200304443 疚、發明說明 (發明說明應敘明：發明所屬之技術領域、先前技術、內容、實施方式及圖式簡單說明) (一） .發明所屬之技術領域 .本發明是關於一種用於製造具有減小孔徑的聚甲基丙烯 醯亞胺發泡體的組成物，關於聚甲基丙烯醯亞胺發泡體， 及關於發泡體的製造方法和用途。 (二） 先前技術 聚甲基丙烯醯亞胺發泡體（PMI發泡體）是由來已久眾所 皆知’由於彼等具有特優機械性質和輕質，被廣泛地使用 於特別是製造疊層式材料、層合物、複合材料、發泡體組 合構材或夾層構造。PMI發泡體之~主要應用是用於夾層 構造，其中PM I發泡體是用作爲芯材料。夾層構造是由低 密度的芯材料和能吸收高拉伸力的外層所組成。芯材料的 密度通常爲介於30與2000kg/m3之間。外層是由例如纖維 補強複合材料或另一選擇爲纟S外層所組成。與整體式（實心 層合物）構造相比較，夾層構造的優點是重量減輕。此對運 輸工具是特別重要的，因爲眾所皆知較高的重量是也意謂 較高的能源消耗。相反地，減輕的重量可再以淨載重量加 以取代。因此對相同能源而言，可運輸更多。 夾層芯的功能是視應用的功能而定。因此，在製造構材 時，芯可用作爲兩種層合物的間隔物和成形物。在此情況 下，發泡體的機械性質對最終構材是無關係的。若芯材料 的機械性質是加以計算入設計，因此層合材料可設計成較 -6 一 200304443 ^此思α目具有重量優點和財務優點，與以層合材料必須 負荷全部必要的力量爲條件所製得之構材相比較。 心材料基本上是具有三種不同類別。在此應該提及白塞 木（Balsa wo〇d)。此爲可再生的原料且具有有利的耐火性 ，但是由於木材的纖維結構，其爲各向異性材料。平均密 度爲約150kg/m3是相對的高，但是對許多應用而言仍然是 足夠低。此類型之芯材料是市售商品級，例如商標名爲 Bal t ec®售自製造廠商dIAB。 另一類別的芯材料是以蜂窩狀物結構，例如N〇mex®蜂窩 狀物售自HEXCEL和Euro複合材料。此等特別顯著的是彼 等之非常低密度。該構造類型是意謂蜂窩狀物可在一空間 方向吸收高力量，且遠優於發泡體在此觀點用於一維應用 。然而右彳頁向力也發生時’此優點會變成缺點：垂直於「 穩定」的方向，蜂窩狀物強度會減少。另一缺點是用於製 造纖維複合材料的樹脂可能會流入蜂窩狀物，因此會非吾 所欲地再增加重量。此太嚴重的話會完全排除使用低黏度 樹脂的情況。因此，其對蜂窩狀物是需要使用正確的樹脂 系統和加工方法。另一難題是蜂窩狀物的可加工性，其是 比發泡體或白塞木的加工更複雜且更昂貴。也有蜂窩狀物 是製自鋁，其係售自HEXCEL。 應該提及的第三類別是包含剛性聚合物發泡體，其通常 是商品級可獲得呈半成品。彼等是呈薄片或加工至最終尺 寸的芯銷售到客戶。發泡體是能傳送全部空間方向的力量 。易加工性是優點：通常僅需要木材加工工具。由於孔隙 - 7 - 200304443 結構，樹脂滲透入芯材料是有點不太像會發生，且在封閉 式孔隙發泡體是完全不可能的。發泡體的另一優點是彼等 之熱可變形性。 上述該等必然導致上述技術特徵，其中芯材料必須具有 足夠的範圍，儘管其是低密度。對發泡體而言，在此孔隙 結構是決定性的準則。接著從理論上的考量，具有相同密 度的開放式孔隙發泡體的穩定性是比封閉式孔隙發泡體較 低。隨著在空氣囊（cell)壁的質量增加，機械性質也變得較 佳。在實務應用上也證實是如此。因此，其顯而易見結構 性發泡體通常具有大比例的封閉式空氣囊。 除了 P U以外，剛性發泡體是製成呈半成品。在ρ μ I發 泡體的案例中，單體是首先加以聚合成薄片。發泡劑已經 存在於聚合物中，結果導致在進一步的烘箱之階段會發泡 。隨後發泡體表皮必須加以切除，且將發泡薄片切削成零 售用形態。 若發泡體是藉由擠製成形所製得時（例如PVC發泡體）， 模製組成物是在添加入發泡劑的擠製機中加以熔化。例如 其經由薄片模頭離開擠製機且在製程中膨脹以製成發泡薄 片。在此切削成所需要的形態也必項是在移除發泡體表皮 後來進行。如前所述’ ρ u發泡體構成一例外，因爲在此情 況下發泡進入模具中是可能的。 不管所使用的外層和芯材料如何，在過去製造夾層構造 是複雜的，基於此理由’此類型的構裝長久以來由於價格 因素無法適當地加以建立。層合製程需要尤其是所謂的「 一 8 - 200304443 預浸膠體」，其係由以局部聚合的樹脂加以預浸膠的纖維 墊所組成。此等樹脂的黏度通常是如此高，致使其滴流並 不會發生。在近年來，新製法已經建立，其特別顯著的事 實是低黏度是被注射入封閉式模具中。模具含有夾層芯， 其係以仍乾燥的纖維材料加以覆蓋。此等方法的優點第一 是可自由選擇樹脂系統和纖維材料，且第二是具有較佳的 潛力自動化。因此，使用此等製造方法通常是較便宜的。 上述方法包括：例如RTM(樹脂移轉模製法）、rim (樹脂 浸漬模製法）、SCRIMP(Seeman樹脂浸漬模製法tm)和vARi( 真空輔助樹脂浸漬法）。進一步的細節是提供於「樹脂移轉 模製法、SAMPE⑧ Monograph No..3」（ISBN 0-93 8994-83 -2) ο 在此情況下，難題是低黏度樹脂會完全塡滿芯材料的空 腔，其係意謂無法使用經常與預浸膠體在一起使用的蜂嵩 狀物。因爲聚合物發泡體的表面是由切削的空氣囊所組成 ’此等也具有孔腔，其結果會導致構材的重量增加。欲能 減少此等孔腔和構材的重量增加，其必須使用具有微細孔 隙的發泡體以製造構材。 微細孔隙的ΡΜΙ發泡體是習知且售自Rohm GmbH & Co. KG，商標名爲Rohacell®。其係可能藉由發泡體的變化來獲 得微細孔隙的結構。然而難題是所獲得的孔隙結構是較少 可變性，且除此之外其係部份受到天然產生的雜質所控制 。因此，本發明的目的是發現用於Ρ ΜI發泡體的配方和製 法，其係具有與習知材料同等優良的熱機械性質，且除此 一 9 - 200304443 之外顯著的事實是彼等之孔隙結構可隨著孔隙大小來加以 調整。 (三）發明內容 上述目的是可藉由使用在德國專利申請案第1〇]Π3899·7 號所揭示方法的輔助所製得的發泡體來達到。此係揭示非 常通用的方法’以將不溶性添加劑引介到藉由箱式製法所 製得的PM I發泡體中。然而所揭示的配方並不能提供任何 可應用的有利條件。 若僅使用非常少量的不溶性固體添加劑，其係令人驚奇 地觀察到可保持發泡體的機械性質，且孔隙結構變得可加 以控制。在此的術語「少量」是意謂少於1重量％數量。相 反地，在固體含量爲大於1 〇重量％時，孔隙結構並不會經 歷任何顯著的變化。此可用以限制如前所述在吸收樹脂之 初期及結果導致構材重量增加的難題。此係假定歸因於不 溶性添加劑的晶核生成作用。在發泡時，晶核的數目會影 響到孔隙形成的數目，其最後會決定在發泡後之孔隙的最 終大小。 適當的晶核形成物質或晶核生成劑是例如無機鹽類和礦 質，其係不溶於製造PM I發泡體所需要的反應混合物中。 此等包括Si02、ZnS、BP04、NaCl或KC1。其他可使用不溶 性聚合物或其鹽類。在此應該提及的是例如聚磷酸銨。 因爲是與晶核形成顆粒的數目相關’其顯而易見若添加 入少量晶核形成物質時，所使用塡充劑的粒徑必須足夠小 以能控制孔隙的大小。 -10- 200304443 在此典型的粒徑爲從10奈米至100微米，較佳爲從100 奈米至3 0微米，且特佳爲從丨微米至1 0微米。 除了所提及的晶核生成劑以外，根據本發明的組成物也 可進一步包含添加劑，例如阻燃劑。除了含鹵素的阻燃劑（ 其在某些情況下也包含氧化銻類）以外，其也可使用含磷化 合物。含磷化合物是較佳的，由於其具有較佳的塑膠再循 環使用性。 磷化合物包括特別是膦類、氧化膦、鱗化合物、膦酸酯 類、亞磷酸鹽類和/或磷酸鹽類。此等化合物可爲有機和/ 或無機類，具有此等化合物的衍生物，例如磷酸單酯類、 膦酸單酯類、磷酸二酯類、膦酸二酯類和磷酸三酯類、及 也包括聚磷酸酯類。 根據本發明用於製造聚（甲基）丙烯醯亞胺發泡體的組成 物是可聚合混合物，其係包含至少一種，通常爲至少兩種 或多種單體（例如（甲基）丙烯酸和（甲基）丙烯腈）、發泡劑 、至少一種聚合起始劑和晶核形成添加劑，及如果需要的 話之阻燃劑。將此等組成物加以聚合以提供先質，藉此經 由溫熱可形成聚（甲基）丙烯醯亞胺發泡體。 在圓括號中的表示法是意指表示選擇性的特徵。因此， 例如（甲基）丙烯是表示丙烯、甲基丙烯及其兩者的混合物 〇 可獲自根據本發明組成物的聚（甲基）丙烯醯亞胺發泡體 是具有如下化學式（II)所示的重覆單元： 200304443200304443 Guilt and invention description (The description of invention should state: the technical field to which the invention belongs, the prior art, the content, the embodiments and the simple description of the drawings) (1). The technical field to which the invention belongs. The invention relates to a method for manufacturing A composition of a polymethacrylamide imine foam having a reduced pore size, a polymethacrylamide imine foam, and a method and application of the foam. (B) the prior art polymethacrylamide imide foam (PMI foam) has been known for a long time. 