a polyamide. Since bisphenol A is cleavable by acid catalysis to phenol and unstable 4-isopropenylphenol [7] , DOPO and bisphenol A are reacted under acid catalysis to form monofunctional Phenolic compounds.

聚醯亞胺(polyimide,PI)具有高熱穩定性、優異的化學阻抗，及良好的機械性質等優點。目前已廣泛使用主鏈為芳香族的聚醯亞胺。由於該等聚醯亞胺結構堅固，故擁有高的玻璃轉移溫度與極高的熔點，但其缺點在於對有機溶劑的溶解度不佳，且無法使用熔融的方法來加工，故該等聚醯亞胺的工業應用性仍有限。因此，加工性的缺乏限制了聚醯亞胺在工業上的應用。目前已知將不對稱的結構導入至聚醯亞胺中，或於聚醯亞胺側鏈中導入巨大取代基[8] 或柔軟基團[9] 等方法，可減少分子堆疊的規則性及結晶性，以改善聚醯亞胺對有機溶劑的溶解度。Polyimide (PI) has the advantages of high thermal stability, excellent chemical resistance, and good mechanical properties. Polyethylenimine whose main chain is aromatic has been widely used. Because of their strong structure, the polyimine has a high glass transition temperature and a very high melting point, but its disadvantage is that it has poor solubility in organic solvents and cannot be processed by melting. The industrial applicability of amines is still limited. Therefore, the lack of processability limits the industrial application of polyimine. It is known to introduce an asymmetric structure into a polyimine or to introduce a large substituent [8] or a soft group [9] into a polyethylenimine side chain, thereby reducing the regularity of molecular stacking and Crystallinity to improve the solubility of polyimine in organic solvents.

據上，如何提升磷系聚醯亞胺對有機溶劑的溶解度，並同時保持其良好的熱穩定性，仍是目前重要的研究課題。According to the above, how to improve the solubility of phosphorus-based polyimine in organic solvents while maintaining its good thermal stability is still an important research topic at present.

[1] Wang,C.S.and Lin,C.H.Polymer 1999;40；747.[1] Wang, C.S. and Lin, C.H.Polymer 1999;40;747.

[2] Lin,C.H.and Wang,C.S.Polymer.,2001,42,1869.[2] Lin, C.H. and Wang, C.S. Polymer., 2001, 42, 1869.

[3] Wang,C.S.；Lin,C.H.and Wu,C.Y.J.Appl.Polym.Sci.2000,78,228.[3] Wang, C.S.; Lin, C.H. and Wu, C.Y.J. Appl.Polym.Sci.2000,78,228.

[4] Lin,C.H.and Wang,C.S.J.Polym.Sci.Part A：Polym.Chem.2000,38,2260.[4] Lin, C.H. and Wang, C.S.J.Polym.Sci.Part A: Polym.Chem.2000, 38, 2260.

[5] Liu,Y.L.and Tsai,S.H.Polymer 2002；43；5757.[5] Liu, Y.L. and Tsai, S.H.Polymer 2002;43;5757.

[6] Wu,C.S.；Liu,Y.L.and Chiu,Y.S.Polymer 2002；43；1773.[6] Wu, C.S.; Liu, Y.L. and Chiu, Y.S. Polymer 2002;43;1773.

[7] Andrew J.C.and Julia L.L.J.Org.Chem.1997,62,1058.[7] Andrew J.C. and Julia L.L.J.Org.Chem.1997, 62, 1058.

[8] Wang,Kun-Li；Liou,Wun-Tai；Liaw,Der-Jang；Huang,Sheng-Tung,Polymer,2008,49,1538[8] Wang, Kun-Li; Liou, Wun-Tai; Liaw, Der-Jang; Huang, Sheng-Tung, Polymer, 2008, 49, 1538

[9] Lin,C.H.；Lin,C.H.J Polym Sci Part A：Polym.Chem.2007,45,2897.[9] Lin, C.H.; Lin, C.H.J Polym Sci Part A: Polym.Chem. 2007, 45, 2897.

本發明頃發現，將不對稱結構的巨大含磷基團導入至聚醯亞胺結構中，與先前技術相比，可有效地提升其有機溶解性。此外，根據本發明之含磷聚醯亞胺具有較佳的阻燃性及熱氧穩定性，並同時具有高的玻璃轉移溫度。The present inventors have found that the introduction of a large phosphorus-containing group of an asymmetric structure into a polymethylene imine structure can effectively enhance its organic solubility as compared with the prior art. Further, the phosphorus-containing polyimine according to the present invention has better flame retardancy and thermo-oxygen stability, and at the same time has a high glass transition temperature.

磷系雙胺化合物Phosphate bisamine compound

本發明提供一種式(I)磷系雙胺化合物： The present invention provides a phosphorus-based bisamine compound of the formula (I):

其中，Y1 及Y2 各獨立為H、C1 -C6 烷基、苯基或CF3 ，或Y1 及Y2 與彼等所連接之碳原子一起形成C5 -C13 碳環；及R1 及R2 各獨立為H、C1 -C6 烷基或C3 -C6 環烷基，其中該環烷基係未經取代或經一或多個C1 -C6 烷基取代。Wherein Y 1 and Y 2 are each independently H, C 1 -C 6 alkyl, phenyl or CF 3 , or Y 1 and Y 2 together with the carbon atom to which they are attached form a C 5 -C 13 carbocycle; And R 1 and R 2 are each independently H, C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl, wherein the cycloalkyl is unsubstituted or via one or more C 1 -C 6 alkyl groups Replace.

於本發明之一實施例中，該式(I)磷系雙胺化合物可為下式之化合物： 其中，Y1 、Y2 、R1 及R2 係如上所定義。In one embodiment of the present invention, the phosphorus-based bisamine compound of the formula (I) may be a compound of the formula: Wherein Y 1 , Y 2 , R 1 and R 2 are as defined above.

於本發明之一具體實例中，該式(I)磷系雙胺化合物可為下式之化合物： In one embodiment of the invention, the phosphorus bisamine compound of formula (I) may be a compound of the formula:

磷系雙胺化合物之製造方法Method for producing phosphorus-based bisamine compound

本發明提供一種式(I)磷系雙胺化合物之製造方法， The present invention provides a method for producing a phosphorus-based bisamine compound of the formula (I),

其包含下列步驟：It contains the following steps:

(i)將式(DOPO)化合物與式(BP)化合物進行反應， (i) reacting a compound of formula (DOPO) with a compound of formula (BP),

以產生式(II)化合物； To produce a compound of formula (II);

(ii)在鹼存在下，將式(II)化合物與式(DN)化合物進行反應， (ii) reacting a compound of formula (II) with a compound of formula (DN) in the presence of a base,

以產生式(III)化合物；及 To produce a compound of formula (III);

(iii)還原式(III)化合物，以產生式(I)磷系雙胺化合物，其中Y1 、Y2 、R1 及R2 係如上述所定義，且L代表芳香性親核取代離去基。(iii) reducing a compound of formula (III) to produce a phosphorus-based bisamine compound of formula (I) wherein Y 1 , Y 2 , R 1 and R 2 are as defined above, and L represents an aromatic nucleophilic substitution leaving base.

