A7 B7A7 B7
^和尺寸安定性，目前廣泛使用在膠合#卜結構材料和 ^複合材料的基材。然而具有高交聯度的環氧樹脂易於 經濟部中央標準局員工消費合作社印製 31S788 '發明説明（/ ”環氧樹脂具有優良的接著性，加工性，抗化學性，電 &裂’如能改善它的破壞純，其使用範圍和耐用程 可大幅提高。 又牙 一般增韌環氧樹脂的方法是摻合橡膠，但使用在複合 材料或接著材料時，往往因爲樹脂存在的空間有限，橡膠 (，）粒子成長容易受到抑制，因此*但無法有效增初樹 知反而使橡膠洛在環氧樹脂内，造成拉伸模數和軟化溫 度大幅下降。 美國太空總署研究員Stoakley和st Clair曾經利用乙 酿丙酮钴來改進環氧樹脂的機械性質（美國專利號碼 4,473,674)，但被評估對韌性的影響有限，增韌效果僅在純 樹脂韌性平均値的可信度範圍之内 aApp.Polym.ScMcu^d^))。本案發明人在研究過程 中曾經利用各種不同過渡金屬複合物來增勒環氧樹脂，结 果發現乙醯丙酮鉻具有顯著的增韌效果，可提高三倍以上 的破壞勃性(Polymer，34,277〇 993))，±要增勒機構乃σ是乙 驢丙酮鉻和環氧樹脂分子鏈上的氫氧基產生化學作用，藉 以增加環氧樹脂結構的結合強度，而乙_酮紗法產』 類似的作用，因此增③效果不大㈣ymeu42i62(l 因此，本發明的目的即爲解決上述缺點，而提供一種 可硬化的環氧樹脂配方及其複合材料配方，由此配方而硬 化生成的環氧樹脂及其複合材料之加工性和_皆可得以 V·纸張尺度適用中國國家標準（CNS ) A4規格（2T〇^297^~y (請先閲讀背面之注意事項再填寫本頁)^ And dimensional stability, currently widely used in gluing # Bu structural materials and ^ composite substrate. However, epoxy resins with a high degree of cross-linking are easy to print 31S788 'Instructions for Invention (/ ”Epoxy resins have excellent adhesion, processability, chemical resistance, electrical & cracking') It can improve its destruction purity, and its use range and durability can be greatly improved. The general method of toughening epoxy resin is to blend rubber, but when used in composite materials or adhesive materials, often because the resin has limited space, Rubber (,) particle growth is easily inhibited, so * but it is not effective to increase the knowledge. Instead, the rubber is contained in the epoxy resin, causing a significant decrease in tensile modulus and softening temperature. NASA researchers Stoakley and st Clair once The use of acetone-cobalt to improve the mechanical properties of epoxy resins (US Patent No. 4,473,674), but the impact on toughness is evaluated to be limited, the toughening effect is only within the credibility range of the average toughness of pure resin aApp.Polym. ScMcu ^ d ^)). The inventor of this case used various transition metal composites to increase the epoxy resin during the research, and found that acetyl Ketone chromium has a significant toughening effect, which can increase the destructiveness by more than three times (Polymer, 34,277〇993)), ± to increase the mechanism is σ is a hydroxyl group on the molecular chain of acetone acetone chromium and epoxy resin It produces a chemical effect to increase the bonding strength of the epoxy resin structure, and the similar effect of the B-keto yarn method, so the effect is not large. Therefore, the purpose of the present invention is to solve the above shortcomings and provide a The formulation of hardenable epoxy resin and its composite material, the workability and _ of the epoxy resin and its composite material hardened by this formula can be applied to the Chinese national standard (CNS) A4 specification of V · paper scale ( 2T〇 ^ 297 ^ ~ y (Please read the notes on the back before filling this page)
