TWI709585B - Self-curable epoxy resins composition, preparation method thereof and epoxy curable product prepared thereby - Google Patents
Self-curable epoxy resins composition, preparation method thereof and epoxy curable product prepared thereby Download PDFInfo
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本發明係關於一種可自身固化的環氧樹脂組成物、其製備方法及其製備之環氧固化物,尤其是關於一種包含含氮觸媒與環氧樹脂的可自身固化的環氧樹脂組成物、其製備方法及其製備之環氧固化物。 The present invention relates to a self-curable epoxy resin composition, its preparation method and the prepared epoxy cured product, and in particular to a self-curable epoxy resin composition containing a nitrogen-containing catalyst and epoxy resin , Its preparation method and the epoxy cured product prepared.
傳統上的環氧樹脂已經應用於塗料、封裝、複合材料和覆銅箔層壓板等領域,因為其在固化後具有優異的性能,通常環氧樹脂需與固化劑或硬化劑反應以獲得高性能之熱固性材料。然而,大多數的商業環氧樹脂的起始材料是石油基材料,由於石油儲存有限且環境汙染問題越漸嚴重,相關業者開始尋找可再生材料來替代石油化工原料,可再生材料具有可再生、生產量大且分布廣等優點,利於降低高分子材料對於不可再生資源的消耗。 Traditionally, epoxy resin has been used in coatings, encapsulation, composite materials, copper clad laminates and other fields, because it has excellent performance after curing, usually epoxy resin needs to react with curing agent or hardener to obtain high performance The thermosetting material. However, most of the starting materials of commercial epoxy resins are petroleum-based materials. Due to limited petroleum storage and the increasingly serious environmental pollution problem, relevant industries have begun to look for renewable materials to replace petrochemical raw materials. Renewable materials are renewable, The advantages of large production volume and wide distribution are beneficial to reduce the consumption of non-renewable resources by polymer materials.
另外,當環氧樹脂與含有活性氫的硬化劑進行固化時,環氧基開環後會形成二級醇,二級醇的高極性會增 加材料的耗散係數,耗散係數與信號傳輸損失成比例,因此,與其他低介電聚合物材料相比,環氧樹脂之熱固性材料通常不具有較佳的介電性能。 In addition, when the epoxy resin is cured with a hardener containing active hydrogen, the epoxy group will form a secondary alcohol after ring opening, and the high polarity of the secondary alcohol will increase. Adding the dissipation factor of the material, the dissipation factor is proportional to the signal transmission loss. Therefore, compared with other low-dielectric polymer materials, epoxy resin thermoset materials generally do not have better dielectric properties.
有鑑於此,如何製備出不添加固化劑或硬化劑之環氧樹脂,使其介電性能提高,遂成相關業者努力的目標。 In view of this, how to prepare an epoxy resin without adding a curing agent or hardener to improve its dielectric properties has become the goal of the relevant industry.
本發明之一目的是在於提供一種可自身固化的環氧樹脂組成物、其製備方法及其製備之環氧固化物,藉由可再生材料作為起始材料合成環氧樹脂,接著搭配催化劑,形成可自身固化的環氧樹脂組成物,使其具有低介電損失。 One purpose of the present invention is to provide a self-curable epoxy resin composition, its preparation method and the epoxy cured product prepared therefrom. Renewable materials are used as starting materials to synthesize epoxy resin, and then combined with a catalyst to form Self-curing epoxy resin composition makes it have low dielectric loss.
本發明之一實施方式提供一種可自身固化的環氧樹脂組成物,包含一含氮觸媒以及一環氧樹脂,其中含氮觸媒為選自由二甲基二氨基吡啶、咪唑與二甲基咪唑所組成之一群組,環氧樹脂具有如式(I)或式(II)所示之一結構:
依據前段所述之可自身固化的環氧樹脂組成物,其中含氮觸媒的含量可為0.1重量百分比至2.0重量百分比。 According to the self-curable epoxy resin composition described in the preceding paragraph, the content of the nitrogen-containing catalyst can be 0.1 wt% to 2.0 wt%.
依據前段所述之可自身固化的環氧樹脂組成物,其中環氧樹脂可具有如式(I-1)、式(I-2)、式(I-3)、式(I-4)、式(I-5)、式(II-1)、式(II-2)、式(II-3)、式(II-4)或式(II-5)所示之一結構:
本發明之另一實施方式提供一種可自身固化的環氧樹脂組成物的製備方法,包含提供一可再生原料、進行一酯化反應步驟、進行一環氧化反應步驟以及進行一催化步驟。所述可再生原料可為一酚類化合物,所述酯化反應步驟係使酚類化合物與一醯氯化合物反應形成一含活性酯之丙烯基化合物。所述環氧化反應步驟係使含活性酯之丙烯基化合物與一間氯過氧苯甲酸進行反應,將含活性酯之丙烯基化合物末段之雙鍵環氧化,形成一環氧樹脂。最後,所述催化步驟係使環氧樹脂加入一含氮觸媒,以形成所述之可自身固化的環氧樹脂組成物,其中含氮觸媒為選自由二甲基二氮基吡啶、咪唑與二甲基咪唑所組成之一群組。 Another embodiment of the present invention provides a method for preparing a self-curable epoxy resin composition, which includes providing a renewable raw material, performing an esterification reaction step, performing an epoxidation reaction step, and performing a catalytic step. The renewable raw material may be a phenolic compound, and the esterification reaction step is to react the phenolic compound with a chlorine compound to form an active ester-containing acrylic compound. The epoxidation reaction step is to react the acrylic compound containing the active ester with a metachloroperoxybenzoic acid to epoxidize the double bond at the end of the acrylic compound containing the active ester to form an epoxy resin. Finally, in the catalyzing step, the epoxy resin is added to a nitrogen-containing catalyst to form the self-curable epoxy resin composition, wherein the nitrogen-containing catalyst is selected from the group consisting of dimethyldiazapyridine and imidazole. A group consisting of dimethylimidazole.
依據前段所述之可自身固化的環氧樹脂組成物的製備方法,其中酚類化合物可具有如式(a1)或式(a2)所示之一結構:
依據前段所述之可自身固化的環氧樹脂組成物的製備方法,其中醯氯化合物可具有如式(b1)或式(b2)所示之一結構:
依據前段所述之可自身固化的環氧樹脂組成物的製備方法,其中含活性酯之丙烯基化合物可具有如式(1)或式(2)所式之一結構:
依據前段所述之可自身固化的環氧樹脂組成物的製備方法,其中含氮觸媒的含量可為0.1重量百分比至2.0重量百分比。 According to the preparation method of the self-curable epoxy resin composition described in the preceding paragraph, the content of the nitrogen-containing catalyst can be 0.1 wt% to 2.0 wt%.
