201037014 六、發明說明： 【發明所屬之技術領域】 ’其尤指一種熱固型樹脂 本發明係有關於一種熱固型樹脂之製造方法 接枝矽氧烷之製造方法。 【先前技術】 按，熱固性樹脂除了使用於-般的複合材料更大量_於積體電路板 基材、半導體封裝材料及航太材料。熱固性樹脂所用原料通常是分子量較 小的液態或固態預聚物，經加熱或是加硬化劑後發生化學反應形成不溶、 Ο 不·溶的三維網狀無定型聚合體。近年來針對P〇iyb_xazine (PBZ)熱固性樹 脂之研究相當多，由於PBZ擁有很高的玻璃轉移溫度（17〇〜35〇。〇，高 模數，低吸水性，好的介電性質，再加上硬化時不會收縮甚至會稍微的^ 脹。由於其製品之尺寸安定性佳可以製造精密之零件。再者，由於pBZ前 驅物的製備可選擇多種不同的單體合成，所製得的PBZ依單體組成及聚合 條件可得到不同的耐熱性質與機械物性，預期可以廣泛應用於電子材料之 封裝與絕緣。 根據Mannich縮和反應’將酚類（phenols)、曱醛（formaldehyde)、 一級胺（primaryamine)加入反應瓶内，以適當之溫度及時間做迴流（不同 Q 結構所需溫度、時間不同），最後可得到黃褐色（不同結構所得到之顏色不 同）之黏性液體。反應式請參閱第1圖。 在反應中會產生副產物水（H20)’benzoxazine合成製備出來後會含 有少量的水’且水並不會與benzoxazine產生任何反應，僅需在純化步驟將 水除掉。合成之benzoxazine具有特殊官能基-矽氧烷（silane)，此官能基極 怕水氣’一遇水氣便會產生反應（水解縮合反應），經此反應便形成高分子， 無法製備出benzoxazine之單體。水解縮合反應如第2圖所示。 又，US Pat. 6,376,080 之 Method for preparing polybenzoxazine ’ 其所揭 示主要是在benzoxazine中加入催化劑(heterocyclic dicarboxylic acid)降低硬 化溫度降低並縮短硬化時間有機會應用於印刷電路板、半導體、電晶體、 201037014 二極體等電子原件塗佈(coating)之原料。 【發明内容】 本發明之轉目的’係在雜供—姆苯並销冑聚物紐魏 製造方法，舖魏之Pdybenz_ine_silane財高的賴娜溫度 模數，低吸水性，好的介電性質。 本發明之次要目的’係在於提供—錄苯並销高雜赌魏院之 製造方法，其係於製造雜中制除水劑，避免發生水解縮合反應而成功 合成 benzoxazine-silane 之單體。 為了達到上述之目的’本發明雜供—種聚笨並補高聚物接枝砂氧 烷之製造綠，錢跡制除_，以產生崎^㈣^細，由於 Polybenzoxazme-silane擁有高的玻璃轉移溫度，高模數，低吸水性好的介 電性質’再加上硬化時不會⑽。由於其製品之尺寸較性佳可以製造精 密之零件，再者φ於其減較低產^設計自由度較高。且由於 Pdybenzoxazine-silane前驅物的製備可選擇多種不同的單體合成，所製得的 polybenzoxazine-si丨ane依單體組成及聚合條件可得到不同的耐熱性質與機 械物性，可以廣泛應用於航太、汽車材料及電子材料之封裝與絕緣。 此單體經聚合後形成p〇lybenzoXazine_siiane是一新穎性之熱固性樹脂 具有較高的玻璃轉移溫度（Tg)及熱穩定性。此外，由於其熱膨脹係數較 低材料的尺寸安定性較佳。 【實施方式】 茲為使責審查委員對本發明之結構特徵及所達成之功效有更進一步 之瞭解與s忍識，謹佐以較佳之實施例及配合詳細之說明，說明如後： 本發明係為解決習知技術之使用Mannich縮和反應，本發明所合成之 benzox_e具有特殊官能基-石夕氧烷（silane)，此官能基極怕水氣，一遇水 氣便會產生反應（水解縮合反應），經此反應便形成高分子，無法製備出 benzoxazine-silane之單體。因此為改善上述缺失，本發明可經由合成時添 i 201037014 加除水劑或除水藥品，並使用二聚 be_az—$ ^來取代㈣水紐，成功合成 供-種聚本並鋪絲物接枝錄紅製造方法其主要步驟係 ^ (^〇〇C) ^ : 、—織除水劑或除水藥品加人步驟S1GG巾，保持60oC ; 步驟纖’將—霞之魏錢慢献步_巾，齡後，升溫至攸 迴流8hr ;201037014 VI. Description of the invention: [Technical field to which the invention pertains] ‘This is particularly a thermosetting resin. The present invention relates to a method for producing a thermosetting resin. [Prior Art] According to the thermosetting resin, in addition to the use of a composite material, a large amount of the composite substrate, the semiconductor package material, and the aerospace material. The raw material used for the thermosetting resin is usually a liquid or solid prepolymer having a relatively small molecular weight, and is chemically reacted by heating or adding a hardener to form an insoluble, non-soluble three-dimensional network amorphous polymer. In recent years, there have been quite a lot of researches on P〇iyb_xazine (PBZ) thermosetting resins, because PBZ has a high glass transition temperature (17〇~35〇.〇, high modulus, low water absorption, good dielectric properties, plus It does not shrink when it is hardened or even slightly swells. Due to the dimensional stability of its products, it is possible to manufacture precision parts. Furthermore, since the preparation of pBZ precursors can be selected from a variety of different monomer synthesis, the resulting PBZ Different heat resistance properties and mechanical properties can be obtained depending on monomer composition and polymerization conditions, and it is expected to be widely used for encapsulation and insulation of electronic materials. According to Mannich condensation reaction, phenols, formaldehyde, primary amines (primaryamine) is added to the reaction flask and refluxed at the appropriate temperature and time (different temperature and time required for different Q structures), and finally a viscous liquid of yellowish brown (different colors obtained by different structures) can be obtained. See Figure 1. In the reaction, by-product water (H20) will be produced. 