TW200734387A - Process for preparing organically modified layered double hydroxide - Google Patents

Abstract

The invention relates to a process for preparing an organically modified layered double hydroxide having a distance between the individual layers of the layered double hydroxide of above 1.5 nm and comprising an organic anion as charge-balancing anion, the process comprising the steps of: (a) preparing a precursor suspension comprising a divalent metal ion source and a trivalent metal ion source;(b) solvothermally treating the precursor suspension to obtain the layered double hydroxide, wherein an organic anion is added before or during the formation of the layered double hydroxide of step (b), or following the formation of the layered double hydroxide, so as to obtain the organically modified layered double hydroxide, with the proviso that deoxycholic acid is not the sole organic anion.; The invention further pertains to a process for preparing an organically modified layered double hydroxide having a distance between the individual layers of the layered double hydroxide of above 1.5 nm and comprising an organic anion as charge-balancing anion, the process comprising the steps of: (a) preparing a precursor suspension comprising a divalent metal ion source and a trivalent metal ion source; (b) thermally treating the precursor suspension to obtain the layered double hydroxide, wherein an organic anion is added before or during the formation of the layered double hydroxide of step (b), or following the formation of the layered double hydroxide, so as to obtain the organically modified layered double hydroxide, with the proviso that in step a) the trivalent metal ion source is not reacted with the organic anion at a temperature of between 60 and 85 DEG C for 4 to 8 hours prior to the addition of the divalent metal ion source and step b) is subsequently carried out at a temperature of 90 to 95 DEG C for 4 to 8 hours.

Description

200734387 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種製備包含聚合物及經改質層狀雙氫氧 化物之奈米複合材料之方法。本發明進一步係關於由該方 法製得之奈米複合材料。 【先前技術】 用於製備奈米複合材料之方法在此項技術中為已知的。200734387 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method of preparing a nanocomposite comprising a polymer and a modified layered double hydroxide. The invention further relates to nanocomposites made by the process. [Prior Art] Methods for preparing nanocomposites are known in the art.

WO 99/35185、US 6,812,273、DE 198 36 580 及 US 2003/0114699揭示經有機改質之層狀雙氫氧化物在各種聚 合基質中之用途。然而，該等參考文獻均未提及聚合基質 為橡膠。 JP 2004/284842揭示以三嗪二硫醇及/或三硫醇化合物改 質之LDH在含自素聚合物中之用途。在此參考文獻中揭示 之二嗪二硫酵及三硫醇化合物作為交聯劑，且其特別適合 作用於含鹵素聚合物之交聯劑。該等硫醇化合物通常不易 併入該LDH中且僅可用於有限數目之橡膠。 【發明内容】 本發明之一目的在於提供一種包含具有改良物理性質之 橡膠的奈米複合材料。 此目的係由包含橡膠及經改質層狀雙氫氧化物之奈米複 合材料達成，該奈米複合材料包含： 具有第一官能基及第二官能基之電荷平衡之有機離子， 其中有機陰離子之至少部分經由該第二官能基化學連接至 橡膠；及/或 116928.doc 200734387 具有至少一烷氧基矽烷基及至少一反應性基團之矽烷偶 合劑，該烷氧基矽烷基經化學連接至該層狀雙氫氧化物， 該反應性基團經化學連接至該橡膠。 與習知奈米複合材料相比，該等奈米複合材料具有改良 之熱穩定性、更佳尺寸穩定性、改良之撕裂強度、改良之 抗刮性、增大之阻燃性及/或改良之強度/重量比。該材料 進一步展現對諸如氮、二氧化碳、氧、水蒸氣及烴之氣體The use of organically modified layered double hydroxides in various polymeric matrices is disclosed in WO 99/35185, US 6,812,273, DE 198 36 580 and US 2003/0114699. However, none of these references mentions that the polymeric matrix is a rubber. JP 2004/284842 discloses the use of LDH modified with triazine dithiol and/or trithiol compounds in a self-containing polymer. The diazine dithiol and trithiol compounds disclosed in this reference serve as crosslinking agents, and are particularly suitable for crosslinking agents containing halogen-containing polymers. These thiol compounds are generally not readily incorporated into the LDH and are only useful for a limited number of rubbers. SUMMARY OF THE INVENTION An object of the present invention is to provide a nanocomposite comprising a rubber having improved physical properties. The object is achieved by a nanocomposite comprising a rubber and a modified layered double hydroxide, the nano composite comprising: an organic ion having a charge balance of a first functional group and a second functional group, wherein the organic anion At least partially chemically linked to the rubber via the second functional group; and/or 116928.doc 200734387 a decane coupling agent having at least one alkoxyalkyl group and at least one reactive group, the alkoxy fluorenyl group being chemically linked To the layered double hydroxide, the reactive group is chemically bonded to the rubber. Compared to conventional nanocomposites, such nanocomposites have improved thermal stability, better dimensional stability, improved tear strength, improved scratch resistance, increased flame retardancy, and/or Improved strength/weight ratio. The material further exhibits gases such as nitrogen, carbon dioxide, oxygen, water vapor and hydrocarbons.

及/或液體降低之滲透性。存在於本發明之奈米材料中之 LDH可進一步吸附及/或吸收在聚合物之聚合作用中所使 用之添加劑或引發劑之副產物。另外，與不包含本發明之 黏土的純橡膠材料相比，本發明之奈米複合材料顯示改良 之斷裂伸長率及斷裂強度。此外，該橡膠奈米複合材料在 恆定力下變形之過程中顯示更佳的動力學性質（例如較低 損耗因子（tan delta))，因此展示改良之黏彈性質，其通常 使包含該橡膠材料之輪胎具有較低熱累積且可得到較低滾 動二力。術語”損耗因子”對於熟f者為已知的，且經定義 為損失模數（G，）與儲存模數（G")之比率。 在本申請案之上下文中，術語"奈米複合材料"係指其中 至少一組份包含具有至少在〇」 iuo不未靶圍内之尺寸的 相之複合材料。另外，術語"橡膠奈米複合材料"係指 包S橡膠之奈米複合材料。 Μ 在本申請案之上下文中，術語， 指補償姓曰u 电何千衡之有機離子”係 伯補1貝、、、口日日LDH薄片之靜電雷共从 LDH、* -目士 ^電何缺乏的有機離子。由於 H通吊具有層狀結構，所以該等 、 ^寺電何平衡之有機離子可 116928.doc 200734387 位於堆疊LDH層之層間、邊緣或外表面上。位於堆疊ldh 層之層間中的該等有機離子被稱作插層離子。以電荷平衡 之有機離子處理之LDH提供親有機物性且亦稱作”有機黏 土"。 該堆疊LDH或有機黏土亦可（例如）在聚合基質中分層或 剝落。在本說明書之上下文中，術語”分層”係經定義為藉 由LDH結構之至少部分去層的LDH顆粒之平均堆疊度之減 小，進而產生每體積含有顯著更多個別LDH薄片之材料。 術§吾π剝洛"係經定義為完全分層，亦即在垂直於Ldh薄片 方向中週期性消失，其導致個別層在介質中隨機分散，進 而未留下任何堆疊次序。 LDH之膨脹或擴展（亦稱作LDH之插層）可由X射線繞射 (XRD)觀測，因為基面反射（亦即d(⑽/)反射）之位置指示層 之間的距離，該距離在插層後增大。 平均堆疊度之減小可觀測為XRD反射加寬直至消失，或 基面反射（0 0 /)之不對稱性增加。 完全分層（亦即剝落）之表徵存在分析挑戰，但通常可自 原始LDH之非（/2A0)反射之完全消失來推斷。 層之次序且因此分層之程度可進一步藉由透射電子顯微 鏡（TEM)來顯現。 本發明之LDH可為熟習此項技術者已知之任何LDH。通 常，該等LDH為能夠擴展或膨脹之無機LDH。該等LDH具 有一電荷平衡之陰離子夾層於其之間之包含帶電荷結晶薄 片（亦稱作個別LDH層）的層狀結構。在本申請案之上下文 116928.doc 200734387 中術語，，擴展，，及"膨脹，，係指帶電荷結晶薄片之間之距離的 增加。可擴展LDH可在例如水之適合溶劑中膨脹且可藉兩 以其他（有機）電荷平衡之離子交換該等電荷平衡之離子而 進一步擴展且改質，該改質在此項技術中亦稱作插層。 亦稱作LDH之經改質層狀雙氫氧化物具有對應於以下通 式之層狀結構： M2；M3；(0H)2m+2n]x-.bH20 (I) 其中 M2+為諸如 Zn2+、Mn2+、Ni2+、Co2+、Fe2+、Cu2+、And / or liquid reduced permeability. The LDH present in the nanomaterial of the present invention can further adsorb and/or absorb by-products of additives or initiators used in the polymerization of the polymer. Further, the nanocomposite of the present invention exhibits improved elongation at break and breaking strength as compared with a pure rubber material not containing the clay of the present invention. In addition, the rubber nanocomposite exhibits better dynamic properties (eg, lower delta) during deformation under constant force, thus exhibiting improved viscoelastic properties, which typically result in the inclusion of the rubber material The tires have a lower heat build-up and a lower rolling force. The term "loss factor" is known to those skilled in the art and is defined as the ratio of the loss modulus (G,) to the storage modulus (G"). In the context of this application, the term "nanocomposite" refers to a composite material in which at least one of the components comprises a phase having a size at least not within the target. In addition, the term "rubber nanocomposite" refers to a nanocomposite of S rubber. Μ In the context of this application, the term refers to the compensation of the organic ion of the surname 曰u, He Qianheng, the electric ray of the LDH sheet, the LDH, and the LDH sheet. Organic ions. Since the H-pass has a layered structure, the organic ions of the balance can be located on the interlayer, edge or outer surface of the stacked LDH layer. These organic ions are referred to as intercalated ions. The LDH treated with charge-balanced organic ions provides organophilicity and is also known as "organic clay". The stacked LDH or organic clay can also be layered or spalled, for example, in a polymeric matrix. In the context of this specification, the term "layering" is defined as the reduction in the average stacking degree of LDH particles de-layered by at least partial LDH structure, thereby producing a material containing significantly more individual LDH flakes per volume. The rule is defined as complete delamination, i.e., periodically disappearing perpendicular to the direction of the Ldh sheet, which causes the individual layers to be randomly dispersed in the medium without leaving any stacking order. The expansion or expansion of LDH (also known as the intercalation of LDH) can be observed by X-ray diffraction (XRD) because the position of the base reflection (ie, d((10)/) reflection) indicates the distance between the layers, which is Increase after inserting. The decrease in the average stacking degree can be observed as the XRD reflection widens until it disappears, or the asymmetry of the base reflection (0 0 /) increases. The characterization of complete stratification (ie, flaking) presents analytical challenges, but can usually be inferred from the complete disappearance of the non-(/2A0) reflection of the original LDH. The order of the layers and thus the degree of delamination can be further visualized by transmission electron microscopy (TEM). The LDH of the present invention can be any LDH known to those skilled in the art. Typically, the LDHs are inorganic LDHs that are capable of expanding or expanding. The LDHs have a charge-balanced anion sandwich between them comprising a layered structure of charged crystalline flakes (also referred to as individual LDH layers). The terms, extensions, and "expansion," in the context of the present application, 116928.doc 200734387, refer to an increase in the distance between charged crystalline sheets. The expandable LDH can be expanded in a suitable solvent such as water and can be further expanded and modified by the exchange of two (organic) charge-balanced ions for the ion-balanced ions, also known in the art. Intercalation. The modified layered double hydroxide, also known as LDH, has a layered structure corresponding to the following formula: M2; M3; (0H)2m+2n]x-.bH20 (I) wherein M2+ is such as Zn2+, Mn2+ , Ni2+, Co2+, Fe2+, Cu2+,

