TWI685499B - Phosphinated compound and cured product thereof - Google Patents

Phosphinated compound and cured product thereof Download PDF

Info

Publication number
TWI685499B
TWI685499B TW107131479A TW107131479A TWI685499B TW I685499 B TWI685499 B TW I685499B TW 107131479 A TW107131479 A TW 107131479A TW 107131479 A TW107131479 A TW 107131479A TW I685499 B TWI685499 B TW I685499B
Authority
TW
Taiwan
Prior art keywords
phosphorus
compound
formula
cured product
present
Prior art date
Application number
TW107131479A
Other languages
Chinese (zh)
Other versions
TW202010747A (en
Inventor
林慶炫
林家民
陳建翰
莊宗原
Original Assignee
國立中興大學
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 國立中興大學 filed Critical 國立中興大學
Priority to TW107131479A priority Critical patent/TWI685499B/en
Application granted granted Critical
Publication of TWI685499B publication Critical patent/TWI685499B/en
Publication of TW202010747A publication Critical patent/TW202010747A/en

Links

Images

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A phosphinated compound and a cured product thereof are provided. The phosphinated compound includes a structure represented by Formula (1):
Figure 01_image001
Formula (1) In Formula (1), R 1, R 2, and R 3are independently hydrogen, C1~C6 alkyl, C1~C6 alkoxy, or phenyl respectively.

Description

磷系化合物及其固化物Phosphorus compounds and their cured products

本發明是有關於一種化合物及其固化物，且特別是有關於一種磷系化合物及其固化物。The present invention relates to a compound and its cured product, and particularly to a phosphorus-based compound and its cured product.

由於石油的存量有限，開發以可再生材料為原料的高分子有其重要性。一般而言，氧代氮代苯并己烷是由酚、一級胺以及甲醛所合成。文獻上合成可再生的氧代氮代苯并己烷（benzoxazine）包括使用可再生的酚（例如，香草醛）以及可再生的單胺（例如， 2-呋喃甲胺（（furfuryl amine））。Due to the limited stock of petroleum, it is of great importance to develop polymers that use renewable materials as raw materials. Generally speaking, oxo-nitrobenzoxane is synthesized from phenol, primary amine and formaldehyde. The synthesis of renewable oxo-nitrobenzoxazine in the literature includes the use of renewable phenols (for example, vanillin) and renewable monoamines (for example, 2-furfuryl amine).

舉例來說，Varma 等人以香草醛以及2-呋喃甲胺製備單官能氧代氮代苯并己烷（Sini, N.; Bijwe, J.; Varma, I. K., Renewable benzoxazine monomer from Vanillin: Synthesis, characterization, and studies on curing behavior. Journal of Polymer Science Part A: Polymer Chemistry2014, 52(1), 7-11.）。然而，香草醛的醛基在高溫會氧化酸，且會在高溫中脫去二氧化碳，而產生不利於機械性質的孔洞。Varma 等人亦以香草醛以及雙胺形成雙官能氧代氮代苯并己烷固化物，其玻璃轉移溫度可達到200℃至255 ℃，然而，二氧化碳釋放的問題仍存在（Sini, N. K.; Bijwe, J.; Varma, I. K., Thermal behaviour of bis-benzoxazines derived from renewable feed stock 'vanillin'. Polymer Degradation and Stability2014, 109, 270-277.）。另外，Sarojadevi 等人以另一種可再生的丁香油酚（eugenol）和2-呋喃甲胺製作氧代氮代苯并己烷，可得到玻璃轉移溫度達101℃的氧代氮代苯并己烷固化物（Thirukumaran, P.; Shakila Parveen, A.; Sarojadevi, M., Synthesis and copolymerization of fully biobased benzoxazines from renewable resources. ACS Sustainable Chemistry & Engineering2014, 2(12), 2790-2801.）。Muthusamy 等人則以丁香油酚和雙胺合成雙官能氧代氮代苯并己烷，其可依據雙胺結構而達不同的玻璃轉移溫度（120℃至150℃）（Thirukumaran, P.; Shakila Parveen, A.; Sarojadevi, M., Synthesis and characterization of novel bio-based benzoxazines from eugenol. RSC Adv., 2014, 4, 7959.）。 For example, Varma et al. used vanillin and 2-furan methylamine to prepare monofunctional oxonitrobenzoxane (Sini, N.; Bijwe, J.; Varma, IK, Renewable benzoxazine monomer from Vanillin: Synthesis, characterization, and studies on curing behavior. Journal of Polymer Science Part A: Polymer Chemistry 2014, 52 (1), 7-11.). However, the aldehyde group of vanillin oxidizes acids at high temperatures and removes carbon dioxide at high temperatures, resulting in holes that are not conducive to mechanical properties. Varma et al. also used vanillin and diamine to form a bifunctional oxonitrobenzoxane cured product, whose glass transition temperature can reach 200 ℃ to 255 ℃, however, the problem of carbon dioxide release still exists (Sini, NK; Bijwe , J.; Varma, IK, Thermal behaviour of bis-benzoxazines derived from renewable feed stock'vanillin'. Polymer Degradation and Stability 2014, 109 , 270-277.). In addition, Sarojadevi et al. used another renewable eugenol and 2-furan methylamine to produce oxo-nitrobenzoxane, and obtained oxo-nitrobenzoxane with a glass transition temperature of 101°C. Cured product (Thirukumaran, P.; Shakila Parveen, A.; Sarojadevi, M., Synthesis and copolymerization of fully biobased benzoxazines from renewable resources. ACS Sustainable Chemistry & Engineering 2014, 2 (12), 2790-2801.). Muthusamy et al. used eugenol and diamine to synthesize bifunctional oxoazabenzoxane, which can reach different glass transition temperatures (120℃ to 150℃) according to the diamine structure (Thirukumaran, P.; Shakila Parveen, A.; Sarojadevi, M., Synthesis and characterization of novel bio-based benzoxazines from eugenol. RSC Adv., 2014, 4, 7959.).

因此，利用可再生原料製作的氧代氮代苯并己烷，如何得到具有高性能的固化物是目前此領域技術人員所欲達成的目標。Therefore, how to obtain a cured product with high performance by using oxo-nitrobenzoxane made from renewable raw materials is currently the goal of those skilled in the art.

本發明提供一種磷系化合物及其固化物，其具有良好的機械性質以及熱性質。The present invention provides a phosphorus compound and its cured product, which has good mechanical properties and thermal properties.

本發明的磷系化合物，具有式（1）所示之結構：

Figure 02_image001
式（1） 在式（1）中，R 1、R 2以及R 3各自獨立地為氫、C 1~C 6烷基、C 1~C 6烷氧基或苯基。 The phosphorus compound of the present invention has a structure represented by formula (1):
Figure 02_image001
Formula (1) In Formula (1), R 1 , R 2, and R 3 are each independently hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, or phenyl.

在本發明的一實施例中，磷系化合物是選自由式（1-a）至式（1-d）所示之化合物所構成的組群中的至少一種：

Figure 02_image003
式（1-a）、
Figure 02_image005
式（1-b）
Figure 02_image007
式（1-c） 以及
Figure 02_image009
式（1-d）。 In an embodiment of the present invention, the phosphorus compound is at least one selected from the group consisting of compounds represented by formula (1-a) to formula (1-d):
Figure 02_image003
Formula (1-a),
Figure 02_image005
Formula (1-b)
Figure 02_image007
Formula (1-c) and
Figure 02_image009
Formula (1-d).