術語「芳香性親核取代離去基」為有機合成領域中所熟知之技術。於本發明方法中，芳香性親核取代離去基係指適於做為芳香性親核取代反應中之離去基之基團。適合的離去基包含但不限於F、Cl、Br、I或磺酸酯(例如甲苯磺酸鹽、甲磺酸鹽、苯磺酸鹽及三氟甲磺酸鹽等)。The term "aromatic nucleophilic substitution leaving group" is a technique well known in the art of organic synthesis. In the process of the present invention, an aromatic nucleophilic substituted leaving group refers to a group suitable as a leaving group in an aromatic nucleophilic substitution reaction. Suitable leaving groups include, but are not limited to, F, Cl, Br, I or sulfonates (e.g., tosylate, methanesulfonate, besylate, triflate, and the like).

於本發明上述方法步驟(i)中，可視情況選用觸媒增加反應速率，該觸媒可為酸觸媒。當酸觸媒存在時，該酸觸媒包括但不限於草酸、醋酸、對-甲基苯磺酸(p-Toluenesulfonic acid,PTSA)、甲基磺酸(Methanesulfonic acid)、氟磺酸(Fluorosulfonic acid)、三氟甲磺酸(Trifluoromethanesulfonic acid)、硫酸(Sulfuric acid)、2-胺基苯磺酸(Orthanilic acid)、3-吡啶磺酸(3-Pyridinesulfonic acid)、對胺基苯磺酸(Sulfanilic acid)、氯化氫(HCl)、溴化氫(HBr)、碘化氫(HI)、氟化氫 (HF)、三氟乙酸(CF3 COOH)、硝酸(HNO3 )及磷酸(H3 PO4 )。此外，該酸觸媒之量為該酚類化合物的0.1 wt%至10 wt%間，較佳為1 wt%至5 wt%。In the step (i) of the above method of the present invention, a catalyst may be used to increase the reaction rate, and the catalyst may be an acid catalyst. When an acid catalyst is present, the acid catalyst includes, but is not limited to, oxalic acid, acetic acid, p-Toluenesulfonic acid (PTSA), methanesulfonic acid, fluorosulfonic acid (Fluorosulfonic acid). ), Trifluoromethanesulfonic acid, Sulfuric acid, Orthanilic acid, 3-Pyridinesulfonic acid, Sufanilic Acid), hydrogen chloride (HCl), hydrogen bromide (HBr), hydrogen iodide (HI), hydrogen fluoride (HF), trifluoroacetic acid (CF 3 COOH), nitric acid (HNO 3 ), and phosphoric acid (H 3 PO 4 ). Further, the amount of the acid catalyst is between 0.1% by weight and 10% by weight of the phenolic compound, preferably between 1% by weight and 5% by weight.

於本發明上述方法步驟(i)中，反應時間可為6至24小時，較佳為12至20小時，且反應溫度為90℃至200℃間。In the above step (i) of the present invention, the reaction time may be from 6 to 24 hours, preferably from 12 to 20 hours, and the reaction temperature is from 90 ° C to 200 ° C.

於本發明上述方法步驟(i)中，可視情況選用溶劑進行反應。當溶劑存在時，該溶劑包括但不限於乙氧基乙醇(ethoxyethanol)、甲氧基乙醇(methoxyethanol)、1-甲氧基-2-丙醇(1-methoxy-2-propanol)、單甲基醚丙二醇(propylene glycol monomethyl ether,DOW PM)、二氧陸圜(dioxane)、或上述溶劑所組成的共溶劑。In the step (i) of the above method of the present invention, a solvent may be optionally used for the reaction. When a solvent is present, the solvent includes, but is not limited to, ethoxyethanol, methoxyethanol, 1-methoxy-2-propanol, monomethyl A cosolvent consisting of propylene glycol monomethyl ether (DOW PM), dioxane, or a solvent as described above.

於本發明上述方法步驟(ii)中，該鹼為一般芳香性親核取代反應中所用的鹼催化劑劑，其包括但不限於碳酸鉀、氫氧化鉀、氫氧化鈉、氫氧化鈣、氫氧化锂。In the above step (ii) of the present invention, the base is a base catalyst used in a general aromatic nucleophilic substitution reaction, including but not limited to potassium carbonate, potassium hydroxide, sodium hydroxide, calcium hydroxide, and hydroxide. lithium.

於本發明上述方法步驟(iii)中，該還原反應為一般習知的硝基還原反應，其包括但不限於在氫氣下以Pd/C催化所進行之還原反應。In step (iii) of the above process of the present invention, the reduction reaction is a conventional nitro reduction reaction including, but not limited to, reduction under Pd/C catalysis under hydrogen.

磷系雙硝基苯化合物Phosphorus bisnitrobenzene compound

本發明另提供一種式(III)之磷系雙硝基苯化合物， The present invention further provides a phosphorus-based bisnitrobenzene compound of the formula (III),

其中Y1 、Y2 、R1 及R2 係如上述所定義。該化合物係做為如上所示之式(I)磷系雙胺化合物之合成中間體使用。Wherein Y 1 , Y 2 , R 1 and R 2 are as defined above. This compound is used as a synthetic intermediate of the phosphorus-based bisamine compound of the formula (I) as shown above.

磷系雙硝基苯化合物之製造方法Method for producing phosphorus-based bisnitrobenzene compound

本發明提供一種式(III)磷系二硝基苯化合物之製造方法，其包含下列步驟：The present invention provides a method for producing a phosphorus-based dinitrobenzene compound of the formula (III), which comprises the steps of:

(i)將式(DOPO)化合物與式(BP)化合物進行反應， (i) reacting a compound of formula (DOPO) with a compound of formula (BP),

以產生式(II)化合物；及 To produce a compound of formula (II);

(ii)在鹼存在下，將式(II)化合物與式(DN)化合物進行反應， (ii) reacting a compound of formula (II) with a compound of formula (DN) in the presence of a base,

以產生式(III)化合物， To produce a compound of formula (III),

其中Y1 、Y2 、R1 、R2、 L及步驟(i)及(ii)之反應條件係如上述所定義。Wherein Y 1 , Y 2 , R 1 , R 2 , L and the reaction conditions of steps (i) and (ii) are as defined above.

磷系聚醯亞胺Phosphorus polyimine

本發明另提供一種磷系聚醯亞胺，其係由如上述式(I)磷系雙胺化合物、雙酸酐單體及視情況選用的一或多種其他雙胺單體所聚合而成。The present invention further provides a phosphorus-based polyimine which is obtained by polymerizing a phosphorus-based bisamine compound of the above formula (I), a dianhydride monomer, and optionally one or more other bisamine monomers.