'Because of their excellent mechanical properties and light weight, they are widely used in manufacturing Laminated materials, laminates, composite materials, foam composites, or sandwich structures. The main application of PMI foam is for sandwich structures, of which PM I foam is used as the core material. The sandwich structure consists of a low-density core material and an outer layer capable of absorbing high tensile forces. The density of the core material is usually between 30 and 2000 kg / m3. The outer layer is composed of, for example, a fiber-reinforced composite material or another outer layer of 纟 S. Compared with monolithic (solid laminate) construction, the advantage of sandwich construction is weight reduction. This is particularly important for transport vehicles, as it is well known that higher weight also means higher energy consumption. Conversely, the reduced weight can be replaced by the payload. So for the same energy, more can be transported. The function of the sandwich core depends on the function of the application. Therefore, the core can be used as a spacer and a molded article of two kinds of laminates when manufacturing a structural material. In this case, the mechanical properties of the foam are irrelevant to the final material. If the mechanical properties of the core material are calculated into the design, the laminated material can be designed to have a weight advantage and a financial advantage over -6200304443. This is subject to the condition that the laminated material must bear all the necessary forces. The resulting structures are compared. Cardio materials are basically of three different categories. Balsa WoOd should be mentioned here. This is a renewable raw material and has favorable fire resistance, but it is an anisotropic material due to the fibrous structure of the wood. An average density of about 150 kg / m3 is relatively high, but still low enough for many applications. This type of core material is a commercial grade, such as sold under the trade name Baltec® from the manufacturer dIAB. Another type of core material is a honeycomb structure, such as Nomex® honeycomb sold from HEXCEL and Euro composites. These are particularly notable for their very low density. This type of construction means that honeycombs can absorb high forces in a spatial direction and are far superior to foams for one-dimensional applications in this view. However, when the right front page force also occurs, this advantage becomes a disadvantage: perpendicular to the "stable" direction, the strength of the honeycomb will decrease. Another disadvantage is that the resin used to make the fiber composite material may flow into the honeycomb, and therefore may increase the weight undesirably. If this is too severe, the use of low viscosity resins will be completely ruled out. Therefore, it is necessary for the honeycomb to use the correct resin system and processing method. Another problem is the processability of honeycombs, which are more complex and expensive than the processing of foam or betel wood. There are also honeycombs made from aluminum, which are sold from HEXCEL. The third category that should be mentioned is the inclusion of rigid polymer foams, which are usually commercially available as semi-finished products. They are sold to customers as thin sheets or cores processed to the final size. Foam is a force that can transmit all directions of space. Workability is an advantage: usually only woodworking tools are required. Due to the porosity-7-200304443 structure, resin penetration into the core material is a bit less likely to occur, and it is completely impossible in closed-cell foams. Another advantage of foams is their thermal deformability. The above-mentioned ones necessarily lead to the above-mentioned technical characteristics, in which the core material must have a sufficient range, despite its low density. For foams, the pore structure is the decisive criterion here. Then, theoretically, the stability of open-cell foams with the same density is lower than that of closed-cell foams. As the mass of the air cell wall increases, the mechanical properties become better. This has also been proven in practical applications. Therefore, it is obvious that the structural foam usually has a large proportion of closed air cells. Except PU, rigid foams are made into semi-finished products. In the case of ρ μ I foams, the monomers are first polymerized into flakes. Foaming agents are already present in the polymer, which results in foaming during further oven stages. The skin of the foam must then be removed, and the foam sheet