本發明的磷系化合物，其是由磷系雙酚化合物與一級胺進行縮合反應而得。The phosphorus-based compound of the present invention is obtained by a condensation reaction between a phosphorus-based bisphenol compound and a primary amine.

在本發明的一實施例中，磷系雙酚化合物具有式（2）所示之結構：

Figure 02_image011
式（2） 在式（2）中，R 1、R 2以及R 3各自獨立地為氫、C 1~C 6烷基、C 1~C 6烷氧基或苯基。 In an embodiment of the invention, the phosphorus-based bisphenol compound has the structure shown in formula (2):
Figure 02_image011
Formula (2) In Formula (2), R 1 , R 2, and R 3 are each independently hydrogen, C 1 to C 6 alkyl, C 1 to C 6 alkoxy, or phenyl.

在本發明的一實施例中，一級胺包括2-呋喃甲胺。In an embodiment of the present invention, the primary amine includes 2-furan methylamine.

在本發明的一實施例中，縮合反應使用之溶劑包括二甲苯/戊醇混和溶液。In an embodiment of the invention, the solvent used in the condensation reaction includes a mixed solution of xylene/pentanol.

本發明的固化物，其是由上述的磷系化合物所製備。The cured product of the present invention is prepared from the above-mentioned phosphorus compound.

本發明的固化物，其是由上述的磷系化合物與環氧樹脂反應所製備。The cured product of the present invention is prepared by reacting the above-mentioned phosphorus-based compound with an epoxy resin.

基於上述，在本發明的實施例中，磷系化合物是由不含醛基的磷系雙酚化合物與一級胺所製備得來，因此，在製備的過程中，即使在高溫下也不會產生二氧化碳。而由於不會產生二氧化碳，在生成的化合物中便不會生成孔洞破壞結構的機械性質，也就是說，本發明的磷系化合物及由其所製備的固化物可具有良好的機械性質。此外，由本發明的磷系化合物所製備的固化物亦具有良好的熱性質。Based on the above, in the embodiments of the present invention, the phosphorus-based compound is prepared from the phosphorus-based bisphenol compound that does not contain an aldehyde group and the primary amine. Therefore, during the preparation process, it does not occur even at high temperatures carbon dioxide. However, since no carbon dioxide is generated, the mechanical properties of the pore-damaging structure are not generated in the generated compound, that is, the phosphorus compound of the present invention and the cured product prepared therefrom can have good mechanical properties. In addition, the cured product prepared from the phosphorus-based compound of the present invention also has good thermal properties.

為讓本發明的上述特徵和優點能更明顯易懂，下文特舉實施例，並配合所附圖式作詳細說明如下。In order to make the above-mentioned features and advantages of the present invention more obvious and understandable, the embodiments are specifically described below in conjunction with the accompanying drawings for detailed description as follows.

以下將藉由實施方式對本發明作進一步說明，但該等實施方式僅為例示說明之用，而非用以限制本發明之範圍。The present invention will be further described below through embodiments, but these embodiments are for illustrative purposes only, and are not intended to limit the scope of the present invention.

本發明提供一種磷系化合物，其具有式（1）所示之結構：

Figure 02_image001
式（1） 在式（1）中，R 1、R 2以及R 3各自獨立地為氫、C 1~C 6烷基、C 1~C 6烷氧基或苯基。在一實施例中，R 1為氫或甲氧基；R 2為氫或甲氧基；R 3為氫或甲基，但本發明不限於此。 The present invention provides a phosphorus compound having a structure represented by formula (1):
Figure 02_image001
Formula (1) In Formula (1), R 1 , R 2, and R 3 are each independently hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, or phenyl. In one embodiment, R 1 is hydrogen or methoxy; R 2 is hydrogen or methoxy; R 3 is hydrogen or methyl, but the invention is not limited thereto.

在本發明的一實施例中，磷系化合物例如是選自由式（1-a）至式（1-d）所示之化合物（A）至化合物（D）所構成的組群中的至少一種： 化合物（A）

Figure 02_image003
式（1-a）、 化合物（B）
Figure 02_image005
式（1-b） 化合物（C）
Figure 02_image007
式（1-c） 以及 化合物（D）
Figure 02_image009
式（1-d）。 In an embodiment of the present invention, the phosphorus-based compound is, for example, at least one selected from the group consisting of compound (A) to compound (D) represented by formula (1-a) to formula (1-d) : Compound (A)
Figure 02_image003
Formula (1-a), Compound (B)
Figure 02_image005
Formula (1-b) Compound (C)
Figure 02_image007
Formula (1-c) and compound (D)
Figure 02_image009
Formula (1-d).

在本發明的一實施例中，磷系化合物例如是由磷系雙酚化合物與一級胺進行縮合反應而得。In an embodiment of the present invention, the phosphorus-based compound is obtained, for example, by a condensation reaction between a phosphorus-based bisphenol compound and a primary amine.

在本發明的一實施例中，磷系雙酚化合物例如具有式（2）所示之結構：

Figure 02_image011
式（2） 在式（2）中，R 1、R 2以及R 3各自獨立地為氫、C 1~C 6烷基、C 1~C 6烷氧基或苯基。在一實施例中，R 1為氫或甲氧基；R 2為氫或甲氧基；R 3為氫或甲基，但本發明不限於此。 In an embodiment of the invention, the phosphorus-based bisphenol compound has a structure represented by formula (2), for example:
Figure 02_image011
Formula (2) In Formula (2), R 1 , R 2, and R 3 are each independently hydrogen, C 1 to C 6 alkyl, C 1 to C 6 alkoxy, or phenyl. In one embodiment, R 1 is hydrogen or methoxy; R 2 is hydrogen or methoxy; R 3 is hydrogen or methyl, but the invention is not limited thereto.

在本發明的一實施例中，磷系雙酚化合物例如是由醛類化合物或酮類化合物與酚類化合物以及含磷氧化物反應而得。In an embodiment of the present invention, the phosphorus-based bisphenol compound is obtained, for example, by reacting an aldehyde compound or a ketone compound with a phenol compound and a phosphorus-containing oxide.

在本發明的一實施例中，醛類化合物或酮類化合物例如具有式（3）所示之結構：

Figure 02_image016
式（3） 在式（3）中，R 1以及R 3各自獨立地為氫、C 1~C 6烷基、C 1~C 6烷氧基或苯基。在一實施例中，R 1為氫或甲氧基；R 3為氫或甲基，但本發明不限於此。在一實施例中，醛類化合物包括香草醛（vanillin）、4-烴基苯甲醛（4-hydroxybenzaldehyde）或其組合。酮類化合物例如包括香草酮、4-烴基苯乙酮（4-hydroxyacetophenone）或其組合，但本發明不限於此。舉例來說，當R 1為甲氧基，R 3為氫時，式（3）所示之結構的結構為香草醛。當R 1以及R 3皆為氫時，式（3）所示之結構的結構為4-烴基苯甲醛。 In an embodiment of the invention, the aldehyde compound or ketone compound has a structure represented by formula (3), for example:
Figure 02_image016
Formula (3) In Formula (3), R 1 and R 3 are each independently hydrogen, C 1 to C 6 alkyl, C 1 to C 6 alkoxy, or phenyl. In one embodiment, R 1 is hydrogen or methoxy; R 3 is hydrogen or methyl, but the invention is not limited thereto. In one embodiment, the aldehyde compound includes vanillin, 4-hydroxybenzaldehyde, or a combination thereof. Ketone compounds include, for example, vanillone, 4-hydroxyacetophenone (4-hydroxyacetophenone), or a combination thereof, but the invention is not limited thereto. For example, when R 1 is methoxy and R 3 is hydrogen, the structure represented by formula (3) is vanillin. When both R 1 and R 3 are hydrogen, the structure represented by formula (3) is 4-hydrocarbylbenzaldehyde.

