TWI408143B - Compounds with asymmetric phosphorus-containing diphenols, derivatives, and one-pot method for preparing thereof - Google Patents
Compounds with asymmetric phosphorus-containing diphenols, derivatives, and one-pot method for preparing thereof Download PDFInfo
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本發明是有關於一種磷系雙酚化合物、其衍生物及其製造方法,且特別是有關於一種具有不對稱結構之磷系雙酚及其環氧樹脂半固化物之衍生物製造方法。The present invention relates to a phosphorus-based bisphenol compound, a derivative thereof, and a process for producing the same, and, in particular, to a process for producing a derivative of a phosphorus-based bisphenol having an asymmetric structure and an epoxy resin semi-cured product.
近年來,含有機磷的化合物已被研究出能提升高分子聚合物之難燃性質,將有機磷反應基團導入高分子的主要結構時,更可使得聚合物具有難燃效果。與含鹵素難燃劑相比,有機磷的化合物不會產生有毒氣體,更具有加工性佳、添加量少及發煙量低等優點。In recent years, organophosphorus-containing compounds have been studied to improve the flame retardant properties of high molecular polymers. When the organophosphorus reactive groups are introduced into the main structure of the polymer, the polymer is more resistant to flame retardation. Compared with halogen-containing flame retardants, organophosphorus compounds do not produce toxic gases, and have the advantages of good processability, low added amount, and low smoke generation.
例如,以含磷化合物9,10-二氫-9-氧雜-10-磷菲-10-氧化物(9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide,DOPO)為例,是一種具可與缺電子化合物反應的活性氫原子的化合物。DOPO可與缺電子化合物如苯二酮(benzoquinone)、環氧乙烷(oxirane)、雙馬來亞醯胺(bismaleimide)、馬來酸(maleic acid)、對苯二甲醛(terephthaldicarboxaldehyde)及二胺基二苯甲酮(diaminobenzophenone)反應。For example, a phosphorus-containing compound 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO) is taken as an example. It is a compound having an active hydrogen atom reactive with an electron-deficient compound. DOPO can be associated with electron-deficient compounds such as benzoquinone, oxirane, bismaleimide, maleic acid, terephthalic arbonaldehyde, and diamines. Diaminobenzophenone reaction.
雙酚化合物為相當重要的工業原料,為合成許多商業化高分子之前趨物,如環氧樹脂(epoxy resins)、氧代氮代苯并環己烷樹脂(benzoxazine resins)、聚醚醯亞胺(polyether imide)、聚醚酮(polyether ketone,PEK)、聚楓(polysulfone)、聚酯(polyester)等。Bisphenol compounds are important industrial raw materials for the synthesis of many commercial polymer precursors, such as epoxy resins, benzoxazine resins, polyether quinones. (polyether imide), polyether ketone (PEK), polysulfone, polyester, and the like.
磷系雙酚單體是應用雙酚化合物的反應性官能基將含磷基團導入高分子材料,藉以合成出具有難燃特性、優良熱性質及熱穩定性的聚合物。例如美國專利公開號US 2010/0016585 A1揭露一種磷系雙酚化合物(DMP)、其衍生物及其製造方法,經測試發現磷系雙酚化合物DMP的衍生物具有高的熱性質及優異的熱穩定性。The phosphorus-based bisphenol monomer is a polymer which uses a reactive functional group of a bisphenol compound to introduce a phosphorus-containing group into a polymer material, thereby synthesizing a polymer having flame retardancy characteristics, excellent thermal properties, and thermal stability. For example, U.S. Patent Publication No. US 2010/0016585 A1 discloses a phosphorus bisphenol compound (DMP), a derivative thereof and a process for producing the same, which have been found to have high thermal properties and excellent heat. stability.
然而,化合物的熱性質及電氣性質會受到材料含水率的影響,過高的含水率會降低材料熱性質及電氣性質,在後續高溫製程中亦會因所含水份的瞬間蒸發而造成材料毀損。因此如何減少磷系雙酚化合物材料的吸水率、並維持其原有性質亦為重要之議題。However, the thermal and electrical properties of the compound are affected by the moisture content of the material. Excessive moisture content will reduce the thermal and electrical properties of the material. In subsequent high-temperature processes, the material will be destroyed due to the instantaneous evaporation of the water. . Therefore, how to reduce the water absorption rate of the phosphorus bisphenol compound material and maintain its original properties is also an important issue.
研究文獻中指出,於化合物結構中導入含氟基團或烷基可有效降低吸水性。但實際合成時,則發現導入烷基等柔軟的鏈段會使得材料的熱性質降低,連帶影響後續衍生物之熱性質。It is pointed out in the research literature that introduction of a fluorine-containing group or an alkyl group into a compound structure can effectively reduce water absorption. However, in actual synthesis, it has been found that the introduction of a soft segment such as an alkyl group causes a decrease in the thermal properties of the material, which in turn affects the thermal properties of the subsequent derivative.
因此,本發明利用於磷系雙酚化合物導入含氟基團及烷基,形成具有不對稱結構的磷系雙酚化合物,不僅可有效降低吸水率,更可因不對稱結構使得材料維持其原有熱性質。Therefore, the present invention utilizes a phosphorus-based bisphenol compound to introduce a fluorine-containing group and an alkyl group to form a phosphorus-based bisphenol compound having an asymmetric structure, which can not only effectively reduce the water absorption rate, but also maintain the original material due to the asymmetric structure. It has thermal properties.