313738 經濟部中央標準局員工消費合作杜印製 A7 B7 五、發明説明（2 ) 改善。 本發明主要針對航太用四官能基環氧樹脂/胺基硬化 劑系統，提供一增初方法，利用乙酿丙嗣路（Cr(acac)3)和 咪唑添加劑改善環氧樹脂的破壞韌性和加工性。此法不但 使環氧樹脂和其複合材料的破壞韌性大幅提高，而且在製 造高性能碳纖維補強環氧樹脂（Gr/Ep)積層板時，可適時提 高黏度使積層板内樹脂含量達到複合材料規格的要求。而 更重要的是，此法對複合材料拉伸模數和軟化溫度的負面 影響不大。 據研究發現，利用1 %摩爾百分率的乙醯丙酮鉻添加於 四官能基環氧樹脂可提高三倍以上的破壞韌性，主要增韌 機構乃是乙醯丙酮鉻和環氧樹脂分子鏈上的氫氧基產生作 用增加環氧樹脂結構的結合強度，但在製造航太用高性能 Gr/Ep複合材料時，爲控制樹脂含量和反應性，如用傳统 的單乙烷基三氟化硼（BF3MEA)硬化促進劑，則BF3MEA會 和乙酿丙0¾絡產生化學反應，使乙酿丙酿]路無法發揮有效 的增韌效果（中國工程學刊第16卷第395頁（1993))。因此 本發明乃針對高性能Gr/Ep複合材料所使用的四官能基環 氧樹脂/胺基硬化劑系統，提供一個新的增韌方法，即在樹 脂配方中同時添加乙醯丙酮鉻和咪唑硬化促進劑，由於咪 唑硬化促進劑可以在積層板製造過程中適時提高環氧樹脂 的黏度，因此可有效控制積膚板内樹脂含量使之達到航太 規格的要求。而且咪唑硬化劑不會影響乙醯丙酮鉻的增韌 效果，使得製造出來的積層板具有相當高的層間破壞韌性 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） --------P —裝-------訂-------線 (請先閱讀背面之注意事項再填寫本頁) 31S7S8 A7 B7 五、發明説明（3 ) 〇 本發明之可硬化的環氧樹脂配方，包括一環氧樹脂， 一胺類硬化劑，一咪唑添加劑，以及乙醯丙酮鉻，其中胺 類硬化劑的用量爲環氧樹脂之10〜60重量百分比，咪唑 添加劑的用量爲環氧樹脂之0.1〜5重量百分比，乙醯丙 酮鉻的用量爲環氧樹脂之0〜5莫耳百分比。 適用於本發明的環氧樹脂可爲二官能基環氧樹脂，三 官能基環氧樹脂，四官能基環氧樹脂，或多官能基環氧樹 脂。較佳者爲四官能基環氧樹脂，例如N,N，N’,N’-四環氧 丙烷基-4,4’-雙胺基雙苯環甲烷（N,N,N',；NT-tetraglycidyl diamino diphenyl methane)(TGDDM)。 適用於本發明的胺類硬化劑可爲芳香族胺類硬化劑或 脂肪族胺類硬化劑。較佳的芳香族胺頬硬化劑例如4,4’-二 胺基二苯现(4,4'-<1彳3111丨11〇(1丨口1^11丫13111【〇116)(008)。 適用於本發明的咪峻添加劑爲 R2313738 Employee consumption cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs Du Printed A7 B7 V. Invention description (2) Improvement. The present invention is mainly directed to a four-functional epoxy resin / amine-based hardener system for aerospace, and provides an initial method to improve the destruction toughness of epoxy resin and the use of propyl alcohol (Cr (acac) 3) and imidazole additives. Processability. This method not only greatly improves the destruction toughness of epoxy resin and its composite materials, but also can increase the viscosity in a timely manner when making high-performance carbon fiber reinforced epoxy resin (Gr / Ep) laminates, so that the resin content in the laminates reaches the specifications of composite materials. Requirements. More importantly, this method has little negative effect on the tensile modulus and softening temperature of the composite. According to the research, the addition of 1% mol of acetone chromium chromium to tetrafunctional epoxy resin can increase the fracture toughness by more than three times. The main toughening mechanism is acetyl acetone chromium and hydrogen on the molecular chain of epoxy resin The effect of oxygen groups increases the bonding strength of epoxy resin structure, but when manufacturing high-performance Gr / Ep composite materials for aerospace, in order to control the resin content and reactivity, such as the use of traditional monoethyl boron trifluoride (BF3MEA) ) A hardening accelerator, BF3MEA will produce a chemical reaction with the B-Propyl alcohol, so that the B-Propuccino can not exert an effective toughening effect (Chinese Journal of Engineering, Volume 16, Page 395 (1993)). Therefore, the present invention is directed to the four-functional epoxy resin / amine-based hardener system used in high-performance Gr / Ep composite materials, providing a new toughening method, that is, adding acetone acetone chromium and imidazole to the resin formulation for hardening Accelerator, because the imidazole hardening accelerator can timely increase the viscosity of epoxy resin in the manufacturing process of the laminate, it can effectively control the resin content in the laminate to meet the requirements of aerospace specifications. And the imidazole hardener will not affect the toughening effect of acetone chromium chromium, so that the manufactured laminate has a very high interlayer failure toughness. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm)- ------ P —installed ------- ordered ------ line (please read the precautions on the back before filling in this page) 31S7S8 A7 B7 Fifth, invention description (3) 〇 copy The inventive hardenable epoxy resin formulation includes an epoxy resin, an amine hardener, an imidazole additive, and acetone chromium acetone, wherein the amount of the amine hardener is 10 to 60 weight percent of the epoxy resin. The amount of imidazole additive is 0.1 ~ 5 weight percent of epoxy resin, and the amount of acetone chromium is 0 ~ 5 mole percent of epoxy resin. The epoxy resin suitable for the present invention may be a difunctional epoxy resin, a trifunctional epoxy resin, a tetrafunctional epoxy resin, or a polyfunctional epoxy resin. The preferred ones are tetrafunctional epoxy resins, such as N, N, N ', N'-tetraglycidoxy-4,4'-bisaminobisphenylcyclomethane (N, N, N' ,; NT -tetraglycidyl diamino diphenyl methane) (TGDDM). The amine hardener suitable for the present invention may be an aromatic amine hardener or an aliphatic amine hardener. Preferred aromatic hardeners such as 4,4'-diaminodiphenyl (4,4 '-< 1 彳 3111 丨 11〇 (1 丨 口 1 ^ 11 丫 13111 【〇116) (008 )。 Mijun additive suitable for the present invention is R2
, 裝 訂 線 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 其中R1和R2獨立地爲Η，碳數1-25之烷基，或苯 基。較具體的例子是，咪唑添加劑可爲2-苯基-4-甲基咪 吐，Ί—炫基咪吐，或十七烷基咪沒。咪吐添加劑之較佳 的例子是十一烷基咪唑。 利用本發明之可硬化的環氧樹脂配方，硬化製成環氧 樹脂的方法是，先將胺類硬化劑加入環氧樹脂中，再加入 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（4 ) 咪唑硬化促進劑，然後採用一般的硬化條件硬化，例如在 溫度100〜200 °C之下硬化。若有添加乙醯丙酮鉻 (Cr(acac)3)，其添加的時機是在胺類硬化劑添加之前，可 以直接加入環氧樹脂中在50-100 °C下攪拌溶解，或者是在 室溫下利用可同時溶解環氧樹脂和Cr(acac)3的溶劑溶 解。適合的溶劑例如丁酮。但若使用溶劑溶解Cr(acac)3， 則需在環氧樹脂硬化前將溶劑去除。 本發明之可硬化的環氧樹脂配方也可與纖維補強材料 共同製成纖維補強環氧樹脂複合材料。所採用的纖維補強 材料可爲碳纖維，玻璃纖維和聚醯胺纖維（如Kevlar纖維) 等。 以下茲舉四個實施例，藉以説明本發明的特點及功 效，但並非用來限制本發明。 實施例1 :增韌四官能基環氧樹脂的方法 本發明選取队队]^，：^-四環氧丙烷基-4,4'-雙胺基雙苯 環甲烷（TGDDM)/4,4'_二胺基二苯现(DDS)四官能基環氧樹 脂系統，此樹脂系統屬高溫反應型樹脂，適合做爲高性能 Gr/Ep複合材料的基材。實驗使用之TGDDM環氧樹月旨爲 美國Ciba-Geigy公司出品的MY720樹脂，其環氧當量經 測定爲122。 試片製備的方法如下：先將1%摩爾百分率的乙醯丙 酮鉻在100 °C下溶解於TGDDM環氧樹脂，此溶液（含乙醯 丙酮鉻之TGDDM樹脂）爲深紫色，在室溫下密封庫存可儲 存半年以上。硬化反應時，將此樹脂溶液加入化學當量比 7 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -------i丨裝------訂------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 319788 A7 __B7 五、發明説明（5 ) (50.8phr)的DDS硬化劑和iphr十一炫基咪唑（CnZ)硬化促 進 劑配成 TGDDM/DDS/Cr(acac)3 和 TGDDM/DDS/Cr(acac)3/CnZ 樹脂配方，在 120 °C 下攪拌至 澄拍後灌模做小型張力試> 片（Compact Tension Specimen)， 撓曲測試試片’和動態機械測試試片。小型張力試片是用 來測試試片的破壞韌性，破壞韌性値之計算公式乃是根據 線性彈性破壞力學理論推導而來，以Clc値表示，單位爲 焦耳/米2。試片灌模後放置於烘箱中以14〇。匸/2小時Η” °C/2小時+200 °C/4小時之硬化條件加溫硬化。此硬化條件 可使試片充分反應，玻璃轉移溫度達到最高點。試片經硬 化反應後，須放置於乾燥m内在室溫下至少一星期，才取 出做破壞韌性測試，撓曲性質測試和動態機械性質測試。 測試的結果和在相同條件下做出的TGDDM/DDS試片做& 較，結果如表一所示。 