在本發明的一實施例中，酚類化合物例如具有式（4）所示之結構：

Figure 02_image018
式（4） 在式（4）中，R 2為氫、C 1~C 6烷基、C 1~C 6烷氧基或苯基。在一實施例中，R 2為氫或甲氧基，但本發明不限於此。舉例來說，酚類化合物例如包括單酚化合物。在一實施例中，酚類化合物例如為可再生的酚類化合物。舉例來說，酚類化合物例如包括愈創木酚（guaiacol），但本發明不限於此。 In an embodiment of the invention, the phenolic compound has a structure represented by formula (4), for example:
Figure 02_image018
Formula (4) In Formula (4), R 2 is hydrogen, C 1 to C 6 alkyl, C 1 to C 6 alkoxy, or phenyl. In one embodiment, R 2 is hydrogen or methoxy, but the invention is not limited thereto. For example, phenolic compounds include monophenol compounds, for example. In one embodiment, the phenolic compound is, for example, a renewable phenolic compound. For example, the phenolic compound includes, for example, guaiacol, but the present invention is not limited thereto.

在本發明的一實施例中，含磷氧化物例如包括9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物（DOPO）。In an embodiment of the present invention, the phosphorus-containing oxide includes, for example, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO).

在本發明的一實施例中，上述醛類化合物或酮類化合物與酚類化合物以及含磷氧化物的反應是在觸媒催化的存在下進行。在一實施例中，觸媒例如為酸性觸媒。舉例來說，酸性觸媒例如為對甲苯磺酸（ p-Toluenesulfonic acid， p-TSA），但本發明不限於此。 In an embodiment of the present invention, the reaction of the aldehyde compound or ketone compound with the phenol compound and the phosphorus-containing oxide is carried out in the presence of catalyst. In one embodiment, the catalyst is, for example, an acid catalyst. For example, the acid catalyst is, for example, p -Toluenesulfonic acid ( p - TSA), but the present invention is not limited thereto.

在本發明的一實施例中，一級胺例如包括2-呋喃甲胺。In an embodiment of the present invention, the primary amine includes 2-furan methylamine, for example.

在本發明的一實施例中，在上述磷系雙酚化合物與一級胺進行的縮合反應例如為曼尼希反應（Mannich reaction）。在一實施例中，磷系雙酚化合物例如是與兩個一級胺進行縮合反應。在一實施例中，在此縮合反應中，更包括醛類化合物。舉例來說，醛類化合物例如為甲醛、三聚甲醛或多聚甲醛。在一實施例中，縮合反應使用之溶劑例如包括二甲苯（Xylene）/戊醇（Pentanol）混和溶液，但本發明不限於此。In an embodiment of the present invention, the condensation reaction between the phosphorus-based bisphenol compound and the primary amine is, for example, a Mannich reaction. In one embodiment, the phosphorus-based bisphenol compound undergoes a condensation reaction with two primary amines, for example. In one embodiment, the condensation reaction further includes aldehyde compounds. For example, the aldehyde compound is, for example, formaldehyde, paraformaldehyde or paraformaldehyde. In one embodiment, the solvent used in the condensation reaction includes, for example, a mixed solution of Xylene/Pentanol, but the invention is not limited thereto.

在本發明的一實施例中，磷系化合物可進一步形成固化物。舉例來說，磷系化合物形成固化物的方法例如藉由階段升溫的方式來進行，但本發明不限於此。只要可使磷系化合物固化形成固化物的方法皆屬於本發明保護的範疇。In an embodiment of the invention, the phosphorus-based compound can further form a cured product. For example, the method of forming the cured product by the phosphorus-based compound is performed by, for example, a stepwise temperature increase method, but the present invention is not limited thereto. As long as the method of curing the phosphorus-based compound to form a cured product is within the protection scope of the present invention.

在本發明的一實施例中，磷系化合物亦可與環氧樹脂反應形成固化物。在本發明中，並不特別對環氧樹脂的種類進行限制，任何有利於固化物的形成或提升可提升固化物性質的環氧樹脂皆屬於本發明保護的範疇。In an embodiment of the invention, the phosphorus-based compound can also react with the epoxy resin to form a cured product. In the present invention, the type of epoxy resin is not particularly limited, and any epoxy resin that is beneficial to the formation of the cured product or enhances the properties of the cured product belongs to the scope of the present invention.

值得一提的是，在本發明的一實施例中，由於磷系雙酚化合物中的醛基已在前置步驟反應，因此，用來與一級胺進行縮合反應以合成磷系化合物的磷系雙酚化合物不含醛基。也就是說，即使在高溫下進行縮合反應，也不會產生二氧化碳，故所合成的磷系化合物在形成固化物的過程中，不會因為二氧化碳的產生而於結構中生成孔洞，進而可達到良好的機械性質。 〈實驗〉 It is worth mentioning that, in an embodiment of the present invention, since the aldehyde group in the phosphorus-based bisphenol compound has been reacted in the pre-step, the phosphorus-based compound used to perform the condensation reaction with the primary amine to synthesize the phosphorus-based compound Bisphenol compounds do not contain aldehyde groups. In other words, even if the condensation reaction is carried out at a high temperature, carbon dioxide will not be generated. Therefore, in the process of forming the cured product, the synthesized phosphorus compound will not generate pores in the structure due to the generation of carbon dioxide, and can achieve good results. Mechanical properties. <experiment>

下文將參照實驗範例，更具體地描述本發明。雖然描述了以下實驗，但是在不逾越本發明範疇的情況下，可適當地改變所用材料、其量及比率、處理細節以及處理流程等等。因此，不應根據下文所述的實驗對本發明作出限制性地解釋。The present invention will be described more specifically below with reference to experimental examples. Although the following experiments are described, the materials used, their amounts and ratios, processing details, processing flow, etc. can be appropriately changed without exceeding the scope of the present invention. Therefore, the present invention should not be interpreted restrictively based on the experiments described below.