於本發明之磷系聚醯亞胺中，該其他雙胺單體為視情況選用，並可選自由任何習知適合用於聚醯亞胺之雙胺單體。舉例言之，該雙胺單體可選自由間苯二胺(m-phenylenediamine)、對苯二胺 (p-phenylenediamine)、4,4'-二胺基苯醚(4,4'-oxydianiline)、3,4'-二胺基苯醚(4,4'-oxydianiline)、1,4-雙(4-胺基苯氧基)苯(1,4-bis(4-aminophenoxy)benzene)、1,3-雙(4-胺基苯氧基)苯(1,3-bis(4-aminophenoxy)benzene)、1,2-雙(4-胺基苯氧基)苯(1,2-bis(4-aminophenoxy)benzene)、1,3-雙(3-胺基苯氧基)苯(1,3-bis(3-aminophenoxy)benzene)、2,5-雙(4-胺基苯氧基)甲苯(2,5-bis(4-aminophenoxy)toluene)、雙[4-(4-氨基苯氧基)苯基]醚(bis[4-(4-aminophenoxy)phenyl]ether)、4,4'-雙(氨基苯氧基)二苯(4,4'-bis[4-aminophenoxy]biphenyl)、2,2-雙[4(4-氨基苯氧基)苯基]丙烷(2,2-bis[4-(4-aminophenoxy)]phenyl)propane)或其類似物所組成之群。於本發明之一實施例中，該其他雙胺單體可以式H2 N-Z-NH2 表示，其中Z可為 In the phosphorus-based polyimine of the present invention, the other bisamine monomer is optionally selected, and any bisamine monomer conventionally suitable for use in polyimine can be selected. For example, the bisamine monomer may be selected from m-phenylenediamine, p-phenylenediamine, and 4,4'-oxydianiline. , 3,4'-diphenylphenyl ether (4,4'-oxydianiline), 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1 , 3-bis(4-aminophenoxy)benzene, 1,2-bis(4-aminophenoxy)benzene (1,2-bis (1,2-bis) 4-aminophenoxy)benzene), 1,3-bis(3-aminophenoxy)benzene, 2,5-bis(4-aminophenoxy) Toluene (2,5-bis(4-aminophenoxy)toluene), bis[4-(4-aminophenoxy)phenyl]ether, 4,4'-4,4'-bis[4-aminophenoxy]biphenyl, 2,2-bis[4(4-aminophenoxy)phenyl]propane (2,2-bis a group consisting of [4-(4-aminophenoxy)]phenyl)propane) or an analogue thereof. In an embodiment of the present invention, the other bisamine monomer may be represented by the formula H 2 NZ-NH 2 , wherein Z may be

於本發明之一實施例中，該磷系聚醯亞胺具有式(V) In one embodiment of the present invention, the phosphorus polyimine has the formula (V)

其中，R為 Where R is

其中Y1 、Y2 、R1 及R2 係如上述所定義；Z為該其他雙胺單體之殘 基；Ar各獨立為四價有機基；x為1至100之整數；且y為0至99之整數。Wherein Y 1 , Y 2 , R 1 and R 2 are as defined above; Z is a residue of the other diamine monomer; Ar is independently a tetravalent organic group; x is an integer from 1 to 100; and y is An integer from 0 to 99.

於式(V)磷系聚醯亞胺中，Ar為無特別限制的四價有機基，較佳可選自由下列所組成之群： 及，其中A為一單鍵、-O-、-CO-、-S-、-SO2 -、-C(CH3 )2 -、-C(CF3 )2 -、-CONH-、-COO-、-(CH2 )n -、-O(CH2 )n2 O-或-COO(CH2 )n3 OCO-，其中n、n2及n3各自獨立為1至10之整數，且*表示鍵結點。In the phosphorus-based polyimine of the formula (V), Ar is a tetravalent organic group which is not particularly limited, and is preferably selected from the group consisting of: and Wherein A is a single bond, -O-, -CO-, -S-, -SO 2 -, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -CONH-, -COO- , -(CH 2 ) n -, -O(CH 2 ) n2 O- or -COO(CH 2 ) n3 OCO-, wherein n, n2 and n3 are each independently an integer from 1 to 10, and * represents a bond point .

於本發明之一較佳實施例中，Ar係選自由、、、、和所組成之群。In a preferred embodiment of the invention, the Ar system is selected from , , , , with The group formed.

本發明另提供一種磷系聚醯亞胺之製造方法，其包含將如上所述之式(I)磷系雙胺化合物、雙酸酐單體及視情況添加的一或多種其他雙胺單體，在溶劑下進行溶液聚合。The present invention further provides a method for producing a phosphorus-based polyimine comprising a phosphorus-based bisamine compound of the formula (I), a dianhydride monomer, and optionally one or more other bisamine monomers, as described above, Solution polymerization is carried out under a solvent.

於本發明一實施例中，該雙酸酐單體之含量係與如上所示之式(I)磷系雙胺化合物與該視情況添加的其他雙胺單體之總含量等當量；式(I)磷系雙胺化合物與該視情況添加選用的其他雙胺單體的比例係介於10：0至1：9之間，較佳為9：1至1：9之間。In one embodiment of the present invention, the content of the bis-anhydride monomer is equivalent to the total content of the phosphorus-based bisamine compound of the formula (I) and the optionally added other bisamine monomer as shown above; The ratio of the phosphorus bisamine compound to the other bisamine monomer optionally added is optionally between 10:0 and 1:9, preferably between 9:1 and 1:9.

圖1為式(IV-A)化合物之1 HNMR光譜圖。Figure 1 is a 1 H NMR spectrum of the compound of the formula (IV-A).

圖2為式(IV-B)化合物之1 HNMR光譜圖。Figure 2 is a 1 H NMR spectrum of the compound of the formula (IV-B).

圖3為式(IV-C)化合物之1 HNMR光譜圖。Figure 3 is a 1 H NMR spectrum of the compound of the formula (IV-C).

圖4為式(IV-D)化合物之1 HNMR光譜圖。Figure 4 is a 1 H NMR spectrum of the compound of the formula (IV-D).

圖5為式(V-C)化合物的動態機械分析圖譜。Figure 5 is a dynamic mechanical analysis of a compound of formula (V-C).

圖6為式(V-C(c))聚醯亞胺的熱機械分析圖譜。Figure 6 is a thermomechanical analysis of the formula (V-C(c)) polyimine.

圖7為聚醯亞胺(ODA-BTDA)的動態機械分析圖譜。Figure 7 is a dynamic mechanical analysis of polyimine (ODA-BTDA).

圖8為聚醯亞胺(ODA-BTDA)的熱機械分析圖譜。Figure 8 is a thermomechanical analysis of polyimine (ODA-BTDA).