依據前段所述之可自身固化的環氧樹脂組成物的製備方法,其中環氧樹脂可具有如式(I-1)、式(I-2)、式(I-3)、式(I-4)、式(I-5)、式(II-1)、式(II-2)、式(II-3)、式(II-4)或式(II-5)所示之一結構:
本發明之又一實施方式提供一種環氧固化物,其係藉由前述可自身固化的環氧樹脂組成物進行一固化反應而得。 Another embodiment of the present invention provides an epoxy cured product, which is obtained by performing a curing reaction on the aforementioned self-curable epoxy resin composition.
藉此,本發明之可自身固化的環氧樹脂組成物係利用可再生材料合成環氧樹脂,再搭配含氮觸媒所形成,以避免使用固化劑造成後續固化環氧樹脂的反應中產生高極性的二級醇,使所製得之環氧固化物具有低介電常數、低介電損失的特性。 Therefore, the self-curable epoxy resin composition of the present invention is formed by using renewable materials to synthesize epoxy resin, and then combined with a nitrogen-containing catalyst to avoid the use of a curing agent to cause high levels in the subsequent curing of the epoxy resin. The polar secondary alcohol makes the epoxy cured product have the characteristics of low dielectric constant and low dielectric loss.
100:可自身固化的環氧樹脂組成物的製備方法 100: Preparation method of self-curing epoxy resin composition
110、120、130、140:步驟 110, 120, 130, 140: steps
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:第1圖係繪示依照本發明之一實施方式之可自身固化的環氧樹脂組成物的製備方法的步驟流程圖;第2圖係繪示合成例5以及合成例7在有無觸媒催化下的 熱分析圖;第3A圖係繪示實施例1之各升溫階段的傅立葉紅外光譜圖;第3B圖係繪示實施例2之各升溫階段的傅立葉紅外光譜圖;以及第4圖係繪示實施例1中自身固化反應的反應機構圖。 In order to make the above and other objects, features, advantages and embodiments of the present invention more comprehensible, the description of the accompanying drawings is as follows: Figure 1 shows a self-curing epoxy according to one embodiment of the present invention The step flow chart of the preparation method of the resin composition; Figure 2 shows the synthesis example 5 and synthesis example 7 with or without catalyst catalysis Thermal analysis diagram; Figure 3A shows the Fourier infrared spectrogram of each heating stage of Example 1; Figure 3B shows the Fourier infrared spectrum of each heating stage of Example 2; and Figure 4 shows the implementation The reaction mechanism diagram of the self-curing reaction in Example 1.
下述將更詳細討論本發明各實施方式。然而,此實施方式可為各種發明概念的應用,可被具體實行在各種不同的特定範圍內。特定的實施方式是僅以說明為目的,且不受限於揭露的範圍。 The various embodiments of the present invention will be discussed in more detail below. However, this embodiment can be an application of various inventive concepts and can be implemented in various specific ranges. The specific implementation is for illustrative purposes only, and is not limited to the scope of disclosure.
本發明提供一種可自身固化的環氧樹脂組成物,包含一含氮觸媒以及一環氧樹脂,其中環氧樹脂具有如式(I)或式(II)所示之一結構:
含氮觸媒為選自由二甲基二氮基吡啶(4-Dimethylaminopyridine,DMAP)、咪唑(imidazole)與二甲基咪唑(2-methylimidazole)所組成之一群組,較佳地,本發明之實施例係選自二甲基二氮基吡啶(DMAP)作為含氮觸媒,且所述之含氮觸媒可包含未共用電子對,可與環氧樹脂的環氧基作用而有利於引發後續的固化反應。具體地,所述含氮觸媒的含量為0.1wt%至2.0wt%。 The nitrogen-containing catalyst is selected from a group consisting of 4-Dimethylaminopyridine (DMAP), imidazole and 2-methylimidazole (2-methylimidazole). Preferably, the present invention The embodiment is selected from dimethyl diazopyridine (DMAP) as the nitrogen-containing catalyst, and the nitrogen-containing catalyst may contain unshared electron pairs, which can interact with the epoxy group of the epoxy resin to facilitate initiation Subsequent curing reaction. Specifically, the content of the nitrogen-containing catalyst is 0.1 wt% to 2.0 wt%.
舉例來說,當環氧樹脂組成物為式(I)之結構且n為2時,R1為式(i)、式(ii)或式(iii)所示之結構且R2為甲氧基,其可具有如式(I-1)、式(I-2)、式(I-3)或式(I-4)所示之一結構;而當n為3時,R1為式(iv)所示之結構且R2為甲氧基,其可具有如式(I-5)所示之一結構:
另外,當環氧樹脂組成物為式(II)之結構且n為2時,R1為式(i)、式(ii)或式(iii)所示之結構且R2為甲氧基,其可具有如式(II-1)、式(II-2)、式(II-3)或式(II-4)所示之一結構;而當n為3時,R1為式(iv)所示之結構且R2為甲氧基,其可具有如式(II-5)所示之一結構: In addition, when the epoxy resin composition has a structure of formula (II) and n is 2, R 1 is a structure represented by formula (i), formula (ii) or formula (iii) and R 2 is a methoxy group, It may have a structure as shown in formula (II-1), formula (II-2), formula (II-3) or formula (II-4); and when n is 3, R 1 is formula (iv ) And R 2 is a methoxy group, which can have a structure as shown in formula (II-5):
藉此,本發明之可自身固化的環氧樹脂組成物中的環氧樹脂可在含氮觸媒的催化下產生交聯而固化,且在固化過程中不會產生高極性的二級醇而使所製得之環氧固化物具有優良的低介電損失,適用於半導體材料,例如,可作為半導體製程中的銅箔基板,特別是可作為多層金屬內連線的銅箔基板。 Thereby, the epoxy resin in the self-curable epoxy resin composition of the present invention can be cross-linked and cured under the catalysis of a nitrogen-containing catalyst, and no high-polarity secondary alcohol is produced during the curing process. The prepared epoxy cured product has excellent low dielectric loss and is suitable for semiconductor materials. For example, it can be used as a copper foil substrate in the semiconductor manufacturing process, especially as a copper foil substrate for multilayer metal interconnections.