is cut into a retail form. If the foam is made by extrusion (for example, PVC foam), the molding composition is melted in an extruder added with a foaming agent. For example, it leaves the extruder via a sheet die and expands during the process to make a foamed sheet. Cutting into the desired shape here must also be performed after removing the foam skin. As mentioned earlier, the 'ρ u foam constitutes an exception, because in this case foaming into the mold is possible. Regardless of the outer layer and core material used, it has been complicated to manufacture sandwich structures in the past, and for this reason 'this type of construction has long been unable to properly build it due to price factors. The lamination process requires, in particular, the so-called "8-200304443 prepreg", which consists of a fibrous mat pre-preg with a locally polymerized resin. The viscosity of these resins is usually so high that dripping does not occur. In recent years, new methods have been established, and it is particularly remarkable that low viscosity is injected into closed molds. The mold contains a sandwich core which is covered with a fibrous material that is still dry. The advantages of these methods are firstly the free choice of resin systems and fiber materials, and secondly the automation with better potential. Therefore, it is generally cheaper to use such manufacturing methods. The above methods include, for example, RTM (resin transfer molding method), rim (resin impregnation molding method), SCRIMP (Seeman resin impregnation molding method tm), and vARi (vacuum assisted resin impregnation method). Further details are provided in "Resin transfer molding method, SAMPE⑧ Monograph No. 3" (ISBN 0-93 8994-83 -2) ο In this case, the problem is that the low viscosity resin will completely fill the core material. Cavity, which means that it is not possible to use a bee moth that is often used with prepregs. Because the surface of the polymer foam is composed of cut air bladders, these also have cavities, and as a result, the weight of the structural member is increased. In order to reduce the weight increase of these cavities and the structure, it is necessary to use a foam having fine pores to manufacture the structure. Microcellular PMI foams are well known and sold from Rohm GmbH & Co. KG under the trade name Rohacell®. It is possible to obtain a fine pore structure by changing the foam. However, the difficulty is that the pore structure obtained is less variable, and in addition, its pore structure is controlled by naturally occurring impurities. Therefore, the object of the present invention is to discover the formulation and manufacturing method for PMI foams, which have the same excellent thermomechanical properties as conventional materials, and the facts other than this 9-200304443 are significant. The pore structure can be adjusted with the pore size. (3) Summary of the Invention The above-mentioned object can be achieved by using a foam produced by using the method disclosed in German Patent Application No. 10] Π3899 · 7. This system discloses a very general method 'to introduce insoluble additives into the PM I foam produced by the box-type method. However, the disclosed formulation does not provide any applicable advantages. If only a very small amount of insoluble solid additive is used, it is surprisingly observed that the mechanical properties of the foam can be maintained and the pore structure becomes controllable. The term "small amount" herein means less than 1% by weight. In contrast, when the solid content is more than 10% by weight, the pore structure does not undergo any significant change. This can be used to limit the problem of increasing the weight of the structure in the initial stage of the absorbent resin and as a result, as described above. This system is assumed to be due to the nucleation of insoluble additives. During foaming, the number of crystal nuclei will affect the number of pores formed, which will ultimately determine the final size of the pores after foaming. Suitable crystal nucleating substances or crystal nucleating agents are, for example, inorganic salts and minerals, which are insoluble in the reaction mixture required to make the PM I foam. These include SiO2, ZnS, BP04, NaCl or KC1. Others may use insoluble polymers or their salts. Mention should be made here, for example, of