實施例2: 製備TGDDM/DDS/Cr(acac)3/C17Z之小型張力戟片， 撓曲測試試片，和動態機械測試試片，方法與實施例j中 製備TGDDM/DDS/Cr(acac)3/CuZ之各項試片相同，但1 pl^ 之十一燒基咪吐以lphr之十七燒基咪吃（Ci 7Z)取代。濟丨_ 結果如表·一所示。 實施例3: 製備TGDDM/DDS/Cr(acac)3/2P4MZ之小型張力試片， 撓曲測試試片，和動態機械測試試片，方法與實施例i中 製備TGDDM/DDS/Cr(acac)3/CHZ之各項試片相同，但！ phr 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇Χ297公釐） --------』1裝------訂------線 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 B7 發明説明（6) 之十一烷基咪唑以1 phr之2-苯基-4-甲基咪唑（2P4MZ)取 代。測試結果如表一所示。 表一、各種不同四官能基環氧樹脂配方之破壞韌性，撓曲, Binding line (please read the precautions on the back before filling this page) Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs where R1 and R2 are independently H, an alkyl group with a carbon number of 1-25, or a phenyl group. A more specific example is that the imidazole additive may be 2-phenyl-4-methyl mitoxime, Ί-hyunyl mitoxime, or heptadecyl imimitide. A preferred example of the mitoxine additive is undecylimidazole. Using the hardenable epoxy resin formulation of the present invention, the method of hardening to make an epoxy resin is to first add an amine hardener to the epoxy resin, and then add this paper standard to the Chinese National Standard (CNS) Α4 specification (210Χ297 Mm) A7 B7 printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (4) Imidazole hardening accelerator, and then hardening under general hardening conditions, such as hardening at a temperature of 100 ~ 200 ° C. If acetylacetone chromium (Cr (acac) 3) is added, the timing of its addition is before the amine hardener is added. It can be directly added to the epoxy resin and dissolved by stirring at 50-100 ° C, or at room temperature Next, it can be dissolved by a solvent that can simultaneously dissolve the epoxy resin and Cr (acac) 3. Suitable solvents are for example butanone. However, if a solvent is used to dissolve Cr (acac) 3, the solvent needs to be removed before the epoxy resin hardens. The hardenable epoxy resin formulation of the present invention can also be made into fiber-reinforced epoxy resin composite materials together with fiber-reinforced materials. The fiber reinforcement used can be carbon fiber, glass fiber and polyamide fiber (such as Kevlar fiber). The following four embodiments are used to illustrate the features and functions of the present invention, but are not intended to limit the present invention. Example 1: A method of toughening a tetrafunctional epoxy resin The present invention selects a team] ^,: ^-tetraglycidoxy-4,4'-bisaminodiphenylcyclomethane (TGDDM) / 4,4 '_Diaminodiphenyl (DDS) tetrafunctional epoxy resin system, this resin system is a high temperature reactive resin, suitable for high-performance Gr / Ep composite substrate. The TGDDM epoxy resin used in the experiment is MY720 resin produced by Ciba-Geigy of the United States, and its epoxy equivalent weight was determined to be 122. The preparation method of the test piece is as follows: first dissolve 1% mol of acetone chromium in TGDDM epoxy resin at 100 ° C. This solution (TGDDM resin containing acetoacetone chromium) is dark purple at room temperature Sealed inventory can be stored for more than half a year. During the hardening reaction, add this resin solution to a stoichiometric ratio of 7. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ------- i 丨 installation ------ order- ----- Line (please read the precautions on the back before filling in this page) 319788 A7 __B7 printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Invention description (5) (50.8phr) DDS hardener and iphr ten A dazzling base imidazole (CnZ) hardening accelerator is formulated into TGDDM / DDS / Cr (acac) 3 and TGDDM / DDS / Cr (acac) 3 / CnZ resin formulations, which are stirred at 120 ° C until clear shot and then poured into small molds Tension test> Compact Tension Specimen, Flex Test Specimen 'and Dynamic Mechanical Test Specimen. The small tensile test piece is used to test the fracture toughness of the test piece. The calculation formula of the fracture toughness value is derived from the theory of linear elastic failure mechanics, expressed as Clc value, the unit is Joule / m2. The test piece was placed in an oven for 14 ° after pouring.庸 / 2 hours Η ”° C / 2 hours +200 ° C / 4 hours of hardening conditions. This hardening condition allows the test piece to fully react and the glass transition temperature reaches the highest point. After the hardening reaction, the test piece must be Place it in a dry place at room temperature for at least one week before taking it out for damage toughness test, flexural property test and dynamic mechanical property test. The test results are compared with the TGDDM / DDS test pieces made under the same conditions. The results are shown in Table 1. Example 2: Preparation of TGDDM / DDS / Cr (acac) 3 / C17Z small tensile halberds, flexural test specimens, and dynamic mechanical test specimens, methods and TGDDM prepared in Example j / DDS / Cr (acac) 3 / CuZ The test pieces are the same, but 1 pl ^ of the 11th burned imimit is replaced by 1 phr of 17th burned imimit (Ci 7Z). 济 丨 _ The results are shown in the table · One is shown in Example 3. Preparation of TGDDM / DDS / Cr (acac) 3 / 2P4MZ small tensile test piece, flexural test test piece, and dynamic mechanical test test piece, method and example i prepared TGDDM / DDS / The test pieces of Cr (acac) 3 / CHZ are the same, but! Phr This paper scale applies the Chinese National Standard (CNS) A4 specification (21〇Χ297 ) -------- "1 set ------ order ------ line (please read the notes on the back before filling in this page) Printed B7 by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Description of the invention (6) Undecylimidazole is replaced with 1 phr of 2-phenyl-4-methylimidazole (2P4MZ). The test results are shown in Table 1. Table 1. Various different tetrafunctional epoxy resin formulations Destructive toughness