本發明之一態樣是在提供一系列具有不對稱結構之磷系雙酚化合物及其一鍋化(one-pot)製程,利用如式(a)所示之有機環狀磷化合物、式(b)化合物、式(c)化合物及一酸觸媒,合成具有如化學式(I)所示具有不對稱結構之磷系雙酚化合物。One aspect of the present invention provides a series of phosphorus-based bisphenol compounds having an asymmetric structure and a one-pot process thereof, using an organic cyclic phosphorus compound represented by the formula (a), b) a compound, a compound of the formula (c) and a monoacid catalyst, which synthesize a phosphorus-based bisphenol compound having an asymmetric structure as shown in the formula (I).
依照本實施方式之一或多個實施例,其中R1 -R6 係各自獨立為氫原子、C1-C10烷基、C1-C10烷氧基、C1-C10鹵烷基、C3-C10環烷基、-CF3 、-OCF3 或鹵原子,且R5 及R6 不同時為氫原子,R7 為氫、苯基、C1-C10烷基、C3-C10環烷基、CF3 或鹵原子。According to one or more embodiments of the present invention, wherein R 1 -R 6 are each independently a hydrogen atom, a C1-C10 alkyl group, a C1-C10 alkoxy group, a C1-C10 haloalkyl group, a C3-C10 naphthenic ring. a group, -CF 3 , -OCF 3 or a halogen atom, and R 5 and R 6 are not simultaneously a hydrogen atom, R 7 is hydrogen, phenyl, C1-C10 alkyl, C3-C10 cycloalkyl, CF 3 or halogen atom.
依照本實施方式之一或多個實施例,合成具有不對稱結構之磷系雙酚化合物,使用的酸觸媒用量為式(a)所示之有機磷化物原料含量的0.1 wt%~30 wt%,酸觸媒可為質子酸或路易士酸。According to one or more embodiments of the present embodiment, a phosphorus-based bisphenol compound having an asymmetric structure is synthesized, and an acid catalyst is used in an amount of 0.1 wt% to 30 wt% of the organic phosphide raw material content represented by the formula (a). %, the acid catalyst can be protonic acid or Lewis acid.
依照本實施方式之一或多個實施例,具有不對稱結構之磷系雙酚化合物可為下列式(1)-(16)所示之化合物:According to one or more embodiments of the present embodiment, the phosphorus-based bisphenol compound having an asymmetric structure may be a compound represented by the following formulas (1) to (16):
本發明之另一態樣是在提供一種由具有通式(I)所示結構的化合物衍生的磷系環氧樹脂半固化物及其製備方法。Another aspect of the present invention provides a phosphorus-based epoxy resin semi-cured product derived from a compound having a structure represented by the general formula (I) and a process for producing the same.
依照本實施方式之一或多個實施例,磷系環氧樹脂半固化物的製備方法,包括以式(I)所示之具有不對稱結構的磷系雙酚化合物(例如式1-16所示之化合物),與如式(d)所示之具環氧基結構之化合物進行鏈延長反應(advancement),得到低吸水率的磷系環氧樹脂半固化物(advanced epoxy resin)。磷系環氧樹脂半固化物可進一步固化形成低吸水率的磷系環氧樹脂固化物。According to one or more embodiments of the present embodiment, a method for producing a phosphorus-based epoxy resin semi-cured product includes a phosphorus-based bisphenol compound having an asymmetric structure represented by formula (I) (for example, Formula 1-16) The compound shown) is subjected to chain extension reaction with a compound having an epoxy group structure as shown in the formula (d) to obtain a phosphorus epoxy resin semi-cured epoxy resin having a low water absorption. The phosphorus-based epoxy resin semi-cured material can be further cured to form a phosphorus-based epoxy resin cured product having a low water absorption rate.
依照本發明實施方式合成之環氧樹脂半固化物衍生物具有如下所示之通式(II)的結構,並可進一步固化形成低吸水率的磷系環氧樹脂固化物,通式(II)中,n為1-5的整數。The epoxy resin semi-cured derivative synthesized according to the embodiment of the present invention has the structure of the general formula (II) shown below, and can be further cured to form a phosphorus-based epoxy resin cured product having a low water absorption ratio, and the general formula (II) Where n is an integer from 1 to 5.
依照本實施方式之一或多個實施例,鏈延長反應可於100-200℃進行;使用的觸媒為咪唑(imidazole)化合物、三級膦、三級胺、季磷鹽、三氟化硼錯合鹽、鋰化物、季磷或季胺化合物。其中環氧基當量數對酚基當量數比為1:1至10:1;所使用的觸媒用量為環氧樹脂含量的0.1-5 wt%。According to one or more embodiments of the present embodiment, the chain extension reaction can be carried out at 100-200 ° C; the catalyst used is an imidazole compound, a tertiary phosphine, a tertiary amine, a quaternary phosphonium salt, boron trifluoride. Mismatched salt, lithium, quaternary phosphorus or quaternary amine compounds. Wherein the ratio of the number of epoxy equivalents to the phenolic equivalent is from 1:1 to 10:1; the amount of the catalyst used is from 0.1 to 5% by weight of the epoxy resin.
根據上述,本發明實施方式具有下列優點:According to the above, the embodiments of the present invention have the following advantages:
一、本發明實施方式提供了一全新合成磷系雙酚化合物的途徑,成功地以一鍋法製程合成具有不對稱磷系雙酚結構的化合物,簡化傳統製程至少需二步驟才能合成磷系雙酚化合物的缺點,適用於工業化量產。1. The present invention provides a novel route for synthesizing a phosphorus-based bisphenol compound, successfully synthesizing a compound having an asymmetric phosphorus-based bisphenol structure by a one-pot process, and simplifying the conventional process requires at least two steps to synthesize a phosphorus double The shortcomings of phenolic compounds are suitable for industrial mass production.