ammonium polyphosphate. Because it is related to the number of crystal nucleation particles, it is obvious that if a small amount of crystal nucleation material is added, the particle size of the filler used must be small enough to control the pore size. -10- 200304443 The typical particle size here is from 10 nm to 100 μm, preferably from 100 nm to 30 μm, and particularly preferably from 1 μm to 10 μm. In addition to the crystal nucleating agent mentioned, the composition according to the present invention may further contain an additive such as a flame retardant. In addition to halogen-containing flame retardants, which in some cases also contain antimony oxides, they can also use phosphorus-containing compounds. Phosphorous compounds are preferred due to their better recyclability in plastics. Phosphorus compounds include, in particular, phosphines, phosphine oxides, scale compounds, phosphonates, phosphites and / or phosphates. These compounds may be organic and / or inorganic, and derivatives of these compounds, such as phosphate monoesters, phosphonic monoesters, phosphodiesters, phosphonic diesters and phosphate triesters, and also Including polyphosphates. The composition for producing a poly (meth) acrylamide imide foam according to the present invention is a polymerizable mixture, which comprises at least one, usually at least two or more monomers, such as (meth) acrylic acid and ( (Meth) acrylonitrile), a blowing agent, at least one polymerization initiator and crystal nucleation additive, and a flame retardant if necessary. These compositions are polymerized to provide a precursor, whereby a poly (meth) acrylamidoimide foam can be formed by warming. The notation in parentheses means a characteristic that indicates selectivity. Therefore, for example, (meth) propylene means propylene, methpropylene, and a mixture of both. The poly (meth) acrylic acid imide foam obtained from the composition according to the present invention has the following chemical formula (II) Repeating unit shown: 200304443
其中’R1和R2是相同或不同且爲氫或甲基，且R3是氫 或具有高達20個碳原子的烷基或芳基。 結構（I I )的單元較佳爲形成30重量％以上，特佳爲5〇重 量％以上，且非常特佳爲80重量％以上的聚（甲基）丙稀醯亞 胺發包體。 硬挺性聚（甲基）丙烯醯亞胺發泡體的製法本質上是習知 的’例如揭示於英國專利第1 ,078, 42 5號、英國專利第 1，0 4 5，2 2 9號、德國專利第1 8 1 7 1 5 6號（=：美國專利第 3,6 2 7,7 1 1號）或德國專利第27 26 2 5 9號（：=美國專利第 4, 1 3 9,68 5 號” 因此，結構化學式（I I )的單元是可特別是藉由從（甲基） 丙烯酸和（甲基）丙烯腈之鄰近單元在加熱從150至2 5 0°C的 環化異構化反應來形成（比較：德國專利第C 1 8 1 7 1 5 6號 、德國專利第C2 7 26 2 5 9號、歐洲專利第B 1 46 892號）。 先質通常是初期藉由單體在游離基起始劑的存在下，在低 溫（例如從30至60°C )，隨著後加熱從60至120°C的聚合 反應所形成，然後藉由所包含的發泡劑，加熱從180至250 t加以膨脹（參閱歐洲專利第B 3 5 6 7 1 4號）。 欲能達到此目的，其可例如首先形成包含（甲基）丙烯酸 和（甲基）丙烯腈的共聚物’較佳的莫耳比率爲介於1 : 4與 -12- 200304443 4 : 1之間。 除此之外，此等共聚物可進一步包含來自例如丙烯 甲基丙烯酸、特別是具有1至4個碳原子的低碳醇類 乙烯、順丁烯二酸或其酐類、分解烏頭酸或其酐類、 基吡咯啶酮（vinylpyrrolidone)、氯化乙烯或氯化亞 的酯類之單體單元。僅能以非常高困難度加以環化之 體的比例不論如何應該不超過3 0重量％，較佳爲不超$ 重量％，且特佳爲不超過10重量％(以單體重量爲基準） 關於額外的單體，其係可能有利的習知方法是使用 交聯劑，例如丙烯酸烯丙酯、甲基丙烯酸烯丙酯、二 酸或二甲基丙烯酸之乙二醇酯、或丙烯酸或甲基丙烯 多價金屬鹽類，例如甲基丙烯酸鎂。此等交聯劑的比 常是在範圍爲從0 . 0 0 5至5重量％，以可聚合單體的總 基準。Where 'R1 and R2 are the same or different and are hydrogen or methyl, and R3 is hydrogen or an alkyl or aryl group having up to 20 carbon atoms. The unit of the structure (I I) preferably forms 30% by weight or more, particularly preferably 50% by weight or more, and very particularly preferably 80% by weight or more of a poly (meth) acrylamidimide inclusion body. The production method of the stiff poly (meth) acrylamide imide foam is conventionally known, for example, disclosed in British Patent No. 1,078, 42 5 and British Patent No. 1, 0 4 5, 2 2 9 , German Patent No. 1 8 1 7 1 5 6 (=: US Patent No. 3, 6 2 7, 7 1 1) or German Patent No. 27 26 2 5 9 (: = US Patent No. 4, 1 3 9 No. 68 5 "Therefore, the units of structural formula (II) are particularly cyclized by heating adjacent units of (meth) acrylic acid and (meth) acrylonitrile from 150 to 250 ° C. Formation by chemical reaction (comparison: German Patent No. C 1 8 1 7 1 5 6; German Patent No. C 2 7 26 2 5 9; European Patent No. B 1 46 892). The polymer is formed in the presence of a radical initiator at a low temperature (for example, from 30 to 60 ° C), followed by a post-heating polymerization reaction from 60 to 120 ° C, and then heated by the included blowing agent. Expansion from 180 to 250 t (see European Patent No. B 3 5 6 7 1 4). To achieve this, it can first be formed, for example, comprising (meth) acrylic acid and (meth) acrylonitrile The copolymer's