實驗experiment 11

以下，參照圖1來詳細說明本發明的磷系雙酚化合物的特性。圖1為磷系雙酚化合物（a）至磷系雙酚化合物（d）的 1H NMR光譜圖。 ＜ 實施例 1＞ Hereinafter, the characteristics of the phosphorus-based bisphenol compound of the present invention will be described in detail with reference to FIG. 1. FIG. 1 is a 1 H NMR spectrum chart of the phosphorus-based bisphenol compound (a) to the phosphorus-based bisphenol compound (d). < Example 1>

將10.8 g（0.05 mol）的DOPO、6.11 g（0.05 mol）的4-烴基苯甲醛（4-hydroxybenzaldehyde）、0.432 g（DOPO含量的4wt%）的 p-TSA以及18.81 g（0.2 mol）的苯酚置入250毫升的玻璃反應器並且通入氮氣與冷凝管，在130 oC條件下反應24小時。反應結束後冷卻至室溫。然後，加入乙醇溶解洗掉過量的苯酚，待產物析出。接著，過濾並重複用乙醇清洗兩次，於60 oC下真空乾燥，得到淡粉色粉體，即為實施例1的磷系雙酚化合物（a）。 ＜ 實施例 2＞ 10.8 g (0.05 mol) of DOPO, 6.11 g (0.05 mol) of 4-hydroxybenzaldehyde (4-hydroxybenzaldehyde), 0.432 g (4 wt% of DOPO content) of p- TSA and 18.81 g (0.2 mol) of phenol placed in 250 ml glass reactor with a condenser and purged with nitrogen, the reaction at 130 o C for 24 hours. After the reaction was completed, it was cooled to room temperature. Then, add ethanol to dissolve and wash off the excess phenol, until the product precipitates. Subsequently, filtered and repeatedly washed with ethanol twice and dried at 60 o C in vacuo to give a pale pink powder, a phosphorus-based bisphenol compound (a) is the embodiment of Example 1. < Example 2>

將10.8 g（0.05 mol）的DOPO、7.61 g（0.05 mol）的香草醛、0.432 g（DOPO含量的4wt%）的 p-TSA以及18.81 g（0.2 mol）的苯酚（phenol）置入250毫升的玻璃反應器並且通入氮氣與冷凝管，在130 oC條件下反應24小時。反應結束後冷卻至室溫，然後，加入乙醇溶解洗掉過量的苯酚，待產物析出。接著，過濾並重複用乙醇清洗兩次，於60 oC下真空乾燥，得到白色粉體，即為實施例2的磷系雙酚化合物（b）。 ＜ 實施例 3＞ Put 10.8 g (0.05 mol) of DOPO, 7.61 g (0.05 mol) of vanillin, 0.432 g (4 wt% of DOPO content) of p- TSA and 18.81 g (0.2 mol) of phenol into 250 ml of glass reactor with a condenser and purged with nitrogen, the reaction at 130 o C for 24 hours. After the reaction is completed, it is cooled to room temperature, and then ethanol is added to dissolve and wash off excess phenol, and the product is precipitated. Subsequently, filtered and repeatedly washed with ethanol twice and dried at 60 o C in vacuo to give a white powder, bisphenol-phosphorus compound of Example 2 (b) is the embodiment. < Example 3>

將10.8 g（0.05 mol）的DOPO、7.61 g（0.05 mol）的香草醛、0.432 g（DOPO含量的4wt%）的 p-TSA以及24.81 g（0.2 mol）的愈創木酚（guaiacol）置入250毫升的玻璃反應器並且通入氮氣與冷凝管，在130 oC條件下反應24小時。反應結束後冷卻至室溫。然後，加入乙醇溶解並滴入去離子水使產物析出。接著，過濾並重複用乙醇/水清洗兩次，於60 oC下真空乾燥，得到白色粉體，即為實施例3的磷系雙酚化合物（c）。 ＜ 實施例 4＞ Put 10.8 g (0.05 mol) of DOPO, 7.61 g (0.05 mol) of vanillin, 0.432 g (4wt% of DOPO content) of p- TSA, and 24.81 g (0.2 mol) of guaiacol (guaiacol) 250 ml glass reactor with a condenser and purged with nitrogen, the reaction at 130 o C for 24 hours. After the reaction was completed, it was cooled to room temperature. Then, add ethanol to dissolve and drop into deionized water to precipitate the product. Next, filtration and repeated / water, washed twice with ethanol, and dried at 60 o C in vacuo to give a white powder, bisphenol-phosphorus compound (c) is the embodiment of Example 3. < Example 4>

將10.8 g（0.05 mol）的DOPO、6.81 g（0.05 mol）的4-烴基苯乙酮（4-hydroxyacetophenone）、0.432 g（DOPO含量的4wt%）的 p-TSA以及18.81 g（0.2 mol）的苯酚置入250毫升的玻璃反應器並且通入氮氣與冷凝管，在130 oC條件下反應24小時。反應結束後冷卻至室溫。然後，加入乙醇溶解洗掉過量的苯酚，待產物析出。接著，過濾並重複用乙醇清洗兩次，於60 oC下真空乾燥，得到白色粉體，即為實施例4的磷系雙酚化合物（d）。 10.8 g (0.05 mol) of DOPO, 6.81 g (0.05 mol) of 4-hydroxyacetophenone (4-hydroxyacetophenone), 0.432 g (4 wt% of DOPO content) of p- TSA and 18.81 g (0.2 mol) phenol into 250 ml glass reactor with a condenser and purged with nitrogen, the reaction at 130 o C for 24 hours. After the reaction was completed, it was cooled to room temperature. Then, add ethanol to dissolve and wash off the excess phenol, until the product precipitates. Subsequently, filtered and repeatedly washed with ethanol twice and dried at 60 o C in vacuo to give a white powder, bisphenol-phosphorus compound of Example 4 (d), is the embodiment.

在圖1中，由上至下依序為磷系雙酚化合物（d）、磷系雙酚化合物（a）、磷系雙酚化合物（b）、磷系雙酚化合物（c）的 1H NMR光譜圖。由圖1可知，磷系雙酚化合物（a）、磷系雙酚化合物（b）、磷系雙酚化合物（c）以及磷系雙酚化合物（d）的結構無誤。接著，繼續進行後續磷系化合物的合成。 In FIG. 1, from the top to the bottom are 1 H of the phosphorus-based bisphenol compound (d), the phosphorus-based bisphenol compound (a), the phosphorus-based bisphenol compound (b), and the phosphorus-based bisphenol compound (c) NMR spectrum. As can be seen from FIG. 1, the structures of the phosphorus-based bisphenol compound (a), the phosphorus-based bisphenol compound (b), the phosphorus-based bisphenol compound (c), and the phosphorus-based bisphenol compound (d) are correct. Then, the subsequent synthesis of the phosphorus-based compound is continued.

實驗experiment 22

以下，參照圖2、圖3以及表1來詳細說明本發明的磷系化合物的特性。圖2為磷系化合物（A）至磷系化合物（D）的 1H NMR光譜圖。圖3為磷系化合物（A）至磷系化合物（C）的 31P NMR光譜圖。 ＜ 實施例 5＞ Hereinafter, the characteristics of the phosphorus-based compound of the present invention will be described in detail with reference to FIGS. 2, 3 and Table 1. 2 is a 1 H NMR spectrum chart of the phosphorus-based compound (A) to the phosphorus-based compound (D). FIG. 3 is a 31 P NMR spectrum chart of the phosphorus-based compound (A) to the phosphorus-based compound (C). < Example 5>