二、本發明實施方式合成之具有不對稱結構的磷系雙酚化合物,可藉由不對稱結構阻礙分子堆疊而改善磷系雙 酚化合物溶解性不佳的問題,此外由於具有不對稱結構的分子鏈旋轉較對稱結構之化合物困難,亦可提升玻璃轉移溫度。2. A phosphorus-based bisphenol compound having an asymmetric structure synthesized by the embodiment of the present invention, which can improve the phosphorus double by hindering molecular stacking by an asymmetric structure The problem of poor solubility of the phenolic compound, in addition to the difficulty of rotating the molecular chain having an asymmetric structure with a more symmetrical structure, can also increase the glass transition temperature.
三、本發明實施方式合成之具有不對稱結構的磷系雙酚化合物,於結構中導入含鹵素的基團或烷基,可有效降低材料的吸水性。3. The phosphorus-based bisphenol compound having an asymmetric structure synthesized in the embodiment of the present invention, wherein a halogen-containing group or an alkyl group is introduced into the structure, can effectively reduce the water absorption of the material.
四、本發明實施例合成之具有不對稱結構的磷系雙酚化合物可和環氧樹脂進行半固化反應,合成具有低吸水率特性的磷系環氧樹脂半固化物,其合成步驟簡易且具有方便加工、可大量生產的優點。4. The phosphorus-based bisphenol compound having an asymmetric structure synthesized in the embodiment of the present invention can be semi-cured with an epoxy resin to synthesize a phosphorus-based epoxy resin semi-cured product having low water absorption characteristics, and the synthesis step is simple and has Convenient for processing and mass production.
五、本發明實施例之磷系環氧樹脂半固化物,其固化物保有高玻璃轉移溫度,並具有低吸水率、良好難燃性質及熱安定性之優異性能。5. A phosphorus-based epoxy resin semi-cured product according to an embodiment of the present invention, which has a high glass transition temperature and has excellent properties of low water absorption, good flame retardancy and thermal stability.
本發明之實施方式包括提供:(一)一系列具有不對稱結構的磷系雙酚化合物及其一鍋化(one-pot)合成方法;(二)具有不對稱結構的磷系雙酚化合物的環氧樹脂半固化物衍生物及其合成方法。Embodiments of the present invention include: (a) a series of phosphorus-based bisphenol compounds having an asymmetric structure and a one-pot synthesis method thereof; (b) a phosphorus-based bisphenol compound having an asymmetric structure Epoxy resin semi-cured product derivative and its synthesis method.
本文中所述之「一鍋化合成方法」,係指是在同一個反應容器中,進行多個反應步驟,中間不需進行分離純化。The "one-pot synthesis method" as used herein refers to a plurality of reaction steps carried out in the same reaction vessel without separation and purification.
依照本發明之實施方式,藉由將具有活性氫原子有機環狀磷系化合物(DOPO),與缺電子化合物例如4-羥基二 苯甲酮(4-Hydroxybenzophenone;4-HA)反應,在酸觸媒存在下,可導入具有不同側鏈的苯酚化合物,合成具有不對稱結構的磷系雙酚化合物。此外,在反應系統中,苯酚化合物可作為反應之溶劑。According to an embodiment of the present invention, an organic cyclic phosphorus compound (DOPO) having an active hydrogen atom and an electron deficient compound such as 4-hydroxyl 4-Hydroxybenzophenone (4-HA) is reacted, and a phenol compound having different side chains can be introduced in the presence of an acid catalyst to synthesize a phosphorus-based bisphenol compound having an asymmetric structure. Further, in the reaction system, a phenol compound can be used as a solvent for the reaction.
依照本實施方式之一或多個實施例,合成具有不對稱結構之磷系雙酚化合物,使用的酸觸媒用量為有機磷化合物(DOPO)含量的0.1 wt%~30 wt%。酸觸媒可為質子酸或路易士酸,例如:醋酸、對-甲基苯璜酸(p-Toluenesulfonic acid,PTSA)、甲基磺酸(Methanesulfonic acid)、三氟甲磺酸(Trifluoromethanesulfonic acid)、氟磺酸(Fluorosulfonic acid)、鈣鎂試劑(Calmagite)、硫酸(Sulfuric acid)、2-胺基苯磺酸(Orthanilic acid)、3-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 )、磷酸(H3 PO4 )、氯化鋁(AlCl3 )、氟化硼(BF3 )、溴化鐵(FeBr3 )、氯化鐵(FeCl3 )、氯化硼(BCl3 )或氯化鈦(TiCl4 )。According to one or more embodiments of the present embodiment, a phosphorus-based bisphenol compound having an asymmetric structure is synthesized, and an acid catalyst is used in an amount of from 0.1% by weight to 30% by weight based on the content of the organophosphorus compound (DOPO). The acid catalyst may be a protonic acid or a Lewis acid, for example, acetic acid, p-Toluenesulfonic acid (PTSA), methanesulfonic acid, and trifluoromethanesulfonic acid. , Fluorosulfonic acid, Calmagite, Sulfuric acid, Orthanilic acid, 3-Pyridinesulfonic acid, p-Aminobenzene 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 ), aluminum chloride (AlCl 3 ), boron fluoride (BF 3 ), iron bromide (FeBr 3 ), ferric chloride (FeCl 3 ), boron chloride (BCl 3 ) or titanium chloride (TiCl 4 ) ).