Sn2+、Ba2+、Ca2+及Mg2+之二價金屬離子，M3+為諸如Divalent metal ions of Sn2+, Ba2+, Ca2+, and Mg2+, such as M3+

Al3+、Cr3+、Fe3+、Co3+、Mn3+、Ni3+、Ce3 +及 Ga3 +之三價 金屬離子’ m及n具有使得m/n=l至l〇之值，且b具有在〇至 1 〇之範圍内之值。X可為热習此項技術者已知之任何適合 的陰離子。通常，X為如以下例示之無機陰離子及/或具有 或不具有第一官能基之有機陰離子。在本發明之一實施例 中，X為具有第一官能基及第二官能基之電荷平衡之有機 離子或熟習此項技術者已知之任何其他陰離子，限制條件 為插層離子的至少部分係由具有第一官能基及第二官能基 之有機離子形成。此項技術中已知之其他陰離子之實例包 括氫氧根，碳酸根，碳酸氫根，硝酸根，氣離子，溴離 子，磺酸根，硫酸根，硫酸氫根，釩酸根，鎢酸根，硼峻 根，磷酸根，諸如 HV04.、V2〇74·、HV2〇i24-、ν3〇93·、 Vn)〇286·、Μο7〇246·、PWl2〇4()3_、Β(〇Η)4·、Β4〇5(〇η)42、 [Β3〇3(〇Η)4]·、[Β303(0η)5]2-、ηΒ〇42·、HGa〇32·、Cr〇斤 之柱撐陰離子，及Keggin離子。其他陰離子亦包括不包含 116928.doc 200734387 第- S此基之有機陰離子，諸如單緩酸根、二叛酸根或聚 羧酉文根’ I膦酸根、二膦酸根或聚膦酸根，丨硫酸根、二 硫酸根或聚硫酸根，及單續酸根、二續酸根或聚績酸根。 本發明之LDH包括水滑石陰離子型£〇11及類水滑石陰離 子型LDH。該等LDH之實例為水滑石材料及類水滑石材 料、羥鎂鋁石、水鎂鋁石、碳鎂鐵礦、水鎂鐵石 (sjagrenite)、碳鎂鉻礦、水鎂鉻礦、水鋁鎳石、水碳鐵鎳 石及水碳錳鎂石。較佳LDH為水滑石，其為具有對應於以 下通式之層狀結構的LDH : [Mg2；Al3；(〇H)2m+2n]x2n-2.bH20 (π) 其中m及η具有使得m/nM至1〇、較佳為1至6之值，且匕具 有在0至10範圍内之值，通常為2至6之值，且經常約4之 值 X為如以上疋義之電荷平衡之離子。較佳地，m/n應具 有2至4之值，更特定言之接近3之值。 LDH可呈諸如由 Cavani等人TWa少，11 (1991)， 第 173-301 頁）或由 Bookin 等人（LD% ㈣d [D77 Μζ·加mAj， (1993)，第41卷（5)，第558-564頁）所描述之此項技術中已 知之任何晶體形式。若LDH為水滑石，則該水滑石可為 (例如）具有3仏、3H2、31^或3112堆疊之多型體。 在LDH基有機黏土中個別LDH層之間的距離通常大於不 含根據本發明之有機陰離子（例如碳酸根離子）之習知LDH 之層之間的距離。較佳地，根據本發明之LDH中層之間的 距離為至少1 ·〇 nm、更佳至少1.5 nm且最佳至少2 nm。如 先前概述，個別層之間的距離可使用X射線繞射來測定。 116928.doc -10- 200734387 根據本發明之電荷平衡之有機離子包含第一官能基及第 二官能基。該第一官能基為能夠與1^)11相互作用之陰離子 型基團。該等第一官能基之實例為羧酸根、硫酸根、磺酸 根、硝酸根、磷酸根及膦酸根。該第二官能基能夠與橡膠 或橡膠前驅物形成化學連接。該等第二官能基之實例為丙 烯酸酯基、曱基丙烯酸酯基、羥基、氯化物基、溴基、胺 基、％氧基、硫醇基、乙烯基及多硫化物基、胺基曱酸酯 基、銨、磺酸基、亞磺酸基、疏、鳞、一元膦酸基、異氰 酸酯基、氫化物基、醯亞胺基、亞硝基苄基、二亞硝基苄 基、紛基、乙醯氧基及酐基。有機陰離子通常具有至少2 個碳原子、較佳至少6個碳原子、甚至更佳至少8個碳原子 且最佳至少10個碳原子，且通常至多1，000個碳原子、較 佳至多500個碳原子，且最佳至多1〇〇個碳原子。根據本發 明之有機陰離子之適合實例包括8_胺基辛酸根、胺基十 一烧酸根、3-(丙烯醯基氧基）丙酸根、4-乙烯基苯曱酸 根、8-(3-辛基-2-axiranyl)辛酸根，及由不飽和脂肪酸衍生 之有機陰離子（諸如油酸根）及由不飽和動物脂酸衍生之陰 離子。亦涵蓋使用包含上述有機陰離子之一或多者或不包 含第二官能基之其他有機陰離子的本發明之LDH。該等其 他有機陰離子之實例在此項技術中為已知的且包括單羧酸 根、二羧酸根或多羧酸根，單磺酸根、二磺酸根或多磺酸 根’單膦酸根、二膦酸根或多膦酸根，及單硫酸根、二硫 酸根或多硫酸根。 通常，在根據本發明之改質LDH中之插層離子的總數的 116928.doc 200734387 至少10%會為本發明之有機陰離子。較佳地，插層離子之 總數的至少30%、更佳至少60%且最佳至少90%為有機陰 離子。 本發明之LDH亦可使用具有至少一烧氧基石夕烧基及至少 一反應性基團之矽烷偶合劑改質，該烷氧基矽烷基經化學 連接至層狀雙氫氧化物，該反應性基團經化學連接至橡 膠。該反應性基團可為與以上定義之第二官能基相同之基 團。該等矽烷偶合劑之實例為雙（3-三乙氧基矽烷基丙基） 四硫化物（得自Degussa之Si69®)、雙（3_三乙氧基矽烷基丙 基）二硫化物、γ-巯基丙基三甲氧基矽烷（得自PCC之SiSiB® PC23 00)及3-辛醯基硫基·ι_丙基_三乙氧基矽烷（得自之 NXT™)。 石夕烧偶合劑之量為使得奈米複合材料中之改質LDH的至 少部分經化學連接至橡膠。若該橡膠為除聚矽氧橡膠之外 的橡膠，則矽烷偶合劑之量通常為以改質LDH之總重量計 至少〇·5重量％，較佳至少1重量％，且最佳至少5重量％， 且石夕烧偶合劑之量通常為以改質LDH之總重量計至多50重 量％ ’較佳至多40重量％，且最佳至多30重量％。 若橡膠為聚矽氧橡膠，則矽烷偶合劑之量通常為以改質 LDH之總重量計至少10重量％，較佳至少20重量％，且最 佳至少30重量％，且矽烷偶合劑之量通常為以改質ldh之 總重量計至多99重量％，較佳至多9〇重量％，且最佳至多 8 0重里/〇在本發明之一實施例中，LDH係以石夕烧偶合劑 改質且進一步包含電荷平衡之有機陰離子，且尤其包含如 116928.doc 12 200734387 以上定義之第一官能基及第二官能基之有機陰離子。 在奈米複合材料中本發明之LDH之量較佳為以奈米複合 材料之總重量計G.G1_75重量％、更佳〇.〇5_6〇重量％，甚至 更佳0.1-50重量％。 -本I明之橡膠_LDH奈米複合材料可進一步包含此項技 術中吊用之添加劑。該等添加劑之實例為顏料、染料、 UV穩疋劑、熱穩定劑、抗氧化劑、填料（諸如羥基磷灰 石、石夕;5、石夕燒偶合劑、相容劑、油、虫鼠、碳黑、玻璃纖 維聚合物纖維、非插層之黏土及其他無機材料）、阻燃 增塑劑、流變改質劑、交聯劑及除氣劑。另一常用添 Μ為牦里油。亦涵蓋在將此混合物添加至橡膠中之前將 改質LDH與增量油混合。此具有將改質ldh分散於油中且 可容易S更均-地混合入橡膠中之優點。 忒等可選附加物及其相應量可根據需要選擇。 本發明進一步係關於一種母體混合物（masterbatch)，亦 φ #包含橡膠或橡膠前驅物及包含具有第-官能基及第二官 月b基之電何平衡之有機離子之經改質層狀雙氫氧化物及/ 或具有至少-烧氧基石夕燒基及至少一反應性基團之石夕燒偶 合劑的高度濃縮的添加劑預混合物，其中經改質層狀雙氫 氧化物之里為以該母體混合物之總重量計介於丨〇重量％與 70重篁％之間’且橡膠之量為以該母體混合物之總重量計 "於30重里/〇與90重垔％之間。較佳地，改質ldh之量為 以母體心a物之總重I計介於丨5重量％與75重量％之間， 且橡膠或橡膠前驅物之量為介於25重量％與85重量％之 116928.doc 200734387 間。該等母體混合物可包含分層或剝落之本發明之lDH。 然而，若該等母體混合物中之LDH未完全分層，貝彳（若需 要）當將母體混合物與橡膠及/或另一橡膠或聚合物摻合以 獲得橡膠基奈米複合材料時，在隨後階段可達成進一步分 層。另外或其他，改質LDH之有機陰離子的至少部分可經 由第二官能基化學連接至橡膠或橡膠前驅物。 本發明進一步係關於一種製備根據本發明之橡膠前驅物 或奈米複合材料的方法，該方法包含以下步驟： al)將視情況與第一溶劑混合之經改質層狀雙氫氧化物添 加至包含一或多種聚合物及視情況第二溶劑之橡膠前 驅物中；或 a2)將視情況與第一溶劑混合之經改質層狀雙氫氧化物添 加至包含橡膠前驅物之一或多種單體及視情況第二溶 劑之橡膠組合物中，且使該等單體聚合以形成橡膠前 驅物； b) 在父聯劑存在下視情況使橡膠前驅物交聯以形成奈米 複合材料；及 c) 視情況在步驟ai)、a2)&b)之任一者期間或之後移除第 一溶劑及/或第二溶劑。 本發明之方法包含兩個替代性步驟al)&a2)。在步驟al) 中，視情況與第一溶劑混合之改質LDH可添加至橡膠前驅 物中，在改質微粒材料與橡膠前驅物之間未發生反應。或 者，改質LDH之添加在有機陰離子的至少部分經由第二官 能基與橡膠前驅物反應之該等條件下進行。在由步驟al) 116928.doc •14- 200734387 產生之組合物固化之後，未與橡膠前驅物反應之剩餘有機 陰離子可至少部分地化學連接至橡膠。 在步驟a2)中，將視情況與第一溶劑混合之改質LDH添 加至橡膠前驅物之一或多種單體中，該等單體隨後得以聚 合。視聚合條件及所選有機陰離子而定，有機陰離子之至 少部分在其聚合過程中經由第二官能基與單體反應，使得 LDH化學連接至橡膠前驅物。或者，在步驟b)中前驅物固 化後’包含第二官能基之有機陰離子之至少部分可與橡膠 前驅物反應，使得改質LDH化學連接至橡膠組合物。 應注意經有機改質LDH之剝落及/或分層可發生在步驟 al)、a2)及b)之任一者中。 在本發明之方法之一實施例中，將改質LDH或母體混合 物添加至橡膠前驅物中，同時橡膠前驅物保持在其為流體 之溫度下。以此方式，確保LDH或母體混合物容易混合於 第一聚合物或第二聚合物中，使得能夠在甚至更短時間内 奈米尺寸之LDH顆粒遍及聚合物均一分佈，使該方法更具 經濟吸引力。該等混合及/或混料步驟可以分批方法（例如 在Banbury混合器或在雙輥筒研磨機中）或以連續模式（例如 在管式反應器、諸如（共旋轉）雙螺桿擠壓機或單螺桿擠壓 機之擠壓機或Buss捏合機（往復式單螺桿擠壓機）及犁式混 合器中）實施。 在本申請案之上下文中，術語"混料”係指藉由施加於聚 合物基混合物上之足夠剪切應力混合在一起以將微米尺寸 之改質LDH顆粒之至少部分轉變為奈米尺寸之顆粒的作 116928.doc -15- 200734387 用。此剪切應力可藉由混合聚合物基混合物於（例 如）Banbury混合器或擠壓機中來施加。 可將在本發明之方法中使用之改質LDH減小尺寸，之後 在步驟al)或a2)中將其添加。改質LDH可具有小於20 μιη之 d50值及小於50 μπα之d90值。較佳地，d50值小於15 μιη且 d90值小於40 μιη，更佳地，d50值小於10 μπι且d90值小於 3 0 μιη，甚至更佳地，d50值小於8 μπι且d90值小於20 μηι， 且最佳地，d50值小於6 μπι且d90值小於10 μιη。粒徑分佈 可使用熟習此項技術者已知之方法來測定，例如使用根據 DIN 13320之雷射繞射測定。使用具有此較小粒徑分佈之 LDH能使改質LDH遍及膠奈米複合材料良好混合以及使改 質LDH更易剝落及/或分層。 適用於本發明之方法中之改質LDH的粒徑分佈可由用於 減小諸如LDH之無機材料之粒徑的此項技術中已知之任何 方法獲得。該等方法之實例為濕式研磨及乾式研磨。或 者，如由WO 02/085787所例示，該等改質LDH可在製備改 質LDH之過程中產生。 用於本發明之方法中之第一溶劑及第二溶劑可為適用於 此方法之任何溶劑且對於熟習此項技術者為已知的。該等 第一溶劑及/或第二溶劑可相同或不同且較佳為與經有機 改質LDH以及與橡膠前驅物、其單體及/或所得橡膠奈米 複合材料相容之溶劑。 第一溶劑及/或第二溶劑包括諸如甲醇、乙醇、異丙醇 及正丁醇之醇；諸如甲基戊基酮、甲基乙基酮、甲基異丁 116928.doc -16- 200734387 基酮及環己酮之酮；諸如乙酸乙酯及乙酸丁酯之酯；諸如 丙烯酸丁酯、甲基丙烯酸甲酯、二丙烯酸己二酯及三甲基 醇丙烷三丙烯酸酯之不飽和丙烯酸酯；諸如己烷、石油 醚、曱苯及二甲苯之芳族烴及非芳族烴；及諸如二丁醚、 四氫呋喃（THF)及曱基第三丁基醚（MTBE)之醚。 由本發明之方法製備之橡膠前驅物為在固化或硫化後可 轉變為橡膠之橡膠前驅物。該等橡膠前驅物以及其形成之 橡膠對於熟習此項技術者為已知的。 橡膠之實例包括天然橡膠（NR)、苯乙烯-丁二烯橡膠 (SBR)、聚異戊二烯（IR)、聚丁二烯或丁基橡膠（BR)、聚 異丁烯橡膠（IIR)、鹵化聚丁二烯橡膠、鹵化聚異丁烯橡 膠、腈丁二烯橡膠（NBR)、氫化腈丁二烯橡膠、苯乙烯-異 戊二烯-苯乙烯（SIS)及類似（氫化）苯乙烯類嵌段共聚物 (SBS、氫化SIS、氫化SBS)、聚（表氣醇）橡膠（CO、ECO、 GPO)、聚矽氧橡膠（Q)、氣丁二烯橡膠（CR)、乙丙橡膠 (EPM)、三元乙丙橡膠（ethylene propylene diene rubber)(EPDM)、敗橡膠（FKM)、乙烯-乙酸乙烯酯橡膠 (EVA)、乙烯基丁二烯橡膠、鹵化丁基橡膠、聚丙烯酸橡 膠（ACM)、聚降冰片烯（PNR)、聚胺基曱酸酯及聚酯/醚熱 塑性彈性體。較佳橡膠為天然橡膠、SBR、EPDM、鹵丁 基橡膠、丁二烯橡膠及聚矽氧橡膠。 在本發明之一實施例中，橡膠為聚矽氧橡膠。聚矽氧橡 膠之製造對於熟習此項技術者通常為已知的，且描述於例 如 Silicones, Kirk Othmer Encyclopedia of Chemical Technology, 116928.doc -17- 200734387The trivalent metal ions 'm and n of Al3+, Cr3+, Fe3+, Co3+, Mn3+, Ni3+, Ce3+, and Ga3+ have values such that m/n = l to l〇, and b has a range from 〇 to 1 〇 The value. X can be any suitable anion known to those skilled in the art. Usually, X is an inorganic anion as exemplified below and/or an organic anion having or not having a first functional group. In one embodiment of the invention, X is an organic ion having a charge balance of a first functional group and a second functional group or any other anion known to those skilled in the art, with the proviso that at least a portion of the intercalated ions are An organic ion having a first functional group and a second functional group is formed. Examples of other anions known in the art include hydroxide, carbonate, bicarbonate, nitrate, gas ion, bromide, sulfonate, sulfate, hydrogen sulfate, vanadate, tungstate, boron , phosphate, such as HV04., V2〇74·, HV2〇i24-, ν3〇93·, Vn)〇286·, Μο7〇246·, PWl2〇4()3_, Β(〇Η)4·,Β4 〇5(〇η)42, [Β3〇3(〇Η)4]·, [Β303(0η)5]2-, ηΒ〇42·, HGa〇32·, the pillar anion of Cr〇, and Keggin ion. Other anions also include organic anions that do not contain 116928.doc 200734387 S-S, such as mono-hypo-acid, di- ortho- or dicarboxylated, 'phosphonic acid, bisphosphonate or polyphosphonate, bismuth sulphate, Sulfate or polysulfate, and a single acid, a second acid or a polyacid. The LDH of the present invention comprises hydrotalcite anionic type 11 and hydrotalcite-like anionic type LDH. Examples of such LDHs are hydrotalcite materials and hydrotalcite-like materials, hydroxyaluminite, bauxite, carbon magnesium iron ore, sjagrenite, carbon magnesium chromite, hydromagnesite, water aluminum nickel. Stone, water carbon iron nickel stone and water carbon manganite. Preferably, LDH is hydrotalcite which is an LDH having a layered