將1.0 g（2.41 mmole）實施例1的磷系雙酚化合物（a）、0.47 g（4.82 mmole）的2-呋喃甲胺（furfuryl amine）、0.3 g（9.61 mmole）的多聚甲醛（paraforaldehyde）以及15 mL的二甲苯/戊醇（xylene/pentanol）（1/1）混和溶液置入100毫升的玻璃反應器並且通入氮氣與冷凝管，在120 oC條件下反應24小時。反應結束後冷卻至室溫，然後，滴入己烷（hexane）使產物析出。接著，過濾並用己烷清洗兩次，並回溶於二氯甲烷（dichloromethane，DCM）中，以1.5N的鹼水萃取兩次，再以去離子水萃取3次，取有機層並用減壓濃縮將二氯甲烷去除，得到黃色粉體，即為實施例5的磷系化合物（A）。 ＜ 實施例 6＞ 1.0 g (2.41 mmole) of the phosphorus bisphenol compound (a) of Example 1, 0.47 g (4.82 mmole) of 2-furfuryl amine (furfuryl amine), 0.3 g (9.61 mmole) of paraformaldehyde (paraforaldehyde) And 15 mL of xylene/pentanol (1/1) mixed solution was placed in a 100 mL glass reactor and passed through a nitrogen and condensing tube, and reacted at 120 o C for 24 hours. After the reaction was completed, it was cooled to room temperature, and then hexane was added dropwise to precipitate the product. Next, filter and wash with hexane twice, and dissolve back in dichloromethane (DCM), extract twice with 1.5N alkaline water, then extract three times with deionized water, take the organic layer and concentrate under reduced pressure The dichloromethane was removed to obtain a yellow powder, that is, the phosphorus compound (A) of Example 5. < Example 6>

將1.0 g（2.25 mmole）實施例2的磷系雙酚化合物（b）、0.44 g（4.50 mmole）的2-呋喃甲胺、0.28 g（9 mmole）的多聚甲醛以及15 mL的二甲苯/戊醇（1/1）混和溶液置入100毫升的玻璃反應器並且通入氮氣與冷凝管，在120 oC條件下反應24小時。反應結束後冷卻至室溫，然後，滴入己烷使產物析出。接著，過濾並用己烷清洗兩次，並回溶於二氯甲烷中，以1.5N的鹼水萃取兩次，再以去離子水萃取3次，取有機層並用減壓濃縮將二氯甲烷去除，得到黃色粉體，即為實施例6的磷系化合物（B）。 ＜ 實施例 7＞ 1.0 g (2.25 mmole) of the phosphorus-based bisphenol compound (b) of Example 2, 0.44 g (4.50 mmole) of 2-furan methylamine, 0.28 g (9 mmole) of paraformaldehyde, and 15 mL of xylene/ The mixed solution of amyl alcohol (1/1) was placed in a 100-ml glass reactor and passed through a nitrogen and condenser tube, and reacted at 120 o C for 24 hours. After the reaction was completed, it was cooled to room temperature, and then hexane was added dropwise to precipitate the product. Next, filter and wash twice with hexane, and dissolve back in dichloromethane, extract twice with 1.5N alkaline water, and extract three times with deionized water. Take the organic layer and concentrate under reduced pressure to remove dichloromethane To obtain a yellow powder, that is, the phosphorus compound (B) of Example 6. < Example 7>

將1.0 g（2.11 mmole）實施例3的磷系雙酚化合物（c）、0.41 g（4.22 mmole）的2-呋喃甲胺、0.26 g（8.44 mmole）的多聚甲醛以及15 mL的二甲苯/戊醇（1/1）混和溶液置入100毫升的玻璃反應器並且通入氮氣與冷凝管，在120 oC條件下反應24小時。反應結束後冷卻至室溫，然後，滴入己烷使產物析出。接著，過濾並用己烷清洗兩次，並回溶於二氯甲烷中，以1.5N的鹼水萃取兩次，再以去離子水萃取3次，取有機層並用減壓濃縮將二氯甲烷去除，得到黃色粉體，即為實施例7的磷系化合物（C）。 ＜ 實施例 8＞ 1.0 g (2.11 mmole) of the phosphorus-based bisphenol compound (c) of Example 3, 0.41 g (4.22 mmole) of 2-furan methylamine, 0.26 g (8.44 mmole) of paraformaldehyde, and 15 mL of xylene/ The mixed solution of amyl alcohol (1/1) was placed in a 100-ml glass reactor and passed through a nitrogen and condenser tube, and reacted at 120 o C for 24 hours. After the reaction was completed, it was cooled to room temperature, and then hexane was added dropwise to precipitate the product. Next, filter and wash twice with hexane, and dissolve back in dichloromethane, extract twice with 1.5N alkaline water, and extract three times with deionized water. Take the organic layer and concentrate under reduced pressure to remove dichloromethane , To obtain a yellow powder, which is the phosphorus compound (C) of Example 7. < Example 8>

將1.0 g（2.33 mmole）實施例4的磷系雙酚化合物（d）、0.45 g（4.66 mmole）的2-呋喃甲胺、0.29 g（9.32 mmole）的多聚甲醛以及15 mL的二甲苯/戊醇（1/1）混和溶液置入100毫升的玻璃反應器並且通入氮氣與冷凝管，在120 oC條件下反應24小時。反應結束後冷卻至室溫，然後，滴入己烷使產物析出。接著，過濾並用己烷清洗兩次，並回溶於二氯甲烷中，以1.5N的鹼水萃取兩次，再以去離子水萃取3次，取有機層並用減壓濃縮將二氯甲烷去除，得到黃色粉體，即為實施例8的磷系化合物（D）。 1.0 g (2.33 mmole) of the phosphorus-based bisphenol compound (d) of Example 4, 0.45 g (4.66 mmole) of 2-furan methylamine, 0.29 g (9.32 mmole) of paraformaldehyde, and 15 mL of xylene/ The mixed solution of amyl alcohol (1/1) was placed in a 100-ml glass reactor and passed through a nitrogen and condenser tube, and reacted at 120 o C for 24 hours. After the reaction was completed, it was cooled to room temperature, and then hexane was added dropwise to precipitate the product. Next, filter and wash twice with hexane, and dissolve back in dichloromethane, extract twice with 1.5N alkaline water, and extract three times with deionized water. Take the organic layer and concentrate under reduced pressure to remove dichloromethane To obtain a yellow powder, that is, the phosphorus compound (D) of Example 8.

在圖2中，由上至下依序為磷系化合物（D）、磷系化合物（A）、磷系化合物（B）、磷系化合物（C）的 1H NMR光譜圖。由圖2可知，磷系化合物（A）、磷系化合物（B）、磷系化合物（C）以及磷系化合物（D）的結構無誤。 In FIG. 2, the 1 H NMR spectrum charts of the phosphorus-based compound (D), the phosphorus-based compound (A), the phosphorus-based compound (B), and the phosphorus-based compound (C) are in order from top to bottom. As can be seen from FIG. 2, the structures of the phosphorus-based compound (A), the phosphorus-based compound (B), the phosphorus-based compound (C), and the phosphorus-based compound (D) are correct.

在圖3中，由上至下依序為磷系化合物（A）、磷系化合物（B）、磷系化合物（C）的 31P NMR光譜圖。在圖3中所示，僅有一個吸收峰，也就是說，產物的純度高，且磷系化合物（A）、磷系化合物（B）、磷系化合物（C）的結構無誤。 In FIG. 3, the 31 P NMR spectrum charts of the phosphorus-based compound (A), the phosphorus-based compound (B), and the phosphorus-based compound (C) are in order from top to bottom. As shown in Fig. 3, there is only one absorption peak, that is, the purity of the product is high, and the structures of the phosphorus-based compound (A), the phosphorus-based compound (B), and the phosphorus-based compound (C) are correct.