第1A-1B圖為依照本發明之多個實施例,繪示有機環狀磷系化合物(式a)與4-羥基二苯甲酮(式b),可分別與含不同取代基的苯酚化合物反應,合成如式1-16所示之具有不對稱結構的磷系雙酚化合物的簡圖下文中的合成例1-4,將再詳細說明第1A-1B圖所示之式1-16化合物之合成步驟。1A-1B is a diagram showing an organic cyclic phosphorus compound (formula a) and 4-hydroxybenzophenone (formula b), respectively, in combination with a phenol compound having a different substituent, in accordance with various embodiments of the present invention. Reaction, synthesis of a phosphorus-based bisphenol compound having an asymmetric structure as shown in Formula 1-16. Synthesis Example 1-4, which will be described later, will further explain the compound of Formula 1-16 shown in Figure 1A-1B. The synthetic steps.
為了降低吸水率,合成例1係於磷系雙酚化合物結構中 導入烷基,再藉由合成不對稱結構阻礙分子堆疊,達到提高溶解性並使分子鏈旋轉困難而提升玻璃轉移溫度。In order to reduce the water absorption rate, Synthesis Example 1 is in the structure of a phosphorus bisphenol compound. The alkyl group is introduced, and the molecular stacking is hindered by synthesizing the asymmetric structure, thereby improving the solubility and making the molecular chain rotation difficult to increase the glass transition temperature.
式(1)-(7)所示之化合物係以DOPO、4-羥基二苯甲酮與一系列含烷基的苯酚化合物在酸性觸媒催化下反應而得,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13.6克(0.1莫耳)的4-羥基二苯甲酮、21.6克(0.1莫耳)的DOPO、50克的苯酚化合物及0.86克的對-甲基苯磺酸,先升高反應溫度達100℃,並將反應系統溫度維持在100℃反應12小時後,將析出產物於乙醇中清洗。清洗後之產物經抽氣過濾後,將濾餅用真空烘箱在110℃下真空烘乾即可得到具有不對稱結構的磷系雙酚化合物。產物之分子量以高解析質譜儀鑑定之。The compounds represented by the formulae (1)-(7) are obtained by reacting DOPO, 4-hydroxybenzophenone with a series of alkyl-containing phenol compounds under acidic catalyst catalysis, and the synthesis steps are as follows: In a 0.5 liter three-neck reactor of a temperature indicating device, 13.6 g (0.1 mol) of 4-hydroxybenzophenone, 21.6 g (0.1 mol) of DOPO, 50 g of a phenol compound, and 0.86 g of a pair were added. Methylbenzenesulfonic acid, the reaction temperature was raised to 100 ° C, and the reaction system temperature was maintained at 100 ° C for 12 hours, and the precipitated product was washed in ethanol. After the cleaned product was filtered by suction, the filter cake was vacuum dried in a vacuum oven at 110 ° C to obtain a phosphorus-based bisphenol compound having an asymmetric structure. The molecular weight of the product was identified by high resolution mass spectrometry.
利用合成例1所示方法,分別使用不同苯酚化合物合成之一系列具有不對稱結構的磷系雙酚化合物(1)-(7),其分子式、分子量及產率等結果整理於下表1:
第2A圖為產物(1)之1 H NMR圖譜。光譜分析的結果顯示,產物(1)之分子式確實為C27 H23 O4 P。利用合成例1 所示之方法合成的單體具有相當高的純度。Figure 2A is a 1 H NMR spectrum of the product (1). The results of the spectral analysis showed that the molecular formula of the product (1) was indeed C 27 H 23 O 4 P. The monomer synthesized by the method shown in Synthesis Example 1 has a relatively high purity.
第2B圖為產物(2)之1 H NMR圖譜。光譜分析的結果顯示,產物(2)之分子式確實為C28 H25 O4 P。利用合成例1所示之方法合成的單體具有相當高的純度。Figure 2B is a 1 H NMR spectrum of the product (2). The results of the spectral analysis showed that the molecular formula of the product (2) was indeed C 28 H 25 O 4 P. The monomer synthesized by the method shown in Synthesis Example 1 has a relatively high purity.
為了有效阻礙分子堆疊,合成例2係將立體障礙較大之烷基導入磷系雙酚化合物結構中,使分子鏈旋轉困難而達到提升玻璃轉移溫度的目的。In order to effectively hinder molecular stacking, Synthesis Example 2 introduces an alkyl group having a large steric hindrance into a structure of a phosphorus-based bisphenol compound, thereby making it difficult to rotate the molecular chain and thereby increasing the glass transition temperature.
合成例2選用如下表2所示之具有較大立體障礙的苯酚化合物,以與合成例1之步驟大致相同之方法,根據選用之苯酚化合物不同將反應系統溫度維持在100-130℃,且反應完成後之產物以甲醇清洗,即可得到如式8-10所示之化合物。In Synthesis Example 2, a phenol compound having a large steric hindrance as shown in Table 2 below was used, and the reaction system temperature was maintained at 100 to 130 ° C depending on the selected phenol compound in substantially the same manner as in the synthesis example 1. The finished product is washed with methanol to give a compound of the formula 8-10.
以合成例2所示方法,使用不同苯酚化合物合成之產物(8)-(10),其分子式、分子量及產率等結果整理於下表2:
第2C圖為產物(8)之1 H NMR圖譜。光譜分析的結果顯示,產物(8)之分子式確實為C30 H29 O4 P。利用合成例2所示之方法合成的單體具有相當高的純度。Figure 2C is a 1 H NMR spectrum of the product (8). The results of the spectral analysis showed that the molecular formula of the product (8) was indeed C 30 H 29 O 4 P. The monomer synthesized by the method shown in Synthesis Example 2 has a relatively high purity.
第2D圖為產物(10)之1 H NMR圖譜。光譜分析的結 果顯示,產物(10)之分子式確實為C34 H37 O4 P。利用合成例2所示之方法合成的單體具有相當高的純度。Figure 2D is a 1 H NMR spectrum of the product (10). The results of the spectral analysis showed that the molecular formula of the product (10) was indeed C 34 H 37 O 4 P. The monomer synthesized by the method shown in Synthesis Example 2 has a relatively high purity.
