TWI522396B - Phosphinated multifunctional phenol polymer and its epoxy thermosets with high glass transition temperature - Google Patents

Description

磷系多官能酚類聚合物與其高玻璃轉移溫度之環氧樹脂固化物 Phosphorus-based polyfunctional phenolic polymer and its high glass transition temperature epoxy resin cured product

本發明係提供一種磷系多官能酚類聚合物，該聚合物可進一步用於製備高玻璃轉移溫度難燃樹脂硬化物。 The present invention provides a phosphorus-based polyfunctional phenolic polymer which can be further used for preparing a high glass transition temperature flame retardant resin cured product.

環氧樹脂具有優良的電氣性質、尺寸安定性、耐高溫、耐溶劑性、低成本及高接著性等優點，適合做印刷電路板及積體電路封裝材料。然而，以碳、氫、氧原子鍵結的環氧樹脂與一般塑膠材料一樣容易燃燒進而危害生命，因此全世界對於使用電子、資訊用材料，其難燃性有嚴格要求。 Epoxy resin has excellent electrical properties, dimensional stability, high temperature resistance, solvent resistance, low cost and high adhesion. It is suitable for printed circuit boards and integrated circuit packaging materials. However, epoxy resins bonded with carbon, hydrogen, and oxygen atoms are as easy to burn as normal plastic materials, which is life-threatening. Therefore, the use of electronic and information materials in the world has strict requirements for flame retardancy.

在阻燃技術上，過去以環氧樹脂中導入溴原子為主。含溴環氧樹脂因優異的難燃特性，廣泛地被應用於具有難燃特性需求的電子材料上。然而，這些含溴環氧樹脂在燃燒過程會釋出溴化氫、四溴二聯苯戴奧辛(tetrabromodibenzo-p-dioxin)與四溴二聯苯呋喃(tetrabromodibenzofuran)等具有腐蝕性及毒性物質。 In the flame retardant technology, in the past, bromine atoms were mainly introduced into the epoxy resin. Brominated epoxy resins are widely used in electronic materials with flame retardant properties due to their excellent flame retardant properties. However, these bromine-containing epoxy resins release corrosive and toxic substances such as hydrogen bromide, tetrabromodibenzo-p-dioxin and tetrabromodibenzofuran during combustion.

除了含鹵素的化合物外，有機磷化合物亦具有高度阻燃性；磷系難燃劑在燃燒時會促使高分子材料先行脫水，使碳氫化合物之氫與空氣中氧形成水，藉以降低周遭環境的溫度，使其低於燃燒溫度而達到難燃效果；另一方面在高溫加熱下會分解出磷酸促進高分子化合物 的碳化，而形成不燃性焦炭層。此外，磷酸在高溫下會進一步脫水酯化形成聚磷酸覆蓋於燃燒物的表面形成保護作用，阻止氧氣進入高分子未燃燒的內層以及抑制揮發性裂解物的釋放。 In addition to halogen-containing compounds, organophosphorus compounds are also highly flame-retardant; phosphorus-based flame retardants promote the dehydration of polymer materials during combustion, allowing hydrogen from hydrocarbons to form water with oxygen in the air, thereby reducing the surrounding environment. The temperature is lower than the combustion temperature to achieve a flame retardant effect; on the other hand, under high temperature heating, the phosphoric acid promotes the polymer compound Carbonization forms a non-combustible coke layer. In addition, phosphoric acid is further dehydrated and esterified at a high temperature to form a polyphosphoric acid covering the surface of the combustion product to form a protective effect, preventing oxygen from entering the unburned inner layer of the polymer and inhibiting the release of volatile lysate.

導入磷元素的方法有二種，一種是直接合成含磷之環氧樹脂，另一種是將含磷硬化劑與環氧樹脂均勻混合。本發明則提供含磷硬化劑，使其與環氧樹脂混合硬化後，便可達到難燃的效果。 There are two methods for introducing phosphorus, one is to directly synthesize a phosphorus-containing epoxy resin, and the other is to uniformly mix a phosphorus-containing hardener with an epoxy resin. The present invention provides a phosphorus-containing hardener which is hardened by mixing with an epoxy resin to achieve a flame retardant effect.

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，因其可與缺電子化合物如苯二酮(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]等進行親核加成反應。 Among the phosphorus-containing derivatives, the reactive 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide, DOPO) is highly regarded because it can be associated with electron-deficient compounds such as benzoquinone ^[1] , oxirane ^[2] , maleic acid ^[3] , and double malaya The nucleophilic addition reaction of bismaleimide ^[4] , diaminobenzophenone ^[5-6] and terephthaldicarboxaldehyde ^[7] .

王等人在2001年提出可利用DOPO中的活性氫以附加型的方式，直接和雙官能或多官能的環氧樹脂的環氧基反應，而形成具有高玻璃轉移溫度(Tg)、高熱裂解溫度及高彈性率，而且對環境無害的難燃環氧樹脂半固化物^[2]。林等人也在2005年揭露三官能硬化劑(dopotriol^[8]與dopo-ta^[9])的合成方法與應用，成功得到難燃且具有高玻璃轉移溫度的環氧樹脂。然而，文獻中合成dopotriol的原料薔薇酸(rosolic acid)非常昂貴，於工業應用上不符合經濟效益，於是林等人接著於2008年以較便宜的4,4'-二羥基二苯基甲酮(4,4'-dihydroxy benzophenone,DHBP)與DOPO及苯酚/苯胺反應，成功合成含磷難燃劑dopotriol以及dopodiolamine^[10]。經由硬化所得之環氧樹脂具有優異玻璃轉移溫度、熱穩定性、尺寸安定性及難燃性。但dopotriol以及dopodiolamine有溶解度不佳的加工性的問題。 Wang et al. proposed in 2001 that the active hydrogen in DOPO can be used in an episodic manner to directly react with the epoxy group of a difunctional or polyfunctional epoxy resin to form a high glass transition temperature (Tg) and high thermal cracking. Temperature and high modulus of elasticity, and environmentally friendly flame retardant epoxy resin semi-cured ^[2] . Lin et al. also unveiled the synthesis method and application of trifunctional hardeners (dopotriol ^[8] and dopo-ta ^[9] ) in 2005, and successfully obtained epoxy resins with flame retardant and high glass transition temperatures. However, the rosolic acid, a raw material for the synthesis of dopotriol in the literature, is very expensive and is not economically viable in industrial applications, so Lin et al. followed the cheaper 4,4'-dihydroxydiphenyl ketone in 2008. (4,4'-dihydroxy benzophenone, DHBP) reacted with DOPO and phenol/aniline to successfully synthesize the phosphorus-containing flame retardant dopotriol and dopodiolamine ^[10] . The epoxy resin obtained by hardening has excellent glass transition temperature, thermal stability, dimensional stability, and flame retardancy. However, dopotriol and dopodiolamine have problems with poor solubility.