另外，本發明亦針對溶劑種類、溶劑體積、反應條件（例如，溫度、時間等）對整體反應結果的影響。以下是以磷系雙酚化合物（b）合成為磷系化合物（B）舉例說明，其測試條件以及結果列於表1。In addition, the present invention also addresses the effects of the type of solvent, solvent volume, and reaction conditions (eg, temperature, time, etc.) on the overall reaction results. The following is an example of the synthesis of the phosphorus bisphenol compound (b) into the phosphorus compound (B). The test conditions and results are listed in Table 1.

表1   溶劑 反應條件 結果   種類 體積(g/mL) 溫度(oC) 時間(h) 反應 產率(%) 實例1 Chloroform 0.1 60 24 不完全 ＜20% 實例2 THF 0.1 65 24 不完全 ＜15% 實例3 Dioxane 0.1 90 24 不完全 ＜25% 實例4 Dioxane/Ethanol (1:1) 0.025 85 24 不完全 ＜25% 實例5 Dioxane/Ethanol (1:1) 0.067 85 24 不完全 ＜25% 實例6 Dioxane/Ethanol (1:1) 0.08 85 24 不完全 ＜25% 實例7 Xylene/Pentanol (1:1) 0.025 115 24 不完全 ＜50% 實例8 Xylene/Pentanol (1:1) 0.05 115 24 完全 85% 實例9 Xylene/Pentanol (1:1) 0.067 115 24 完全 93% 實例10 Xylene/Pentanol (1:1) 0.1 115 24 完全 94% Chloroform：氯仿； THF：四氫呋喃； Dioxane：二惡烷； Dioxane/Ethanol：二惡烷/乙醇； Xylene/Pentanol：二甲苯/戊醇 Table 1 Solvent Reaction conditions result species Volume (g/mL) Temperature ( o C) Time (h) reaction Yield(%) Example 1 Chloroform 0.1 60 twenty four incomplete ＜20% Example 2 THF 0.1 65 twenty four incomplete ＜15% Example 3 Dioxane 0.1 90 twenty four incomplete ＜25% Example 4 Dioxane/Ethanol (1:1) 0.025 85 twenty four incomplete ＜25% Example 5 Dioxane/Ethanol (1:1) 0.067 85 twenty four incomplete ＜25% Example 6 Dioxane/Ethanol (1:1) 0.08 85 twenty four incomplete ＜25% Example 7 Xylene/Pentanol (1:1) 0.025 115 twenty four incomplete ＜50% Example 8 Xylene/Pentanol (1:1) 0.05 115 twenty four complete 85% Example 9 Xylene/Pentanol (1:1) 0.067 115 twenty four complete 93% Example 10 Xylene/Pentanol (1:1) 0.1 115 twenty four complete 94% Chloroform: chloroform; THF: tetrahydrofuran; Dioxane: dioxane; Dioxane/Ethanol: dioxane/ethanol; Xylene/Pentanol: xylene/pentanol

由表1可知，使用常用於合成氧代氮代苯并己烷的單一溶劑（例如，氯仿、四氫呋喃、二惡烷等）時，反應不完全（實例1至實例3）。使用混和溶劑（例如，二惡烷/乙醇）時，即使在85 oC下進行，反應仍是不完全（實例4至實例6）。而在使用混和溶劑（例如，二甲苯/戊醇）且當濃度高於0.05 g/mL時，反應完全，且產率高（實例8至實例10）。 It can be seen from Table 1 that when a single solvent (for example, chloroform, tetrahydrofuran, dioxane, etc.) commonly used in the synthesis of oxonitrobenzohexane is used, the reaction is incomplete (Examples 1 to 3). When using a mixed solvent (e.g., dioxane / ethanol), even if carried out at 85 o C, the reaction is still incomplete (Example 4 to Example 6). Whereas when a mixed solvent (for example, xylene/pentanol) is used and the concentration is higher than 0.05 g/mL, the reaction is complete and the yield is high (Example 8 to Example 10).

實驗experiment 33

以下，參照圖4A、圖4B以及圖5來詳細說明本發明的固化物的特性。圖4A以及圖4B分別為磷系化合物（A）至磷系化合物（C）在180 oC以及200 oC下的流變圖。圖5為固化物（1）以及固化物（2）的動態機械分析（Dynamic Mechanical Analysis，DMA）圖。 Hereinafter, the characteristics of the cured product of the present invention will be described in detail with reference to FIGS. 4A, 4B, and 5. 4A and 4B are phosphorus-based compound (A) to the phosphorus-based compound (C) in FIG rheology and 180 o C to 200 o C. FIG. 5 is a dynamic mechanical analysis (DMA) diagram of the cured product (1) and the cured product (2).

在圖4A以及圖4B中，假設當損失模數高於儲存模數時所對應的時間為凝膠化時間，則可得知反應性由高至低依序為磷系化合物（A）、磷系化合物（B）以及磷系化合物（C），其中實心標記以及連續線代表儲存模數G’，空心標記以及虛線代表損失模數G”。In FIGS. 4A and 4B, assuming that the time when the loss modulus is higher than the storage modulus is the gelation time, it can be known that the reactivity is the phosphorus compound (A), phosphorus in order from high to low The compound (B) and the phosphorus compound (C), where the solid mark and the continuous line represent the storage modulus G', the hollow mark and the dashed line represent the loss modulus G".

在此，值得一提的是，根據磷系化合物的結構，會形成三種型式的固化結構，如下所示：

Figure 02_image020
Here, it is worth mentioning that according to the structure of the phosphorus-based compound, three types of cured structures are formed, as follows:
Figure 02_image020

也就是說，在磷系化合物（A）的結構中，反應點有6個，如下所示（以灰底圈圈代表反應點）：

Figure 02_image022
That is to say, in the structure of the phosphorus-based compound (A), there are 6 reaction points, as shown below (representing the reaction points with gray circles):
Figure 02_image022

在磷系化合物（B）的結構中，反應點有5個，如下所示：

Figure 02_image024
In the structure of the phosphorus compound (B), there are 5 reaction points, as shown below:
Figure 02_image024

在磷系化合物（C）的結構，中，反應點有4個，如下所示：

Figure 02_image026
In the structure of the phosphorus compound (C), there are 4 reaction points, as shown below:
Figure 02_image026

因此，根據各個磷系化合物的結構，其固化反應性的結果與上述流變圖的結果相符。Therefore, according to the structure of each phosphorus-based compound, the result of the curing reactivity is consistent with the result of the rheological diagram described above.

此外，在本發明的實施例中，可對各個磷系化合物加熱升溫使其固化。因此，固化磷系化合物（A）可得到固化物（1），固化磷系化合物（B）可得到固化物（2），固化磷系化合物（C）可得到固化物（3）。In addition, in the embodiments of the present invention, each phosphorus-based compound may be heated and heated to be cured. Therefore, the cured product (1) can be obtained by curing the phosphorus compound (A), the cured product (2) can be obtained by curing the phosphorus compound (B), and the cured product (3) can be obtained by curing the phosphorus compound (C).

接著，將所製備的固化物（1）、固化物（2）以及固化物（3）藉由下述方法評估熱性質，其結果列於表2。Next, the thermal properties of the prepared cured product (1), cured product (2), and cured product (3) were evaluated by the following method, and the results are shown in Table 2.