structure corresponding to the following general formula: [Mg2; Al3; (〇H) 2m+2n] x2n-2.bH20 (π) wherein m and η have such /nM to 1〇, preferably a value of 1 to 6, and 匕 has a value in the range of 0 to 10, usually a value of 2 to 6, and often a value of about 4 X is a charge balance as described above. ion. Preferably, m/n should have a value of 2 to 4, more specifically a value close to 3. LDH can be presented as TWa by Cavani et al., 11 (1991), pp. 173-301) or by Bookin et al. (LD% (d) d [D77 Μζ·加mAj, (1993), vol. 41 (5), p. Any of the crystal forms known in the art are described on pages 558-564. If the LDH is hydrotalcite, the hydrotalcite can be, for example, a polytype having a stack of 3, 3, 2, 31 or 3112. The distance between individual LDH layers in an LDH-based organic clay is generally greater than the distance between layers of a conventional LDH that does not contain an organic anion (e.g., carbonate ion) according to the present invention. Preferably, the distance between the layers of the LDH according to the invention is at least 1 · 〇 nm, more preferably at least 1.5 nm and most preferably at least 2 nm. As previously outlined, the distance between individual layers can be determined using X-ray diffraction. 116928.doc -10- 200734387 The charge-balanced organic ion according to the present invention comprises a first functional group and a second functional group. The first functional group is an anionic group capable of interacting with 1^)11. Examples of such first functional groups are carboxylates, sulfates, sulfonates, nitrates, phosphates and phosphonates. The second functional group is capable of forming a chemical linkage with the rubber or rubber precursor. Examples of such second functional groups are acrylate groups, mercapto acrylate groups, hydroxyl groups, chloride groups, bromo groups, amine groups, % oxygen groups, thiol groups, vinyl and polysulfide groups, and amine groups. Acid ester group, ammonium, sulfonic acid group, sulfinic acid group, sparing, scaly, monobasic phosphonic acid group, isocyanate group, hydride group, quinone imine group, nitrosobenzyl group, dinitrosobenzyl group Base, ethoxylated and anhydride groups. The organic anion usually has at least 2 carbon atoms, preferably at least 6 carbon atoms, even more preferably at least 8 carbon atoms and most preferably at least 10 carbon atoms, and usually up to 1,000 carbon atoms, preferably up to 500 A carbon atom, and optimally up to 1 carbon atom. Suitable examples of organic anions according to the invention include 8-aminooctanoate, aminoundecanoate, 3-(acrylenyloxy)propionate, 4-vinylbenzoate, 8-(3-octyl) Alkyl-2-axiranyl)octanoate, and an organic anion derived from an unsaturated fatty acid (such as oleate) and an anion derived from an unsaturated animal fatty acid. Also contemplated is the use of an LDH of the invention comprising one or more of the above organic anions or other organic anions that do not comprise a second functional group. Examples of such other organic anions are known in the art and include monocarboxylate, dicarboxylate or polycarboxylate, monosulfonate, disulfonate or polysulfonate 'monophosphonate, bisphosphonate or Polyphosphonate, and monosulfate, disulfate or polysulfate. Typically, at least 10% of the total number of intercalated ions in the modified LDH according to the present invention will be at least 10% of the organic anion of the present invention. Preferably, at least 30%, more preferably at least 60% and most preferably at least 90% of the total number of intercalated ions are organic anions. The LDH of the present invention may also be modified with a decane coupling agent having at least one alkoxy group and at least one reactive group which is chemically bonded to the layered double hydroxide, the reactivity The group is chemically attached to the rubber. The reactive group may be the same group as the second functional group defined above. Examples of such decane coupling agents are bis(3-triethoxydecylpropyl) tetrasulfide (Si69® from Degussa), bis(3-triethoxydecylpropyl) disulfide, Gamma-mercaptopropyltrimethoxydecane (SiSiB® PC23 00 from PCC) and 3-octylthiol·ι_propyl-triethoxydecane (from NXTTM). The amount of the sulphur coupling agent is such that at least a portion of the modified LDH in the nanocomposite is chemically bonded to the rubber. If the rubber is a rubber other than polyoxyxene rubber, the amount of the decane coupling agent is usually at least 〇 5% by weight, preferably at least 1% by weight, and most preferably at least 5 parts by weight based on the total weight of the modified LDH. %, and the amount of the sulphur coupling agent is usually up to 50% by weight, preferably up to 40% by weight, and most preferably up to 30% by weight, based on the total weight of the modified LDH. If the rubber is a polyoxyxene rubber, the amount of the decane coupling agent is usually at least 10% by weight, preferably at least 20% by weight, and most preferably at least 30% by weight, based on the total weight of the modified LDH, and the amount of the decane coupling agent. Usually up to 99% by weight, preferably up to 9% by weight, and most preferably up to 80% by weight, based on the total weight of the modified ldh. In one embodiment of the invention, the LDH is modified with a sulphur coupling agent. And further comprising a charge-balanced organic anion, and especially comprising an organic anion such as a first functional group and a second functional group as defined above in 116928.doc 12 200734387. The amount of the LDH of the present invention in the nanocomposite is preferably G.G1_75 wt%, more preferably _5_6 〇 wt%, even more preferably 0.1-50 wt%, based on the total weight of the nanocomposite. - The rubber_LDH nanocomposite of the present invention may further comprise an additive for use in the art. Examples of such additives are pigments, dyes, UV stabilizers, heat stabilizers, antioxidants, fillers (such as hydroxyapatite, Shi Xi; 5, Shi Xi Shao coupling agent, compatibilizer, oil, pest, Carbon black, glass fiber polymer fiber, non-intercalated clay and other inorganic materials), flame retardant plasticizer, rheology modifier, crosslinker and deaerator. Another common addition is eucalyptus oil. It is also contemplated to mix the modified LDH with the extender oil prior to adding the mixture to the rubber. This has the advantage that the modified ldh is dispersed in the oil and can be easily and more uniformly mixed into the rubber. Optional add-ons such as 忒 and their corresponding amounts can be selected as needed. The invention further relates to a masterbatch, which also comprises a rubber or rubber precursor and a modified layered dihydrogen comprising an organic ion having a first functional group and a second functional group b. a highly concentrated additive premix of an oxide and/or a scouring coupler having at least an alkoxylated group and at least one reactive group, wherein the modified layered double hydroxide is The total weight of the parent mixture is between 丨〇% by weight and 70% by weight' and the amount of rubber is between 30 mph and 90% by weight based on the total weight of the parent mixture. Preferably, the amount of the modified ldh is between 5% and 75% by weight based on the total weight I of the parent core, and the amount of the rubber or rubber precursor is between 25% and 85% by weight. % of 116928.doc between 200734387. The parent mixture may comprise the layered or exfoliated lDH of the present invention. However, if the LDH in the parent mixture is not completely stratified, the shellfish (if needed) when the parent mixture is blended with