'Benzoxazine will be prepared and will contain a small amount of water' and the water will not be produced with benzoxazine. In any reaction, it is only necessary to remove the water in the purification step. The synthesized benzoxazine has a special functional group, silane, which is extremely afraid of moisture, and reacts with water vapor (hydrolysis condensation reaction). After this reaction, a polymer is formed, and a monomer of benzoxazine cannot be prepared. The hydrolysis condensation reaction is shown in Fig. 2. Further, the method of preparing a polybenzoxazine of US Pat. 6, 376, 080 discloses that a catalyst is mainly added to benzoxazine (heterocyclic Dicarboxylic acid) reduces the hardening temperature and shortens the hardening time, and has the opportunity to be applied to electronic substrate coating materials such as printed circuit boards, semiconductors, transistors, 201037014 diodes, etc. [Summary of the Invention] In the method of manufacturing miscellaneous supply-m-benzopyrene polymer Newwei, the Lai Na temperature modulus of Pdybenz_ine_silane is high, low water absorption, good dielectric properties. The secondary purpose of the present invention is to provide The method of manufacturing benzene and selling high-gambling gambling Weiyuan is based on the manufacture of miscellaneous water-removing agent to avoid hydrolysis and condensation reaction. A monomer of benzoxazine-silane. In order to achieve the above-mentioned purpose, the hybridization of the present invention, the polystyrene and the high-polymer grafted methane, are produced in green, and the money is removed to produce a fine (4). Because Polybenzoxazme-silane has a high glass transition temperature, high modulus, low water absorption and good dielectric properties' plus hardening (10). Due to the better size of the products, it is possible to manufacture the precise parts, and the φ is lower in design and lower in design. And because the preparation of Pdybenzoxazine-silane precursor can be selected from a variety of different monomer synthesis, the obtained polybenzoxazine-si丨ane can obtain different heat resistance and mechanical properties depending on the monomer composition and polymerization conditions, and can be widely applied to aerospace. Packaging and insulation of automotive materials and electronic materials. The monomer is polymerized to form p〇lybenzoXazine_siiane which is a novel thermosetting resin having a high glass transition temperature (Tg) and thermal stability. In addition, the dimensional stability of the material is lower due to its lower coefficient of thermal expansion. [Embodiment] The following is a description of the preferred embodiment and the detailed description of the preferred embodiment and the detailed description of the present invention. In order to solve the conventional Mannich condensation reaction using the Mannich condensation reaction, the benzox_e synthesized by the present invention has a special functional group - silane, which is extremely afraid of water vapor, and reacts when it is in contact with water (hydrolysis condensation). The reaction) forms a polymer by this reaction, and it is impossible to prepare a monomer of benzoxazine-silane. Therefore, in order to improve the above-mentioned deficiency, the present invention can add a water-removing agent or a water-removing drug through the synthesis, and use the dimeric be_az-$^ to replace the (four) water, successfully synthesize the donor-type polymer and graft the graft. The main steps of the recording red manufacturing method are ^ (^〇〇C) ^ : , - weaving water removal agent or water removal medicine plus step S1GG towel, keep 60oC; step fiber 'will - Xia Zhi Wei money slow step _ towel After the age, the temperature is raised to reflux for 8 hr;