<可自身固化的環氧樹脂組成物的製備方法><Preparation method of self-curing epoxy resin composition>
請參閱第1圖,第1圖係繪示依照本發明之一實施方式之可自身固化的環氧樹脂組成物的製備方法100的步驟流程圖。可自身固化的環氧樹脂組成物的製備方法100包含步驟110、步驟120、步驟130以及步驟140。
Please refer to FIG. 1. FIG. 1 is a flowchart of a
步驟110為提供一可再生原料,其可為一酚類化合物,所述酚類化合物具有如式(a1)或式(a2)所示之一結構:
步驟120為進行一酯化反應步驟,係使酚類化合物與一醯氯化合物反應形成一含活性酯之丙烯基化合物,其中醯氯化合物具有如式(b1)或式(b2)所示之一結構:
所述含活性酯之丙烯基化合物具有如式(1)或式(2)所式之一結構:
具體來說,當式(a1)之酚類化合物與式(b1)之雙官能醯氯反應,並以三乙胺催化時,會形成式(1)之含活性酯之丙烯基化合物,且其中式(a1)之酚類化合物為丁香酚,式(b1)之雙官能醯氯為間苯二醯氯,因此所得式(1)之含活性酯之丙烯基化合物(以下簡稱IPEU),其n為2,R1為式(ii)之結構,R2為甲氧基。另外,將上述反應中之式(b1)之雙官能醯氯替換成式(b2)之三官能醯氯,且三官能醯氯為1,3,5-苯三甲醯氯,所得式(1)之含活性酯之丙烯基化合物(以下簡稱BTEU),其n為3,R1為式(iv)之結構,R2為甲氧基。 Specifically, when the phenolic compound of formula (a1) reacts with the difunctional chlorin of formula (b1) and is catalyzed by triethylamine, the active ester-containing acrylic compound of formula (1) is formed, and wherein The phenolic compound of formula (a1) is eugenol, and the bifunctional chlorin of formula (b1) is isophthalic dichloride. Therefore, the acrylic compound containing active ester of formula (1) (hereinafter referred to as IPEU) is obtained. Is 2, R 1 is the structure of formula (ii), and R 2 is methoxy. In addition, the difunctional chlorin of formula (b1) in the above reaction is replaced with the trifunctional chlorin of formula (b2), and the trifunctional chlorin is 1,3,5-benzenetrimethylchloride, and the resulting formula (1) For the active ester-containing propenyl compound (hereinafter referred to as BTEU), n is 3, R 1 is a structure of formula (iv), and R 2 is a methoxy group.
而當式(a2)之酚類化合物與式(b1)之雙官能醯氯反應,並以三乙胺催化時,會形成式(2)之含活性酯之丙烯基化合物,且其中式(a2)之酚類化合物為異丁香酚,式(b1)之雙官能醯氯為間苯二醯氯,因此所得式(2)之含活性酯之丙烯基化合物(以下簡稱IPIEU),其n為2,R1為式(ii)之結構,R2為甲氧基。另外,將上述反應中之式(b1)之雙官能醯氯替換成式(b2)之三官能醯氯,且三官能醯氯為1,3,5-苯三甲醯氯,所得式(2)之含活性酯之丙烯基化合物(以下簡稱BTIEU),其n為3,R1為式(iv)之結構,R2為甲氧基。 When the phenolic compound of formula (a2) reacts with the difunctional chlorin of formula (b1) and is catalyzed by triethylamine, the active ester-containing acrylic compound of formula (2) is formed, and the formula (a2) The phenolic compound of the formula (b1) is isoeugenol, and the bifunctional chlorin of formula (b1) is isophthalic acid chloride. Therefore, the acrylic compound containing active ester (hereinafter referred to as IPIEU) of formula (2) is obtained, and n is 2 , R 1 is the structure of formula (ii), and R 2 is methoxy. In addition, the difunctional chlorin of formula (b1) in the above reaction is replaced with the trifunctional chlorin of formula (b2), and the trifunctional chlorin is 1,3,5-benzenetrimethylchloride, and the resulting formula (2) The active ester-containing propenyl compound (hereinafter referred to as BTIEU), where n is 3, R 1 is the structure of formula (iv), and R 2 is methoxy.
步驟130為進行一環氧化反應步驟,係使含活性酯之丙烯基化合物與一間氯過氧苯甲酸(mCPBA)進行反應,將含活性酯之丙烯基化合物末端之雙鍵環氧化,形成環氧樹脂,使所述環氧樹脂亦具有活性酯結構。其中所述環氧樹脂具有如式(I-1)、式(I-2)、式(I-3)、式(I-4)或式(I-5)所示之一結構: Step 130 is an epoxidation reaction step, which is to react the acrylic compound containing active ester with a metachloroperoxybenzoic acid (mCPBA) to epoxidize the double bond at the end of the acrylic compound containing active ester to form epoxy Resin, so that the epoxy resin also has an active ester structure. The epoxy resin has a structure as shown in formula (I-1), formula (I-2), formula (I-3), formula (I-4) or formula (I-5):
具體來說,當IPEU與間氯過氧苯甲酸反應時,會形成式(I-2)之環氧樹脂(以下簡稱IPEU-EP),而當BTEU與間氯過氧苯甲酸反應時,則會形成式(I-5)之環氧樹脂(以下簡稱BTEU-EP)。 Specifically, when IPEU reacts with m-chloroperoxybenzoic acid, an epoxy resin of formula (I-2) (hereinafter referred to as IPEU-EP) is formed, and when BTEU reacts with m-chloroperoxybenzoic acid, then It will form an epoxy resin of formula (I-5) (hereinafter referred to as BTEU-EP).
另外,所述環氧樹脂亦具有如式(II-1)、式(II-2)、式(II-3)、式(II-4)或式(II-5)所示之一結構: In addition, the epoxy resin also has a structure as shown in formula (II-1), formula (II-2), formula (II-3), formula (II-4) or formula (II-5):
具體來說,當IPIEU與間氯過氧苯甲酸反應時,會形成式(II-2)之環氧樹脂(以下簡稱IPIEU-EP),而當BTIEU與間氯過氧苯甲酸反應時,則會形成式(II-5)之環氧樹脂(以下簡稱BTIEU-EP)。 Specifically, when IPIEU reacts with m-chloroperoxybenzoic acid, an epoxy resin of formula (II-2) (hereinafter referred to as IPIEU-EP) is formed, and when BTIEU reacts with m-chloroperoxybenzoic acid, then It will form an epoxy resin of formula (II-5) (hereinafter referred to as BTIEU-EP).
步驟140為進行一催化步驟,係使環氧樹脂加入含氮觸媒,以形成所述可自身固化的環氧樹脂組成物。具體來說,環氧樹脂IPEU-EP、BTEU-EP與含氮觸媒可形成含有可自身固化組成物的一前驅物溶液,其中含氮觸媒的細節請參照前文,在此不予以贅述。具體來說,可透過加熱前驅物溶液使環氧樹脂IPEU-EP以及BTEU-EP在含氮觸媒催化下產生交聯,且加熱之固化溫度可為120℃至240℃,而加熱時間可為1小時至6小時,以形成可自身固化環氧樹脂組成物(以下分別簡稱SC-IPEU-EP以及SC-BTEU-EP)。更具體地,前述加熱方式可採用多段加熱固化方式加熱前驅物溶液,例如,以120℃、180℃、200℃ 以及220℃各加熱2小時。關於加入之固化溫度與加熱時間可隨所使用環氧樹脂的種類彈性調整,本發明並不以此為限。 Step 140 is a catalyzing step in which epoxy resin is added to a nitrogen-containing catalyst to form the self-curable epoxy resin composition. Specifically, the epoxy resin IPEU-EP, BTEU-EP and the nitrogen-containing catalyst can form a precursor solution containing a self-curing composition. For details of the nitrogen-containing catalyst, please refer to the foregoing, and will not be repeated here. Specifically, the epoxy resin IPEU-EP and BTEU-EP can be cross-linked under the catalysis of a nitrogen-containing catalyst by heating the precursor solution, and the heating curing temperature can be 120°C to 240°C, and the heating time can be 1 hour to 6 hours to form a self-curing epoxy resin composition (hereinafter referred to as SC-IPEU-EP and SC-BTEU-EP). More specifically, the foregoing heating method may adopt a multi-stage heating and curing method to heat the precursor solution, for example, at 120°C, 180°C, and 200°C. And heating at 220°C for 2 hours each. Regarding the added curing temperature and heating time can be flexibly adjusted according to the type of epoxy resin used, the present invention is not limited to this.