the rubber and/or another rubber or polymer to obtain the rubber based nanocomposite, The stage can achieve further stratification. Additionally or alternatively, at least a portion of the organic anion of the modified LDH can be chemically coupled to the rubber or rubber precursor via a second functional group. The invention further relates to a process for the preparation of a rubber precursor or nanocomposite according to the invention, the process comprising the steps of: a) adding a modified layered double hydroxide, optionally mixed with a first solvent, to a rubber precursor comprising one or more polymers and optionally a second solvent; or a2) a modified layered double hydroxide, optionally mixed with a first solvent, added to one or more of the rubber precursors And optionally treating the second solvent in the rubber composition, and polymerizing the monomers to form a rubber precursor; b) crosslinking the rubber precursor in the presence of a parent binder to form a nanocomposite; c) removing the first solvent and/or the second solvent during or after either of steps ai), a2) & b) as appropriate. The method of the invention comprises two alternative steps a) & a2). In step a1, the modified LDH, optionally mixed with the first solvent, may be added to the rubber precursor without reaction between the modified particulate material and the rubber precursor. Alternatively, the addition of the modified LDH is carried out under conditions such that at least a portion of the organic anion is reacted with the rubber precursor via the second functional group. After curing of the composition resulting from step a) 116928.doc • 14- 200734387, the remaining organic anion that is not reacted with the rubber precursor can be at least partially chemically bonded to the rubber. In the step a2), the modified LDH mixed with the first solvent as the case may be added to one or more monomers of the rubber precursor, which are subsequently polymerized. Depending on the polymerization conditions and the selected organic anion, at least a portion of the organic anion reacts with the monomer via the second functional group during its polymerization, such that the LDH is chemically attached to the rubber precursor. Alternatively, at least a portion of the organic anion comprising the second functional group can be reacted with the rubber precursor after the precursor is solidified in step b) such that the modified LDH is chemically bonded to the rubber composition. It should be noted that spalling and/or delamination via organically modified LDH can occur in any of steps a), a2) and b). In one embodiment of the method of the invention, the modified LDH or parent mixture is added to the rubber precursor while the rubber precursor is maintained at the temperature at which it is a fluid. In this way, it is ensured that the LDH or the precursor mixture is easily mixed in the first polymer or the second polymer, so that the nano-sized LDH particles can be uniformly distributed throughout the polymer in an even shorter time, making the method more economical. force. The mixing and/or mixing steps can be batchwise (for example in a Banbury mixer or in a two-roll mill) or in a continuous mode (for example in a tubular reactor, such as a (co-rotating) twin-screw extruder Or a single screw extruder extruder or a Buss kneader (reciprocating single screw extruder) and a plow mixer). In the context of this application, the term "mixing" refers to mixing together sufficient shear stress applied to a polymer based mixture to convert at least a portion of the micron sized modified LDH particles to nanometer dimensions. The use of the particles is 116928.doc -15- 200734387. This shear stress can be applied by mixing a polymer-based mixture in, for example, a Banbury mixer or extruder. It can be used in the method of the present invention. The modified LDH is reduced in size and then added in step a) or a2). The modified LDH may have a d50 value of less than 20 μηη and a d90 value of less than 50 μπα. Preferably, the d50 value is less than 15 μιη and d90 The value is less than 40 μηη, more preferably, the d50 value is less than 10 μπι and the d90 value is less than 30 μιη, and even more preferably, the d50 value is less than 8 μπι and the d90 value is less than 20 μηι, and optimally, the d50 value is less than 6 μπι and The d90 value is less than 10 μηη. The particle size distribution can be determined using methods known to those skilled in the art, for example using a laser diffraction measurement according to DIN 13320. The use of LDH having this smaller particle size distribution enables the modified LDH to be used throughout. Rubber nano composite Good mixing and improved flaking and/or delamination of the modified LDH. The particle size distribution of the modified LDH suitable for use in the process of the present invention can be known in the art for reducing the particle size of inorganic materials such as LDH. Any method is obtained. Examples of such methods are wet milling and dry milling. Alternatively, as exemplified by WO 02/085787, the modified LDH can be produced during the preparation of the modified LDH. The first solvent and the second solvent may be any solvent suitable for use in the process and are known to those skilled in the art. The first solvent and/or the second solvent may be the same or different and preferably An organically modified LDH and a solvent compatible with the rubber precursor, its monomer, and/or the resulting rubber nanocomposite. The first solvent and/or the second solvent includes, for example, methanol, ethanol, isopropanol, and n-butanol. An alcohol; a ketone such as methyl amyl ketone, methyl ethyl ketone, methyl isobutyl 116928.doc -16-200734387 ketone and cyclohexanone; an ester such as ethyl acetate and butyl acetate; Ester, methyl methacrylate, dipropylene Unsaturated acrylates of hexamethylene diester and trimethylol propane triacrylate; aromatic hydrocarbons such as hexane, petroleum ether, toluene and xylene, and non-aromatic hydrocarbons; and such as dibutyl ether, tetrahydrofuran (THF) And an ether of decyl tertiary butyl ether (MTBE). The rubber precursor prepared by the method of the present invention is a rubber precursor which can be converted into rubber after curing or vulcanization. The rubber precursors and the rubber formed thereof are familiar to It is known to the skilled person. Examples of rubber include natural rubber (NR), styrene-butadiene rubber (SBR), polyisoprene (IR), polybutadiene or butyl rubber (BR). , polyisobutylene rubber (IIR), halogenated polybutadiene rubber, halogenated polyisobutylene rubber, nitrile butadiene rubber (NBR), hydrogenated nitrile butadiene rubber, styrene-isoprene-styrene (SIS) and Similar (hydrogenated) styrenic block copolymers (SBS, hydrogenated SIS, hydrogenated SBS), poly(gas alcohol) rubber (CO, ECO, GPO), polyoxyxene rubber (Q), gas butadiene rubber ( CR), ethylene propylene rubber (EPM), ethylene propylene diene rubber (EP) DM), ruin rubber (FKM), ethylene-vinyl acetate rubber (EVA), vinyl butadiene rubber, halogenated butyl rubber, polyacrylic rubber (ACM), polynorbornene (PNR), polyamine ruthenium Acid esters and polyester/ether thermoplastic elastomers. Preferred rubbers are natural rubber, SBR, EPDM, halogenated butadiene rubber, butadiene rubber and polyoxyethylene rubber. In one embodiment of the invention, the rubber is a polyoxyxene rubber. The manufacture of polyoxyxene rubber is generally known to those skilled in the art and is described, for example, in Silicones, Kirk Othmer Encyclopedia of Chemical Technology, 116928.doc -17- 200734387