以下實施例將對本發明作進一步之說明，唯非用以限制本發明之範圍，任何熟悉本發明技術領域者，在不違背本發明之精神下所得以達成之修飾及變化，均屬本發明之範圍。The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention, and any modifications and variations which may be obtained without departing from the spirit of the invention are range.

實施例1、式(IV-A)化合物之合成Example 1, Synthesis of Compound of Formula (IV-A)

取9,9-二(4-羥苯基)芴(9,9-Bis(4-hydroxyphenyl)fluorene)35.041克(0.1莫耳)、DOPO 43.234克(0.2莫耳)、對-甲基苯磺酸(p-Toluene sulfonic acid)及1.729克(4wt% of DOPO)，置入250毫升三頸瓶中，通入氮氣，升溫至140℃，反應12小時。反應結束後冷卻至室溫，加入少量 乙醇至三頸瓶中洗滌，抽氣過濾後取濾餅，放入真空烘箱100℃下烘乾，可得式(II-A)化合物之白色粉體，產率為90%。Take 9,9-bis(4-hydroxyphenyl)fluorene 35.041 g (0.1 mol), DOPO 43.234 g (0.2 mol), p-methylbenzenesulfonate Acid (p-Toluene sulfonic acid) and 1.729 g (4 wt% of DOPO) were placed in a 250 ml three-necked flask, and nitrogen gas was introduced thereto, and the temperature was raised to 140 ° C for 12 hours. After the reaction is completed, cool to room temperature and add a small amount. The ethanol was washed into a three-necked flask, and the filter cake was taken by suction filtration, and dried in a vacuum oven at 100 ° C to obtain a white powder of the compound of the formula (II-A) in a yield of 90%.

取式(II-A)化合物23.624克(0.05莫耳)、2,4-二硝基氯苯(2,4-dinitrochlorobenzene)11.14克(0.055莫耳)、碳酸鉀(Potassium carbonate)7.602克(0.055莫耳)、二甲基乙醯胺(N,N-Dimethylacetamide)100毫升於250毫升三頸瓶中，通入氮氣，升溫至80℃，反應12小時，反應結束後冷卻至室溫，抽氣過濾取濾液，將濾液倒入飽和食鹽水中清洗數次，抽氣過濾取濾餅，放於真空烘箱100℃烘乾，可得式(III-A)化合物之黃色粉體，產率80%。23.624 g (0.05 mol) of compound of formula (II-A), 11.14 g (0.055 mol) of 2,4-dinitrochlorobenzene, and 7.602 g of potassium carbonate (0.055) 100 ml of dimethyl acetamide (N, N-Dimethylacetamide) in a 250 ml three-necked flask, nitrogen gas, heating to 80 ° C, reaction for 12 hours, cooling to room temperature after the reaction, pumping The filtrate was filtered, and the filtrate was poured into a saturated brine for several times, and the filter cake was taken by suction filtration, and dried in a vacuum oven at 100 ° C to obtain a yellow powder of the compound of the formula (III-A) in a yield of 80%.

取式(III-A)化合物6.38克(0.01莫耳)、鈀碳催化劑(Pd/C)0.255克(4wt% of III-A)、乙醇30毫升於高壓反應器中升溫至乙醇沸點攪拌。通入氮氣充氣放氣重複三次，之後再通入氫氣充氣放氣重複三次。將壓力維持在140psi反應至壓力不再下降。反應結束後，過濾掉Pd/C。濾液滴入500毫升去離子水中析出收集產物。用真空烘箱70℃下真空烘乾，可得式(IV-A)化合物之深紅色粉末，產率75%。IV-A的1 H-NMR光譜如圖1所示。6.38 g (0.01 mol) of the compound of the formula (III-A), palladium carbon catalyst (Pd/C) 0.255 g (4 wt% of III-A), and 30 ml of ethanol were heated in a high pressure reactor to a boiling point of ethanol and stirred. It was repeated three times by introducing a nitrogen gas inflating gas, and then it was repeated three times by introducing a hydrogen gas inflating gas. The pressure was maintained at 140 psi until the pressure no longer decreased. After the reaction was completed, Pd/C was filtered off. The filtered droplets were precipitated into 500 ml of deionized water to collect the product. Drying in a vacuum oven at 70 ° C gave a dark red powder of the compound of formula (IV-A) in a yield of 75%. The 1 H-NMR spectrum of IV-A is shown in Fig. 1 .

實施例2、式(IV-B)化合物之合成Example 2 Synthesis of a compound of the formula (IV-B)

取2,2-雙(4-羥基-3,5-二甲基苯基)丙烷(2,2-Bis(4-hydroxy-3,5-dimethylphenyl)propane)28.439克(0.1莫耳)、DOPO 43.234克(0.2莫耳)、對-甲基苯磺酸(p-Toluene sulfonic acid)1.729克(4wt% of DOPO)，置入250毫升三頸瓶中，通入氮氣，升溫至140℃，反應12小時。反應結束後冷卻至室溫，加入少量乙醇至三頸瓶中洗滌，抽氣過濾後取濾餅，放入真空烘箱100℃下烘乾，可得式(II-B)化合物之白色粉體，產率為92%。Take 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane (28.439 g (0.1 mol)), DOPO 43.234 g (0.2 mol), p-Toluene sulfonic acid 1.729 g (4 wt% of DOPO), placed in a 250 ml three-necked flask, purged with nitrogen, and warmed to 140 ° C, the reaction 12 hours. After the reaction is completed, the mixture is cooled to room temperature, and a small amount of ethanol is added to the three-necked flask for washing. After suction filtration, the filter cake is taken and dried in a vacuum oven at 100 ° C to obtain a white powder of the compound of the formula (II-B). The yield was 92%.

取式(II-B)化合物18.92克(0.05莫耳)、2,4-二硝基氯苯(2,4-dinitrochlorobenzene)11.14克(0.055莫耳)、碳酸鉀(Potassium carbonate)7.602克(0.055莫耳)、二甲基乙醯胺(N,N-Dimethylacetamide)100毫升於250毫升三頸瓶中，通入氮氣，升溫至80℃，反應12小時，反應結束後冷卻至室溫，抽氣過濾取濾液，將濾液倒入飽和食鹽水中清洗數次，抽氣過濾取濾餅，放於真空烘箱100℃烘乾，可得式(III-B)化合物之黃色粉體，產率85%。18.92 g (0.05 mol) of compound of formula (II-B), 11.14 g (0.055 mol) of 2,4-dinitrochlorobenzene, 7.602 g of potassium carbonate (0.055 g (0.055) 100 ml of dimethyl acetamide (N, N-Dimethylacetamide) in a 250 ml three-necked flask, nitrogen gas, heating to 80 ° C, reaction for 12 hours, cooling to room temperature after the reaction, pumping The filtrate was filtered, and the filtrate was poured into a saturated saline solution for several times. The filter cake was taken by suction filtration, and dried in a vacuum oven at 100 ° C to obtain a yellow powder of the compound of the formula (III-B) in a yield of 85%.