酚醛樹脂是最早工業化的合成樹脂，由於原料易得，吸水率低，加工性良好以及樹脂固化後性能能滿足很多使用要求，因此在模 塑膠、絕緣材料、塗料、木材黏接等方面得到廣泛應用。近年來隨著人們對安全等要求的提高，具有阻燃、少煙、無毒等特性的酚醛樹脂重新引起人們重視，尤其在飛機場、火車站、學校、醫院等公共建築設施及飛機的內部裝飾材料等方面的應用越來越多。 Phenolic resin is the earliest industrial synthetic resin. Due to the availability of raw materials, low water absorption, good processability and performance after curing, the resin can meet many requirements. Plastics, insulation materials, coatings, wood bonding and other aspects have been widely used. In recent years, with the improvement of people's requirements for safety, phenolic resin with characteristics of flame retardancy, less smoke, and no toxicity has attracted people's attention, especially in public buildings such as airports, railway stations, schools, hospitals, and interior decoration of aircraft. There are more and more applications in materials and so on.

文獻指出，雙酚A會在酸催化下裂解成酚及不安定的4-isopropenylphonel^[11]。林等人即利用DOPO與雙酚A，在酸催化下進行反應，使DOPO鍵結於剛形成之4-isopropenylphonel上，合成單官能酚類化合物。接著利用DOPO與三官能酚1,1,1-三(4-羟基苯基)乙烷(1,1,1-tris(4-hydroxyphenyl)ethane)，在酸催化下進行反應，形成雙官能酚類化學物。此外，林等人亦將DOPO與多官能雙酚A酚醛樹脂(BPA novolac)在酸催化下合成磷系多官能雙酚A酚醛樹脂^[12]，並護得良好的阻燃性。 The literature indicates that bisphenol A will be cleaved by acid catalysis into phenol and unstable 4-isopropenylphonel ^[11] . Lin et al. used DOPO and bisphenol A to react under acid catalysis to bond DOPO to the newly formed 4-isopropenylphonel to synthesize monofunctional phenolic compounds. Then, using DOPO and trifunctional phenol 1,1,1-tris(4-hydroxyphenyl)ethane, the reaction is carried out under acid catalysis to form a bifunctional phenol. Chemicals. In addition, Lin et al. also synthesized phosphorus-based polyfunctional bisphenol A phenolic resin with DOPO and polyfunctional bisphenol A phenolic resin (BPA novolac) under acid catalysis ^[12] , and maintained good flame retardancy.

在中華民國專利I432445中，林等人將DOPO與雙酚A酚醛樹脂反應以獲致磷系酚醛聚合物(P-BPN)。該專利揭露DOPO會和雙酚A酚醛樹脂(BPN)的亞異丙基基團(isopropylidiene)反應；DOPO可能是和雙酚A酚醛樹脂末端位置的亞異丙基基團或雙酚A酚醛樹脂中間位置的亞異丙基基團反應，因此有多種反應途徑。以下列出其中一種途徑作為示意： In Republic of China Patent I432445, Lin et al. reacted DOPO with a bisphenol A phenolic resin to obtain a phosphorus-based phenolic polymer (P-BPN). This patent discloses that DOPO will react with the isopropylidiene of bisphenol A phenolic resin (BPN); DOPO may be an isopropylidene group or a bisphenol A phenolic resin at the terminal position of the bisphenol A phenolic resin. The isopropylidene group in the intermediate position reacts, so there are multiple reaction pathways. One of the ways is listed below as an illustration:

然而多官能雙酚A酚醛樹脂與DOPO反應後，會降低其分子量，導致硬化物的玻璃轉移溫度偏低。 However, when the polyfunctional bisphenol A phenolic resin is reacted with DOPO, its molecular weight is lowered, resulting in a low glass transition temperature of the cured product.

本發明為中華民國專利I432445的改良，方法為增加產物的分子量，以獲得高玻轉移溫度的環氧樹脂固化物。 The present invention is an improvement of the Republic of China Patent I432445 by increasing the molecular weight of the product to obtain a cured epoxy resin having a high glass transition temperature.

參考文獻： references:

[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] Liu, Y.L.; Wang, C.S.; Hsu, K.Y. and Chang, T.C. J. Polym. Sci. Part A: Polym. Chem. 2002, 40, 2329. [7] Liu, Y.L.; Wang, C.S.; Hsu, K.Y. and Chang, T.C. J. Polym. Sci. Part A: Polym. Chem. 2002, 40, 2329.

[8] Lin, C.H.; Cai, S.X. and Lin, C.H. J. Polym. Sci. Polym. Chem. 2005, 43, 5971. [8] Lin, C.H.; Cai, S.X. and Lin, C.H. J. Polym. Sci. Polym. Chem. 2005, 43, 5971.

[9] Cai, S.X. and Lin, C.H. J. Polym. Sci. Polym. Chem. 2005, 43, 2862. [9] Cai, S.X. and Lin, C.H. J. Polym. Sci. Polym. Chem. 2005, 43, 2862.

[10] Lin, C.H.; Lin, T.L.; Chang S.L.; Dai, S.H. A.; Cheng, R.J.; Hwang, K.U.; Tu, A.P.; Su, W.C. J. Polym. Sci. Part A: Polym. Chem. 2008, 46, 7898. [10] Lin, CH; Lin, TL; Chang SL; Dai, SHA; Cheng, RJ; Hwang, KU; Tu, AP; Su, WCJ Polym. Sci. Part A: Polym. Chem. 2008, 46, 7898.

[11] Andrew J.C. and Julia L.L. J. Org. Chem. 1997, 62, 1058. [11] Andrew J.C. and Julia L.L. J. Org. Chem. 1997, 62, 1058.

[12] 中華民國專利I432445 [12] Republic of China Patent I432445

本發明係提供新穎磷系多官能酚類聚合物及其製備方法；該磷系多官能酚類聚合物可進一步與環氧樹脂硬化，製備高玻璃轉移溫度之難燃樹脂硬化物。 The present invention provides a novel phosphorus-based polyfunctional phenolic polymer and a process for preparing the same; the phosphorus-based polyfunctional phenolic polymer can be further hardened with an epoxy resin to prepare a flame retardant resin cured product having a high glass transition temperature.

應瞭解在此說明書中所引用的任何數值範圍欲包含其內所涵括之所有次範圍。例如，從「60℃至200℃」的範圍包括陳述的最小數值60℃及陳述的最大數值200℃之間所有的次範圍(如從91℃至182℃、103℃至168℃、62℃或133℃)且包含該兩數值，亦即包含等於或大於60℃之最小值以及等於或小於200℃之最大值之範圍。因為所揭示的數值範圍是連續的，因此他們包含最小值和最大值之間的每個數值。除非另加說明，否則此說明書中指明的各種數值範圍是概略值。 It is to be understood that any range of values recited in this specification is intended to include all sub-ranges For example, the range from "60 ° C to 200 ° C" includes all the sub-ranges between the stated minimum value of 60 ° C and the stated maximum value of 200 ° C (eg from 91 ° C to 182 ° C, 103 ° C to 168 ° C, 62 ° C or 133 ° C) and includes the two values, that is, a range including a minimum value equal to or greater than 60 ° C and a maximum value equal to or lower than 200 ° C. Because the ranges of values disclosed are continuous, they contain each value between the minimum and maximum values. Unless otherwise stated, the various numerical ranges indicated in this specification are approximate.