Job Wiley & Sons，Inc，線上公告日期：2〇〇2年12月2〇日 之第3、4及5章中。大體上，聚矽氧之製造經由單體聚合 开y成聚矽氧則驅物，其後聚矽氧前驅物經交聯形成聚矽氧 而進行。在本發明之方法中使用之聚石夕氧前驅物對於熟習 此項技術者為已知的。應注意聚矽氧前驅物較佳為液體， 以使知改貝冑粒材料及第一《容劑之混合物可容易地與前驅 物此5以獲得微粒材料遍及聚矽氧前驅物的均質及均一分 佈0 在本發明之方法之另一實施例中，將步驟al)及a2)之任 者中獲得之聚矽氧前驅物固化以形成聚矽氧，例如聚矽 氧橡膠或聚矽氧發泡體橡膠。該等固化通常致使形成由交 聯聚一有機基矽氧烷鏈組成之三維網路結構。固化通常經 由過氧化物誘發之自由基方法、經由使用第vm族金屬（諸 如Pt及Ru)錯合物或經負載第νπ族金屬催化劑之氫化矽烷 化加成方法、或經由縮合反應來進行。該等固化方法之每 一者的實例可見於"silic〇ne Network Formation” ofJob Wiley & Sons, Inc., online publication date: Chapters 3, 4 and 5 of December 2nd, 2nd, 2nd. In general, the production of polyoxymethylene is carried out by polymerization of a monomer to form a polyfluorene precursor, after which the polyfluorene precursor is crosslinked to form polyfluorene. The polysulfide precursors used in the process of the present invention are known to those skilled in the art. It should be noted that the polyoxonium precursor is preferably a liquid so that the mixture of the shellfish material and the first "capacity" can be easily combined with the precursor to obtain a homogenous and uniform particulate material throughout the polyoxon precursor. Distribution 0 In another embodiment of the method of the present invention, the polyoxonium precursor obtained in any of steps a1) and a2) is cured to form a polyoxyxene, such as polyoxyxene or polyoxygenated foam. Body rubber. These curings generally result in the formation of a three-dimensional network structure consisting of a crosslinked poly-organosiloxane chain. The curing is usually carried out by a peroxide-induced radical method, via a hydrogenation oximation addition method using a v-th metal (such as Pt and Ru) or a supported νπ-group metal catalyst, or via a condensation reaction. Examples of each of these curing methods can be found in "silic〇ne Network Formation"