本發明進一步提供一種環氧固化物,其係藉由前述可自身固化的環氧樹脂組成物進行一固化反應而得,而前述固化反應則參照第1圖之可自身固化的環氧樹脂組成物的製備方法100,在此不另贅述。
The present invention further provides an epoxy cured product, which is obtained by a curing reaction of the aforementioned self-curable epoxy resin composition, and the aforementioned curing reaction refers to the self-curable epoxy resin composition of Figure 1 The
茲以下列具體實施例進一步示範說明本發明,用以有利於本發明所屬技術領域通常知識者,可在不需過度解讀的情形下完整利用並實踐本發明,而不應將這些實施例視為對本發明範圍的限制,但用於說明如何實施本發明的材料及方法。 The following specific examples are used to further illustrate the present invention, so as to facilitate those skilled in the art to which the present invention pertains to fully utilize and practice the present invention without excessive interpretation. These embodiments should not be regarded as It limits the scope of the present invention, but is used to illustrate how to implement the materials and methods of the present invention.
<合成例><Synthesis example>
合成例1、IPEU的合成:在500mL的玻璃反應器中加入丁香酚16.19g(98.6mmole)、三乙基胺9.98g(98.6mmole)以及二氯甲烷200mL,並且通入氮氣與冷凝管,之後將間苯二醯氯10.00g(49.3mmole)溶於100mL的二氯甲烷中,並在3~5℃的條件下緩慢滴入1小時,之後在升溫至25℃下攪拌12小時。反應結束後過濾掉鹽類,並利用減壓蒸餾將二氯甲烷去除,析出之固體再用甲醇/水(1/4)之混合溶劑清洗數次,並在60℃下真空乾燥以得到白色固體。1H-NMR光譜(ppm,CDCl3):δ=3.4(4H,H8),3.8(6H,H13),5.1(4H,H10),5.9(2H,H9),6.8(4H,H6, H11),7.1(2H,H5),7.6(1H,H15),8.4(2H,H14),9.0(1H,H1)。合成例1的反應方程式如下表一所示。 Synthesis Example 1. Synthesis of IPEU: 16.19g (98.6mmole) of eugenol, 9.98g (98.6mmole) of triethylamine and 200mL of dichloromethane were added to a 500mL glass reactor, and nitrogen gas and condenser were introduced. Dissolve 10.00 g (49.3 mmole) of isophthalic dichloride in 100 mL of dichloromethane, slowly drip it at 3~5°C for 1 hour, and then stir at 25°C for 12 hours. After the reaction, the salts were filtered out, and the dichloromethane was removed by distillation under reduced pressure. The precipitated solid was washed several times with a mixed solvent of methanol/water (1/4) and dried under vacuum at 60°C to obtain a white solid . 1 H-NMR spectrum (ppm, CDCl 3 ): δ=3.4 (4H, H 8 ), 3.8 (6H, H 13 ), 5.1 (4H, H 10 ), 5.9 (2H, H 9 ), 6.8 (4H, H 6 , H 11 ), 7.1 (2H, H 5 ), 7.6 (1H, H 15 ), 8.4 (2H, H 14 ), 9.0 (1H, H 1 ). The reaction equation of Synthesis Example 1 is shown in Table 1 below.
合成例2、IPIEU的合成:在500mL的玻璃反應器中加入異丁香酚16.19g(98.6mmole)、三乙基胺9.98g(98.6mmole)以及二氯甲烷200mL,並且通入氮氣與冷凝管,之後將間苯二醯氯10.00g(49.3mmole)溶於100mL的二氯甲烷中,並在3~5℃的條件下緩慢滴入1小時,之後在升溫至25℃下攪拌12小時。反應結束後過濾掉鹽類,並利用減壓蒸餾將二氯甲烷去除,析出之固體再用甲醇/水(1/4)之混合溶劑清洗數次,並在60℃下真空乾燥以得到白色固體。1H-NMR光譜(ppm,CDCl3):δ=3.4(4H),3.8(6H13),5.1(4H,H10),5.9(2H,H9),6.8(4H,H6,H11),7.1(2H,H5),7.6(1H,H15),8.4(2H,H14),9.0(1H,H1)。合成例2的反應方程式如下表二所示。 Synthesis Example 2. Synthesis of IPIEU: In a 500mL glass reactor, 16.19g (98.6mmole) of isoeugenol, 9.98g (98.6mmole) of triethylamine and 200mL of dichloromethane were added, and nitrogen and condenser were introduced. Then, 10.00 g (49.3 mmole) of isophthalic acid chloride was dissolved in 100 mL of dichloromethane, and slowly dripped at 3~5°C for 1 hour, and then heated to 25°C and stirred for 12 hours. After the reaction, the salts were filtered out, and the dichloromethane was removed by distillation under reduced pressure. The precipitated solid was washed several times with a mixed solvent of methanol/water (1/4) and dried under vacuum at 60°C to obtain a white solid . 1 H-NMR spectrum (ppm, CDCl 3 ): δ=3.4(4H), 3.8(6H 13 ), 5.1(4H, H 10 ), 5.9(2H, H 9 ), 6.8(4H, H 6 , H 11 ), 7.1 (2H, H 5 ), 7.6 (1H, H 15 ), 8.4 (2H, H 14 ), 9.0 (1H, H 1 ). The reaction equation of Synthesis Example 2 is shown in Table 2 below.