由於將烷基導入結構中可有效降低吸水率,因此合成例3利用含有較長碳鏈之苯酚化合物,與DOPO及4-羥基二苯甲酮在酸性觸媒催化下反應,合成具有低吸水率的不對稱磷系雙酚化合物。Since the introduction of an alkyl group into the structure can effectively reduce the water absorption rate, Synthesis Example 3 utilizes a phenol compound containing a longer carbon chain to react with DOPO and 4-hydroxybenzophenone under acidic catalyst catalysis, and has a low water absorption rate. An asymmetric phosphorus bisphenol compound.
合成例3與合成例1之步驟大致相同,差別之處在於反應完成後之產物需先溶於乙醇後再滴入於水中析出。The procedure of Synthesis Example 3 was substantially the same as that of Synthesis Example 1, except that the product after completion of the reaction was dissolved in ethanol and then dropped into water to precipitate.
以合成例3所示方法,使用不同苯酚化合物合成之產物(11)及(12),其分子式、分子量及產率等結果整理於下表3:
由於將含氟基團導入結構中可有效降低吸水性,因此合成例4利用含有氟基之苯酚化合物,與DOPO及4-羥基二苯甲酮在酸性觸媒催化下反應,可合成具有低吸水率的不對稱磷系雙酚化合物。Since the introduction of the fluorine-containing group into the structure can effectively reduce the water absorption, the synthesis example 4 utilizes a fluorine-containing phenol compound, reacts with DOPO and 4-hydroxybenzophenone under acidic catalyst catalysis, and can be synthesized to have low water absorption. The rate of asymmetric phosphorus bisphenol compounds.
合成例4與合成例1之步驟大致相同,差別之處在於反應完成後之產物需先溶於乙醇後再滴入於水中析出。The procedure of Synthesis Example 4 was substantially the same as that of Synthesis Example 1, except that the product after the completion of the reaction was dissolved in ethanol and then dropped into water to precipitate.
利用合成例4所示方法,使用不同苯酚化合物合成之產
物(13)-(16),其分子式、分子量及產率等結果整理於下表4:
依照本實施方式之一或多個實施例,上述合成例1-4所合成之具有不對稱結構的磷系雙酚化合物(1)-(16),可於觸媒存在下,進一步與具有環氧基結構之化合物進行鏈延長反應,以合成低吸水性的磷系環氧樹脂半固化物。According to one or more embodiments of the present embodiment, the phosphorus-based bisphenol compounds (1) to (16) having an asymmetric structure synthesized in the above Synthesis Examples 1-4 may further have a ring in the presence of a catalyst. The compound having an oxy structure is subjected to a chain extension reaction to synthesize a low water-absorbent phosphorus-based epoxy resin semi-cured product.
依照本實施方式之一或多個實施例,具有環氧基結構之化合物可為任何適用之環氧樹脂,包含但不僅限於丙二酚A樹脂(diglycidyl ether of bisphenol A,DGEBA)、雙酚F樹脂(diglycidyl ether of bisphenol F,DGEBF)、雙酚S樹脂(diglycidyl ether of bisphenol S,DGEBS)、雙酚樹脂(diglycidyl ether of biphenol)等雙官能環氧化合物。環氧基當量數對酚基當量數比為1:1至10:1。According to one or more embodiments of the present embodiment, the compound having an epoxy group structure may be any suitable epoxy resin, including but not limited to diglycidyl ether of bisphenol A (DGEBA), bisphenol F. A difunctional epoxy compound such as diglycidyl ether of bisphenol F (DGEBF), diglycidyl ether of bisphenol S (DGEBS), or diglycidyl ether of biphenol. The ratio of the number of equivalents of epoxy groups to the number of equivalents of phenol groups is from 1:1 to 10:1.
鏈延長反應可於100-200℃進行,觸媒用量為環氧樹脂含量的0.1-5 wt%;使用的觸媒可為咪唑(imidazole)化合物、三級膦、三級胺、季磷鹽、三氟化硼錯合鹽、鋰化物、季磷或季胺化合物。其中咪唑化合物例如可為2-苯基咪唑 (2-phenylimidazole)、2-甲基咪唑(2-methylimidazole,2MI);三級膦例如可為三苯基膦(triphenylphosphine,TPP);季磷化合物例如可為乙基三苯基醋酸膦(ethyltriphenyl phosphonium acetate)或乙基三苯基膦鹵化物(ethyltriphenyl phosphonium halides);季胺化合物例如可為苄基三甲基氯化銨(benzyltrimethyl ammonium chloride)、苄基三乙基氯化銨(benzyltriethyl ammonium chloride)或四丁基氯化銨(tetrabutyl ammonium chloride)。The chain extension reaction can be carried out at 100-200 ° C, and the amount of the catalyst is 0.1-5 wt% of the epoxy resin content; the catalyst used may be an imidazole compound, a tertiary phosphine, a tertiary amine, a quaternary phosphonium salt, Boron trifluoride complex salt, lithium compound, quaternary phosphorus or quaternary amine compound. Wherein the imidazole compound can be, for example, 2-phenylimidazole (2-phenylimidazole), 2-methylimidazole (2MI); the tertiary phosphine may be, for example, triphenylphosphine (TPP); the quaternary phosphorus compound may be, for example, ethyltriphenylphosphonate (ethyltriphenyl) Phosphonium acetate) or ethyltriphenyl phosphonium halides; the quaternary amine compound may be, for example, benzyltrimethyl ammonium chloride or benzyltriethyl ammonium chloride Or tetrabutyl ammonium chloride.