本專利申請人曾嘗試將含磷的單官能酚(DOPP-phenol)和甲醛在 不同的酸催化下反應(實施例1)，形成磷系酚醛樹脂(DOPO-PN)： The applicant of the present patent has attempted to react a phosphorus-containing monofunctional phenol (DOPP-phenol) and formaldehyde under different acid catalysis (Example 1) to form a phosphorus phenolic resin (DOPO-PN):

惟，根據多方嘗試的結果，申請人發現該反應無法進行；推測其原因為拉電子基團P=O雙鍵的存在降低酚的反應性。 However, based on the results of various attempts, the Applicant found that the reaction could not be carried out; it is speculated that the reason is that the presence of the P=O double bond of the electron-withdrawing group reduces the reactivity of the phenol.

然而，根據酚和甲醛形成酚醛樹脂以及雙酚A和甲醛形成雙酚A型酚醛樹脂的化學 However, the chemistry of phenolic resin based on phenol and formaldehyde, and bisphenol A and formaldehyde to form bisphenol A phenolic resin

可進一步推論前述中華民國專利I432445之產物，與甲醛或多聚甲醛反應的位置可能為 It can be further inferred that the product of the aforementioned Republic of China Patent I432445 may react with formaldehyde or paraformaldehyde.

其中標定是不會和甲醛反應的位置，而標定是會和甲醛反應的位置。據此，若依該途徑，其所得聚合物(P-BPN-CH₂)具如下結構： 。 Calibration Is the location that will not react with formaldehyde, and calibration It is the place where it will react with formaldehyde. Accordingly, according to this route, the obtained polymer (P-BPN-CH ₂ ) has the following structure: .

新穎磷系多官能酚類聚合物Novel phosphorus-based polyfunctional phenolic polymers

據上所述，本發明係提供一種新穎磷系多官能酚類聚合物，其包含如下式(I)及(II)之結構 According to the above, the present invention provides a novel phosphorus-based polyfunctional phenolic polymer comprising the structures of the following formulas (I) and (II)

其中0≦a≦30，1≦b≦30；Y為-CH₂-或-CH₂OCH₂-；且各R₀係相同或不同，獨立選自於由氫原子、C₁~C₆烷基、C₁~C₆烷氧基、苯基、硝基、苯氧基、C₁~C₁₀鹵烷基、C₃~C₇環烷基、C₁~C₁₀鹵烷氧基和鹵素所組成之群。 Wherein 0≦a≦30,1≦b≦30; Y is -CH ₂ - or -CH ₂ OCH ₂ -; and each R ₀ is the same or different and is independently selected from a hydrogen atom, a C ₁ -C ₆ alkane , C ₁ -C ₆ alkoxy, phenyl, nitro, phenoxy, C ₁ -C ₁₀ haloalkyl, C ₃ -C ₇ cycloalkyl, C ₁ -C ₁₀ haloalkoxy and halogen The group formed.

於本發明之一實施例中，當全部R₀係氫原子且Y為-CH₂-時，該式(II)具有式(IV)之結構 該式(III)具有式(V)之結構 In one embodiment of the invention, when all of R ₀ are hydrogen atoms and Y is -CH ₂ -, the formula (II) has the structure of formula (IV) The formula (III) has the structure of the formula (V)

於本發明，上述聚合物通常係以寡聚物之形式存在。 In the present invention, the above polymers are usually present in the form of oligomers.

新穎磷系多官能酚類聚合物之製備方法Method for preparing novel phosphorus-based polyfunctional phenolic polymer

本發明提供一種如前述包含式(II)及(III)之結構的磷系多官能酚類聚合物的製備方法，其包含以下步驟： (1)將如下式之DOPO化合物與式(I)之雙酚型酚醛樹脂(BPN)在酸觸媒存在下進行反應 The present invention provides a method for producing a phosphorus-based polyfunctional phenolic polymer comprising the structures of the formulae (II) and (III), which comprises the following steps: (1) a DOPO compound of the following formula and a formula (I) Bisphenol novolac resin (BPN) reacts in the presence of an acid catalyst

以得到包含如下式(II-1)及(III-1)之結構的中間產物 To obtain an intermediate product comprising the structures of the following formulas (II-1) and (III-1)

(2)將該中間產物與多聚甲醛或甲醛在酸觸媒存在下反應而得到包含式(II)及(III)之結構的磷係多官能酚類聚合物；其中0≦a≦30，1≦b≦30；Y為-CH₂-或-CH₂OCH₂-；且各R₀係相同或不同，獨立選自於由氫原子、C₁~C₆烷基、C₁~C₆烷氧基、苯基、硝基、苯氧基、C₁~C₁₀鹵烷基、C₃~C₇環烷基、C₁~C₁₀鹵烷氧基和鹵素所組成之群。 (2) reacting the intermediate product with paraformaldehyde or formaldehyde in the presence of an acid catalyst to obtain a phosphorus-based polyfunctional phenolic polymer comprising the structures of the formulae (II) and (III); wherein 0≦a≦30, 1≦b≦30; Y is -CH ₂ - or -CH ₂ OCH ₂ -; and each R ₀ is the same or different and is independently selected from a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₁ ~C ₆ A group consisting of an alkoxy group, a phenyl group, a nitro group, a phenoxy group, a C ₁ -C ₁₀ haloalkyl group, a C ₃ -C ₇ cycloalkyl group, a C ₁ -C ₁₀ haloalkoxy group, and a halogen.

本發明上述方法中，當全部R₀係氫原子時式(I)具有以下結構 而其所產生的式(II)及式(III)分別具有如上述式(IV)及式(V)之結構。 In the above method of the present invention, the formula (I) has the following structure when all of the R ₀ is a hydrogen atom; Further, the formula (II) and the formula (III) produced by the formula have the structures of the above formula (IV) and formula (V).

本發明上述方法中，該多聚甲醛係三聚甲醛。 In the above method of the present invention, the paraformaldehyde is trioxane.

本發明上述方法中，該中間產物之總磷含量係3wt%至8wt%，較佳為4wt%至7wt%。 In the above process of the present invention, the intermediate product has a total phosphorus content of from 3 wt% to 8 wt%, preferably from 4 wt% to 7 wt%.

本發明上述方法中，該酸觸媒係選自由草酸、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(CF₃COOH)、硝酸(HNO₃)、磷酸(H₃PO₄)所組成之群；該酸觸媒較佳係對-甲基苯磺酸。 In the above method of the present invention, the acid catalyst is selected from the group consisting of oxalic acid, acetic acid, p-Toluenesulfonic acid (PTSA), methanesulfonic acid, and fluorosulfonic acid. Trifluoromethanesulfonic acid, Sulfuric acid, Orthanilic acid, 3-Pyridinesulfonic acid, Sulfanilic acid Hydrogen chloride (HCl), hydrogen bromide (HBr), hydrogen iodide (HI), hydrogen fluoride (HF), trifluoroacetic acid (CF ₃ COOH), nitric acid (HNO ₃ ), phosphoric acid (H ₃ PO ₄ ) The acid catalyst is preferably p-toluenesulfonic acid.

本發明上述方法中，其中該酸觸媒之量為該中間產物總合之的0.1wt%至10wt%，較佳為0.1wt%至5wt%，更佳0.5wt%至3wt%。 In the above process of the present invention, the amount of the acid catalyst is from 0.1% by weight to 10% by weight, preferably from 0.1% by weight to 5% by weight, more preferably from 0.5% by weight to 3% by weight based on the total of the intermediate product.