Xj -TSC ^6L· 〇 樹脂配方 Gic , 焦耳/米2 挽曲模數， 米 2 撓曲強度， ίο6牛頓/米2 玻璃轉移 溫度，。C TGDDM/DDS 108 土 30.9 hj^± 0.25 1 16 土 31.7 260 TGDDM/DDS /Cr(acac)3 298 ± 38.0 2 78 i Oil 126 土 10.7 250 TGDDM/DDS /Cr(acac)3/ c,,z 369 土 17.0 2 76 ± 0.08 81 土 18.1 222 TGDDM/DDS /Cr(acac)3/ c17z 343 土 100.0 2.90 ± 0.22 94 土 20.8 240 TGDDM/DDS /Cr(acac)3/ 2P4MZ 325 ± 41.1 2.98 ± 0.25 — 231 由表中可看出，添加Cr(acac)3和C!!Z、或Cr(acac)3和 C17Z、或 Cr(acac)3 和 2P4MZ 於 TGDDM/DDS 環氧樹脂中， 均可提高3倍以上的破壞韌性，而且對其它機械性質的負 面影響不大。 實施例4 :改善高性能Gr/£p積層板層間破壞韌性和加工 性的方法 將實施例 1 所採用的 TGDDM/DDS ，和 TGDDM/DDS/CuZ/Cr(acac)3 以及 TGDDM/DDS 添加 1 phr 之 C„Z(以 TGDDM/DDS/CUZ 表示），和 TGDDM/DDS 添加 本紙張尺度適用中國國家榡準（CNS ) A4規格（210X297公釐） mf κ ^^^^1 ^^^^1 ^^1 (請先閱讀背面之注意事項再填寫本頁) 訂 線 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（7 ) lphr 之 BF3MEA(以 TGDDM/DDS/BE3MEA 表示）樹脂配方 個別混合均勻澄清後，以兩階段熱熔法製造Gr/Ep單方向 預浸布。其中 BF3MEA(boron trifluoride-monoethylene amine) 是一種傳統用於樹脂的硬化促進劑。首先將樹脂倒入刀式 塗布機在120 °C下塗布於離型紙上，樹脂塗布厚度控制在 0.06±0.01mm。第二階段將塗布後的離型紙覆蓋於纏繞機 的鼓輪上，再將碳纖維束控制在一定張力下，利用導輪將 纖維束展開在鼓輪上進行纏繞，纏繞時單位面積纖維的重 量控制在137 士 lg/m2，此時將鼓輪表面溫度升高到100 。(：，並利用橡皮輪擠壓樹脂使之充分濕潤纖維。如此製造 出來的單方向預浸布樹脂含量經測試爲4〇±2wt°/。。預浸布 製造出來後，依照各種不同測試規格要求疊層，再進行眞 空包裝，然後置於熱壓釜加壓加熱硬化。硬化條件主要是 在140 °C 2小時和m °C 2小時，空氣壓力控制在4.1 土 0.1Kg/cm2。積層板從壓力釜取出後，將切割成短樑剪力強 度（SBS)測試[0]16試片，三點撓曲測試[〇]16試片，和雙懸 樑（DCB)破壞能量測試[〇]24試片。試片切割後置於烘箱内 在200。(：下過硬化4小時，再以〜1 °c /min的冷卻速率冷 卻至室溫，最後試片置於乾燥m内至少一星期，始進行 SBS，三點撓曲和DCB破壞能量測試，以及樹脂含量測試 (採用ASTM D3171-765之基材裂化法），測試結果列於表 二 ° 表二、各種不同樹脂配方製成的Gr/Ep單方向積層板樹脂 含量和機械性質比較表。 10 本紙張尺度適用中國國家標準（CNS ) A4规格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) -裝. 1T. 經濟部中央標準局員工消費合作社印製 319788Xj -TSC ^ 6L · 〇 Resin formulation Gic, Joule / m 2 flexural modulus, m 2 flexural strength, 6 Newtons / m 2 glass transition temperature, C TGDDM / DDS 108 soil 30.9 hj ^ ± 0.25 1 16 soil 31.7 260 TGDDM / DDS / Cr (acac) 3 298 ± 38.0 2 78 i Oil 126 soil 10.7 250 TGDDM / DDS / Cr (acac) 3 / c ,, z 369 soil 17.0 2 76 ± 0.08 81 soil 18.1 222 TGDDM / DDS / Cr (acac) 3 / c17z 343 soil 100.0 2.90 ± 0.22 94 soil 20.8 240 TGDDM / DDS / Cr (acac) 3 / 2P4MZ 325 ± 41.1 2.98 ± 0.25 — 231 It can be seen from the table that adding Cr (acac) 3 and C !! Z, or Cr (acac) 3 and C17Z, or Cr (acac) 3 and 2P4MZ in TGDDM / DDS epoxy resin can increase 3 It has more than twice the breaking toughness and has little negative impact on other mechanical properties. Example 4: Method for improving interlayer failure toughness and workability of high-performance Gr / £ p laminates. Add TGDDM / DDS, TGDDM / DDS / CuZ / Cr (acac) 3 and TGDDM / DDS used in Example 1 to 1 phr of C „Z (expressed as TGDDM / DDS / CUZ), and TGDDM / DDS are added. This paper scale is applicable to China National Standard (CNS) A4 specification (210X297mm) mf κ ^^^^ 1 ^^^^ 1 ^^ 1 (Please read the precautions on the back before filling out this page) A7 B7 printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economics and Development 5. Invention description (7) lphr of BF3MEA (indicated by TGDDM / DDS / BE3MEA) resin After the formula is mixed and clarified individually, the Gr / Ep unidirectional prepreg is manufactured by a two-stage hot melt method. Among them, BF3MEA (boron trifluoride-monoethylene amine) is a traditional hardening accelerator for resin. First, pour the resin into the knife type The coating machine is coated on the release paper at 120 ° C, and