依照本實施方式合成之具有不對稱結構的磷系雙酚化合物之環氧樹脂半固化物衍生物,具有如下所示之通式(II)的結構:
其中R1 -R6 係各自獨立為氫原子、C1-C10烷基、C1-C10烷氧基、C1-C10鹵烷基、C3-C10環烷基、-CF3 、-OCF3 或鹵原子,且R5 及R6 不同時為氫原子,R7 為氫、苯基、C1-C10烷基、C3-C10環烷基、CF3 或鹵原子,n為1-5的整數。為了證明導入烷基或含氟基團之側鏈對於磷系雙酚環氧樹脂固化物性質之影響,以下合成例5-9係以式(1)、(2)、(8)及(10)所示之單體為例,合成具不對稱結構之磷系雙酚環氧樹脂半固化物,其產物分別命名為(1-2.0)、(2-2.0)、(8-2.0)及(10-2.0),並與具對稱結構 之比較例(DMP-2.0)比較其吸水性及玻璃轉移溫度之差異。不同單體合成之磷系雙酚環氧樹脂半固化物之固化係以硬化劑4,4-雙胺基雙苯碸(4-Aminophenyl Sulfone;DDS)硬化後測定其性質,包括:玻璃轉移溫度(Tg)、UL-94耐燃測試及吸水率測試,UL-94耐燃測試係測試在設備及裝置中塑膠材料的耐燃性標準。數據顯示於下表5。Wherein R 1 to R 6 are each independently a hydrogen atom, a C1-C10 alkyl group, a C1-C10 alkoxy group, a C1-C10 haloalkyl group, a C3-C10 cycloalkyl group, a —CF 3 , an —OCF 3 or a halogen atom. And R 5 and R 6 are not simultaneously a hydrogen atom, R 7 is hydrogen, phenyl, C1-C10 alkyl, C3-C10 cycloalkyl, CF 3 or a halogen atom, and n is an integer of 1-5. In order to demonstrate the influence of the side chain of the alkyl group or the fluorine-containing group on the properties of the phosphorus-based bisphenol epoxy resin cured product, the following Synthesis Examples 5-9 are based on the formulas (1), (2), (8) and (10). Taking the monomer shown as an example, a phosphorus-based bisphenol epoxy resin semi-cured product having an asymmetric structure is synthesized, and the products are named (1-2.0), (2-2.0), (8-2.0) and ( 10-2.0), and compared with the comparative example (DMP-2.0) with a symmetrical structure, the difference in water absorption and glass transition temperature. The curing of the phosphorus-based bisphenol epoxy resin semi-cured product synthesized by different monomers is determined by hardening the hardener 4,4-aminophenyl sulfonate (DDS), including: glass transition temperature. (Tg), UL-94 flame resistance test and water absorption test, UL-94 flame test is a test of the flame resistance of plastic materials in equipment and equipment. The data is shown in Table 5 below.
比較例為將20克雙酚A環氧樹脂置入100毫升反應器中,並升溫至150℃預先攪拌1小時。加入7.63克具有對稱磷系雙酚結構之單體(DMP)及0.1克之2-甲基咪唑後,維持150℃反應2小時,之後將產物倒出即為具有對稱磷系雙酚結構、磷含量為2.0 wt%之環氧樹脂半固化物(DMP -2.0),其化學式如下所示:
比較例之環氧樹脂半固化物(DMP -2.0)的固化物,其玻璃轉移溫度為195℃,UL-94測定為V-0(不燃)等級。在吸水性測試中,於12、24及48小時之吸水率分別為1.44、2.07及2.49 wt%。The cured product of the epoxy resin semi-cured product (DMP-2.0) of the comparative example had a glass transition temperature of 195 ° C and a UL-94 ratio of V-0 (non-combustible). In the water absorption test, the water absorption rates at 1, 24, and 48 hours were 1.44, 2.07, and 2.49 wt%, respectively.
合成例5為環氧樹脂半固化物(1-2.0)之合成。係將20克雙酚A環氧樹脂置入100毫升反應器中,並升溫至150℃預先攪拌1小時。加入7.98克具有不對稱結構之磷系雙酚單體(1)及0.1克之2-甲基咪唑後,維持150℃反應2小時,之後將產物倒出即為磷含量為2.0 wt%之環氧樹脂半固化物(1-2.0),具有如下之化學式:Synthesis Example 5 is a synthesis of an epoxy resin semi-cured product (1-2.0). Twenty grams of bisphenol A epoxy resin was placed in a 100 ml reactor and heated to 150 ° C for 1 hour with stirring. After adding 7.98 g of the phosphorus-based bisphenol monomer (1) having an asymmetric structure and 0.1 g of 2-methylimidazole, the reaction was maintained at 150 ° C for 2 hours, and then the product was poured out to be an epoxy having a phosphorus content of 2.0 wt%. Resin semi-cured (1-2.0) with the following chemical formula:
產物之環氧當量滴定值為406克/當量,理論值為398克/當量。The product had an epoxy equivalent titration of 406 g/eq and a theoretical value of 398 g/eq.
由下表5中可得知環氧樹脂半固化物(1-2.0)的固化物,其玻璃轉移溫度為193℃,UL-94測定為V-0(不燃)等級。在吸水性測試中,於12、24及48小時之吸水率分別為1.41、1.82及2.05 wt%,可發現導入甲基可使得吸水性下降,相較於比較例之具有對稱磷系雙酚結構之DMP-2.0的固化物,吸水率明顯下降,且其玻璃轉移溫度仍可維持一定水準。The cured product of the epoxy resin semi-cured product (1-2.0) having a glass transition temperature of 193 ° C and a UL-94 rating of V-0 (non-combustible) was obtained from Table 5 below. In the water absorption test, the water absorption rates at 1, 24, and 48 hours were 1.41, 1.82, and 2.05 wt%, respectively, and it was found that the introduction of a methyl group caused a decrease in water absorption, compared with the symmetrical phosphorus bisphenol structure of the comparative example. The cured product of DMP-2.0 has a significant decrease in water absorption, and its glass transition temperature can still maintain a certain level.