取式(III-B)化合物5.44克(0.01莫耳)、鈀碳催化劑(Pd/C)0.218克(4wt% of III-B)、乙醇30毫升於高壓反應器中升溫至乙醇沸點攪拌。通入氮氣充氣放氣重複三次，之後再通入氫氣充氣放氣重複三次。將壓力維持在140psi反應至壓力不再下降。反應結束後，過濾掉Pd/C。 靜置於室溫下可得深紅色結晶IV-B，產率65%。IV-B的1 H-NMR光譜如圖2所示。5.44 g (0.01 mol) of the compound of the formula (III-B), 0.218 g (4 wt% of III-B) of palladium carbon catalyst (Pd/C), and 30 ml of ethanol were heated in a high pressure reactor to a boiling point of ethanol and stirred. It was repeated three times by introducing a nitrogen gas inflating gas, and then it was repeated three times by introducing a hydrogen gas inflating gas. The pressure was maintained at 140 psi until the pressure no longer decreased. After the reaction was completed, Pd/C was filtered off. The deep red crystal IV-B was obtained by standing at room temperature, and the yield was 65%. The 1 H-NMR spectrum of IV-B is shown in Fig. 2 .

實施例3、式(IV-C)化合物之合成Example 3, Synthesis of a compound of formula (IV-C)

取雙酚A(Bisphenol A)22.829克(0.1莫耳)、DOPO 43.234克(0.2莫耳)、對-甲基苯磺酸(p-Toluene sulfonic acid)1.729克(4wt% of DOPO)，置入250毫升三頸瓶中，通入氮氣，升溫至130℃，反應12小時。反應結束後冷卻至室溫，加入少量乙醇至三頸瓶中洗滌，抽氣過濾後取濾餅，放入真空烘箱100℃下烘乾，可得式(II-C)化合物之白色粉體，產率為88%。其結構式如下 Take bisphenol A (Bisphenol A) 22.829 g (0.1 mol), DOPO 43.234 g (0.2 mol), p-Toluene sulfonic acid 1.729 g (4 wt% of DOPO), placed In a 250 ml three-necked flask, nitrogen gas was introduced, and the temperature was raised to 130 ° C for 12 hours. After the reaction is completed, it is cooled to room temperature, and a small amount of ethanol is added to the three-necked flask for washing. After filtering with air, the filter cake is taken and dried in a vacuum oven at 100 ° C to obtain a white powder of the compound of the formula (II-C). The yield was 88%. Its structural formula is as follows

取式(II-C)化合物17.518克(0.05莫耳)、2,4-二硝基氯苯(2,4-dinitrochlorobenzene)11.14克(0.055莫耳)、碳酸鉀(Potassium carbonate)7.602克(0.055莫耳)、二甲基乙醯胺(N,N-Dimethylacetamide)100毫升於250毫升三頸瓶中，通入氮氣，升溫至80℃，反應12小時，反應結束後冷卻至室溫，抽氣過濾取濾液，將濾液倒入飽和食鹽水中清洗數次，抽氣過濾取濾餅，放於真空烘箱100℃烘乾，可得式(III-C)化合物之黃色粉體，產率82%。Taking 17.518 g (0.05 mol) of compound of formula (II-C), 11.14 g (0.055 mol) of 2,4-dinitrochlorobenzene, 7.602 g of potassium carbonate (0.055 g (0.055) 100 ml of dimethyl acetamide (N, N-Dimethylacetamide) in a 250 ml three-necked flask, nitrogen gas, heating to 80 ° C, reaction for 12 hours, cooling to room temperature after the reaction, pumping The filtrate was filtered, and the filtrate was poured into a saturated brine for several times, and the filter cake was taken by suction filtration, and dried in a vacuum oven at 100 ° C to obtain a yellow powder of the compound of the formula (III-C) in a yield of 82%.

取式(III-C)化合物5.16克(0.01莫耳)、Pd/C 0.206克(4wt% of III-C)、乙醇30毫升於高壓反應器中升溫至乙醇沸點攪拌。通入氮氣 充氣放氣重複三次，之後再通入氫氣充氣放氣重複三次。將壓力維持在140psi反應至壓力不再下降。反應結束後，過濾掉Pd/C。濾液滴入500毫升去離子水中析出收集產物。用真空烘箱70℃下真空烘乾，得式(IV-C)化合物之深紅色粉末，產率72%。IV-C的1 H-NMR光譜如圖3所示。5.16 g (0.01 mol) of the compound of the formula (III-C), 0.26 g of Pd/C (4 wt% of III-C), and 30 ml of ethanol were heated in a high pressure reactor to a boiling point of ethanol and stirred. It was repeated three times by introducing a nitrogen gas inflating gas, and then it was repeated three times by introducing a hydrogen gas inflating gas. The pressure was maintained at 140 psi until the pressure no longer decreased. After the reaction was completed, Pd/C was filtered off. The filtered droplets were precipitated into 500 ml of deionized water to collect the product. Drying in a vacuum oven at 70 ° C gave a dark red powder of the compound of formula (IV-C) in a yield of 72%. The 1 H-NMR spectrum of IV-C is shown in Fig. 3.

實施例4、式(IV-D)化合物之合成Example 4 Synthesis of a compound of formula (IV-D)

取1,1'-雙(4-羥基苯基)環己烷(Bis(4-hydroxyphenyl)cyclohexane)26.835克(0.1莫耳)、DOPO 43.234克(0.2莫耳)、對-甲基苯磺酸(p-Toluene sulfonic acid)1.729克(4wt% of DOPO)，置入250毫升三頸瓶中，通入氮氣，升溫至130℃，反應12小時。反應結束後冷卻至室溫，加入少量乙醇至三頸瓶中洗滌，抽氣過濾後取濾餅，放入真空烘箱100℃烘乾，可得式(II-D)化合物之白色粉體，產率為92%。Take 1,1'-bis(4-hydroxyphenyl)cyclohexane (26.835 g (0.1 mol), DOPO 43.234 g (0.2 mol), p-toluenesulfonic acid (p-Toluene sulfonic acid) 1.729 g (4 wt% of DOPO), placed in a 250 ml three-necked flask, purged with nitrogen, heated to 130 ° C, and reacted for 12 hours. After the reaction is completed, it is cooled to room temperature, and a small amount of ethanol is added to the three-necked flask for washing. After suction filtration, the filter cake is taken and dried in a vacuum oven at 100 ° C to obtain a white powder of the compound of the formula (II-D). The rate is 92%.