合成例3、BTEU的合成:在500mL的玻璃反應器中加入丁香酚18.57g(113.1mmole)、三乙基胺11.44g(113.1mmole)以及二氯甲烷200mL,並且通入氮氣與冷凝管,之後將1,3,5苯三甲醯氯10.00g(37.7mmole)溶於100mL的二氯甲烷中,並在3~5℃的條件下緩慢滴入1小時,之後在升溫至25℃下攪拌12小時。反應結束後過濾掉鹽類,並利用減壓蒸餾將二氯甲烷去除,析出之固體再用甲醇/水(1/4)之混合溶劑清洗數次,並在60℃下真空乾燥以得到淡黃色固體。1H-NMR光譜(ppm,CDCl3):δ=3.4(6H,H8),3.8(9H,H13),5.1(6H,H10),5.9(3H,H9),6.8(6H,H6,H11),7.1(3H,H5),9.2(3H,H1)。合成例3的反應方程式如下表三所示。 Synthesis Example 3. Synthesis of BTEU: Add 18.57g (113.1mmole) of eugenol, 11.44g (113.1mmole) of triethylamine, and 200mL of dichloromethane into a 500mL glass reactor, and pass nitrogen and condenser into the reactor. Dissolve 10.00g (37.7mmole) of 1,3,5 trimellityl chloride in 100mL of dichloromethane, and slowly drip it at 3~5℃ for 1 hour, and then stir at 25℃ for 12 hours . After the reaction, the salts were filtered out, and the dichloromethane was removed by distillation under reduced pressure. The precipitated solid was washed several times with a mixed solvent of methanol/water (1/4) and dried under vacuum at 60°C to obtain a pale yellow solid. 1 H-NMR spectrum (ppm, CDCl 3 ): δ=3.4 (6H, H 8 ), 3.8 (9H, H 13 ), 5.1 (6H, H 10 ), 5.9 (3H, H 9 ), 6.8 (6H, H 6 , H 11 ), 7.1 (3H, H 5 ), 9.2 (3H, H 1 ). The reaction equation of Synthesis Example 3 is shown in Table 3 below.
合成例4、BTIEU的合成:在500mL的玻璃反應器中加入異丁香酚18.57g(113.1mmole)、三乙基胺11.44g(113.1mmole)以及二氯甲烷200mL,並且通入氮氣與冷凝管,之後將1,3,5苯三甲醯氯10.00g(37.7mmole)溶於100mL的二氯甲烷中,並在3~5℃的條件下緩 慢滴入1小時,之後在升溫至25℃下攪拌12小時。反應結束後過濾掉鹽類,並利用減壓蒸餾將二氯甲烷去除,析出之固體再用甲醇/水(1/4)之混合溶劑清洗數次,並在60℃下真空乾燥以得到淡黃色固體。1H-NMR光譜(ppm,CDCl3):δ=3.4(6H,H8),3.8(9H,H13),5.1(6H,H10),5.9(3H,H9),6.8(6H,H6,H11),7.1(3H,H5),9.2(3H,H1)。 Synthesis Example 4. Synthesis of BTIEU: In a 500mL glass reactor, 18.57g (113.1mmole) of isoeugenol, 11.44g (113.1mmole) of triethylamine and 200mL of dichloromethane were added, and nitrogen and condenser were introduced. Then, 10.00g (37.7mmole) of 1,3,5 trimellityl chloride was dissolved in 100mL of dichloromethane, and slowly dripped at 3~5℃ for 1 hour, and then heated to 25℃ and stirred for 12 hour. After the reaction, the salts were filtered out, and the dichloromethane was removed by distillation under reduced pressure. The precipitated solid was washed several times with a mixed solvent of methanol/water (1/4) and dried under vacuum at 60°C to obtain a pale yellow solid. 1 H-NMR spectrum (ppm, CDCl 3 ): δ=3.4 (6H, H 8 ), 3.8 (9H, H 13 ), 5.1 (6H, H 10 ), 5.9 (3H, H 9 ), 6.8 (6H, H 6 , H 11 ), 7.1 (3H, H 5 ), 9.2 (3H, H 1 ).
合成例4的反應方程式如下表四所示。 The reaction equation of Synthesis Example 4 is shown in Table 4 below.
合成例5、IPEU-EP的合成:在500mL的玻璃反應器中加入IPEU 10.00g(21.8mmole)以及二氯甲烷200mL,並且通入氮氣與冷凝管,並在0℃的條件下加入間氯過氧苯甲酸18.81g(109mmole),待其全溶後,升溫至40℃下反應12小時。反應結束後過濾不溶物,並將濾液與10wt%之硫酸鈉(Na2SO3)萃取數次至水層為透明,取出有機層後加入硫酸鎂除水,過濾取濾液在用減壓濃縮將二氯甲烷去除,以得到黃色粉體。1H-NMR光譜(ppm,CDCl3):δ=2.5,2.8(4H,H10),2.9(4H,H8),3.2(2H,H9),3.8(6H,H13),6.8(2H,H6),6.9(2H,H11),7.1(2H,H5), 7.6(1H,H15),8.4(4H,H14),9.0(1H,H1)。合成例5的反應方程式如下表五所示。 Synthesis Example 5. Synthesis of IPEU-EP: In a 500mL glass reactor, 10.00g (21.8mmole) of IPEU and 200mL of dichloromethane were added, and nitrogen and condenser were introduced, and m-chlorine was added at 0℃. Oxybenzoic acid 18.81g (109mmole), after it is completely dissolved, the temperature is raised to 40°C and reacted for 12 hours. After the reaction, the insoluble matter was filtered, and the filtrate was extracted with 10wt% sodium sulfate (Na 2 SO 3 ) several times until the water layer became transparent. After removing the organic layer, magnesium sulfate was added to remove water, and the filtrate was filtered and concentrated under reduced pressure. Dichloromethane was removed to obtain yellow powder. 1 H-NMR spectrum (ppm, CDCl 3 ): δ=2.5,2.8(4H,H 10 ),2.9(4H,H 8 ),3.2(2H,H 9 ),3.8(6H,H 13 ),6.8( 2H, H 6 ), 6.9 (2H, H 11 ), 7.1 (2H, H 5 ), 7.6 (1H, H 15 ), 8.4 (4H, H 14 ), 9.0 (1H, H 1 ). The reaction equation of Synthesis Example 5 is shown in Table 5 below.
合成例6、IPIEU-EP的合成:在500mL的玻璃反應器中加入IPIEU 10.00g(21.8mmole)以及二氯甲烷200mL,並且通入氮氣與冷凝管,並在0℃的條件下加入間氯過氧苯甲酸18.81g(109mmole),待其全溶後,升溫至40℃下反應12小時。反應結束後過濾不溶物,並將濾液與10wt%之硫酸鈉(Na2SO3)萃取數次至水層為透明,取出有機層後加入硫酸鎂除水,過濾取濾液在用減壓濃縮將二氯甲烷去除,以得到黃色粉體。1H-NMR光譜(ppm,CDCl3):δ=1.3(6H,H6),3.1(2H,H5),3.7(2H,H4),3.7(6H,H8),6.9,7.0,7.2(6H,H2,H3,H7),7.8(1H,H10),8.4(2H,H9),8.7(1H,H1)。合成例6的反應方程式如下表六所示。 Synthesis Example 6. Synthesis of IPIEU-EP: Add 10.00g (21.8mmole) of IPIEU and 200mL of dichloromethane into a 500mL glass reactor, and pass nitrogen and condenser into it, and add m-chlorine under the condition of 0℃. Oxybenzoic acid 18.81g (109mmole), after it is completely dissolved, the temperature is raised to 40°C and reacted for 12 hours. After the reaction, the insoluble matter was filtered, and the filtrate was extracted with 10wt% sodium sulfate (Na 2 SO 3 ) several times until the water layer became transparent. After removing the organic layer, magnesium sulfate was added to remove water, and the filtrate was filtered and concentrated under reduced pressure. Dichloromethane was removed to obtain yellow powder. 1 H-NMR spectrum (ppm, CDCl 3 ): δ=1.3 (6H, H 6 ), 3.1 (2H, H 5 ), 3.7 (2H, H 4 ), 3.7 (6H, H 8 ), 6.9, 7.0, 7.2 (6H, H 2 , H 3 , H 7 ), 7.8 (1H, H 10 ), 8.4 (2H, H 9 ), 8.7 (1H, H 1 ). The reaction equation of Synthesis Example 6 is shown in Table 6 below.