合成例6為環氧樹脂半固化物(2-2.0)之合成,其步驟與合成例5大致相同,差別在於加入8.34克具有不對稱磷系雙酚結構之單體(2),可得到具有如下化學式之環氧樹脂半固化物:Synthesis Example 6 is a synthesis of an epoxy resin semi-cured product (2-2.0), and the procedure thereof is substantially the same as that of Synthesis Example 5, except that 8.34 g of a monomer (2) having an asymmetric phosphorus-based bisphenol structure is added, and An epoxy resin semi-cured product of the following chemical formula:
合成例6的產物之環氧當量滴定值為411克/當量,理論值為405克/當量。以硬化劑4,4-雙胺基雙苯碸(DDS)硬化後測定其性質,數據亦顯示於上表5。The epoxy equivalent titration value of the product of Synthesis Example 6 was 411 g/eq, and the theoretical value was 405 g/eq. The properties were determined by hardening the hardener 4,4-diaminobisbenzoquinone (DDS), and the data are also shown in Table 5 above.
由表5中可得知環氧樹脂半固化物(2-2.0)的固化物,其玻璃轉移溫度為196℃,UL-94測定為V-0(不燃)等級。在吸水性測試中,於12、24及48小時之吸水率分別為1.36、1.71及1.84 wt%,顯見導入不對稱磷系雙酚結構,可使得其固化物維持原有高Tg特性,且因二甲基的導入使得吸水性較DMP-2.0明顯來得低。From Table 5, a cured product of an epoxy resin semi-cured product (2-2.0) having a glass transition temperature of 196 ° C and a UL-94 ratio of V-0 (non-combustible) was obtained. In the water absorption test, the water absorption rates at 1, 24, and 48 hours were 1.36, 1.71, and 1.84 wt%, respectively. It was obvious that the introduction of the asymmetric phosphorus bisphenol structure allowed the cured product to maintain the original high Tg characteristics, and The introduction of dimethyl group makes the water absorption lower than that of DMP-2.0.
合成例7為環氧樹脂半固化物(8-2.0)之合成,其步驟與合成例5大致相同,差別在於加入9.08克具有不對稱磷系雙酚結構之單體(8),可得到具有如下化學式之環氧樹脂半固化物:Synthesis Example 7 is a synthesis of an epoxy resin semi-cured product (8-2.0), and the procedure thereof is substantially the same as that of Synthesis Example 5, except that 9.08 g of a monomer (8) having an asymmetric phosphorus-based bisphenol structure is added, and An epoxy resin semi-cured product of the following chemical formula:
合成例7的產物之環氧當量滴定值為426克/當量,理論值為422克/當量。以硬化劑4,4-雙胺基雙苯碸(DDS)硬化後測定其性質,數據亦顯示於上表5。The epoxy equivalent titration value of the product of Synthesis Example 7 was 426 g/eq, and the theoretical value was 422 g/eq. The properties were determined by hardening the hardener 4,4-diaminobisbenzoquinone (DDS), and the data are also shown in Table 5 above.
由表5中可得知環氧樹脂半固化物(2-2.0)的固化物,其UL-94測定為V-0(不燃)等級。雖然導入長鏈段的特丁基使其玻璃轉移溫度略為下降至191℃,但仍因不對稱磷系雙酚結構使得固化物維持高Tg特性。在吸水性測試中,於12、24及48小時之吸水率分別為1.17、1.50及1.63 wt%,吸水性較DMP-2.0有顯著的下降。The cured product of the epoxy resin semi-cured product (2-2.0) was found in Table 5, and its UL-94 was measured to be a V-0 (non-combustible) grade. Although the long-chain segment of the tert-butyl group was introduced to slightly lower the glass transition temperature to 191 ° C, the cured product maintained high Tg characteristics due to the asymmetric phosphorus-based bisphenol structure. In the water absorption test, the water absorption rates at 1, 24, and 48 hours were 1.17, 1.50, and 1.63 wt%, respectively, and the water absorption was significantly lower than that of DMP-2.0.
合成例8為環氧樹脂半固化物(10-2.0)之合成,其步驟與合成例5大致相同,差別在於加入10.07克具有不對稱磷系雙酚結構之單體(8),可得到具有如下化學式之環氧樹脂半固化物:Synthesis Example 8 is a synthesis of an epoxy resin semi-cured product (10-2.0), the procedure of which is substantially the same as that of Synthesis Example 5, except that 10.07 g of a monomer (8) having an asymmetric phosphorus-based bisphenol structure is added, and An epoxy resin semi-cured product of the following chemical formula:
合成例8的產物之環氧當量滴定值為471克/當量,理論值為460克/當量。以硬化劑4,4-雙胺基雙苯碸(DDS)硬化後測定其性質,數據亦顯示於上表5。The product of Synthesis Example 8 had an epoxy equivalent titration value of 471 g/eq and a theoretical value of 460 g/eq. The properties were determined by hardening the hardener 4,4-diaminobisbenzoquinone (DDS), and the data are also shown in Table 5 above.