Silicones，Kirk Othmer Encyclopedia of Chemical Technology, John Wiley & Sons，Inc·，線上公告日期：2002年 12月 20 日 之第5章中。在聚矽氧前驅物固化之後，可獲得聚矽氧橡 膠或橡膠發泡體。 本發明之橡膠組合物可適用於輪胎製造中，諸如用於綠 色輪胎、卡車輪胎、拖拉機輪胎、工程建設用輪胎及飛機 輪胎中，用於冬季輪胎中，用於包括手套、避孕套、氣 球、導管、乳膠絲、發泡體、地毯背襯及橡膠化椰棕及毛 116928.doc -18 · 200734387 髮之乳膠產品中’用於鞋類中，用於諸如橋樑支撐物、橡 膠-金屬層壓支撐物之土木工程產品中，用於皮帶及軟管 中用於包括引擎#、橡膠支撐物、封閉件、絕緣環、塾 圈及車廂之非輪胎汽車應用巾1於導線及電繞中，及用 於管密封件、醫學封閉件、滾筒、小實心輪胎、家用器具 及商業裔具之座架、橡膠球及管、擠奶設備及其他農業基 礎應用中。 若橡膠組合物為包含聚♦氧橡膠及根據本發明之改質微 粒材料之聚梦氧組合物，則該等橡膠組合物可適用於包括 壓敏黏著劑、㈣硬殼及釋紙塗料之塗料產品、適用於包 括織物及毛髮護理應用之纖維加工應用、密封劑、黏著 劑、封裝物及太陽能電池裝置。 在本發明之一實施例中’經改質層狀雙氫氧化物以橡膠 組合物形式用於輪胎、尤其用於汽車輪胎中。橡膠組合物 中之橡膠可為輪胎中慣常使用之任何橡膠。 該等橡膠之實例為天然橡膠、苯乙m歸橡膠、丁 二烯橡膠、乙燁基·τ二稀橡膠及基橡膠。通常亦使 用該等橡膠之混合物。 、根據本發明之橡膠組合物可用於其中慣f使用諸如碳黑 或沉澱矽石之無機填料之輪胎的任何部分中。詳言之，橡 膠組合物可用於底胎面或胎面基部、胎面、側壁、輪緣 内層月木、頂點、凸緣及膠帶層中。亦預計使用本 發明之改質微粒材料及如碳黑或沉澱矽石之習知無機填料 之組合。使用經改質層狀雙氫氧化物使得橡膠組合物中無 116928.doc -19- 200734387 機填料之總量減少，而同時維持相似或改良的機械性質。 在輪胎中使用本發明之橡膠組合物可改良輪胎之機械及動 力學性貝，其可進一步增強不同橡膠之間的黏結或黏著， 例如在輪胎之不同部分中、或輪胎與金屬之間（例如在金 屬索中）、或橡膠與纖維之間。胎面中使用之橡膠（通常為 溶液SBR橡膠）可由例如乳液SBR橡膠之更廉價橡膠代替， 而胎面無機械或動力學性質損失。本發明之改質]^1311亦使 橡膠具有改良之抗刺穿性。 ► 在一較佳實施例中，經改質層狀雙氫氧化物係經包含可 硫化基團之偶合劑、或經具有可硫化基團之有機陰離子來 改質。此偶合劑可為如雙（3_三乙氧基矽烷基丙基）四硫化 物（得自Degussa之Si69⑧）、雙（3_三乙氧基矽烷基丙基）二 硫化物、γ-疏基丙基三甲氧基矽烷（得自pcc之SiSiBd> PC2300)及3-辛醯基硫基丙基三乙氧基石夕烧（得自之 NXTtm)。可硫化有機陰離子之實例為12_經基硬脂酸、12_ > 氯硬脂酸、12-胺基十二烷酸、環氧化脂肪酸、巯基丙 酸、油酸、共輛不飽和脂肪酸、二硫代二丙酸、對經基苯 曱酸及馬來醯亞胺丙酸。該等經改質層狀雙氫氧化物之優 點在於可減少製造輪胎、尤其綠色輪胎所需之時間。此 外，未固化輪胎及最終輪胎之尺寸穩定性得以改良。在習 知方法中，將沉澱矽石與如雙（3-三乙氧基矽烷基丙基）四 硫化物之偶合劑一起添加至橡膠中，容許橡膠組合物在高 溫下反應’移除產生之乙醇’且獲得未固化之輪胎，其隨 後在更南溫度下固化以開始硫化且形成輪胎。在輪胎製造 116928.doc -20- 200734387 中使用本發明之經改質層狀雙氫 化基團之偶合劑改質之層狀雙氣氧=其以具有可硫 =粒材料且無乙醇形成之優點，使得連: 可增加（綠色）輪胎之生產率。若使用 夺間減少’其 物與諸如沉澱矽石之習知填 、曰狀雙氫氧化 添加至混合物中以使得’則可將偶合劑分別 τ 乂使仔其可與沉澱石夕石反應。 雙氫氧化物可以於適合溶劑（不含或幾乎不含水）中之曰(膠 狀）懸洋液形式添加至橡膠中，或其可於增量油中或作為 !體添加。在增量油或固體之情況下，無溶劑待移除，使 侍加工時間進一步減少且得到改良之加工安全性。 本發明進-步係關純據本發明之轉 電池裝置中之…在一較佳實施例中，橡膠組 膠為透明橡膠。該透明橡膠為對可見光透明之橡膠。該等 透明橡膝之實例為聚胺基甲酸醋、乙稀乙酸乙婦醋橡膠及 聚矽氧橡膠。該透明橡膠較佳為聚矽氧橡膠。太陽能電池 裝置可為此項技術中已知之任何太陽能電池裝置。該等太 陽能電池裝置之實例為結晶si太陽能電池、非晶形矽太陽 月b電池、結晶梦薄膜太陽能電池及以（例如）cdTe、Silicones, Kirk Othmer Encyclopedia of Chemical Technology, John Wiley & Sons, Inc., online publication date: Chapter 5 of December 20, 2002. After the polyoxyxene precursor is cured, a polyoxyethylene rubber or a rubber foam can be obtained. The rubber composition of the present invention can be suitably used in tire manufacturing, such as in green tires, truck tires, tractor tires, construction tires, and aircraft tires, in winter tires, including gloves, condoms, balloons, Catheter, Latex, Foam, Carpet Backing and Rubberized Coir and Hair 116928.doc -18 · 200734387 Latex Products in 'Used in Footwear for Bridge Support, Rubber-Metal Lamination Among the civil engineering products of the support, the non-tire automobile application towel 1 for the engine #, the rubber support, the sealing member, the insulating ring, the ring and the carriage is used in the belt and the hose, and in the wire and the electric winding, and Used in tube seals, medical closures, rollers, small solid tires, home appliances and commercial frame, rubber balls and tubes, milking equipment and other agricultural basic applications. If the rubber composition is a polyoxymethylene composition comprising a polyoxo rubber and a modified particulate material according to the present invention, the rubber composition can be applied to a coating comprising a pressure sensitive adhesive, (4) a hard shell and a release coating. Products for fiber processing applications including fabric and hair care applications, sealants, adhesives, encapsulants and solar cell devices. In one embodiment of the invention, the modified layered double hydroxide is used in the form of a rubber composition for tires, particularly in automotive tires. The rubber in the rubber composition may be any rubber conventionally used in tires. Examples of such rubbers are natural rubber, styrene-butadiene rubber, butadiene rubber, acetylidene-tau-rubber rubber and base rubber. Mixtures of such rubbers are also commonly used. The rubber composition according to the present invention can be used in any portion of a tire in which an inorganic filler such as carbon black or precipitated vermiculite is used. In particular, the rubber composition can be used in the base tread or tread base, tread, sidewall, rim inner moon, apex, flange and tape layer. Combinations of the modified particulate material of the present invention with conventional inorganic fillers such as carbon black or precipitated vermiculite are also contemplated. The use of the modified layered double hydroxide results in a reduction in the total amount of filler in the rubber composition while maintaining similar or improved mechanical properties. The use of the rubber composition of the present invention in a tire improves the mechanical and dynamic properties of the tire, which can further enhance adhesion or adhesion between different rubbers, such as in different portions of the tire, or between the tire and the metal (eg, In the metal cable), or between the rubber and the fiber. The rubber used in the tread (usually solution SBR rubber) can be replaced by a less expensive rubber such as an emulsion SBR rubber without loss of mechanical or dynamic properties of the tread. The modification of the present invention] 1311 also provides improved puncture resistance to rubber. ► In a preferred embodiment, the modified layered double hydroxide is modified with a coupling agent comprising a sulfidable group or with an organic anion having a sulfidable group. The coupling agent may be, for example, bis(3-triethoxydecylpropyl)tetrasulfide (Si698 from Degussa), bis(3-triethoxydecylpropyl)disulfide, γ-spar Propyltrimethoxydecane (SiSiBd from PCC > PC2300) and 3-octylthiopropyltriethoxylate (from NXTtm). Examples of vulcanizable organic anions are 12-base stearic acid, 12_> chlorostearic acid, 12-aminododecanoic acid, epoxidized fatty acid, mercaptopropionic acid, oleic acid, co-unsaturated fatty acid, Thiopropionic acid, p-benzoic acid and maleic imine propionic acid. The improved layered double hydroxides are advantageous in that the time required to manufacture tires, particularly green tires, can be reduced. In addition, the dimensional stability of the uncured tire and the final tire is improved. In a conventional method, a precipitated vermiculite is added to a rubber together with a coupling agent such as bis(3-triethoxydecylpropyl)tetrasulfide, allowing the rubber composition to react at a high temperature. Ethanol' and an uncured tire is obtained which is subsequently cured at a further south temperature to initiate vulcanization and form a tire. Layered double gas oxygen modified with the modified layered dihydrogenated coupler of the present invention in tire manufacturing 116928.doc -20- 200734387 = the advantage of having a sulfur-containing material and no ethanol formation , so that: can increase the productivity of (green) tires. If a thixotropy reduction is used, and a conventionally filled, sigma-like dihydrogenation such as precipitated vermiculite is added to the mixture so that the coupling agent can be separately τ 乂, it can react with the precipitated stone. The double hydroxide may be added to the rubber in the form of a sputum (gel) suspension in a suitable solvent (without or almost no water), or it may be added in an extender oil or as a body. In the case of an extender oil or solid, no solvent is removed, allowing for further processing time and improved process safety. The present invention is further directed to a battery device according to the present invention. In a preferred embodiment, the rubber rubber is a transparent rubber. The transparent rubber is a rubber that is transparent to visible light. Examples of such transparent rubber knees are polyurethane acetonate, ethyl acetate vinegar rubber and polyoxymethylene rubber. The transparent rubber is preferably a polyoxyethylene rubber. The solar cell device can be any solar cell device known in the art. Examples of such solar cell devices are crystalline si solar cells, amorphous 矽 solar moon b cells, crystalline dream thin film solar cells, and, for example, cdTe,