合成例7、BTEU-EP的合成:在500mL的玻璃反應器中加入BTEU 10.00g(15.4mmole)以及二氯甲烷200mL,並且通入氮氣與冷凝管,並在0℃的條件下加入間氯過氧苯甲酸19.96g(115.7mmole),待其全溶後,升溫至40℃下反應12小時。反應結束後過濾不溶物,並將濾液與10wt%之硫酸鈉(Na2SO3)萃取數次至水層為透明,取出有機層後加入硫酸鎂除水,過濾取濾液在用減壓濃縮將二氯甲烷去除,以得到黃色粉體。1H-NMR光譜(ppm,CDCl3):δ=2.5,2.8(6H,H10),2.9(6H,H8),3.2(3H,H9),3.8(9H,H13),6.8(3H,H6),6.9(3H,H11),7.1(3H,H5),9.2(3H,H1)。合成例7的反應方程式如下表七所示。 Synthesis Example 7. Synthesis of BTEU-EP: In a 500mL glass reactor, 10.00g (15.4mmole) of BTEU and 200mL of dichloromethane were added, and nitrogen and condenser were introduced, and meta-chlorine was added at 0℃. Oxybenzoic acid 19.96g (115.7mmole), after it is completely dissolved, the temperature is raised to 40°C and reacted for 12 hours. After the reaction, the insoluble matter was filtered, and the filtrate was extracted with 10wt% sodium sulfate (Na 2 SO 3 ) several times until the water layer became transparent. After removing the organic layer, magnesium sulfate was added to remove water, and the filtrate was filtered and concentrated under reduced pressure. Dichloromethane was removed to obtain yellow powder. 1 H-NMR spectrum (ppm, CDCl 3 ): δ=2.5,2.8(6H,H 10 ),2.9(6H,H 8 ),3.2(3H,H 9 ),3.8(9H,H 13 ),6.8( 3H, H 6 ), 6.9 (3H, H 11 ), 7.1 (3H, H 5 ), 9.2 (3H, H 1 ). The reaction equation of Synthesis Example 7 is shown in Table 7 below.
合成例8、BTIEU-EP的合成:在500mL的玻璃反應器中加入BTIEU 10.00g(21.8mmole)以及二氯甲烷200mL,並且通入氮氣與冷凝管,並在0℃的條件下加入間氯過氧苯甲酸18.81g(109mmole),待其全溶後,升溫至40℃下反應12小時。反應結束後過濾不溶物,並將濾 液與10wt%之硫酸鈉(Na2SO3)萃取數次至水層為透明,取出有機層後加入硫酸鎂除水,過濾取濾液在用減壓濃縮將二氯甲烷去除,以得到黃色粉體。1H-NMR光譜(ppm,CDCl3):δ=1.3(9H,H1),3.1(3H,H9),3.7(3H,H8),3.7(9H,H5),6.9,7.0,7.2(9H,H6,H11,H12),7.9(3H,H1)。合成例8的反應方程式如下表八所示。 Synthesis Example 8. Synthesis of BTIEU-EP: In a 500mL glass reactor, 10.00g (21.8mmole) of BTIEU and 200mL of dichloromethane were added, and nitrogen gas and condenser were introduced, and meta-chlorine was added at 0℃. Oxybenzoic acid 18.81g (109mmole), after it is completely dissolved, the temperature is raised to 40°C and reacted for 12 hours. After the reaction, the insoluble matter was filtered, and the filtrate was extracted with 10wt% sodium sulfate (Na 2 SO 3 ) several times until the water layer became transparent. After removing the organic layer, magnesium sulfate was added to remove water, and the filtrate was filtered and concentrated under reduced pressure. Dichloromethane was removed to obtain yellow powder. 1 H-NMR spectrum (ppm, CDCl 3 ): δ=1.3 (9H, H 1 ), 3.1 (3H, H 9 ), 3.7 (3H, H 8 ), 3.7 (9H, H 5 ), 6.9, 7.0, 7.2 (9H, H 6 , H 11 , H 12 ), 7.9 (3H, H 1 ). The reaction equation of Synthesis Example 8 is shown in Table 8 below.
<實施例及比較例><Examples and Comparative Examples>
實施例1、以溶劑法製備可自身固化的環氧樹脂組成物(以下簡稱SC-IPEU-EP):將IPEU-EP加入二甲基二氨基吡啶,溶於二甲基甲醯胺(Dimethylformamide)中,形成固含量30%的前驅物溶液,接著利用玻璃塗佈機將溶液塗佈於玻璃上,階段升溫至80℃進行12小時熱處理以去除大部份溶劑,接著在氮氣下,以120℃、180℃、200℃以及220℃各2小時階段升溫固化,以得到SC-IPEU-EP。 Example 1. Preparation of self-curing epoxy resin composition (hereinafter referred to as SC-IPEU-EP) by solvent method: Add IPEU-EP to dimethyldiaminopyridine and dissolve in dimethylformamide (Dimethylformamide) In the process, a precursor solution with a solid content of 30% is formed, and then the solution is coated on the glass using a glass coater. The temperature is raised to 80°C for 12 hours to remove most of the solvent, and then the solution is heated at 120°C under nitrogen. , 180 ℃, 200 ℃ and 220 ℃ each 2 hours stage heating and curing to obtain SC-IPEU-EP.
實施例2、以溶劑法製備可自身固化的環氧樹脂組成物(以下簡稱SC-BTEU-EP):將BTEU-EP加入二甲基 二氨基吡啶,溶於二甲基甲醯胺中,形成固含量30%的前驅物溶液,接著利用玻璃塗佈機將溶液塗佈於玻璃上,階段升溫至80℃進行12小時熱處理以去除大部份溶劑,接著在氮氣下,以120℃、180℃、200℃以及220℃各2小時階段升溫固化,以得到SC-BTEU-EP。 Example 2. Preparation of self-curable epoxy resin composition (hereinafter referred to as SC-BTEU-EP) by solvent method: adding BTEU-EP to dimethyl Diaminopyridine is dissolved in dimethylformamide to form a precursor solution with a solid content of 30%, and then the solution is coated on the glass using a glass coater, and the temperature is gradually raised to 80°C for 12 hours of heat treatment to remove the bulk Part of the solvent was then cured under nitrogen at 120°C, 180°C, 200°C, and 220°C for 2 hours each to obtain SC-BTEU-EP.