本發明上述方法中，該多聚甲醛之量係該中間產物之總酚基當量數之10%至150%，較佳45%至150%，更佳85%至150%。 In the above method of the present invention, the amount of the paraformaldehyde is from 10% to 150%, preferably from 45% to 150%, more preferably from 85% to 150%, based on the total phenolic equivalents of the intermediate product.

本發明上述方法中，該步驟(1)之反應時間係3至24小時，較佳7 至20小時，更佳10至14小時。 In the above method of the present invention, the reaction time of the step (1) is 3 to 24 hours, preferably 7 Up to 20 hours, preferably 10 to 14 hours.

本發明上述方法中，該步驟(2)之反應時間係3至24小時，較佳7至20小時，更佳10至14小時。 In the above method of the present invention, the reaction time of the step (2) is from 3 to 24 hours, preferably from 7 to 20 hours, more preferably from 10 to 14 hours.

本發明上述方法中，該步驟(1)之反應溫度係60℃至200℃間，較佳100至℃至170℃間，更佳130至℃至150℃間。 In the above method of the present invention, the reaction temperature of the step (1) is between 60 ° C and 200 ° C, preferably between 100 and ° C to 170 ° C, more preferably between 130 and 150 ° C.

本發明上述方法中，該步驟(2)之反應溫度係60℃至180℃間，較佳75至℃至155℃間，更佳100至℃至120℃間。 In the above method of the present invention, the reaction temperature of the step (2) is between 60 ° C and 180 ° C, preferably between 75 ° C and 155 ° C, more preferably between 100 ° C and 120 ° C.

本發明上述方法中，該反應壓力可在常壓或減壓下反應。 In the above method of the present invention, the reaction pressure can be reacted under normal pressure or reduced pressure.

本發明上述方法中，該等反應可使用或不使用溶劑進行。若反應係在溶劑中進行，該溶劑可選自由乙氧基乙醇(ethoxy ethanol)、甲氧基乙醇(methoxy ethanol)、1-甲氧基-2-丙醇(1-methoxy-2-propanol)、DOW PM、二噁烷及上述溶劑所組成的共溶劑所組成之群；該溶劑較佳係1-甲氧基-2-丙醇。 In the above process of the invention, the reactions can be carried out with or without a solvent. If the reaction is carried out in a solvent, the solvent may be selected from ethoxy ethanol, methoxy ethanol, 1-methoxy-2-propanol. a group consisting of DOW PM, dioxane and a cosolvent composed of the above solvents; the solvent is preferably 1-methoxy-2-propanol.

新穎磷系多官能酚類聚合物之用途Use of novel phosphorus-based polyfunctional phenolic polymers

本發明另提供一種新穎硬化劑，其包含如上所述之該磷系多官能酚類聚合物。 The present invention further provides a novel hardener comprising the phosphorus-based polyfunctional phenolic polymer as described above.

本發明另提供一種製備高玻璃轉移溫度難燃環氧樹脂硬化物之方法，其包括將環氧樹脂與如上所述之硬化劑進行硬化反應。 The present invention further provides a method of preparing a high glass transition temperature flame retardant epoxy resin hardened comprising reacting an epoxy resin with a hardener as described above.

於本發明一實施例中，其中該環氧樹脂與該硬化劑之當量比例為1：0.1至1：1，較佳係1：1。 In an embodiment of the invention, the equivalent ratio of the epoxy resin to the hardener is 1:0.1 to 1:1, preferably 1:1.

於本發明一實施例中，其中該環氧樹脂係選自雙酚A環氧樹脂(diglycidyl ether of bisphenol A,DGEBA)、二氧化雙環戊二烯環氧樹脂(dicyclopentadiene epoxy,HP 7200)、磷甲基酚醛環氧樹脂(cresol novolac epoxy,CNE)或酚醛環氧樹脂(phenol novolac epoxy,PNE)。 In an embodiment of the invention, the epoxy resin is selected from the group consisting of diglycidyl ether of bisphenol A (DGEBA), dicyclopentadiene epoxy (HP 7200), and phosphorus. Cresol novolac epoxy (CNE) or phenol novolac epoxy (PNE).

本發明另提供一種高玻璃轉移溫度難燃環氧樹脂硬化物，其係依如上所述之高玻璃轉移溫度難燃環氧樹脂硬化物製備方法所製備之 產物。 The invention further provides a high glass transition temperature flame retardant epoxy resin hardened material, which is prepared according to the high glass transition temperature flame retardant epoxy resin hardened material preparation method as described above. product.

本發明頃發現，依據本發明製備難燃環氧樹脂硬化物之方法所製備之硬化物，相較於未經多聚甲醛改質之磷系多官能酚醛樹脂所製備的硬化物，本發明之硬化物能明顯達成優異的熱性質及穩定性。 The present invention has found that the cured product prepared by the method for preparing a hardened epoxy resin hardened material according to the present invention is compared with the hardened material prepared by the phosphorus-based polyfunctional phenolic resin which has not been modified with paraformaldehyde. The cured product can clearly achieve excellent thermal properties and stability.

圖1為DOPO-PN的¹H-NMR圖光譜圖。。 Figure 1 is a ¹ H-NMR chart of DOPO-PN. .

圖2為P-BPN、P-BPN-F10及P-BPN-F30的¹H-NMR圖光譜疊圖。 2 is a ¹ H-NMR chart spectral overlay of P-BPN, P-BPN-F10, and P-BPN-F30.

圖3為P-BPN、P-BPN-F85-o、P-BPN-F85-p及P-BPN-F150-o的¹H-NMR圖光譜疊圖。 3 is a ¹ H-NMR chart spectral overlay of P-BPN, P-BPN-F85-o, P-BPN-F85-p, and P-BPN-F150-o.

圖4為以P-BPN、P-BPN-F10及P-BPN-F30作為硬化劑之BNE硬化物的DMA圖。 Figure 4 is a DMA diagram of a BNE cured product using P-BPN, P-BPN-F10 and P-BPN-F30 as hardeners.

圖5為以P-BPN、P-BPN-F85-o及P-BPN-F85-p作為硬化劑之DGEBA硬化物的DMA圖。 Figure 5 is a DMA diagram of a DGEBA hardened material using P-BPN, P-BPN-F85-o, and P-BPN-F85-p as hardeners.

圖6為以P-BPN、P-BPN-F85-o及P-BPN-F85-p作為硬化劑之DGEBA硬化物的TGA圖。 Figure 6 is a TGA diagram of a DGEBA hardened material using P-BPN, P-BPN-F85-o, and P-BPN-F85-p as hardeners.

圖7為以P-BPN、P-BPN-F85-o及P-BPN-F85-p作為硬化劑之CNE硬化物的DMA圖。 Figure 7 is a DMA diagram of a CNE cured product using P-BPN, P-BPN-F85-o, and P-BPN-F85-p as hardeners.

圖8為以P-BPN、P-BPN-F85-o及P-BPN-F85-p作為硬化劑之CNE硬化物的TGA圖。 Figure 8 is a TGA diagram of a CNE cured product using P-BPN, P-BPN-F85-o, and P-BPN-F85-p as hardeners.