取式(II-D)化合物19.521克(0.05莫耳)、2,4-二硝基氯苯(2,4-dinitrochlorobenzene)11.14克(0.055莫耳)、碳酸鉀(Potassium carbonate)7.602克(0.055莫耳)、二甲基乙醯胺(N,N-Dimethylacetamide)100毫升於250毫升三頸瓶中，通入氮氣，升溫至80℃，反應12小時，反應結束後冷卻至室溫，抽氣過濾取濾液，將濾液倒入飽和食鹽水中清洗數次，抽氣過濾取濾餅，放於真空烘箱100℃烘乾，得黃色粉體，產率86%。用乙醇再結晶得產物式(III-D)化合物，產率59%。19.521 g (0.05 mol) of compound of formula (II-D), 11.14 g (0.055 mol) of 2,4-dinitrochlorobenzene, 7.602 g of potassium carbonate (0.055 g (0.055) 100 ml of dimethyl acetamide (N, N-Dimethylacetamide) in a 250 ml three-necked flask, nitrogen gas, heating to 80 ° C, reaction for 12 hours, cooling to room temperature after the reaction, pumping The filtrate was filtered, and the filtrate was poured into a saturated brine for several times, and the filter cake was taken by suction filtration, and dried in a vacuum oven at 100 ° C to obtain a yellow powder with a yield of 86%. Recrystallization from ethanol gave the compound of formula (III-D) in a yield of 59%.

取式(III-D)化合物5.56克(0.01莫耳)、Pd/C 0.222克(4wt% of III-D)、乙醇30毫升於高壓反應器中升溫至乙醇沸點攪拌。通入氮氣充氣放氣重複三次，之後再通入氫氣充氣放氣重複三次。將壓力維持在140psi反應至壓力不再下降。反應結束後，過濾掉Pd/C。靜置於室溫下，可得式(IV-D)化合物之深紅色結晶，產率75%。式(IV-D)的1 H-NMR光譜如圖4所示。5.56 g (0.01 mol) of the compound of the formula (III-D), 0.222 g (4 wt% of III-D) of Pd/C, and 30 ml of ethanol were heated in a high pressure reactor to a boiling point of ethanol and stirred. It was repeated three times by introducing a nitrogen gas inflating gas, and then it was repeated three times by introducing a hydrogen gas inflating gas. The pressure was maintained at 140 psi until the pressure no longer decreased. After the reaction was completed, Pd/C was filtered off. Upon standing at room temperature, a deep red crystal of the compound of the formula (IV-D) was obtained in a yield of 75%. The 1 H-NMR spectrum of the formula (IV-D) is shown in Fig. 4 .

實施例5、式(V-C(c))聚醯亞胺的合成Example 5, Synthesis of Poly(imine) of Formula (V-C(c))

取式(IV-C)雙胺化合物1.0克(2.19毫莫耳)與4,4'-二氨基二苯醚(4,4'-Oxydianiline,ODA)0.4387克(2.19毫莫耳)溶於間-甲苯酚(m-cresol)16毫升，通入氮氣維持30分鐘，待完全溶解後，加入4,4'-四羧基二苯酮酐(4,4'-carbonyldiphthalic anhydride,BTDA)1.412克(2.19*2毫莫耳)，固含量約配置12wt%。同時快速加入少量異喹啉(isoquinoline)，來幫助閉環反應，接著快速升溫至170℃進行高溫閉環，反應結束後倒入甲醇中析出，重複清洗數次，置於真空烘箱70℃烘乾，得膚色纖維狀產物。接著以N-甲基咯烷酮(NMP)配置固含量15wt%溶液，將此溶液利用自動薄膜塗佈機控制膜厚約45μm，均勻塗佈於玻璃基板上。置於循環烘箱升溫至60℃維持12小時，去除大部分溶劑後，階段升溫100℃ 1小時、200℃ 1小時、300℃ 1小時，進行熱 亞胺化(thermal imidization)。接著將玻璃基板浸於水中使薄膜與基板分離，得式(V-C(c))聚醯亞胺之薄膜。如圖5所示，動態機械分析儀係顯示其儲存模數為4.70GPa，玻璃轉移溫度為296℃。如圖6所示，熱機械分析儀顯示其熱膨脹係數為39ppm/℃，玻璃轉移溫度為275℃。1.0 g (2.19 mmol) of the bis-amine compound of the formula (IV-C) and 0.4387 g (2.19 mmol) of 4,4'-Oxydianiline (ODA) were dissolved. M-cresol (m-cresol) 16 ml, maintained with nitrogen for 30 minutes, after complete dissolution, add 4,4'-carbonyldiphthalic anhydride (BTDA) 1.412 g (2.19) *2 millimolar), the solid content is approximately 12% by weight. At the same time, a small amount of isoquinoline is quickly added to help the ring-closing reaction, and then the temperature is rapidly raised to 170 ° C for high-temperature ring closure. After the reaction is completed, it is poured into methanol to precipitate, repeated washing several times, and placed in a vacuum oven at 70 ° C to dry. Skin color fibrous product. Next, a 15 wt% solid solution was prepared with N-methylrrolidone (NMP), and the solution was controlled to a thickness of about 45 μm by an automatic film coater to be uniformly coated on a glass substrate. The temperature was raised to 60 ° C in a circulating oven for 12 hours. After removing most of the solvent, the temperature was raised to 100 ° C for 1 hour, 200 ° C for 1 hour, and 300 ° C for 1 hour. Thermal imidization. Next, the glass substrate is immersed in water to separate the film from the substrate to obtain a film of the formula (V-C(c)) polyimine. As shown in Fig. 5, the dynamic mechanical analyzer showed a storage modulus of 4.70 GPa and a glass transition temperature of 296 °C. As shown in Fig. 6, the thermomechanical analyzer showed a coefficient of thermal expansion of 39 ppm/° C. and a glass transition temperature of 275 ° C.

實施例6、化合物V-A(c)之合成Example 6, Synthesis of Compound V-A (c)

反應條件同實施例5，唯將式(IV-C)雙胺化合物改為式(IV-A)雙胺化合物。動態機械分析儀顯示其儲存模數為3.84 GPa，玻璃轉移溫度為312℃。熱機械分析儀顯示其熱膨脹係數為36ppm/℃，玻璃轉移溫度為288℃。The reaction conditions were the same as in Example 5 except that the bisamine compound of the formula (IV-C) was changed to the bisamine compound of the formula (IV-A). The dynamic mechanical analyzer showed a storage modulus of 3.84 GPa and a glass transition temperature of 312 °C. The thermomechanical analyzer showed a coefficient of thermal expansion of 36 ppm/° C. and a glass transition temperature of 288 ° C.

實施例7、化合物V-B(c)之合成Example 7, Synthesis of Compound V-B(c)

反應條件同實施例5，唯將式(IV-C)雙胺化合物改為式(IV-B)雙胺化合物。動態機械分析儀顯示其儲存模數為3.11 GPa，玻璃轉移溫度為306℃。熱機械分析儀顯示其熱膨脹係數為32ppm/℃，玻璃轉移溫度為282℃。The reaction conditions were the same as in Example 5 except that the bisamine compound of the formula (IV-C) was changed to the bisamine compound of the formula (IV-B). The dynamic mechanical analyzer showed a storage modulus of 3.11 GPa and a glass transition temperature of 306 °C. The thermomechanical analyzer showed a coefficient of thermal expansion of 32 ppm/° C. and a glass transition temperature of 282 ° C.