比較例1、製備二氨基二苯甲烷硬化之環氧樹脂(以下簡稱IPEU-EP/DDM):將等當量的二氨基二苯甲烷(Diaminodiphenyl methane)與IPEU-EP溶於二甲基甲醯胺中,形成固含量30%的前驅物溶液,接著利用玻璃塗佈機將溶液塗佈於玻璃上,階段升溫至80℃進行12小時熱處理以去除大部份溶劑,接著在氮氣下,以120℃、180℃、200℃以及220℃各2小時階段升溫固化,以得到IPEU-EP/DDM。而比較例1與實施例1不同之處在於比較例1採用二氨基二苯甲烷作為環氧樹脂的固化劑。 Comparative example 1. Preparation of epoxy resin cured by diaminodiphenylmethane (hereinafter referred to as IPEU-EP/DDM): Dissolve equivalent amounts of diaminodiphenyl methane and IPEU-EP in dimethylformamide In the process, a precursor solution with a solid content of 30% is formed, and then the solution is coated on the glass using a glass coater. The temperature is raised to 80°C for 12 hours to remove most of the solvent, and then the solution is heated at 120°C under nitrogen. , 180 ℃, 200 ℃ and 220 ℃ each 2 hours stage heating and curing to obtain IPEU-EP/DDM The difference between Comparative Example 1 and Example 1 is that Comparative Example 1 uses diaminodiphenylmethane as the curing agent of the epoxy resin.
比較例2、製備二氨基二苯甲烷硬化之環氧樹脂(以下簡稱BTEU-EP/DDM):將等當量的二氨基二苯甲烷與BTEU-EP溶於二甲基甲醯胺中,形成固含量30%的前驅物溶液,接著利用玻璃塗佈機將溶液塗佈於玻璃上,階段升溫至80℃進行12小時熱處理以去除大部份溶劑,接著在氮氣下,以120℃、180℃、200℃以及220℃各2小時階段升溫固化,以得到BTEU-EP/DDM。而比較例2與實施例2不同之處在於比較例2採用二氨基二苯甲烷作為環氧樹脂的固化劑。 Comparative Example 2. Preparation of epoxy resin cured by diaminodiphenylmethane (hereinafter referred to as BTEU-EP/DDM): Dissolve equivalent amounts of diaminodiphenylmethane and BTEU-EP in dimethylformamide to form a solid Precursor solution with a content of 30%, then use a glass coater to coat the solution on the glass, gradually increase the temperature to 80°C for 12 hours heat treatment to remove most of the solvent, and then under nitrogen at 120°C, 180°C, 200 ℃ and 220 ℃ each 2 hours of heating and curing to obtain BTEU-EP/DDM. The difference between Comparative Example 2 and Example 2 is that Comparative Example 2 uses diaminodiphenylmethane as the curing agent of the epoxy resin.
<可自身固化的環氧樹脂組成物之熱性質量測><Thermal quality measurement of self-curing epoxy resin composition>
將實施例1、實施例2、比較例1以及比較例2進行熱性質以及介電能力的性質評估,熱性質評估包括玻璃轉移溫度(Tg)、5%熱重損失溫度(Td5%)以及焦炭殘餘率,介電能力包括介電常數以及介電損失,、評估方法如下。 Example 1, Example 2, Comparative Example 1, and Comparative Example 2 were evaluated for thermal properties and dielectric properties. The thermal property evaluations included glass transition temperature (Tg), 5% thermogravimetric loss temperature (T d5% ), and The residual rate of coke, the dielectric capacity, including the dielectric constant and dielectric loss, are evaluated as follows.
(一)玻璃轉移溫度:使用動態機械分析儀(Dynamic Mechanical Analyzer,DMA;型號:Perkin-Elmer Pyris Diamond)測量固化物樣品的儲存模數(Storage Modulus)及Tan delta曲線和溫度的關係以及玻璃轉移溫度。另外使用熱機械分析法(Thermo-Mechanical Analysis,TMA)來測量玻璃轉移溫度,熱機械分析法的條件為在5℃/min的加熱速率下量測。 (1) Glass transition temperature: use a dynamic mechanical analyzer (Dynamic Mechanical Analyzer, DMA; model: Perkin-Elmer Pyris Diamond) to measure the storage modulus (Storage Modulus) of the cured product sample and the relationship between the Tan delta curve and temperature and the glass transfer temperature. In addition, thermo-mechanical analysis (Thermo-Mechanical Analysis, TMA) is used to measure the glass transition temperature. The conditions of the thermo-mechanical analysis are measured at a heating rate of 5°C/min.
(二)5%熱重損失溫度及焦炭殘餘率:使用熱重分析法(Thermo-Gravimetric Analysis,TGA)來量測樣品的5%熱重損失溫度以及800℃的焦炭殘餘率(Char yield)。熱重量分析的條件是在氮氣氣氛下、以20℃/min的加熱速率,使用熱重分析儀(型號:Perkin-Elmer Pyrisl)量測樣品的重量變化。5%熱重損失溫度是指固化物樣品的重量損失達5%的溫度,其中5%熱重損失溫度愈高代表樣品的熱穩定性愈佳。800℃的焦炭殘餘率是指加熱溫度達800℃時的樣品的殘餘重量比率,其中800℃的殘餘重量比率愈高代表樣品的熱穩定性愈佳。 (2) 5% thermogravimetric loss temperature and coke residual rate: Thermo-Gravimetric Analysis (TGA) is used to measure the 5% thermogravimetric loss temperature and the char yield of the sample at 800°C. The condition of thermogravimetric analysis is to measure the weight change of the sample using a thermogravimetric analyzer (model: Perkin-Elmer Pyrisl) at a heating rate of 20°C/min under a nitrogen atmosphere. The 5% thermogravimetric loss temperature refers to the temperature at which the weight loss of the cured product sample reaches 5%. The higher the 5% thermogravimetric loss temperature, the better the thermal stability of the sample. The coke residual ratio at 800°C refers to the residual weight ratio of the sample when the heating temperature reaches 800°C. The higher the residual weight ratio at 800°C, the better the thermal stability of the sample.
(三)介電常數及介電損失:在25℃、1G Hz下使用安捷倫介電分析儀(Agilent;型號:E4991A)量測樣品的介電常數以及介電損失。量測結果如下表九所示: (3) Dielectric constant and dielectric loss: Use Agilent dielectric analyzer (Agilent; model: E4991A) to measure the dielectric constant and dielectric loss of the sample at 25°C and 1G Hz. The measurement results are shown in Table 9 below:
由表九的結果可見,當使用動態機械分析法量測時,實施例1、實施例2、比較例1以及比較例2的玻璃轉移溫度皆高於180℃以上,而在熱重分析的測試中,實施例1以及實施例2之5%熱重損失溫度為374℃以及373℃,在800℃之焦炭殘餘率為29~40%,顯示實施例1以及實施例2具有極為優異的熱穩定性。 It can be seen from the results in Table 9 that when the dynamic mechanical analysis method is used for measurement, the glass transition temperature of Example 1, Example 2, Comparative Example 1, and Comparative Example 2 are all higher than 180°C, and in the test of thermogravimetric analysis Among them, the 5% thermogravimetric loss temperatures of Example 1 and Example 2 are 374°C and 373°C, and the coke residual rate at 800°C is 29-40%, indicating that Example 1 and Example 2 have extremely excellent thermal stability Sex.