❹ 步驟漏’將步驟·之產物再添加除水劑或除水藥品，麟； 步驟S500 ’將步驟400之產物過遽'，得到淡黃色或無色之渡液；及 步驟觸’將步驟500之滤液，以真空方式除去溶劑，可得到深黃褐色黏 稠狀液體，即為產物。 本發明可經由合成時添加除水贼除水藥品，並側三聚甲路來取代 甲駿水溶液，成功合成benz0Xazine_silane之單體，根據Mannich、缩和反應， 將酚類（phenols)、三聚甲醛（parafonnaidehyde)、一級胺之矽氧烷（prima^ amine)加入反應瓶内後再添加除水藥品（無水硫酸鎂、氣化鈣），以適當 之溫度及時間做迴流（不同結構所需溫度、時間不同），得到黃褐色（不同 結構所得到之顏色不同）之黏稠狀液體。其反應式如下第4圖所示。 其申，酚類（phenols):苯環上接有-0H之官能基，都可稱做酚類。其 係選自於下列所組成之群組之一者。❹ Step Leaking 'Add the product of the step to the de-watering agent or the dehydrating drug, Lin; Step S500 'Turn the product of Step 400' to obtain a pale yellow or colorless liquid; and step to 'Step 500' The filtrate is vacuum-removed to obtain a dark yellow-brown viscous liquid which is the product. The invention can add a water removal thief water-removing drug during synthesis, and replace the aqueous solution of the Azure with a side trimeric road, and successfully synthesize the monomer of the benz0Xazine_silane, and according to the Mannich, the condensation reaction, the phenols and the acetaldehyde (parafonnaidehyde), a primary amine prima^ amine is added to the reaction bottle and then added with water-removing drugs (anhydrous magnesium sulfate, calcium carbonate), and refluxed at appropriate temperature and time (temperature required for different structures, The time is different), and a viscous liquid of yellowish brown (different colors obtained by different structures) is obtained. The reaction formula is shown in Fig. 4 below. Its phenols: phenyl rings with a -OH functional group, can be called phenols. It is selected from one of the following groups.
4f4'-(propane-2,2-diyl)diphenoi 4,4’-sulfonyldiphenol 5 201037014 其中，一級胺之石夕氧烧（primary amine)其係選自於下列所組成之群組 之一者。4f4'-(propane-2,2-diyl)diphenoi 4,4'-sulfonyldiphenol 5 201037014 wherein the primary amine is selected from one of the group consisting of the following.
4-(trimethoxy sily l)butan-1 -amine4-(trimethoxy sily l)butan-1 -amine
4-(triethoxy sily l)butan-1 -amine4-(triethoxy sily l)butan-1 -amine
(trimethoxysilyl)methanamine(trimethoxysilyl)methanamine
h2nH2n
.n (triethoxy si ly l)m ethanam ine.n (triethoxy si ly l)m ethanam ine
其中，除水劑其係選自無水硫酸鎂及氣化鈣所組成之群組之一者。 其中，莫耳數比例： 單官能基酚類：三聚甲醛：一級胺之矽氧烷: 2/3 : 1 雙官能基酚類：三聚甲醛：一級胺之矽氧烷=1 : 4/3 : 2 二官能基酚類：三聚甲醛：一級胺之矽氧烷=1 : 2 : 3 ★综上所述，本發明係實為一具有新穎性、進步性及可供產業利用者， 1符合我目專利法所規定之專利申請要件紐，纽法糾發明 3月’祈鈞局早日賜准利，至感為禱。 明實’僅為本發明之—較佳實施例而已，並非用來限定本發 發明㈣專利範圍所述之形狀、構造、特徵及精 申斤為之均4變化與修飾，均應包括於本發明之f請專利範_。 【圖式簡單說明】 第1圖係為習知技術之反應式之示意圖； 第2圖係為f知技術之水解縮合反應之示意圖； =3圖係本發明之_触實關之製造流程圖 ;以及 第4圖係本發明之—較佳實施例之反應式之示意圖。 201037014 【主要元件符號說明】Wherein, the water removing agent is selected from the group consisting of anhydrous magnesium sulfate and calcium carbonate. Among them, molar ratio: monofunctional phenols: trioxane: primary amine oxane: 2/3: 1 difunctional phenols: trioxane: primary amine oxane = 1: 4 / 3 : 2 Difunctional phenols: trioxane: primary amine oxane = 1: 2 : 3 ★ In summary, the present invention is a novelty, progressive and available for industrial use, 1 In accordance with the patent application requirements stipulated in my patent law, Newfare invented the March 'Praying Bureau to grant the benefits as soon as possible, to the feeling of prayer. The present invention is merely a preferred embodiment of the present invention, and is not intended to limit the shape, structure, characteristics, and variations and modifications of the invention described in the scope of the invention. Invention f please patent _. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic diagram of a reaction formula of a conventional technique; Fig. 2 is a schematic diagram of a hydrolysis condensation reaction of a known technique; = 3 is a manufacturing flow diagram of the invention And Figure 4 is a schematic representation of the reaction scheme of the preferred embodiment of the invention. 201037014 [Main component symbol description]