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 DOPO-PN之合成Example 1 Synthesis of DOPO-PN

DOPO-PN之合成係將DOPO-AP與多聚甲醛試圖於酸或鹼催化下反應而得。 The synthesis of DOPO-PN is obtained by reacting DOPO-AP with paraformaldehyde under acid or base catalysis.

其合成步驟如下：在一附有溫度指示裝置之0.1升三頸反應器中，加入1克DOPO-AP、0.0643克多聚甲醛及10克1-甲氧基-2-丙醇(丙二醇甲醚)做為溶劑，於不同成分比例之催化劑配方中(列於表1中)反應，使反應系統溫度維持在110℃，反應12小時後，將反應溶劑滴入去離子水中析出，抽氣過濾後，濾餅以真空烘箱於70℃下烘乾得到白色產物。 The synthesis procedure is as follows: 1 gram of DOPO-AP, 0.0643 gram of paraformaldehyde and 10 grams of 1-methoxy-2-propanol (propylene glycol methyl ether) are added to a 0.1 liter three-neck reactor equipped with a temperature indicating device. As a solvent, react in different proportions of the catalyst formulation (listed in Table 1) to maintain the temperature of the reaction system at 110 ° C. After 12 hours of reaction, the reaction solvent is dropped into deionized water and precipitated. The filter cake was dried in a vacuum oven at 70 ° C to give a white product.

圖1為實施例1之產物¹H-NMR光譜。由圖1可得知實施例1中嘗試之不同催化劑配方皆無法使反應進行。 Figure 1 is a ¹ H-NMR spectrum of the product of Example 1. It can be seen from Figure 1 that the different catalyst formulations tried in Example 1 were unable to carry out the reaction.

實施例2 聚合物P-BPN之合成Example 2 Synthesis of Polymer P-BPN

磷含量5%的磷系酚醛聚合物(P-BPN)係將BPN與DOPO在酸催化 下反應而得(依中華民國專利I432445之實施例8)。其合成步驟如下：在一附有溫度指示裝置之0.5升三頸反應器中，加入50克BPN、26.765克DOPO、及2克(BPN的4wt%)的對-甲基苯磺酸將反應系統溫度維持在140℃，反應12小時後，利用甲醇水將黏稠物洗去殘餘的對-甲基苯磺酸，抽氣過濾後，過濾分離，濾餅用真空烘箱在100℃下真空烘乾真空烘乾得磷含量5%的磷系酚醛聚合物(P-BPN)。 Phosphorus phenolic polymer (P-BPN) with a phosphorus content of 5% will catalyze BPN and DOPO in acid catalysis The reaction is obtained (in accordance with Example 8 of the Republic of China Patent I432445). The synthesis procedure is as follows: 50 g of BPN, 26.765 g of DOPO, and 2 g (4 wt% of BPN) of p-toluenesulfonic acid are added to a 0.5 liter three-necked reactor equipped with a temperature indicating device. The temperature was maintained at 140 ° C. After 12 hours of reaction, the sticky material was washed away with methanol-water to remove residual p-toluenesulfonic acid, filtered by suction, separated by filtration, and the filter cake was vacuum dried at 100 ° C in a vacuum oven. A phosphorus phenolic polymer (P-BPN) having a phosphorus content of 5% was dried.

實施例3 聚合物P-BPN-F10之合成Example 3 Synthesis of Polymer P-BPN-F10

高分子量二代5%磷系酚醛聚合物(P-BPN-F10)係將磷含量5%之磷系酚醛樹脂(P-BPN)(來自於實施例2)與多聚甲醛在酸催化下反應而得，其合成步驟如下：在一附有溫度指示裝置之0.1升三頸反應器中，加入30克P-BPN、0.4505克多聚甲醛、0.03克(P-BPN之1wt%)的對-甲基苯磺酸以及1-甲氧基-2-丙醇30克做為溶劑，使反應系統之固含量維持於50%，而反應系統溫度維持在110℃，反應12小時，過程中反應溶液維持澄清，反應結束後將反應溶液利用水將產物析出並洗去殘留之對-甲基苯磺酸。抽氣過濾後，濾餅用真空烘箱在70℃下真空烘乾得到淺紅色粉末產物P-BPN-F10。 The high molecular weight second generation 5% phosphorus phenolic polymer (P-BPN-F10) is a phosphate phenolic resin (P-BPN) having a phosphorus content of 5% (from Example 2) reacted with paraformaldehyde under acid catalysis. The synthesis procedure was as follows: In a 0.1 liter three-neck reactor equipped with a temperature indicating device, 30 g of P-BPN, 0.4505 g of paraformaldehyde, and 0.03 g (1 wt% of P-BPN) were added. 30 g of methylbenzenesulfonic acid and 1-methoxy-2-propanol were used as solvents to maintain the solid content of the reaction system at 50%, while the temperature of the reaction system was maintained at 110 ° C for 12 hours, and the reaction solution was in the process. The clarification was maintained, and after the reaction was completed, the reaction solution was precipitated with water and the residual p-toluenesulfonic acid was washed away. After suction filtration, the filter cake was vacuum dried in a vacuum oven at 70 ° C to obtain a pale red powder product P-BPN-F10.

實施例4 聚合物P-BPN-F30之合成Example 4 Synthesis of Polymer P-BPN-F30

高分子量二代5%磷系酚醛聚合物(P-BPN-F30)係將磷含量5%之磷系酚醛樹脂(P-BPN)(來自於實施例2)與多聚甲醛在酸催化下反應而得，其合成步驟如下：在一附有溫度指示裝置之0.1升三頸反應器中，加入30克P-BPN、1.3514克多聚甲醛、0.03克(P-BPN之1wt%)的對-甲基苯磺酸以及1-甲氧基-2-丙醇30克做為溶劑，使反應系統之固含量維持於50%，而反應系統溫度維持在110℃，反應12小時，過程中反應溶液維持澄清，反應結束後將反應溶液利用水將產物析出並洗去殘留之對-甲基苯磺酸。抽氣過濾後，濾餅用真空烘箱在70℃下真空烘乾得到淺紅色粉末產物P-BPN-F30。 High molecular weight second generation 5% phosphorus phenolic polymer (P-BPN-F30) is a phosphorus phenolic resin (P-BPN) with a phosphorus content of 5% (from Example 2) reacted with paraformaldehyde under acid catalysis The synthesis procedure was as follows: In a 0.1 liter three-neck reactor equipped with a temperature indicating device, 30 g of P-BPN, 1.3514 g of paraformaldehyde, and 0.03 g (1 wt% of P-BPN) were added. 30 g of methylbenzenesulfonic acid and 1-methoxy-2-propanol were used as solvents to maintain the solid content of the reaction system at 50%, while the temperature of the reaction system was maintained at 110 ° C for 12 hours, and the reaction solution was in the process. The clarification was maintained, and after the reaction was completed, the reaction solution was precipitated with water and the residual p-toluenesulfonic acid was washed away. After suction filtration, the filter cake was vacuum dried at 70 ° C in a vacuum oven to obtain a pale red powder product P-BPN-F30.