（1）玻璃轉移溫度（T g）以及熱膨脹係數（Coefficient of thermal expansion，CTE） (1) Glass transition temperature (T g ) and coefficient of thermal expansion (CTE)

分別使用動態機械分析儀（Dynamic Mechanical Analyzer，DMA）以及熱機械分析儀（Thermo-mechanical Analyzer，TMA）測量玻璃轉移溫度。測量的條件為在5°C/min的加熱速率下測量樣品的玻璃轉移溫度。此外，同時利用熱機械分析儀測量樣品在50 oC至150 oC下的熱膨脹係數。 The glass transition temperature was measured using a Dynamic Mechanical Analyzer (DMA) and a Thermo-mechanical Analyzer (TMA), respectively. The measurement condition is to measure the glass transition temperature of the sample at a heating rate of 5°C/min. In addition, the thermal expansion coefficient of the sample at 50 o C to 150 o C is also measured with a thermomechanical analyzer.

（2）5%熱重損失溫度（T d5%）以及焦炭殘餘率 (2) 5% thermogravimetric loss temperature (T d5% ) and coke residual rate

使用熱重量分析儀（Thermo-gravimetric Analyzer，TGA）量測樣品的5%熱重損失溫度以及800°C的焦炭殘餘率（Char yield）。5%熱重損失溫度是指樣品的重量損失達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°C的焦炭殘餘率是指加熱溫度達800°C時的樣品的殘餘重量比率，其中800°C的殘餘重量比率愈高代表樣品的熱穩定性愈佳。A thermogravimetric analyzer (TGA) was used to measure the 5% thermogravimetric weight loss temperature of the sample and the char yield at 800°C. The 5% thermogravity loss temperature refers to the temperature at which the weight loss of the sample reaches 5%, and the higher the 5% thermogravity loss temperature, the better the thermal stability of the sample. The coke residual rate at 800°C refers to the residual weight ratio of the sample when the heating temperature reaches 800°C, where the higher the residual weight ratio at 800°C, the better the thermal stability of the sample.

表2   Tg(oC)a (DMA) Tg(oC)b (TMA) CTEc (ppm/oC) Td5(oC)d 焦炭殘餘率(%)e 固化物（1） 306 257 25 404 74 固化物（2） 283 254 39 371 63 固化物（3） - - - 379 62 a. 升溫速度為5 oC/min的動態機械分析儀（DMA） b. 升溫速度為5 oC/min的熱機械分析儀（TMA） c. 50 oC至150 oC的熱膨脹係數 d. 升溫速率為5 oC/min的熱重量分析儀（TGA）在熱降解為重量比5% e. 800 oC下的焦炭殘餘率 Table 2 T g ( o C) a (DMA) T g ( o C) b (TMA) CTE c (ppm/ o C) T d5 ( o C) d Coke residual rate (%) e Cured product (1) 306 257 25 404 74 Cured product (2) 283 254 39 371 63 Cured product (3) - - - 379 62 thermal expansion coefficient a. a heating rate of 5 o C / min in a dynamic mechanical analyzer (DMA) b. heating rate of 5 o C / min in a thermal mechanical analyzer (TMA) c. 50 o C to 150 o C. d. The thermal gravimetric analyzer (TGA) with a heating rate of 5 o C/min thermally degrades the coke residual rate at 5% e. 800 o C by weight

請同時參照圖5以及表2，由圖可知，固化物（1）以及固化物（2）的玻璃轉移溫度分別可高達306 oC以及283 oC（動態機械分析儀量測）；固化物（1）以及固化物（2）的玻璃轉移溫度分別可高達257 oC以及254 oC（熱機械分析儀量測）。固化物（1）以及固化物（2）的熱膨脹係數則可分別低至25 ppm/ oC以及39 ppm/ oC。然而，由於磷系化合物（C）的反應性較差，較難以形成堅固的塊材，故無法量測固化物（3）的玻璃轉移溫度以及熱膨脹係數。 Please refer to Figure 5 and Table 2 at the same time, as can be seen from the figure, the glass transition temperature of the cured product (1) and the cured product (2) can be as high as 306 o C and 283 o C (measured by dynamic mechanical analyzer); the cured product ( 1) The glass transition temperature of the cured product (2) can be as high as 257 o C and 254 o C (measured by thermomechanical analyzer). The thermal expansion coefficients of the cured product (1) and the cured product (2) can be as low as 25 ppm/ o C and 39 ppm/ o C, respectively. However, since the phosphorus-based compound (C) has poor reactivity and it is difficult to form a solid block, it is impossible to measure the glass transition temperature and thermal expansion coefficient of the cured product (3).

此外，固化物（1）、固化物（2）以及固化物（3）所量測之5%熱重損失溫度皆可達371 oC以上，且在800 oC的殘餘重量比率（即焦炭殘餘率）皆可達62%以上。也就是說，固化物（1）、固化物（2）以及固化物（3）具有良好的熱性質（即耐熱性）。 In addition, the measured 5% thermogravimetric weight loss temperature of the cured product (1), cured product (2) and cured product (3) can reach above 371 o C, and the residual weight ratio at 800 o C (that is, coke residual Rate) can reach more than 62%. That is, the cured product (1), the cured product (2), and the cured product (3) have good thermal properties (ie, heat resistance).

綜上所述，在本發明的實施例中，磷系化合物是由不含醛基的磷系雙酚化合物與一級胺所製備得來，因此，在製備的過程中，即使在高溫下也不會產生二氧化碳。而由於不會產生二氧化碳，在生成的化合物中便不會生成孔洞破壞結構的機械性質，也就是說，本發明的磷系化合物及由其所製備的固化物可具有良好的機械性質。此外，由本發明的磷系化合物所製備的固化物亦具有良好的熱性質。In summary, in the embodiments of the present invention, the phosphorus-based compound is prepared from a phosphorus-based bisphenol compound that does not contain an aldehyde group and a primary amine. Therefore, in the preparation process, even at high temperatures Will produce carbon dioxide. However, since no carbon dioxide is generated, the mechanical properties of the pore-damaging structure are not generated in the generated compound, that is, the phosphorus compound of the present invention and the cured product prepared therefrom can have good mechanical properties. In addition, the cured product prepared from the phosphorus-based compound of the present invention also has good thermal properties.

雖然本發明已以實施例揭露如上，然其並非用以限定本發明，任何所屬技術領域中具有通常知識者，在不脫離本發明的精神和範圍內，當可作些許的更動與潤飾，故本發明的保護範圍當視後附的申請專利範圍所界定者為準。Although the present invention has been disclosed as above with examples, it is not intended to limit the present invention. Any person with ordinary knowledge in the technical field can make some changes and modifications without departing from the spirit and scope of the present invention. The scope of protection of the present invention shall be subject to the scope defined in the appended patent application.

無。no.

圖1為磷系雙酚化合物（a）至磷系雙酚化合物（d）的 1H NMR光譜圖。 圖2為磷系化合物（A）至磷系化合物（D）的 1H NMR光譜圖。 圖3為磷系化合物（A）至磷系化合物（C）的 31P NMR光譜圖。 圖4A以及圖4B分別為磷系化合物（A）至磷系化合物（C）在180 oC以及200 oC下的流變圖。 圖5為固化物（1）以及固化物（2）的動態機械分析（Dynamic Mechanical Analysis，DMA）圖。 FIG. 1 is a 1 H NMR spectrum chart of the phosphorus-based bisphenol compound (a) to the phosphorus-based bisphenol compound (d). 2 is a 1 H NMR spectrum chart of the phosphorus-based compound (A) to the phosphorus-based compound (D). FIG. 3 is a 31 P NMR spectrum chart of the phosphorus-based compound (A) to the phosphorus-based compound (C). 4A and 4B are phosphorus-based compound (A) to the phosphorus-based compound (C) in FIG rheology and 180 o C to 200 o C. FIG. 5 is a dynamic mechanical analysis (DMA) diagram of the cured product (1) and the cured product (2).