由表5中可得知環氧樹脂半固化物(2-2.0)的固化物,其UL-94測定為V-0(不燃)等級。雖然經導入長鏈段的二特丁基,然而由於其不對稱磷系雙酚結構使得固化物仍得以維持高Tg特性,其玻璃轉移溫度略為至194℃。在吸水性測試中,於12、24及48小時之吸水率分別為0.98、1.17及1.25 wt%,吸水性較DMP-2.0有顯著的下降。The cured product of the epoxy resin semi-cured product (2-2.0) was found in Table 5, and its UL-94 was measured to be a V-0 (non-combustible) grade. Although the long-chain segment of di-tert-butyl was introduced, the cured product was maintained at a high Tg characteristic due to its asymmetric phosphorus-based bisphenol structure, and its glass transition temperature was slightly up to 194 °C. In the water absorption test, the water absorption rates at 12, 24, and 48 hours were 0.98, 1.17, and 1.25 wt%, respectively, and the water absorption was significantly lower than that of DMP-2.0.
根據合成例5-8之產物性質測試發現,具有不對稱磷系雙酚結構的環氧樹脂固化物不僅具有維持良好之熱性質,且相較於具有對稱磷系雙酚結構的環氧樹脂固化物,其吸水率可藉由導入烷基而有效降低。According to the product property test of Synthesis Examples 5-8, it was found that the cured epoxy resin having an asymmetric phosphorus-based bisphenol structure not only has good thermal properties but also is cured as compared with an epoxy resin having a symmetrical phosphorus-based bisphenol structure. The water absorption rate of the substance can be effectively reduced by introducing an alkyl group.
由上述合成例5-8之性質測試亦可知本發明實施例之具有不對稱磷系雙酚之環氧樹脂固化物,很適合應用於有低吸水性需求的電路板基材、半導體封裝材料及其他相關領域。It is also known from the properties of the above Synthesis Examples 5-8 that the epoxy resin cured product having the asymmetric phosphorus bisphenol of the embodiment of the present invention is suitable for the circuit board substrate, the semiconductor packaging material and the low water absorption requirement. Other related fields.
雖然本發明已以實施方式揭露如上,然其並非用以限定本發明,任何熟習此技藝者,在不脫離本發明之精神和範圍內,當可作各種之更動與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and the present invention can be modified and modified without departing from the spirit and scope of the present invention. The scope is subject to the definition of the scope of the patent application attached.
為讓本發明之上述和其他目的、特徵、優點與實施例能更明顯易懂,所附圖式之說明如下:The above and other objects, features, advantages and embodiments of the present invention will become more apparent and understood.
第1A圖為本發明實施例之具有不對稱磷系雙酚結構之化合物(1)-(8)的合成簡圖;1A is a schematic diagram showing the synthesis of compounds (1) to (8) having an asymmetric phosphorus bisphenol structure according to an embodiment of the present invention;
第1A圖為本發明實施例之具有不對稱磷系雙酚結構之化合物(9)-(16)的合成簡圖;1A is a schematic diagram showing the synthesis of compounds (9) to (16) having an asymmetric phosphorus-based bisphenol structure according to an embodiment of the present invention;
第1B圖為本發明一實施例之磷系雙酚化合物(I-a)的1 H NMR圖譜;1B is a 1 H NMR spectrum of the phosphorus-based bisphenol compound (Ia) according to an embodiment of the present invention;
第2A圖為本發明實施例之化合物(1)的1 H NMR圖譜;2A is a 1 H NMR spectrum of the compound (1) according to an example of the present invention;
第2B圖為本發明實施例之化合物(2)的1 H NMR圖譜;2B is a 1 H NMR spectrum of the compound (2) according to an example of the present invention;
第2C圖為本發明實施例之化合物(8)的1 H NMR圖譜;以及2C is a 1 H NMR spectrum of the compound (8) according to an example of the present invention;
第2D圖為本發明實施例之化合物(10)的1 H NMR圖譜。Fig. 2D is a 1 H NMR spectrum of the compound (10) according to an example of the present invention.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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TW498084B (en) * | 2000-07-19 | 2002-08-11 | Chang Chun Plastics Co Ltd | Flame-retardant resin and flame retardant composition containing the same |
TW555809B (en) * | 2000-04-06 | 2003-10-01 | Matsushita Electric Works Ltd | Epoxy resin compositions containing phosphorus, flame retardant resin sheet using said epoxy resin containing phosphorus, resin clad metal foil, prepreg and laminated board, multilayer board |
TW575633B (en) * | 2002-10-21 | 2004-02-11 | Chang Chun Plastics Co Ltd | Flame retardant epoxy resin composition and phosphorus containing compound |
TWI296001B (en) * | 2002-10-22 | 2008-04-21 | Chang Chun Plastics Co Ltd | |
TW201002732A (en) * | 2008-07-15 | 2010-01-16 | Univ Nat Chunghsing | Preparation of novel phosphorus-containing biphenols and their derivatives |
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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TW555809B (en) * | 2000-04-06 | 2003-10-01 | Matsushita Electric Works Ltd | Epoxy resin compositions containing phosphorus, flame retardant resin sheet using said epoxy resin containing phosphorus, resin clad metal foil, prepreg and laminated board, multilayer board |
TW498084B (en) * | 2000-07-19 | 2002-08-11 | Chang Chun Plastics Co Ltd | Flame-retardant resin and flame retardant composition containing the same |
TW575633B (en) * | 2002-10-21 | 2004-02-11 | Chang Chun Plastics Co Ltd | Flame retardant epoxy resin composition and phosphorus containing compound |
TWI296001B (en) * | 2002-10-22 | 2008-04-21 | Chang Chun Plastics Co Ltd | |
TW201002732A (en) * | 2008-07-15 | 2010-01-16 | Univ Nat Chunghsing | Preparation of novel phosphorus-containing biphenols and their derivatives |
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