圖2為實施例1及2之產物P-BPN-F10及P-BPN-F30與反應物P-BPN之¹H NMR光譜疊圖。由圖2可知，位於9~9.6ppm之間之特徵峰為產物之Ar-OH訊號，位於3.6~3.8ppm之間之特徵峰為Ar-CH2-Ar之訊號。將上述三者以Ar-OH之訊號積分值為基準，比較Ar-CH2-Ar之積分值於上述三者之間的差異。可發現Ar-CH2-Ar之積分值隨多聚甲醛添加比例增加而增加，表示反應確實發生，使其分子量提高。 2 is a ¹ H NMR spectral overlay of the products P-BPN-F10 and P-BPN-F30 of Examples 1 and 2 and the reactant P-BPN. It can be seen from Fig. 2 that the characteristic peak between 9 and 9.6 ppm is the Ar-OH signal of the product, and the characteristic peak between 3.6 and 3.8 ppm is the signal of Ar-CH2-Ar. The above three values were compared based on the signal integral value of Ar-OH, and the difference between the integral values of Ar-CH2-Ar and the above three was compared. It can be found that the integral value of Ar-CH2-Ar increases as the proportion of addition of paraformaldehyde increases, indicating that the reaction does occur and the molecular weight thereof is increased.

實施例5 聚合物P-BPN-F45之合成Example 5 Synthesis of Polymer P-BPN-F45

在一附有溫度指示裝置之0.5升三頸反應器中，加入5%的磷系酚醛聚合物(P-BPN)(來自於實施例2)30克、三聚甲醛2.027克(酚基當量數之45%)、甲基苯磺酸1.2克(P-BPN的4wt%)與1-甲氧基-2-丙醇300毫升作為溶劑，將反應系統溫度維持在110℃，反應12小時後，將反應溶劑滴入取離子水中析出並洗去殘留之對-甲基苯磺酸，抽氣過濾後，濾餅用真空烘箱在70℃下真空烘乾得聚合物P-BPN-F45。 In a 0.5 liter three-necked reactor equipped with a temperature indicating device, 5% phosphorus phenolic polymer (P-BPN) (from Example 2) 30 g, and terephthalaldehyde 2.027 g (phenol equivalents) were added. 45%), 1.2 g of methylbenzenesulfonic acid (4 wt% of P-BPN) and 300 ml of 1-methoxy-2-propanol as a solvent, the reaction system temperature was maintained at 110 ° C, after 12 hours of reaction, The reaction solvent was dropped into deionized water to precipitate and the residual p-toluenesulfonic acid was washed away, and after suction filtration, the filter cake was vacuum-dried at 70 ° C in a vacuum oven to obtain a polymer P-BPN-F45.

實施例6 聚合物P-BPN-F85-o之合成Example 6 Synthesis of Polymer P-BPN-F85-o

在一附有溫度指示裝置之0.5升三頸反應器中，加入5%的磷系酚醛聚合物(P-BPN)(來自於實施例2)30克、三聚甲醛3.829克(酚基當量數之85%)、草酸1.2克(P-BPN的4wt%)與1-甲氧基-2-丙醇300毫升作為溶劑，將反應系統溫度維持在110℃，反應12小時後，將反應溶劑滴入取離子水中析出並洗去殘留之草酸，抽氣過濾後，濾餅用真空烘箱在70℃下真空烘乾得聚合物P-BPN-F85-o。 In a 0.5 liter three-neck reactor equipped with a temperature indicating device, 5% phosphorus phenolic polymer (P-BPN) (from Example 2), 30 g, and 3.903 g of paraformaldehyde (phenol equivalents) were added. 85%), 1.2 g of oxalic acid (4 wt% of P-BPN) and 300 ml of 1-methoxy-2-propanol as a solvent, the reaction system temperature was maintained at 110 ° C, and after 12 hours of reaction, the reaction solvent was dropped. The ionic acid was precipitated and washed away, and the residual oxalic acid was washed away. After suction filtration, the filter cake was vacuum-dried at 70 ° C in a vacuum oven to obtain a polymer P-BPN-F85-o.

實施例7 聚合物P-BPN-F85-p之合成Example 7 Synthesis of Polymer P-BPN-F85-p

在一附有溫度指示裝置之0.5升三頸反應器中，加入5%的磷系酚醛聚合物(P-BPN)(來自於實施例2)30克、三聚甲醛3.829克(酚基當量數之85%)、甲基苯磺酸1.2克(P-BPN的4wt%)與1-甲氧基-2-丙醇300毫升作為溶劑，將反應系統溫度維持在110℃，反應12小時後，將反應溶劑滴入取離子水中析出並洗去殘留之對-甲基苯磺酸，抽氣過 濾後，濾餅用真空烘箱在70℃下真空烘乾得聚合物P-BPN-F85-p。 In a 0.5 liter three-neck reactor equipped with a temperature indicating device, 5% phosphorus phenolic polymer (P-BPN) (from Example 2), 30 g, and 3.903 g of paraformaldehyde (phenol equivalents) were added. 85%), 1.2 g of methylbenzenesulfonic acid (4 wt% of P-BPN) and 300 ml of 1-methoxy-2-propanol as a solvent, the reaction system temperature was maintained at 110 ° C, after 12 hours of reaction, The reaction solvent is dropped into the ionic water to precipitate and the residual p-toluenesulfonic acid is washed away, and the gas is exhausted. After filtration, the filter cake was vacuum dried at 70 ° C in a vacuum oven to give the polymer P-BPN-F85-p.

實施例8 聚合物P-BPN-F150-o之合成Example 8 Synthesis of Polymer P-BPN-F150-o

在一附有溫度指示裝置之0.5升三頸反應器中，加入5%的磷系酚醛聚合物(P-BPN)(來自於實施例2)30克、三聚甲醛6.757克(酚基當量數之150%)、草酸1.2克(P-BPN的4wt%)與1-甲氧基-2-丙醇300毫升作為溶劑，將反應系統溫度維持在110℃，反應12小時後，將反應溶劑滴入取離子水中析出並洗去殘留之對-甲基苯磺酸，抽氣過濾後，濾餅用真空烘箱在70℃下真空烘乾得聚合物P-BPN-F150-o。 In a 0.5 liter three-necked reactor equipped with a temperature indicating device, 5% phosphorus phenolic polymer (P-BPN) (from Example 2) 30 g, and paraformaldehyde 6.757 g (phenol equivalents) were added. 150%), 1.2 g of oxalic acid (4 wt% of P-BPN) and 300 ml of 1-methoxy-2-propanol as a solvent, the reaction system temperature was maintained at 110 ° C, and after 12 hours of reaction, the reaction solvent was dropped. The precipitated ionic water was precipitated and the residual p-toluenesulfonic acid was washed away, and after suction filtration, the filter cake was vacuum-dried at 70 ° C in a vacuum oven to obtain a polymer P-BPN-F150-o.

圖3為P-BPN-F85-o,P-BPN-F85-p及P-BPN-F150-o的¹H-NMR光譜疊圖。在以9-10ppm之羥基為基準下，可發現位於約3.6ppm之Ar-CH2-Ar之積分值有隨著加入多聚甲醛之量增加而增加，因此可確認反應確實有進行。 Figure 3 is a ¹ H-NMR spectral overlay of P-BPN-F85-o, P-BPN-F85-p and P-BPN-F150-o. Based on the hydroxyl group of 9 to 10 ppm, it was found that the integral value of Ar-CH2-Ar at about 3.6 ppm increased as the amount of paraformaldehyde added increased, so that it was confirmed that the reaction did proceed.