preferred molar ratio is between 1: 4 and -12-200304443 4: 1. In addition, these copolymers can further comprise, for example, propylene methacrylic acid, especially having Single-carbon alcohols of 4 to 4 carbon atoms, ethylene, maleic acid or its anhydrides, decomposed aconitic acid or its anhydrides, vinylpyrrolidone, vinyl chloride or ethylene chloride esters Body unit. The proportion of bodies that can only be cyclized with very high difficulty should not exceed 30% by weight, preferably not more than $% by weight, and particularly preferably not more than 10% by weight (in terms of monomer weight) For additional monomers, a conventional method that may be advantageous with regard to additional monomers is the use of cross-linking agents such as allyl acrylate, allyl methacrylate, diacid or glycol dimethacrylate, Polyvalent metal salts of acrylic acid or methacrylic acid, such as magnesium methacrylate. The ratio of these cross-linking agents is usually in the range from 0.05 to 5% by weight, based on the total basis of polymerizable monomers.
其係更進一步可使用金屬鹽類添加劑。此等包括特 丙烯酸酯類或甲基丙烯酸酯類之鹼土金屬類或鋅。較 是（甲基）丙烯酸酯鋅和（甲基）丙烯酸酯鎂。所使用的 起始劑是慣用於（甲基）丙烯酸酯的聚合反應之該等， 偶氮化合物（例如偶氮二異丁腈）和過氧化物（例如過氧 甲醯基或過氧化二月桂基），或其他過氧化物（例如過 第三丁酯）或過縮酮類，而且如果需要的話，氧化還原 劑（在此方面可參考例如H. Rauch-Puntigam，Th，Vol Acryl-und Methacrylverbindungen(丙烯酸和甲基丙 化合物），Springer，Heidelberg，1967，或 Kirk-CM 酸或 、苯 乙烯 乙烯 共單 i 20 〇 少量 丙烯 酸之 例經 量爲 別是 佳的 聚合 例如 化苯 辛酸 起始 k e r , 烯酸 hme r 200304443 ，化學技術百科全書，第1冊，第286頁，JohnWiley&Sons， New York，1 97 8 )。聚合反應起始劑較佳的使用量爲從0 · 01 至0 . 3重量％，以所使用單體的總重量爲基準。 其也有利的是結合對時間和溫度具有不同分解性質的聚 合反應起始劑。例如同時使用過特戊酸第三丁酯、過苯甲 酸第三丁酯和過-2-乙基己醇第三丁酯或過苯甲酸第三丁酯 、2，2 -偶氮二異-2 ,4 -二甲基-戊腈、2,2 -偶氮二異丁腈和 過氧化二-第三丁基是較適當的。 聚合反應較佳爲經由不同的本體聚合反應來進行，例如 所謂的箱式製法，而且並無限制。 聚合物的重量平均分子量較佳爲大於1 06克/莫耳，特別 是大於3X 106克/莫耳，且並不受限於此。 共聚物在轉化成含醯亞胺基的膨脹是根據習知的方法使 用在150至2 50°C經由分解或蒸發形成氣相的發泡劑來進行 。具有醯胺結構的發泡劑，例如尿素、單甲基·或N，N ’ -二 甲基脲、甲醯胺或單甲基甲醯胺，在分解時會釋放氛或胺 類，其可有助於朝向額外地形成醯亞胺基。然而其也能使 用無氮發泡劑，例如甲酸、水或具有從3至8個碳原子的 一元脂肪族醇類，例如1-丙醇、2 -丙醇、正-丁 - 1 _醇、正 -丁 - 2 -醇、異丁 - 1 -醇、異丁 - 2 -醇、第三丁醇、戊醇類和/ 或己醇類。所使用發泡劑的數量是視吾所欲得密度而定， 在反應批次中所使用發泡劑的數量爲〇 · 5至1 5重量％，以 所使用單體的總重量爲基準。 此外，先質可包含傳統慣用的添加劑。此等包括特別是 一 14- 200304443 抗靜電劑、抗氧化劑、模具脫模劑、潤滑劑、染料、阻燃 劑、流動改良劑、塡充劑、光安定劑或膦酸酯類、顏料、 脫模劑、耐候劑和塑化劑。 可預防發泡體靜電電荷的導電性顆粒是另一類型較佳的 添加劑。此等包括特別是金屬和碳黑顆粒，其也可呈纖維 的形態，具有大小範圍爲從1 0奈米至1 0毫米，如在歐洲 專利第0 3 5 6 7 1 4 A 1號所揭示者。 除此之外，抗沈澱劑是較佳的添加劑，因爲此等物質可 φ 有效地穩定用於製造聚丙烯醯亞胺發泡體的組成物。此等 包括特別是碳黑（例如KB EC- 600 JD製自Akzo Nobel )、 和氣相二氧化矽類（Aerosils)(例如 Aerosil 200製自 Degussa AG)、或聚合物型增稠劑（高分子量聚甲基丙烯酸 甲酯）。 根據本發明的聚（甲基）丙烯醯亞胺發泡體是可藉由將一 種由下列諸成份所組成的混合物進行聚合反應來製得： (M20至60重量％之（甲基）丙烯腈、 φ 40至80重量％之（甲基）丙嫌酸、和 0至20重量％之額外的乙嫌系不飽和單體’ 其中成份（A )之組成份添加入直到1 〇 〇重量％ ; (B ) 0 . 5至1 5重量％之發泡劑（以成份（A )之重量爲基準）； (C) 0.0001至1重量％之晶核生成劑（以成份（A)之重重爲基 準）； (D) 0.01至0.3重量％之聚合反應起始劑（以成份（A)之重量 爲基準）； -15- 200304443 (E) 0至200重量％之傳統慣用的添加劑（以成份（A)之重量 爲基準），以製成薄片，且此聚合物薄片是隨後在溫度 爲從1 5 0至2 5 0 °C加以發泡。 根據本發明的聚（甲基）丙烯醯亞胺發泡體可配備有外層 ’用以例如增加強度。除此之外，疊層式材料是習知的， 其係僅經由選擇外層以賦予某些阻燃性。在使用根據本發 明的發泡體時，可顯著地減少由於充塡切削孔隙而造成重 量增加。所使用的外層可爲任何習知的薄片狀結構，其在 用於製造複合材料結構所需要的加工參數（例如壓力和溫度） 下是穩定的。此等包括特別是例如薄膜和/或薄片，其係包 含聚丙烯、聚酯、聚醚、聚醯胺、聚氨基甲酸酯、聚氨乙 、聚（甲基）丙烯酸甲酯，藉由硬化反應所獲得的塑膠，例 如環氧樹脂（EP樹脂）、甲基丙烯酸酯樹脂（MA樹脂）、不飽 和聚酯樹脂（UP樹脂）、異氰酸酯樹脂和苯基丙烯酸酯樹脂 (PHA樹脂）、雙順丁烯二醯亞胺樹脂和酚樹脂、和/或金屬 (例如鋁）。此外，所使用的外層較佳爲墊或纖維網包含玻 璃纖維、碳纖維和/或芳族聚醯胺纖維，其中所使用的外層 也可爲具有多層結構的纖維網。 此等含纖維的纖維網可應用到發泡體，特別是用作爲預 浸膠體。此等是纖維墊，通常爲玻璃纖維墊或機織玻璃長 纖材，其係已經預浸漬可硬化塑膠，且其可藉由熱壓製轉The system can further use metal salt additives. These include alkali earth metals of special acrylates or methacrylates or zinc. Compared to zinc (meth) acrylate and magnesium (meth) acrylate. The initiators used are those conventionally used in the polymerization of (meth) acrylates, azo compounds (such as azobisisobutyronitrile), and peroxides (such as permethamyl or dilaurate Group), or other peroxides (such as tert-butyl esters) or perketals, and if necessary, redox agents (refer to, for example, H. Rauch-Puntigam, Th, Vol Acryl-und Methacrylverbindungen (Acrylic acid and methacrylic compounds), Springer, Heidelberg, 1967, or Kirk-CM acid or styrene-vinyl monomer alone, a small amount of acrylic acid is an example of a particularly good polymerization such as a phenyloctanoic acid starting ker, Hme r 200304443, Encyclopedia of Chemical Technology, Volume 1, page 286, John Wiley & Sons, New York, 1 97 8). The polymerization initiator is preferably used in an amount of from 0.01 to 0.3% by weight, based on the total weight of the monomers used. It is also advantageous to incorporate a polymerization