CuInSe2、Cu(In，Ga)(Se，S)2(所謂CIGS)為基礎之化合物半 導體太陽能電池，及Gratzel電池。其他細節可獲自f.CuInSe2, Cu(In,Ga)(Se,S)2 (so-called CIGS)-based compound semiconductor solar cells, and Gratzel cells. Other details are available from f.

Pfisterer (’’Photovoltaic Cells，，，第 4章："Types of PhotovoltaicPfisterer (’’Photovoltaic Cells,,, Chapter 4: "Types of Photovoltaic

Cells3n Ullmannfs Encyclopedia of Industrial Technology 5 線上公告日期：2000年6月15日）。 在太陽能電池裝置中使用之橡膠組合物可用於連接裝置 116928.doc -21 - 200734387 本發明之橡膠組合物之優點為其對可見Cells3n Ullmannfs Encyclopedia of Industrial Technology 5 Online Announcement Date: June 15, 2000). The rubber composition used in the solar cell device can be used for the connection device 116928.doc -21 - 200734387 The rubber composition of the present invention has the advantage that it is visible to the visible

需透明。通常，橡膠組合物顯示比f知橡膠組合物改良之 中之兩個鄰接層。 光之透明性，其使 電池之部分之前， 機械性質。Need to be transparent. Generally, the rubber composition exhibits two adjacent layers in the modification of the rubber composition. The transparency of light, which makes the battery part before the mechanical properties.

層、一前電極及一透明頂層之太陽能電池裝置，其中本發 明之橡膠組合物之一層存在於該前電極與該透明頂層^ 間。如以上所指示，橡膠組合物之橡膠較佳為透明橡膠， 且該橡膠最佳為聚矽氧橡膠。橡膠組合物充當透明頂層與 前電極之黏著層或結合層。歸因於前述改良之機械性質， 橡膠組合物之黏著力及撕裂強度增加且太陽能電池裝置 (使用中）能夠更佳經受其所暴露於其中之天氣影響或其他 機械力。因此，太陽能電池裝置之壽命增加。此外，本發 明之橡膠組合物對可見光透明，與包含具有在可見光波長 (亦即介於400 nm與800 nm之間）之範圍内或超過可見光波 長之尺寸之顆粒的橡膠組合物的太陽能電池裝置相比，其 致使改良光產率及太陽能採收。 包δ 月電極、一光電層、一月電極及一透明頂層之太 陽能電池裝置對於熟習此項技術者為已知的。通常，該背 電極、一光電層、一前電極及一透明頂層係以一者位於另 一者之上之層提供。該等太陽能電池裝置之更詳細描述可 116928.doc -22- 200734387 見於EP 1 397 83 7及EP 1 290 736中，其對背電極、光電 層、前電極及透明頂層之特定描述係以引用的方式併入本 文中。 【實施方式】 本發明係由以下實例進行說明。 實例 在該等實例中，市售飽和脂肪酸混合物及不飽和脂肪酸 混合物係以所接受之形式使用。該飽和脂肪酸混合物為 > Kortacid® PH05(棕櫊酸與硬脂酸之摻合物），其係由Akzo Nobel Chemicals之一公司 Oleochemicals GmbH供應。該不 飽和脂肪酸混合物為Kortacid® PZ05(蒸餾棕櫚油），其係 由 Akzo Nobel Chemicals之一公司 Oleochemicals GmbH供 應。 實例1 將 50 公克之氧化鎂（Zolitho® 40，來自 Martin Marietta Magnesia Specialties LLC)與 39 公克之氫氧化铭（Alumill > F505)混合於648公克之去礦質水中且研磨至2·5 μηι之平均 粒徑（d5G)。將研磨漿饋入裝備有高速攪拌器之油加熱之高 壓釜中且加熱至80°C。隨後經15分鐘之時間將102公克之 Kortacid® PH05添加至該高壓釜中。在添加之前，將該脂 肪酸摻合物加熱至80°C。在酸添加後，將高壓釜關閉並加 熱至170°C且保持於此狀況下歷時1小時。隨後將高壓釜冷 卻至約40°C且移出所得研磨漿。隨後以2,000 rpm將該研磨 漿離心約10分鐘。將液體傾析出且將固體在80°C下在真空 116928.doc -23- 200734387 下於一烘箱中乾燥隔夜。 以X射線繞射分析包含脂肪酸摻合物之所得類水滑石黏 土以測定中間通道間距或d間距。如上製備之類水滑石黏 土之XRD圖展示微小水滑石相關非-(hkO)反射，指示陰離 子型黏土之插層。插層顯示29A之特徵d(001)值。 實例2 除使用Kortacid®PZ05代替Kortacid⑧PH05之外，根據實 例1製備經改質層狀雙氫氧化物。 > 實例3 使用一 Hosokawa Alpine 50 ZPS circoplex多次處理研磨 機研磨實例1之經改質層狀雙氫氧化物。如根據DIN 13320 所測定，所得粉末具有1.7 μιη之d50值及3·4 μιη之d90值。 製備包含50重量％之實例1之粉末狀改質LDH及50重量％ 之 Vistalon® 2504N(得自 ExxonMobil之 EPDM橡膠前驅物） 之母體混合物。將該EPDM橡膠前驅物饋入一開放雙輥筒 研磨機（具有直徑為110 mm及長度為250 mm之尺寸及0.2-5 > mm之可變夾壓設定之Dr Collin雙輥筒研磨機）中，其後經 10分鐘之時間添加粉末狀改質LDH。雙輥筒研磨機係在介 於50°C與70°C之間之溫度下以1.2之摩擦因子操作。在60°C 及50 rpm下於一内部分批混合器（安裝有含有滾筒轉子之 60 CC 混合腔室 Rheomix® 600 之 Rheocord® 9000)中將所得 母體混合物以相同橡膠前驅物稀釋歷時30分鐘。以此方 式，製備具有改變量之實例1之改質LDH的三個樣品，亦 即以EPDM橡膠前驅物及改質LDH之總重量計4重量％、6 116928.doc -24- 200734387 重量％或8重量％之改質LDH。該等樣品表示為實例3A(4重 量％)、實例3B(6重量％)及實例3C(8重量。/〇)。 在一雙輥筒研磨機中，隨後將約50公克之該等樣品之每 一者與1.3 5公克之過氧化二異丙苯（來自Akzo Nobel之 Perkadox® BC-ff)混合。該雙輥筒研磨機係在介於50°C與 70°C之間的溫度下以1.2之摩擦因子操作。 將所得混合物在170°C及400 kN下最終壓縮模製為2 mm 厚之薄片歷時1 5分鐘以獲得EPDM橡膠之奈米複合材料。 • 出於參照之目的，除不將改質LDH添加至橡膠中之外， 使用上述方法製備EPDM橡膠。 實例4 除使用實例2之改質LDH代替實例1之改質LDH之外，重 複實例3之程序，且如根據DIN 13320所測定，研磨粉末具 有1.7 μιη之d50值及3.4 μηι之d90值。該等樣品表示為實例 4八(4重量％)、實例43(6重量％)及實例4C(8重量％)。 分別根據ISO 37-2及ISO 34在一 Zwick Z010抗張測試器 ® 上進行拉伸測試及撕裂強度測試。包含EPDM橡膠之各種 奈米複合材料之結果展示於以下表1中。 表1 實例 性質 純橡膠 3A 4A 3B 4B 3C 4C 斷裂應力(MPa) 1.4 1.9 2.1 1.9 2.5 2.2 2.3 斷裂伸長率(％) 122 161 150 169 175 209 194 撕裂強度(N) 7.8 11.1 12.5 11.5 13.9 12.4 14 116928.doc -25- 200734387A layer, a front electrode and a transparent top layer solar cell device, wherein a layer of the rubber composition of the present invention is present between the front electrode and the transparent top layer. As indicated above, the rubber of the rubber composition is preferably a transparent rubber, and the rubber is preferably a polyoxymethylene rubber. The rubber composition acts as an adhesive or bonding layer between the transparent top layer and the front electrode. Due to the improved mechanical properties described above, the adhesion and tear strength of the rubber composition are increased and the solar cell device (in use) is better able to withstand the weather effects or other mechanical forces to which it is exposed. Therefore, the life of the solar cell device increases. Further, the rubber composition of the present invention is transparent to visible light, and a solar cell device comprising a rubber composition having particles having a size in the visible light wavelength (i.e., between 400 nm and 800 nm) or exceeding the visible light wavelength. In comparison, it results in improved light yield and solar energy harvesting. Solar cell devices comprising a δ month electrode, a photovoltaic layer, a January electrode, and a transparent top layer are known to those skilled in the art. Typically, the back electrode, a photovoltaic layer, a front electrode, and a transparent top layer are provided in a layer on one of the other. A more detailed description of such solar cell devices can be found in EP 1 397 83 7 and EP 1 290 736, the specific description of which is directed to the back electrode, the photovoltaic layer, the front electrode and the transparent top layer. The manner is incorporated herein. [Embodiment] The present invention is illustrated by the following examples. EXAMPLES In these examples, commercially available saturated fatty acid mixtures and unsaturated fatty acid mixtures are used in accepted form. The saturated fatty acid mixture is > Kortacid® PH05 (a blend of palmitic acid and stearic acid) supplied by Oleochemicals GmbH, a company of Akzo Nobel Chemicals. The unsaturated fatty acid mixture is Kortacid® PZ05 (distilled palm oil) supplied by Oleochemicals GmbH, one of Akzo Nobel Chemicals. Example 1 50 grams of magnesium oxide (Zolitho® 40 from Martin Marietta Magnesia Specialties LLC) and 39 grams of hydrazine (Alumill > F505) were mixed in 648 grams of demineralized water and ground to an average of 2·5 μηι Particle size (d5G). The slurry was fed into an oil heated autoclave equipped with a high speed stirrer and heated to 80 °C. Then 102 grams of Kortacid® PH05 was added to the autoclave over 15 minutes. The fatty acid blend was heated to 80 °C prior to addition. After the acid addition, the autoclave was closed and heated to 170 ° C and maintained in this condition for 1 hour. The autoclave was then cooled to about 40 ° C and the resulting slurry was removed. The slurry was then centrifuged at 2,000 rpm for about 10 minutes. The liquid was decanted and the solid was dried overnight at 80 ° C under vacuum 116928.doc -23-200734387 in an oven. The resulting hydrotalcite-like clay comprising the fatty acid blend was analyzed by X-ray diffraction to determine the intermediate channel spacing or d spacing. The XRD pattern of the hydrotalcite clay prepared as above shows a micro-hydrotalcite-related non-(hkO) reflection indicating the intercalation of the anionic clay. The intercalation shows the characteristic d(001) value of 29A. Example 2 A modified layered double hydroxide was prepared according to Example 1, except that Kortacid® PZ05 was used instead of Kortacid 8PH05. > Example 3 The modified layered double hydroxide of Example 1 was ground using a Hosokawa Alpine 50 ZPS circoplex multiple treatment mill. The resulting powder had a d50 value of 1.7 μηη and a d90 value of 3·4 μηη as determined according to DIN 13320. A precursor mixture comprising 50% by weight of the powdered modified LDH of Example 1 and 50% by weight of Vistalon® 2504N (EPDM rubber precursor from ExxonMobil) was prepared. Feeding the EPDM rubber precursor into an open double roller mill (Dr Collin double roller mill with a diameter of 110 mm and a length of 250 mm and a variable clamping setting of 0.2-5 mm) The powdered modified LDH was then added over a period of 10 minutes. The twin roll mill operates at a temperature between 50 ° C and 70 ° C with a friction factor of 1.2. The resulting precursor mixture was diluted with the same rubber precursor for 30 minutes at 60 ° C and 50 rpm in an internal batch mixer (Rhoeocord® 9000 fitted with a 60 CC mixing chamber Rheomix® 600 containing a roller rotor). In this manner, three samples having a modified amount of the modified LDH of Example 1 were prepared, i.e., 4 wt%, 6 116928.doc -24 - 200734387 wt%, based on the total weight of the EPDM rubber precursor and the modified LDH. 8 wt% modified LDH. The samples are shown as Example 3A (4 wt%), Example 3B (6 wt%), and Example 3C (8 wt./〇). In a twin roll mill, approximately 50 grams of each of these samples was subsequently mixed with 1.35 grams of dicumyl peroxide (from Perkadox® BC-ff from Akzo Nobel). The twin roll mill operates at a temperature between 50 ° C and 70 ° C with a friction factor of 1.2. The resulting mixture was finally compression molded into a 2 mm thick sheet at 170 ° C and 400 kN for 15 minutes to obtain a EPDM rubber nanocomposite. • For the purpose of reference, EPDM rubber was prepared using the above method except that modified LDH was not added to the rubber. Example 4 The procedure of Example 3 was repeated except that the modified LDH of Example 2 was used instead of the modified LDH of Example 1, and the abrasive powder had a d50 value of 1.7 μηη and a d90 value of 3.4 μηι as determined according to DIN 13320. The samples are shown as Examples 4-8 (4% by weight), Example 43 (6% by weight), and Example 4C (8% by weight). Tensile testing and tear strength testing were performed on a Zwick Z010 tensile tester ® according to ISO 37-2 and ISO 34, respectively. The results for various nanocomposites comprising EPDM rubber are shown in Table 1 below. Table 1 Example properties Pure rubber 3A 4A 3B 4B 3C 4C Fracture stress (MPa) 1.4 1.9 2.1 1.9 2.5 2.2 2.3 Elongation at break (%) 122 161 150 169 175 209 194 Tear strength (N) 7.8 11.1 12.5 11.5 13.9 12.4 14 116928.doc -25- 200734387