表2為P-BPN原料及P-BPN-F的GPC數據。由表2可發現經由酸性環境催化下，加入多聚甲醛確實可助於P-BPN分子量之延長，且催化效果對-甲基苯磺酸較草酸更佳。 Table 2 shows the GPC data of P-BPN raw materials and P-BPN-F. It can be seen from Table 2 that the addition of paraformaldehyde under the catalysis of an acidic environment can indeed contribute to the prolongation of the molecular weight of P-BPN, and the catalytic effect of p-toluenesulfonic acid is better than that of oxalic acid.

實施例9至11 固化雙酚A型酚醛環氧樹脂的製備與分析Examples 9 to 11 Preparation and Analysis of Curing Bisphenol A Type Novolac Epoxy Resin

將實施例2至4三種硬化劑作為環氧樹脂的硬化劑，使用的環氧樹脂為雙酚A型酚醛環氧樹脂(BNE)。環氧樹脂與硬化劑以當量比為1：1的比例下在模具中均勻混合，量外添加了咪唑(添加量為環氧樹脂 的0.2wt%)當作反應的硬化促進劑。利用動態機械分析儀(DMA)所測得玻璃轉移溫度於表3及圖4中，當多聚甲醛添加量增加，其玻璃轉移溫度也隨之提升，代表實施例3及例4中之產物的分子量有確實提升，擁有更優異之熱性質。 The three hardeners of Examples 2 to 4 were used as a hardener for the epoxy resin, and the epoxy resin used was a bisphenol A type novolac epoxy resin (BNE). Epoxy resin and hardener are uniformly mixed in the mold at an equivalent ratio of 1:1, and imidazole is added in an amount (addition amount is epoxy resin) 0.2 wt%) as a hardening accelerator for the reaction. The glass transition temperature measured by a dynamic mechanical analyzer (DMA) is shown in Table 3 and Figure 4. As the amount of paraformaldehyde added increases, the glass transition temperature also increases, representing the products of Examples 3 and 4. The molecular weight is indeed improved and has superior thermal properties.

實施例12至14 固化雙酚A環氧樹脂的製備與分析Preparation and Analysis of Solidified Bisphenol A Epoxy Resin of Examples 12 to 14

P-BPN，P-BPN-F85-o以及P-BPN-F85-p三種硬化劑作為雙酚A環氧樹脂(DGEBA)環氧樹酯的硬化劑。講環氧樹脂與硬化劑以當量比為1：1的比例下在模具中均勻混合，量外添加了咪唑(添加量為環氧樹脂的0.2wt%)當作反應的硬化促進劑。利用DMA及熱重量分析儀(TGA)所量測其熱性質如圖5及6所示。 P-BPN, P-BPN-F85-o and P-BPN-F85-p three hardeners act as hardeners for bisphenol A epoxy resin (DGEBA) epoxy resin. The epoxy resin and the hardener are uniformly mixed in the mold at an equivalent ratio of 1:1, and imidazole (addition amount is 0.2 wt% of the epoxy resin) is added as an amount of the hardening accelerator for the reaction. The thermal properties measured by DMA and thermogravimetric analyzer (TGA) are shown in Figures 5 and 6.

由圖5可知，P-BPN/DGEBA之Tg為126℃、P-BPN-F85-o/DGEBA之Tg為142℃、P-BPN-F85-p/DGEBA之Tg為160℃，即改質過後之P-BPN-F與環氧樹脂固化物之熱性質確實有進一步提升，可印證先前所述。 As can be seen from Fig. 5, the Tg of P-BPN/DGEBA is 126 ° C, the Tg of P-BPN-F85-o/DGEBA is 142 ° C, and the Tg of P-BPN-F85-p/DGEBA is 160 ° C, that is, after the modification. The thermal properties of P-BPN-F and epoxy resin cured materials are indeed further enhanced, as evidenced by the foregoing.

由圖6可知，P-BPN/DGEBA、P-BPN-F85-o/DGEBA及P-BPN-F85-p/DGEBA之T_d5%分別為430℃、434℃及435℃，而殘餘灰份(char yield)分別為19%、23%及24%，可進一步證實此系列硬化物具有良好的熱穩定性。 It can be seen from Fig. 6 that the T _{d5% of} P-BPN/DGEBA, P-BPN-F85-o/DGEBA and P-BPN-F85-p/DGEBA are 430 ° C, 434 ° C and 435 ° C, respectively, and residual ash ( Char yield) is 19%, 23% and 24%, respectively, which further confirms that the series of hardened materials have good thermal stability.

實施例15至17 固化磷甲基酚醛環氧樹脂的製備與分析Preparation and Analysis of Curing Phosphomethyl Methyl Resin Epoxy Resins of Examples 15 to 17

P-BPN，P-BPN-F85-o以及P-BPN-F85-p三種硬化劑作為磷甲基酚醛環氧樹脂(CNE)的硬化劑。環氧樹脂與硬化劑以當量比為1：1的比例下在模具中均勻混合，量外添加了咪唑(添加量為環氧樹脂的0.2wt%)當作反應的硬化促進劑。利用DMA及TGA所量測其熱性質如圖7及8所示。 P-BPN, P-BPN-F85-o and P-BPN-F85-p three hardeners act as hardeners for phosphomethyl novolac epoxy resin (CNE). The epoxy resin and the hardener were uniformly mixed in a mold at a ratio of an equivalent ratio of 1:1, and an imidazole (added in an amount of 0.2 wt% of the epoxy resin) was added in an amount as a hardening accelerator for the reaction. The thermal properties measured by DMA and TGA are shown in Figures 7 and 8.

由圖7可知，P-BPN/CNE之Tg為160℃、P-BPN-F85-o/CNE之Tg為172℃及P-BPN-F85-p/CNE之Tg為196℃，即改質過後之P-BPN-F與環氧樹脂固化物之熱性質確實有進一步提升，可印證先前所述。 As can be seen from Fig. 7, the Tg of P-BPN/CNE is 160 ° C, the Tg of P-BPN-F85-o/CNE is 172 ° C, and the Tg of P-BPN-F85-p/CNE is 196 ° C, that is, after the modification. The thermal properties of P-BPN-F and epoxy resin cured materials are indeed further enhanced, as evidenced by the foregoing.

由圖8可知，P-BPN/CNE、P-BPN-F85-o/CNE及P-BPN-F85-p/CNE之T_d5%分別為400℃、412℃及413℃，而殘餘灰份分別為28%、29%及32%，可進一步證實此系列硬化物具有良好的熱穩定性。 It can be seen from Fig. 8 that the T _{d5% of} P-BPN/CNE, P-BPN-F85-o/CNE and P-BPN-F85-p/CNE are 400 ° C, 412 ° C and 413 ° C, respectively, and the residual ash is respectively At 28%, 29% and 32%, it was further confirmed that the cured product of this series has good thermal stability.