reaction initiator having different decomposition properties with respect to time and temperature. For example, simultaneous use of third butyl pervalerate, third butyl perbenzoate, and third butyl per-2-ethylhexanol or third butyl perbenzoate, 2,2-azobisiso- 2,4-Dimethyl-valeronitrile, 2,2-azobisisobutyronitrile, and di-tertiarybutyl peroxide are more suitable. The polymerization reaction is preferably carried out via different bulk polymerization reactions, such as the so-called box-type production method, and is not limited. The weight average molecular weight of the polymer is preferably greater than 106 g / mole, particularly greater than 3 x 106 g / mole, and is not limited thereto. The swelling of the copolymer into the fluorene-imide-containing group is carried out according to a conventional method using a foaming agent at 150 to 250 ° C to form a gas phase through decomposition or evaporation. Foaming agents with amidine structures, such as urea, monomethyl · or N, N′-dimethylurea, formamidine, or monomethylformamide, can release atmospheres or amines when decomposed. Facilitates the formation of sulfonium imino groups in addition. However, it is also possible to use nitrogen-free blowing agents, such as formic acid, water or monohydric aliphatic alcohols having from 3 to 8 carbon atoms, such as 1-propanol, 2-propanol, n-but-1-ol, N-but-2-ol, isobut-1-ol, isobut-2-ol, tertiary butanol, pentanols and / or hexanols. The amount of foaming agent used depends on the density we want. The amount of foaming agent used in the reaction batch is from 0.5 to 15% by weight, based on the total weight of the monomers used. In addition, the precursor may contain conventional additives. These include, in particular, 14-200304443 antistatic agents, antioxidants, mold release agents, lubricants, dyes, flame retardants, flow improvers, fillers, light stabilizers or phosphonates, pigments, Molding agents, weathering agents and plasticizers. Conductive particles that can prevent the electrostatic charge of the foam are another preferred type of additive. These include, in particular, metal and carbon black particles, which can also be in the form of fibers, having a size ranging from 10 nm to 10 mm, as disclosed in European Patent No. 0 3 5 6 7 1 4 A 1 By. In addition, anti-settling agents are preferred additives because these materials can effectively stabilize the composition used to make polypropylene / imine foam. These include, in particular, carbon black (e.g. KB EC-600 JD from Akzo Nobel), and fumed silicas (e.g. Aerosil 200 from Degussa AG), or polymeric thickeners (high molecular weight polymer Methyl methacrylate). The poly (meth) acrylamide imide foam according to the present invention can be prepared by polymerizing a mixture of the following components: (M20 to 60% by weight of (meth) acrylonitrile , Φ40 to 80% by weight of (meth) propionic acid, and 0 to 20% by weight of additional ethyl benzene unsaturated monomers' wherein the component (A) is added up to 100% by weight; (B) 0.5 to 15% by weight of foaming agent (based on the weight of ingredient (A)); (C) 0.0001 to 1% by weight of crystal nucleating agent (based on the weight of ingredient (A) ); (D) 0.01 to 0.3% by weight of polymerization initiator (based on the weight of component (A)); -15-200304443 (E) 0 to 200% by weight of conventional additives (based on component (A) ) As a basis) to make a sheet, and the polymer sheet is subsequently foamed at a temperature of from 150 to 250 ° C. The poly (meth) acrylic acid imine according to the present invention is foamed. The foam may be equipped with an outer layer, for example to increase strength. In addition, laminated materials are conventional, which are obtained only by selecting the outer layer In order to impart certain flame retardancy. When using the foam according to the present invention, the weight increase caused by filling and cutting the pores can be significantly reduced. The outer layer used can be any conventional sheet-like structure, which is in use Stable under the processing parameters (such as pressure and temperature) required to make the composite structure. These include, for example, films and / or sheets, which include polypropylene, polyester, polyether, polyamide, poly Carbamate, polyurethane, poly (meth) acrylate, plastics obtained by curing reaction, such as epoxy resin (EP resin), methacrylate