the resin coating thickness is controlled at 0.06 ± 0.01mm. In the second stage, the coated release paper is covered on the drum of the winding machine, and then the carbon fiber bundle is controlled under a certain tension , Using the guide wheel to spread the fiber bundle on the drum When winding, the weight of the fiber per unit area is controlled at 137 ± lg / m2. At this time, the surface temperature of the drum is increased to 100. (:, and the rubber is pressed to squeeze the resin to fully wet the fiber. So manufactured The resin content of the unidirectional prepreg was tested to be 40 ± 2wt ° /. After the prepreg was manufactured, it was laminated in accordance with various test specifications, and then packed in empty space, and then placed in an autoclave to heat and harden under pressure. The hardening conditions are mainly at 140 ° C for 2 hours and m ° C for 2 hours, the air pressure is controlled at 4.1 soil 0.1Kg / cm2. After the laminate is removed from the autoclave, it will be cut into short beam shear strength (SBS) test [0 ] 16 test pieces, three-point flexure test [〇] 16 test pieces, and double cantilever (DCB) destruction energy test [〇] 24 test pieces. The test pieces were cut and placed in an oven at 200. (: 4 hours under hardening , And then cooled to room temperature with a cooling rate of ~ 1 ° c / min, and finally the test piece was placed in dry m for at least one week before starting SBS, three-point deflection and DCB destruction energy test, and resin content test (using ASTM D3171-765 substrate cracking method), the test results are listed in the table ° Table 2. Comparison of resin content and mechanical properties of Gr / Ep unidirectional laminates made with various resin formulations. 10 This paper scale is applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) (please read first Note on the back and then fill out this page)-installed. 1T. Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 319788
樹脂配方 樹脂含 量，wt% 層間破壞 能量， 焦耳/米2 SBS 強 度，106 牛頡/米2 撓曲強 度，109 牛頓/米2 玻璃轉 移 溫 度，。C TGDDM/ DDS 22 - 67.7 ± 4.1 1.73 士 0.04 280 TGDDM/ DDS/ BF3MEA 29 (33) 324 土 7 (270 土 7) 70.3 ± 4.0 1.36 土 0.06 267 TGDDM/ DDS/CnZ 32 406 土 22 77.6 ± 4.4 1.21 土 0.03 242 TGDDM/ DDS/CuZ /Cr(acac)3 33 560 土 22 85.5 土 4.0 1.32 土 0.06 23S 量只有22%，因此結構内產生很多空孔和殘留應力，機械 性質變化很大無法商業化《如僅添加Cr(acac)3於 TGDDM/DDS樹脂配方則無法提高樹脂含量，仍然無法使 用。但添加CUZ於TGDDM/DDS樹脂配方時，可使積層板 的樹脂含量由22%提高到32%，達到複合材料規格的要 求。主要原因乃是CUZ硬化促進劑在140 °C加壓階段提前 和TGDDM反應，適時提高樹脂黏度使樹脂流失量減少， 因此含量得以增加。CnZ屬相當溫和的硬化促進劑，在製 造預浸布時不會產生早期膠化的現象，比BF3MEA更容易 控制反應。除此之外，CnZ與TGDDM反應後會產生含酸 基的分子鏈，對環氧樹脂和其複合材料提供相當程度的;I曽 韌效果。將Cr(acac)3 *CnZ合併使用添加於TGDDM/DDS 樹脂配方，其積層板樹脂含量可提高到33%，與採用 TGDDM/DDS/C"Z樹脂配方者接近，但層間破壞韌性卻大 幅提高，由406焦耳增加到560焦耳/米2，比傳統採用 11 尽紙張尺度適用中國國家標準（CNS ) M規格（210x297公楚 --------> —裝------訂-----卜線 (請先閲讀背面之注意事項再填寫本頁) A7 五、發明説明（9 ) TGDDM/DDS/BFgMEA者在相同樹脂含量時增加一倍以 上。由於受到纖維架橋影響，積層板每降低1%樹脂含量约 升高14焦耳/米2的層間破壞韌性，因此必須在相同的樹脂 含量才能比較樹脂配方對層間破壞韌性的貢獻。另外，添 加Cr(acac)3和C„Z於TGDDM/DDS樹脂配方亦可提高層 間剪力強度，但撓曲強度和玻璃轉移溫度則稍微降低如表 二所示。撓曲強度降低原因主要受到纖維含量減少影響。 