Claims (16)

一種磷系多官能酚類聚合物，其包含如下式(II)及(III)之結構 其中0≦a≦30，1≦b≦30；Y為-CH₂-或-CH₂OCH₂-；且各R₀係相同或不同，獨立選自於由氫原子、C₁~C₆烷基、C₁~C₆烷氧基、苯基、硝基、苯氧基、C₁~C₁₀鹵烷基、C₃~C₇環烷基、C₁~C₁₀鹵烷氧基和鹵素所組成之群。 A phosphorus-based polyfunctional phenolic polymer comprising the structures of the following formulae (II) and (III) Wherein 0≦a≦30,1≦b≦30; Y is -CH ₂ - or -CH ₂ OCH ₂ -; and each R ₀ is the same or different and is independently selected from a hydrogen atom, a C ₁ -C ₆ alkane , C ₁ -C ₆ alkoxy, phenyl, nitro, phenoxy, C ₁ -C ₁₀ haloalkyl, C ₃ -C ₇ cycloalkyl, C ₁ -C ₁₀ haloalkoxy and halogen The group formed. 如請求項1之聚合物，其中當全部R₀係氫原子且Y為-CH₂-時，該式(II)具有式(IV)之結構 ；且 該式(III)具有式(V)之結構 The polymer of claim 1, wherein when all of R ₀ is a hydrogen atom and Y is -CH ₂ -, the formula (II) has the structure of formula (IV) And the formula (III) has the structure of the formula (V) 如請求項1或2之聚合物，其係以寡聚物之形式存在。 A polymer according to claim 1 or 2 which is in the form of an oligomer. 一種製造包含下式(II)及(III)之結構的磷系多官能酚類聚合物的方法， 其包含以下步驟(1)將如下式之DOPO化合物與式(I)之雙酚型酚醛樹脂在酸觸媒存在下進行反應 以得到包含如下式(II-1)及(III-1)之結構的中間產物 ；及 (2)將該中間產物與多聚甲醛或甲醛在酸觸媒存在下反應而得到具有式(II)及(III)之結構的磷系多官能酚類聚合物；其中 0≦a≦30，1≦b≦30；Y為-CH₂-或-CH₂OCH₂-；且各R₀係相同或不同，獨立選自於由氫原子、C₁~C₆烷基、C₁~C₆烷氧基、苯基、硝基、苯氧基、C₁~C₁₀鹵烷基、C₃~C₇環烷基、C₁~C₁₀鹵烷氧基和鹵素所組成之群。 A method for producing a phosphorus-based polyfunctional phenolic polymer comprising the structures of the following formulas (II) and (III), It comprises the following steps (1): reacting a DOPO compound of the following formula with a bisphenol novolac resin of the formula (I) in the presence of an acid catalyst To obtain an intermediate product comprising the structures of the following formulas (II-1) and (III-1) And (2) reacting the intermediate product with paraformaldehyde or formaldehyde in the presence of an acid catalyst to obtain a phosphorus-based polyfunctional phenolic polymer having the structures of the formulae (II) and (III); wherein 0≦a≦ 30,1≦b≦30; Y is -CH ₂ - or -CH ₂ OCH ₂ -; and each R ₀ is the same or different and is independently selected from a hydrogen atom, a C ₁ -C ₆ alkyl group, C ₁ ~ a group consisting of C ₆ alkoxy, phenyl, nitro, phenoxy, C ₁ -C ₁₀ haloalkyl, C ₃ -C ₇ cycloalkyl, C ₁ -C ₁₀ haloalkoxy and halogen. 如請求項4之方法，其中：當全部R₀係氫原子且Y為-CH₂-時，式(I)具有以下結構 而式(II)具有式(IV)之結構 ；且 式(III)具有式(V)之結構 The method of claim 4, wherein: when all R ₀ are hydrogen atoms and Y is -CH ₂ -, formula (I) has the following structure Wherein formula (II) has the structure of formula (IV) And the formula (III) has the structure of the formula (V) 如請求項4之方法，其中該多聚甲醛係三聚甲醛。 The method of claim 4, wherein the paraformaldehyde is trioxane. 如請求項4之方法，其中該中間產物之總磷含量係3wt%至8wt%。 The method of claim 4, wherein the intermediate product has a total phosphorus content of from 3 wt% to 8 wt%. 如請求項4之方法，其中該酸觸媒係選自由草酸、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(CF₃COOH)、硝酸(HNO₃)、磷酸(H₃PO₄)所組成之群。 The method of claim 4, wherein the acid catalyst is selected from the group consisting of oxalic acid, acetic acid, p-Toluenesulfonic acid (PTSA), methanesulfonic acid, and 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 ), phosphoric acid (H ₃ PO ₄ ) a group of people. 如請求項4之方法，其中該多聚甲醛之量係該中間產物之酚基當量數之10至150%。 The method of claim 4, wherein the amount of paraformaldehyde is from 10 to 150% of the phenolic equivalent of the intermediate product. 如請求項4之方法，其中該酸觸媒之量為該中間產物的0.1wt%至10wt%。 The method of claim 4, wherein the amount of the acid catalyst is from 0.1% by weight to 10% by weight of the intermediate product. 如請求項4之方法，其中反應係在溶劑中進行，該溶劑係選自由乙氧基乙醇(ethoxy ethanol)、甲氧基乙醇(methoxy ethanol)、1-甲氧基-2-丙醇(1-methoxy-2-propanol)、DOW PM、二噁烷及上述溶劑所組成的共溶劑所組成之群。 The method of claim 4, wherein the reaction is carried out in a solvent selected from the group consisting of ethoxy ethanol, methoxy ethanol, and 1-methoxy-2-propanol (1). a group consisting of -methoxy-2-propanol), DOW PM, dioxane, and a cosolvent consisting of the above solvents. 一種硬化劑，其包含如請求項1至3中任一項之磷系多官能酚類 聚合物。 A hardener comprising the phosphorus-based polyfunctional phenol according to any one of claims 1 to 3. polymer. 一種製備高玻璃轉換溫度難燃環氧樹脂硬化物之方法，其包括將環氧樹脂與如請求項12之硬化劑進行硬化反應。 A method of preparing a high glass transition temperature flame retardant epoxy resin cured product comprising subjecting an epoxy resin to a hardening reaction with a hardener according to claim 12. 如請求項13之方法，其中該環氧樹脂與該硬化劑之當量比例為1：0.1至1：1。 The method of claim 13, wherein the equivalent ratio of the epoxy resin to the hardener is 1:0.1 to 1:1. 如請求項13或14之方法，其中該環氧樹脂係選自雙酚A環氧樹脂(diglycidyl ether of bisphenol A,DGEBA)、二氧化雙環戊二烯環氧樹脂(dicyclopentadiene epoxy,HP 7200)、磷甲基酚醛環氧樹脂(cresol novolac epoxy,CNE)或酚醛環氧樹脂(phenol novolac epoxy,PNE)。 The method of claim 13 or 14, wherein the epoxy resin is selected from the group consisting of diglycidyl ether of bisphenol A (DGEBA), dicyclopentadiene epoxy (HP 7200), Cresol novolac epoxy (CNE) or phenol novolac epoxy (PNE). 一種高玻璃轉換溫度難燃環氧樹脂硬化物，其係依請求項13至15中任一項方法所製備之產物。 A high glass transition temperature flame retardant epoxy resin cured product produced by the method of any one of claims 13 to 15.