resin (MA resin), unsaturated polyester Resin (UP resin), isocyanate resin and phenyl acrylate resin (PHA resin), bis-cis butylene diimide resin and phenol resin, and / or metal (such as aluminum). In addition, the outer layer used is preferably The mat or fiber web contains glass fiber, carbon fiber and / or aromatic polyamide fiber, and the outer layer used therein may also be a fiber web having a multilayer structure. These fiber-containing fiber webs can be applied to foams, especially Is used as a pre-dipping material. Such a fiber mat, generally long-fiber material is a woven glass mat or woven glass fibers, which has been pre-impregnated with hardenable based plastic, and which may be transferred by hot pressing
變成模製品或半成品。此等包括特別是所謂的GMT和SMC 〇 也習知的是碳纖維補強塑膠，其係特別適用爲外層。 - 1 6 - 200304443 外層的厚度較佳的範圍爲從0 . 1至1 0 0毫米，更佳的範 圍爲從0.5至10毫米。 欲能改良黏著性，其也可使用黏著劑。此並不是必要條 件，其係視外層的材料而定。 根據本發明的聚（甲基）丙烯醯亞胺也可藉由例如上述方 法加以轉變成夾層構材，例如RTM (樹脂移轉模製法）、R I Μ ( 樹脂浸漬模製法）、SCRIMP(Seeman樹脂浸漬模製法ΤΜ)或 VAR I (真空輔助樹脂浸漬法）。與此等方法特別有利的是經 由使用本發明之微細孔隙發泡體可避免構材的重量增加。 在此觀點中，由於發泡體所吸收的樹脂是可藉由下列方 法來測得： 將一已知體積的孔腔（例如長方形）是切入足夠厚度的 PLEXIGLAS®片。圓形輪廓是切入PLEXIGLAS⑧片圍繞此孔腔 ，且將密封之簾子布（cord)放置於此輪廓中。孔腔是經由 鑽孔連接到真空泵，且經由第二鑽孔連接到含有植物油的 容器。兩個入口可藉由使用斷流旋塞加以堵塞。孔腔是以 另一相同厚度的PLEXIGLAS®片加以密封。 欲能測定全部孔腔，將空孔腔稱重，因此可測定 PLEXIGLAS®片的重量。接著孔腔是以植物油加以充塡，其 係藉由首先將孔腔抽真空至〇 · 2巴，隨後藉由使用真空將 油吸入，直到將孔腔完全充滿爲止。然後測定經充滿之量 測系統的重量。孔腔的體積可從增加的重量和油密度加以 測定。 欲能測定一發泡體的孔隙度，將被測試之已知尺寸的發 - 17 - 200304443 泡體之試樣放置於孔腔中，將孔腔密封並加以抽真空，且 將量測系統如上所述以油重新充塡。發泡體試樣在此是藉 由使用間隔物以與孔腔的邊緣保持距離，以確保可將孔隙 充分充塡。間隔物的固有重量可包括於如上所述的空白量 測中。 體積差異和被試樣所置換的體積是可從介於空白量測與 具有試樣的量測之間的質量差異，且藉由油之密度的輔助 來計算得。此體積是低於試樣的體積，若其孔隙結構是忽 | 略不計。位於試樣片表面之開放式孔隙的體積是可從此等 兩個置換之體積的差異計算得。然後試樣由於吸收樹脂所 增加的重量是可從樹脂密度的知識計算得。 根據本發明的聚（甲基）丙烯醯亞胺發泡體及特別是含有 此等發泡體的疊層式材料是可用於例如航空器構造和用於 船舶、軌道車或自動車的構造。 (四）實施方式 實施例1 · 將290克（2.9重量份）異丙醇和290克（2.9重量份）甲醯 安作爲發泡劑添加到一種含有5，0 0 0克甲基丙烯酸（5 0 · 0 重量份）、5，000克甲基丙烯腈（50 .0重量份）和17克（0 · 17 重量份）甲基丙烯酸烯丙酯的混合物中。40克（0.40重量份） 過特戊酸第三丁酯、3 · 6克（0 . 〇 3 6重量份）過-乙基己酸 第三丁酯、10克（0.10重量份）過苯甲酸第三丁酯、10.3 克（0 · 103重量份）過新癸酸異丙苯酯、400克（4 . 0重量份 )Degalan BM 310(高分子量聚甲基丙烯酸甲酯）、〇.5克 - 1 8 - 200304443 (0.005重量份）苯醒和16.0克（〇·32重量份）PAT 1037(銷 售· E. and P. Wurtz GmbH & Co. KG, Industriegebiet， In der Weide 13 + 18，55411 Bingen，Sponsheim)作爲脫模劑 是進一步添加到混合物中。 將5克粒徑爲< 1 5微米的S i 〇2顆粒（石英粉，商標名爲Become a molded product or a semi-finished product. These include, in particular, the so-called GMT and SMC. Also known are carbon fiber reinforced plastics, which are particularly suitable as outer layers. -16-200304443 The thickness of the outer layer preferably ranges from 0.1 to 100 mm, and more preferably ranges from 0.5 to 10 mm. To improve adhesion, adhesives can also be used. This is not necessary and depends on the material of the outer layer. The poly (meth) acrylamidoimide according to the present invention can also be converted into a sandwich structure by, for example, the above-mentioned methods, such as RTM (resin transfer molding method), RIM (resin impregnation molding method), SCRIMP (Seeman resin) Dip molding method TM) or VAR I (vacuum assisted resin impregnation method). These methods are particularly advantageous in that the weight of the structural material can be avoided by using the fine-cell foamed body of the present invention. In this view, since the resin absorbed by the foam can be measured by the following methods: A known volume of cavity (such as a rectangle) is cut into a PLEXIGLAS® sheet of sufficient thickness. The circular contour is cut into PLEXIGLAS cymbals to surround this cavity, and a sealed cord is placed in this contour. The cavity is connected to the vacuum pump via a borehole and to a container containing vegetable oil via a second borehole. Both inlets can be blocked by using a stopcock. The cavity is sealed with another PLEXIGLAS® sheet of the same thickness. To measure all cavities, weigh the cavities, so you can measure the weight of PLEXIGLAS® tablets. The cavity is then filled with vegetable oil by first evacuating the cavity to 0.2 bar and then sucking the oil by using a vacuum until the cavity is completely filled. The weight of the filled measuring system is then determined. The volume of the cavity can be determined from the increased weight and oil density. To be able to determine the porosity of a foam, place a sample of the known size of the hair-17-200304443 into the cavity, seal the cavity and apply a vacuum, and set the measurement system as above Said refilling