實施例8、化合物V-D(c)之合成Example 8, Synthesis of Compound V-D(c)

反應條件同實施例5，唯將式(IV-C)雙胺化合物改為式(IV-D)雙胺化合物。動態機械分析儀顯示其儲存模數為6.23 GPa，玻璃轉移溫度為305℃。熱機械分析儀顯示其熱膨脹係數為37ppm/℃，玻璃轉移溫度為285℃。The reaction conditions were the same as in Example 5 except that the bisamine compound of the formula (IV-C) was changed to the bisamine compound of the formula (IV-D). The dynamic mechanical analyzer showed a storage modulus of 6.23 GPa and a glass transition temperature of 305 °C. The thermomechanical analyzer showed a coefficient of thermal expansion of 37 ppm/° C. and a glass transition temperature of 285 ° C.

比較例、聚醯亞胺(ODA-BTDA)之合成Comparative Example, Synthesis of Polyimine (ODA-BTDA)

聚醯亞胺(ODA-BTDA)係由4,4'-二氨基二苯醚(ODA)與4,4'-四羧基二苯酮酐(4,4'-carbonyldiphthalic anhydride,BTDA)所聚合而成。Polyimine (ODA-BTDA) is polymerized from 4,4'-diaminodiphenyl ether (ODA) and 4,4'-carbonyldiphthalic anhydride (BTDA). to make.

取4,4'-二氨基二苯醚(ODA)1.0克(4.99毫莫耳)與4,4'-四羧基二苯酮酐(BTDA)1.609克(4.99毫莫耳)溶於除水二甲基乙醯胺(N,N-Dimethylacetamide)，在氮氣填充下冰浴攪拌12小時，形成聚醯胺酸黏稠溶液後，利用塗佈機塗膜於玻璃基板上，。置於循環烘箱升 溫至60℃維持12小時，去除大部分溶劑後，階段升溫100℃ 1小時、200℃ 1小時、300℃ 1小時，進行熱亞胺化(thermal imidization)。接著將玻璃基板浸於水中使薄膜與基板分離，得聚醯亞胺之薄膜。Take 4,4'-diaminodiphenyl ether (ODA) 1.0 g (4.99 mmol) and 4,4'-tetracarboxybenzophenone anhydride (BTDA) 1.609 g (4.99 mmol) dissolved in water N,N-Dimethylacetamide was stirred in an ice bath under nitrogen for 12 hours to form a polyamic acid viscous solution, which was then coated on a glass substrate by a coater. Placed in a circulating oven After heating to 60 ° C for 12 hours, most of the solvent was removed, and the temperature was raised by 100 ° C for 1 hour, 200 ° C for 1 hour, and 300 ° C for 1 hour to carry out thermal imidization. Next, the glass substrate was immersed in water to separate the film from the substrate to obtain a film of polyimine.

圖7顯現聚醯亞胺(ODA-BTDA)動態機械分析數據，其中儲存模數為8.91 GPa，玻璃轉移溫度為294℃。圖8顯現聚醯亞胺(ODA-BTDA)熱機械分析數據，其中熱膨脹係數為53ppm/℃，玻璃轉移溫度為270℃。Figure 7 shows dynamic mechanical analysis data for polyimine (ODA-BTDA) with a storage modulus of 8.91 GPa and a glass transition temperature of 294 °C. Figure 8 shows thermoelastic analysis data of polyimine (ODA-BTDA) with a coefficient of thermal expansion of 53 ppm/°C and a glass transition temperature of 270 °C.

相較於未使用本發明雙胺化合物所得之聚醯亞胺，本發明之磷系聚醯亞胺具有較低的儲存模數及熱膨脹係數及具有較高的玻璃轉移溫度。此外，由於本發明於聚醯亞胺中引入磷系化合物，進而可提升該聚醯亞胺阻燃性及熱氧穩定性。The phosphorus-based polyimine of the present invention has a lower storage modulus and thermal expansion coefficient and a higher glass transition temperature than the polyimine obtained without using the bisamine compound of the present invention. Further, since the present invention introduces a phosphorus-based compound into the polyimine, the flame retardancy and thermo-oxidation stability of the polyimide can be improved.

溶解度測試Solubility test

下表顯示根據本發明之實例化合物V-A(c)、V-B(c)、V-C(c)及V-D(c)與比較例化合物ODA-BTDA之溶解度實驗結果。該實驗係將5 mg之測試化合物加至0.5 mL之表中對應溶劑所進行。於下表中，符號「+」表示測試化合物在室溫下即可溶解於對應溶劑中；符號「+h」表示測試化合物在加熱下才可溶解於對應溶劑中；符號「+-」表示測試化合物在加熱下僅部分溶解於對應溶劑中；符號「-」表示測試化合物在加熱下亦不溶解於對應溶劑中。由下表可知，相較於比較例化合物ODA-BTDA，根據本發明之實例化合物V-A(c)、V-B(c)、V-C(c)及V-D(c)於不同溶劑中皆具有較佳之溶解度。The table below shows the results of solubility experiments of the example compounds V-A(c), V-B(c), V-C(c) and V-D(c) according to the present invention and the comparative compound ODA-BTDA. This experiment was carried out by adding 5 mg of the test compound to the corresponding solvent in the 0.5 mL table. In the table below, the symbol "+" indicates that the test compound can be dissolved in the corresponding solvent at room temperature; the symbol "+h" indicates that the test compound is soluble in the corresponding solvent under heating; the symbol "+-" indicates the test. The compound is only partially dissolved in the corresponding solvent under heating; the symbol "-" indicates that the test compound is not dissolved in the corresponding solvent under heating. As is apparent from the following table, the compounds V-A(c), V-B(c), V-C(c) and V-D(c) according to the present invention have better solubility in different solvents than the comparative compound ODA-BTDA.