接著,再以介電分析結果可知,實施例1以及實施例2的介電常數與介電損失皆較比較例1以及比較例2低,由此可知,本發明之實施例1以及實施例2之可自身固化的環氧樹脂組成物確實具有低介電常數與低介電損失等特性。 Then, the dielectric analysis results show that the dielectric constant and dielectric loss of Example 1 and Example 2 are lower than those of Comparative Example 1 and Comparative Example 2. From this, it can be seen that Example 1 and Example 2 of the present invention The self-curing epoxy resin composition does have the characteristics of low dielectric constant and low dielectric loss.
請參閱第2圖,其係繪示合成例5及合成例7在有無觸媒催化下的熱分析圖,由第2圖的結果可見,合成例5中活性酯與環氧基反應的放熱峰為305℃(熱焓約240 J/g),但含0.5wt%二甲基二氨基吡啶催化的合成例5(實施例1),其放熱峰下降至166℃(熱焓約263J/g)。合成例7中活性酯與環氧基反應的放熱峰為224℃(熱焓約226J/g),但含0.5wt%二甲基二氨基吡啶催化的合成例7(實施例2),其放熱峰下降至183℃(熱焓約258J/g),由上述結果顯示含氮觸媒二甲基二氨基吡啶對於活性酯和環氧基反應是一種有效的催化觸媒。 Please refer to Figure 2, which shows the thermal analysis diagrams of Synthesis Example 5 and Synthesis Example 7 with or without catalyst catalysis. From the results in Figure 2, it can be seen that the exothermic peak of the active ester and epoxy group in Synthesis Example 5 Is 305℃ (enthalpy is about 240 J/g), but containing 0.5wt% dimethyldiaminopyridine catalyzed Synthesis Example 5 (Example 1), its exothermic peak dropped to 166°C (enthalpy about 263 J/g). The exothermic peak of the reaction between the active ester and the epoxy group in Synthesis Example 7 is 224°C (the enthalpy is about 226J/g), but the synthesis example 7 (Example 2) catalyzed by 0.5wt% dimethyldiaminopyridine is exothermic The peak drops to 183°C (the enthalpy is about 258J/g). The above results show that the nitrogen-containing catalyst dimethyldiaminopyridine is an effective catalyst for the reaction of active esters and epoxy groups.
請參閱第3A圖以及第3B圖,其中第3A圖係繪示實施例1之各升溫階段的傅立葉紅外光譜圖,第3B圖係繪示實施例2之各升溫階段的傅立葉紅外光譜圖,由第3A圖以及第3B圖的結果可見,隨著固化溫度增加(室溫至240℃),對於IPEU-EP,其酯基吸收峰從硬化前的1739cm-1降至1726cm-1,而對於BTEU-EP,其酯基吸收峰從硬化前的1746cm-1降至1730cm-1。根據紅外光吸收原理,芳香酯基(Ar-O-C(=O)-)的吸收峰較脂肪酯基(R-O-C(=O)-)的吸收峰高,因此可證明在自身固化的過程中,實施例1及實施例2之酯基結構的變化。 Please refer to Figure 3A and Figure 3B. Figure 3A shows the Fourier infrared spectrogram of each heating stage of Example 1, and Figure 3B shows the Fourier infrared spectrum of each heating stage of Example 2. the results of FIG. 3A and FIG. 3B is visible as the curing temperature increases (from room temperature to 240 deg.] C), for IPEU-EP, an ester group absorption peak of 1739cm -1 decreased from before curing 1726cm -1, while for BTEU -EP, the absorption peak of its ester group decreased from 1746cm -1 before hardening to 1730cm -1 . According to the principle of infrared light absorption, the absorption peak of aromatic ester group (Ar-OC(=O)-) is higher than that of fatty ester group (ROC(=O)-), so it can be proved that the implementation of the Changes in the structure of the ester group in Example 1 and Example 2.
基於第2圖、第3A圖以及第3B圖的結果,可推定出本發明之可自身固化的環氧樹脂組成物之自身固化的反應機構,如第4圖所示,第4圖係繪示實施例1中自身固化反應的反應機構圖,其包含步驟1至步驟4。步驟1:二甲基二氨基吡啶攻擊環氧基形成具有烷基陰離子的中間物(I),步驟2:中間物(I)的烷基陰離子和活性酯基形成複合體,步驟3:中間物(I)的烷基陰離子攻擊活性酯基,形成中間物
(II)及帶有酚基陰離子,步驟4:酚基陰離子攻擊中間物(II),形成中間物(III),並釋放出二甲基二氨基吡啶,之後二甲基二氨基吡啶再重複步驟1進行攻擊環氧基。
Based on the results of Fig. 2, Fig. 3A and Fig. 3B, the self-curing reaction mechanism of the self-curing epoxy resin composition of the present invention can be inferred, as shown in Fig. 4, which is shown in Fig. 4 The reaction mechanism diagram of the self-curing reaction in Example 1, which includes
由第4圖的結果可見,在上述可自身固化的環氧樹脂組成物之自身固化的反應機構中,不會產生具有極性的二級醇,有助於降低所製得之環氧固化物的介電常數。 From the results in Figure 4, it can be seen that in the self-curing reaction mechanism of the self-curing epoxy resin composition described above, no polar secondary alcohol is produced, which helps to reduce the epoxy cured product. Dielectric constant.
綜上所述,依據本發明之可自身固化的環氧樹脂組成物,其可在含氮觸媒的催化下,與環氧樹脂產生交聯而固化,並可避免在固化過程中產生高極性的二級醇,進而具有優良的熱性質,即高玻璃轉移溫度與熱穩定性,且可進一步提升介電能力有利於電器材料方面的應用。 In summary, according to the self-curable epoxy resin composition of the present invention, it can be cured by cross-linking with the epoxy resin under the catalysis of a nitrogen-containing catalyst, and can avoid high polarity during the curing process. The secondary alcohol has excellent thermal properties, that is, high glass transition temperature and thermal stability, and can further improve the dielectric capacity, which is beneficial to the application of electrical materials.
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. Anyone familiar with the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection of the present invention The scope shall be subject to those defined in the attached patent scope.
100:可自身固化的環氧樹脂組成物的製備方法 100: Preparation method of self-curing epoxy resin composition
110、120、130、140:步驟 110, 120, 130, 140: steps
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