with oil. The foam specimen is here kept at a distance from the edge of the cavity by using a spacer to ensure that the pores are sufficiently filled. The inherent weight of the spacer may be included in a blank measurement as described above. The volume difference and the volume replaced by the sample can be calculated from the mass difference between the blank measurement and the measurement with the sample, with the aid of the density of the oil. This volume is lower than the volume of the sample, and its pore structure is negligible. The volume of the open pores on the surface of the test piece can be calculated from the difference between the volumes of these two displacements. The added weight of the sample due to the resin absorption can then be calculated from knowledge of the resin density. The poly (meth) acrylamide imide foam according to the present invention and, particularly, a laminated material containing such a foam are useful in, for example, aircraft construction and construction for ships, railcars, or automobiles. (IV) Embodiments Example 1 · 290 g (2.9 parts by weight) of isopropanol and 290 g (2.9 parts by weight) of metformin were added as a foaming agent to a kind containing 5,000 g of methacrylic acid (50% · 0 parts by weight), 5,000 g of methacrylonitrile (50.0 parts by weight), and 17 g (0. 17 parts by weight) of allyl methacrylate. 40 g (0.40 parts by weight) tert-butyl pervalerate, 3.6 g (0.03 parts by weight) per-ethylhexanoic acid tert-butyl ester, 10 g (0.10 parts by weight) perbenzoic acid Third butyl ester, 10.3 g (0.013 parts by weight) cumyl perdecanoate, 400 g (4.0 parts by weight) Degalan BM 310 (high molecular weight polymethyl methacrylate), 0.5 g -1 8-200304443 (0.005 parts by weight) benzophenone and 16.0 grams (0.32 parts by weight) PAT 1037 (sale · E. and P. Wurtz GmbH & Co. KG, Industriegebiet, In der Weide 13 + 18,55411 Bingen, Sponsheim) as a release agent is further added to the mixture. 5 g of Si particles (quartz powder, trade name:
Mikrosil®LM300，售自 Euroquarz GmbH， Kirch-hellener Allee 53，46282 Dorsten)作爲晶核生成劑添加到混合物 中〇 將混合物加以攪拌直到均一爲止，且接著在由兩玻璃板（ 尺寸爲50x 50公分，框架厚度爲2 . 3公分）所形成的箱中 ，在3 9 °C下進行聚合反應爲期18.5小時。接著將聚合物經 歷在所設定的程序下，從40擴展至115°C爲期17.25小時 至進行最後的聚合反應。後續的發泡是在20 5 °C進行爲期2 小時。 以此方法所獲得的發泡體的密度爲77 kg/m3。以此方法 所獲得發泡體的樹脂吸收藉由上述方法所測得爲0 . 〇 6 1 kg/m2 〇 實施例2 根據實施例1所述的步驟’例外的是使用25克 MikrosH⑧LM3 00作爲晶核生成劑。以此方法所獲得發泡體 的密度爲7 4 kg / m3。以此方法所獲得發泡體的樹脂吸收藉 由上述方法所測得爲〇 . 0 8 7 kg/m2 ° 竇施例3 根據實施例1所述的步驟，例外的是使用50克Mlkr0Sl1® -19 一 200304443 LM3 0 0作爲晶核生成劑。以此方法所獲得發泡體的密度爲 8 2kg/m3。以此方法所獲得發泡體的樹脂吸收藉由上述方法 所測得爲0 . 1 1 6 k g / m2。 比較例3 根據實施例所述的步驟，例外的是並未使用晶核生成劑 。以此方法所獲得發泡體的密度爲77kg/m3。以此方法所獲 得發泡體的樹脂吸收藉由上述方法所測得爲0 . 287k2/m2 °Mikrosil® LM300, sold from Euroquarz GmbH, Kirch-hellener Allee 53, 46282 Dorsten) was added to the mixture as a crystal nucleating agent. The mixture was stirred until homogeneous, and then was passed through two glass plates (50x 50 cm in size, The thickness of the frame was 2.3 cm), and the polymerization reaction was carried out at 39 ° C for 18.5 hours. The polymer was then extended from 40 to 115 ° C for 17.25 hours under the set procedure to the final polymerization reaction. Subsequent foaming was performed at 20 5 ° C for 2 hours. The density of the foam obtained in this way was 77 kg / m3. The resin absorption of the foam obtained in this way was measured by the above method to be 0.06 kg / m2. Example 2 The procedure according to Example 1 was used except that 25 g of MikrosH⑧LM3 00 was used as the crystal. Nuclear generator. The density of the foam obtained in this way was 74 kg / m3. The resin absorption of the foam obtained in this way was 0.08 7 kg / m2 ° as measured by the method described above. Example 3 According to the procedure described in Example 1, with the exception of using 50 g of Mlkr0Sl1®- 19 A 200304443 LM3 0 0 as a crystal nucleating agent. The density of the foam obtained by this method was 8 2 kg / m3. The resin absorption of the foam obtained in this way was measured to be 0.116 kg / m2 by the above method. Comparative Example 3 According to the procedure described in the example, the exception was that no crystal nucleating agent was used. The density of the foam obtained in this way was 77 kg / m3. The resin absorption of the foam obtained by this method was 0.287 k2 / m2 ° as measured by the above method.
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