Figure 01_image001
Figure 01_image001

Claims (7)

一種磷系化合物，具有式(1)所示之結構：
Figure 107131479-A0305-02-0023-1
 在式(1)中，R1、R2以及R3各自獨立地為氫、C1~C6烷基、C1~C6烷氧基或苯基。 A phosphorus compound with the structure shown in formula (1):
Figure 107131479-A0305-02-0023-1
 In formula (1), R 1 , R 2 and R 3 are each independently hydrogen, C 1 to C 6 alkyl, C 1 to C 6 alkoxy or phenyl. 一種磷系化合物，其是具有式(2)所示之結構的磷系雙酚化合物與含呋喃結構的一級胺及甲醛進行縮合反應而得，
Figure 107131479-A0305-02-0023-2
 在式(2)中，R1、R2以及R3各自獨立地為氫、C1~C6烷基、C1~C6烷氧基或苯基。 A phosphorus compound, which is obtained by a condensation reaction between a phosphorus bisphenol compound having a structure represented by formula (2) and a primary amine containing furan structure and formaldehyde,
Figure 107131479-A0305-02-0023-2
 In formula (2), R 1 , R 2 and R 3 are each independently hydrogen, C 1 to C 6 alkyl, C 1 to C 6 alkoxy or phenyl. 如申請專利範圍第2項所述的磷系化合物，其中所述磷系雙酚化合物是選自由式(1-a)至式(1-d)所示之化合物所構成的組群中的至少一種：
Figure 107131479-A0305-02-0023-3
Figure 107131479-A0305-02-0024-4
Figure 107131479-A0305-02-0024-5
 以及
Figure 107131479-A0305-02-0024-6
 The phosphorus-based compound according to item 2 of the patent application scope, wherein the phosphorus-based bisphenol compound is at least one selected from the group consisting of compounds represented by formula (1-a) to formula (1-d) One:
Figure 107131479-A0305-02-0023-3
Figure 107131479-A0305-02-0024-4
Figure 107131479-A0305-02-0024-5
 as well as
Figure 107131479-A0305-02-0024-6
 如申請專利範圍第2項所述的磷系化合物，其中所述一級胺包括2-呋喃甲胺。 The phosphorus compound as described in item 2 of the patent application, wherein the primary amine includes 2-furan methylamine. 如申請專利範圍第2項所述的磷系化合物，其中所述縮合反應使用之溶劑包括二甲苯/戊醇混和溶液。 The phosphorus compound as described in item 2 of the patent application, wherein the solvent used in the condensation reaction includes a mixed solution of xylene/pentanol. 一種固化物，其是由如申請專利範圍第1項所述的磷系化合物所製備。 A cured product prepared from the phosphorus compound as described in item 1 of the patent application scope. 一種固化物，其是由如申請專利範圍第1項所述的磷系化合物與環氧樹脂反應所製備。 A cured product prepared by reacting a phosphorus compound as described in item 1 of the patent application with an epoxy resin.
TW107131479A 2018-09-07 2018-09-07 Phosphinated compound and cured product thereof TWI685499B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
TW107131479A TWI685499B (en) 2018-09-07 2018-09-07 Phosphinated compound and cured product thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
TW107131479A TWI685499B (en) 2018-09-07 2018-09-07 Phosphinated compound and cured product thereof

Publications (2)

Publication Number Publication Date
TWI685499B true TWI685499B (en) 2020-02-21
TW202010747A TW202010747A (en) 2020-03-16

Family

ID=70413370

Family Applications (1)

Application Number Title Priority Date Filing Date
TW107131479A TWI685499B (en) 2018-09-07 2018-09-07 Phosphinated compound and cured product thereof

Country Status (1)

Country Link
TW (1) TWI685499B (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201002732A (en) * 2008-07-15 2010-01-16 Univ Nat Chunghsing Preparation of novel phosphorus-containing biphenols and their derivatives

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201002732A (en) * 2008-07-15 2010-01-16 Univ Nat Chunghsing Preparation of novel phosphorus-containing biphenols and their derivatives

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Chia-Min Lin, Chien-Han Chen, Ching-Hsuan Lin, Tzong-Yuan Juang; High-performance bio-based benzoxazines derived from phosphinated biphenols and furfurylamine; European Polymer Journal, Volume 108, Pages 48-56, Available online 11 August 2018 *

Also Published As

Publication number Publication date
TW202010747A (en) 2020-03-16

Similar Documents

Publication Publication Date Title
Hao et al. An apigenin-based bio-benzoxazine with three polymerizable functionalities: Sustainable synthesis, thermal latent polymerization, and excellent thermal properties of its thermosets
Zhang et al. Synthesis and copolymerization of benzoxazines with low-dielectric constants and high thermal stability
JP4895537B2 (en) Calixarene polymer and process for producing the same
Cai et al. Development of a fully bio-based hyperbranched benzoxazine
CN103865101A (en) Efficient phosphorus-nitrogen type fire retardant and preparation method thereof
JP5750004B2 (en) Thermosetting composition, its varnish and its thermoset
CN110066371A (en) A kind of polyhydroxy anacardol benzoxazine resin and preparation method thereof
CN101921242A (en) Fluorenyl benzoxazine and preparation method thereof
Jiang et al. A biomass-based Schiff base vitrimer with both excellent performance and multiple degradability
CN110591091A (en) Main chain type benzoxazine containing daidzein group and preparation method thereof
CN107573334B (en) Monofunctional benzoxazine containing alicyclic hydrocarbon imide group and preparation method thereof
EP3679083A1 (en) Crosslinkable fluorinated poly(arylene ether)
Shah et al. Synthesis and characterisation of cycloaliphatic and aromatic amines based cardanol benzoxazines: a comparative study
TWI685499B (en) Phosphinated compound and cured product thereof
Terekhov et al. Hexa-para-aminophenoxycyclo-triphosphazene as a curing agent/modifier for epoxy resins
CN104650144B (en) A kind of phenol monomer of phosphorus system four, cyanic acid ester derivant and copolymer and preparation method
KR101579387B1 (en) Benzoxazine intermediate and preparation method thereof
Lu et al. Facile and eco-friendly synthesis of hydrogen bonding-rich bio-based bisbenzoxazine resins with low surface free energy, strong adhesion strength and high thermal stability
TWI625346B (en) Development of dicyclopentadiene-derived polyethers with low dielectric and flame retardancy application
TWI573813B (en) Main structure of adamantane - containing oxo - nitrobenzene cyclohexane resin
TWI513703B (en) Novel phosphinated compounds, phosphinated curable polyimides, and the preparation thereof
JP7177809B2 (en) Phosphorus-based (2,6-dimethylphenyl ether) oligomer, method for producing the same, and cured product
CN113149856B (en) Amide-containing bio-based benzoxazine resin and preparation method thereof
CN102796141A (en) Phosphor series benzoxazine and preparation method
CN113956416A (en) Triazine ring-containing bio-based benzoxazine resin and preparation method thereof