n fn · (請先閲讀背面之注意事項再填寫本頁} -裂· 線 經濟部中央標準局員工消費合作社印製 12 表紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）Resin formulation Resin content, wt% interlayer destruction energy, Joules / m 2 SBS strength, 106 NJ / m 2 flexural strength, 109 N / m 2 glass transition temperature, C TGDDM / DDS 22-67.7 ± 4.1 1.73 ± 0.04 280 TGDDM / DDS / BF3MEA 29 (33) 324 ± 7 (270 ± 7) 70.3 ± 4.0 1.36 ± 0.06 267 TGDDM / DDS / CnZ 32 406 ± 22 77.6 ± 4.4 1.21 Soil 0.03 242 TGDDM / DDS / CuZ / Cr (acac) 3 33 560 Soil 22 85.5 Soil 4.0 1.32 Soil 0.06 23S The amount is only 22%, so there are many voids and residual stresses in the structure, the mechanical properties change greatly and cannot be commercialized. If only adding Cr (acac) 3 to the TGDDM / DDS resin formulation, the resin content cannot be increased and it cannot be used. However, when CUZ is added to the TGDDM / DDS resin formulation, the resin content of the laminate can be increased from 22% to 32%, meeting the requirements of composite materials. The main reason is that the CUZ hardening accelerator reacts with TGDDM in advance during the 140 ° C pressurization stage, and the resin viscosity is increased to reduce the resin loss, so the content can be increased. CnZ is a fairly mild hardening accelerator. It does not produce early gelation during the manufacture of prepreg, and it is easier to control the reaction than BF3MEA. In addition, after the reaction of CnZ and TGDDM, a molecular chain containing acid groups is generated, which provides a considerable degree of toughness to epoxy resins and their composite materials. When Cr (acac) 3 * CnZ is used in combination with TGDDM / DDS resin formulations, the resin content of the laminate can be increased to 33%, which is close to those using TGDDM / DDS / C " Z resin formulations, but the interlayer destruction toughness is greatly improved , Increased from 406 Joules to 560 Joules / m2, which is 11 times larger than the traditional paper standard. Applicable to China National Standards (CNS) M specifications (210x297 Gongchu --------> installed ------ Order ---- Bu Line (please read the precautions on the back before filling in this page) A7 V. Invention description (9) TGDDM / DDS / BFgMEA more than doubled at the same resin content. Due to the influence of fiber bridging For every 1% reduction in the laminate's resin content, the interlayer failure toughness increases by about 14 Joules / m2, so the same resin content must be used to compare the contribution of the resin formulation to the interlayer failure toughness. In addition, add Cr (acac) 3 and C "Z in TGDDM / DDS resin formulation can also increase the interlaminar shear strength, but the flexural strength and glass transition temperature are slightly reduced as shown in Table 2. The reason for the decrease in flexural strength is mainly affected by the decrease in fiber content. N fn · (please Read the precautions on the back before filling this page} -Cracked line Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 12 Sheets of paper apply the Chinese National Standard (CNS) A4 specification (210X297 mm)