自上表可推斷，與實例3A、實例3B及實例3C之奈米複 合材料（其並非根據本發明）相比，實例4A、實例4B及實例 4C之EPDM橡膠奈米複合材料（其係根據本發明）分別展示 改良之物理性質，尤其改良之斷裂應力及撕裂強度。 116928.doc 26-From the above table, it can be inferred that the EPDM rubber nanocomposites of Examples 4A, 4B and 4C are compared with the nanocomposites of Example 3A, Example 3B and Example 3C, which are not according to the present invention. Invention) The improved physical properties, especially the improved fracture stress and tear strength, respectively. 116928.doc 26-

Claims (1)

• 200734387 十、申請專利範圍： 1· 一種包含橡膠及經改質層狀雙氫氧化物之奈米複合材 料，其包含： 具有一第一官能基及一第^一官能基之電荷平衡之有機 離子，其中有機陰離子的至少部分經由該第二官能基化 學連接至該橡膠；及/或 具有至少一烧氧基石夕烧基及至少一反應性基團之石夕烧 偶合劑，至少一烷氧基矽烷基經化學連接至該層狀雙氫 # 氧化物，至少一反應性基團經化學連接至該橡膠。 2.如睛求項1之奈米複合材料，其包含包括一第二官能基 之電荷平衡之離子，該第二官能基係選自由丙烯酸酯 基、甲基丙烯酸酯基、羥基、氯化物基、胺基、環氧 基、硫醇基、乙烯基及多硫化物基、胺基甲酸酯基、 一元膦酸基、異氰酸 錢、續酸基、亞績酸基、錄、鐫、 酗基、巯基、羥基苯基、氫化物基、乙醯氧基及酐基組 成之群。• 200734387 X. Patent Application Range: 1. A nanocomposite comprising rubber and modified layered double hydroxide, comprising: organically having a charge balance of a first functional group and a first functional group An ion, wherein at least a portion of the organic anion is chemically linked to the rubber via the second functional group; and/or a sulphur coupling agent having at least one alkoxy group and at least one reactive group, at least one alkoxy The sulfhydryl group is chemically bonded to the layered dihydrogen #oxide, and at least one reactive group is chemically bonded to the rubber. 2. The nanocomposite of claim 1, which comprises a charge-balanced ion comprising a second functional group selected from the group consisting of an acrylate group, a methacrylate group, a hydroxyl group, and a chloride group. , amine, epoxy, thiol, vinyl and polysulfide, urethane, monophosphonic acid, isocyanate, acid, acid, acid, hydrazine, A group consisting of a mercapto group, a mercapto group, a hydroxyphenyl group, a hydride group, an ethoxy group, and an anhydride group. 聚矽氧橡膠組成之群。A group of polyoxymethylene rubber. 母體混合物（masterbatch)， 久！改質層狀雙氳氧化物之 其包含具有一第一官能基及 116928.doc .200734387 一第一官能基之電荷平偷 ^ 、之有機離子及/或具有至少一烧 氧基矽烷基及至少一及施 久應性基團之矽烷偶合劑，其中經 改質層狀雙氣氧化物之量為以該母體混合物之總重量計 "於ίο重里％與70重量％之間且橡膠之量為以該母體混 6. 合物之總重量計介於30重量。/❶與90重量％之間。 -種製備橡膠前驅物或如請求項⑴中任一項之奈米複 a材料之方法，該方法包含以下步驟： al)將視情況與第一溶劑混合之經改質層狀雙氫氧化物 添加至包含一或多種聚合物及視情況第二溶劑之橡 膠前驅物中；或 a2)將視情況與第一溶劑混合之該經改質層狀雙氫氧化 物添加至包含橡膠前驅物之一或多種單體及視情況 第二溶劑之橡膠組合物中，且使該等單體聚合以形 成橡膠前驅物； b)視情況在交聯劑存在下使該橡膠前驅物交聯以形成 該奈米複合材料；及 Θ視情況在步驟ai)、a2)及b)之任一者期間或之後移除 该第一溶劑及/或第二溶劑。 一種如請求項1至4中任一項之奈米複合材料在輪胎中之 用途，該橡膠較佳為天然橡膠或SBR。 一種如請求項1至4中任一項之奈米複合材料在太陽能電 池裝置中之用途，其中該橡膠為聚矽氧橡膠。 116928.doc 200734387 七、指定代表圖： (一) 本案指定代表圖為：（無） (二) 本代表圖之元件符號簡單說明： 八、本案若有化學式時，請揭示最能顯示發明特徵的化學式： (無） 116928.docMasterbatch, long! The modified layered biguanide oxide comprises a charge having a first functional group and 116928.doc.200734387 a first functional group, an organic ion and/or having at least one alkoxyalkyl group and at least And a decane coupling agent for a long-acting group, wherein the amount of the modified layered double gas oxide is between the total weight of the parent mixture " between ίο重里% and 70% by weight and the amount of rubber It is 30 parts by weight based on the total weight of the parent compound. /❶ is between 90% by weight. A method of preparing a rubber precursor or a nanocomposite material according to any one of the items (1), which comprises the steps of: a) modifying a modified layered double hydroxide as appropriate with the first solvent Adding to a rubber precursor comprising one or more polymers and optionally a second solvent; or a2) adding the modified layered double hydroxide, optionally mixed with the first solvent, to one of the rubber-containing precursors Or a plurality of monomers and optionally a second solvent in the rubber composition, and polymerizing the monomers to form a rubber precursor; b) optionally crosslinking the rubber precursor in the presence of a crosslinking agent to form the naphthalene The rice composite; and the first solvent and/or the second solvent are removed during or after any of steps ai), a2) and b). A use of the nanocomposite according to any one of claims 1 to 4 in a tire, preferably a natural rubber or SBR. A use of a nanocomposite according to any one of claims 1 to 4 in a solar battery device, wherein the rubber is a polyoxyxene rubber. 116928.doc 200734387 VII. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 8. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: (none) 116928.doc