Claims (18)

一種式(I)磷系雙胺化合物， 其中Y1 及Y2 各獨立為H、C1 -C6 烷基、苯基或CF3 ，或Y1 及Y2 與彼等所連接之碳原子一起形成C5 -C13 碳環；及R1 及R2 各獨立為H、C1 -C6 烷基或C3 -C6 環烷基，其中該環烷基係未經取代或經一或多個C1 -C6 烷基取代。a phosphorus-based bisamine compound of the formula (I), Wherein Y 1 and Y 2 are each independently H, C 1 -C 6 alkyl, phenyl or CF 3 , or Y 1 and Y 2 together with the carbon atom to which they are attached form a C 5 -C 13 carbocycle; R 1 and R 2 are each independently H, C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl, wherein the cycloalkyl is unsubstituted or substituted by one or more C 1 -C 6 alkyl groups . 如請求項1之化合物，其為下式之化合物： A compound of claim 1 which is a compound of the formula: 一種具有式(I)之磷系雙胺化合物之製造方法， 其包含下列步驟：(i)將式(DOPO)化合物與式(BP)化合物進行反應， 以產生式(II)化合物； (ii)在鹼存在下，將式(II)化合物與式(DN)化合物進行反應， 以產生式(III)化合物；及 (iii)還原式(III)化合物，以產生式(I)之磷系雙胺化合物，其中Y1 、Y2 、R1 及R2 係如請求項1中所定義，且L代表芳香親核取代離去基。A method for producing a phosphorus-based bisamine compound having the formula (I), It comprises the steps of: (i) reacting a compound of formula (DOPO) with a compound of formula (BP), To produce a compound of formula (II); (ii) reacting a compound of formula (II) with a compound of formula (DN) in the presence of a base, To produce a compound of formula (III); (iii) reducing a compound of formula (III) to produce a phosphorus-based bisamine compound of formula (I) wherein Y 1 , Y 2 , R 1 and R 2 are as defined in claim 1 and L represents aromatic nucleophile Substituting the leaving group. 如請求項3之方法，其中步驟(i)係在酸觸媒存在下進行。The method of claim 3, wherein the step (i) is carried out in the presence of an acid catalyst. 如請求項4之方法，其中該酸觸媒係選自由對-甲基苯磺酸(p-Toluenesulfonic acid,PTSA)、甲基磺酸(Methanesulfonic acid)、硫酸(Sulfuric acid)及草酸所組成之群。The method of claim 4, wherein the acid catalyst is selected from the group consisting of p-Toluenesulfonic acid (PTSA), Methanesulfonic acid, Sulfuric acid, and oxalic acid. group. 如請求項3之方法，其中該鹼為碳酸鉀。The method of claim 3, wherein the base is potassium carbonate. 如請求項3之方法，其中該還原係在氫氣下以Pd/C催化所進行。The method of claim 3, wherein the reduction is carried out under Pd/C catalysis under hydrogen. 如請求項3之方法，其中該芳香親核取代離去基為F、Cl、Br、I或磺酸酯。The method of claim 3, wherein the aromatic nucleophilic substitution leaving group is F, Cl, Br, I or a sulfonate. 一種式(III)之磷系雙硝基苯化合物， 其中Y1 、Y2 、R1 及R2 係如請求項1中所定義。a phosphorus-based bisnitrobenzene compound of the formula (III), Wherein Y 1 , Y 2 , R 1 and R 2 are as defined in claim 1. 一種具有式(III)之磷系雙硝基苯化合物之製造方法， 其包含下列步驟：(i)將式(DOPO)化合物與式(BP)化合物進行反應， 以產生式(II)化合物；及 (ii)在鹼存在下，將式(II)化合物與式(DN)化合物進行反應， 以產生式(III)化合物，其中Y1 、Y2 、R1 及R2 係如請求項1中所定義，且L代表芳香親核取代離去基。A method for producing a phosphorus-based bisnitrobenzene compound having the formula (III), It comprises the steps of: (i) reacting a compound of formula (DOPO) with a compound of formula (BP), To produce a compound of formula (II); (ii) reacting a compound of formula (II) with a compound of formula (DN) in the presence of a base, To produce a compound of formula (III) wherein Y 1 , Y 2 , R 1 and R 2 are as defined in claim 1 and L represents an aromatic nucleophilic substituted leaving group. 一種磷系聚醯亞胺，其係由如請求項1之式(I)磷系雙胺化合物、 雙酸酐單體及視情況添加選用的其他雙胺單體所聚合而成。A phosphorus-based polyimine, which is a phosphorus-based bisamine compound of the formula (I) of claim 1 The dianhydride monomer and other diamine monomers selected as needed are polymerized. 如請求項11之磷系聚醯亞胺，其為式(V)之磷系聚醯亞胺 其中，R為 其中Y1 、Y2 、R1 及R2 係如請求項1中所定義；Z為該雙胺單體之殘基；Ar各獨立為四價有機基；x為1至100之整數；且y為0至99之整數。The phosphorus-based polyimine of claim 11, which is a phosphorus-based polyimine of the formula (V) Where R is Wherein Y 1 , Y 2 , R 1 and R 2 are as defined in claim 1; Z is a residue of the bisamine monomer; each of Ar is independently a tetravalent organic group; and x is an integer from 1 to 100; y is an integer from 0 to 99. 如請求項12之磷系聚醯亞胺，其中Ar係選自由下列所組成之群： 及，其中A為一單鍵、-O-、-CO-、-S-、-SO2 -、-C(CH3 )2 -、-C(CF3 )2 -、-CONH-、-COO-、-(CH2 )n -、-O(CH2 )n2 O-或-COO(CH2 )n3 OCO-，其中n、n2及n3各自獨立為1至10之整數，且*表示鍵結點。The phosphorus-based polyimine of claim 12, wherein the Ar is selected from the group consisting of: and Wherein A is a single bond, -O-, -CO-, -S-, -SO 2 -, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -CONH-, -COO- , -(CH 2 ) n -, -O(CH 2 ) n2 O- or -COO(CH 2 ) n3 OCO-, wherein n, n2 and n3 are each independently an integer from 1 to 10, and * represents a bond point . 如請求項13之磷系聚醯亞胺，其中Ar係選自由下列所組成之群： The phosphorus-based polyimine of claim 13, wherein the Ar is selected from the group consisting of: 如請求項12之磷系聚醯亞胺，其中Z為 The phosphorus-based polyimine of claim 12, wherein Z is 一種如請求項11之磷系聚醯亞胺之製造方法，其包含將如請求項1之式(I)磷系雙胺化合物、雙酸酐單體及視情況添加的其他雙胺單體，在溶劑下進行溶液聚合。A method for producing a phosphorus-based polyimine according to claim 11, which comprises a phosphorus-based bisamine compound of the formula (I), a dianhydride monomer, and optionally other diamine monomers, as in claim 1 Solution polymerization is carried out under a solvent. 如請求項16之方法，其中該雙酸酐單體之含量係與如請求項1之式(I)磷系雙胺化合物與該視情況添加的其他雙胺單體之總含量等當量。The method of claim 16, wherein the content of the bis-anhydride monomer is equivalent to the total content of the phosphorus-based bisamine compound of the formula (I) of claim 1 and the optionally added other bisamine monomer. 如請求項17之方法，其中如請求項1之式(I)磷系雙胺化合物與該視情況添加選用的其他雙胺單體的比例係介於10：0至1：9之間。The method of claim 17, wherein the ratio of the phosphorus bisamine compound of the formula (I) of claim 1 to the other bisamine monomer optionally added is optionally between 10:0 and 1:9.
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