TWI399297B - Surface modification with polyhedral oligomeric silsesquioxanes silanols - Google Patents

Surface modification with polyhedral oligomeric silsesquioxanes silanols Download PDF

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TWI399297B
TWI399297B TW095103086A TW95103086A TWI399297B TW I399297 B TWI399297 B TW I399297B TW 095103086 A TW095103086 A TW 095103086A TW 95103086 A TW95103086 A TW 95103086A TW I399297 B TWI399297 B TW I399297B
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substrate
poss
nanostructure
chemical
coating
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TW200639058A (en
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Joseph D Lichtenhan
Joseph J Schwab
Yi-Zhong An
William Reinerth
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Hybrid Plastics Inc
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/11—Compounds covalently bound to a solid support

Description

利用多面體寡聚倍半矽氧烷矽醇之表面改質技術Surface modification technology using polyhedral oligomeric sesquiterpene sterol

本申請案乃主張美國專利臨時申請案案號60/648,327(申請日：2005年1月27日)之優勢。This application claims the advantages of U.S. Patent Provisional Application No. 60/648,327 (filed on Jan. 27, 2005).

發明領域Field of invention

本發明概括有關於具有改良疏水性、熱安定性、硬度及耐用性之奈米強化塗層。The present invention is generally directed to nano strength coatings having improved hydrophobicity, thermal stability, hardness and durability.

發明背景Background of the invention

能造成不同材料的界面之間產生相容性的技術存在有明顯優勢的機會。聚合物尤其利用多種無機材料作為填料，使最終組成物具有所要的電子、熱、機械及其它物理性質。聚合物之碳氫化合物組成通常使得它們與大部份填料系統的無機組成不相容。聚合物包括脂肪族、烯烴族、芳香族及雜官能系統(代表性的例子包括聚乙烯、聚丙烯、聚丁二烯、聚醚、聚醯亞胺、環氧化物、丙烯酸類、苯乙類、多硫化物、聚碸類、聚碳酸酯類、聚酯、聚醯胺類)。還包括各種聚合物，例如玻璃、半晶質、結晶體及彈性質。(代表性的填料包括例如多層矽酸鹽、黏土、碳酸鈣、滑石、矽灰石、矽藻土、高嶺土、ATH(三水合鋁)、蛭石、重晶石、玻璃、金屬、金屬氧化物及木材的填料)。一般的實施方式係用表面處理劑及甲矽烷偶合劑來處理顆粒填料表面以提高這些不同材料類型之間的表面相容性。此實施方式已延伸為利用甲矽烷及表面處理劑作為礦物及合成矽酸鹽的通道層的剝離劑。(礦物及合成矽酸鹽包括膨潤土、鋰蒙脫土、蒙脫土)這些內表面與外表面的改質已能夠擴張相鄰矽酸層之間的空間並且使其內表面與聚合物相容，因而改良其分散特性及強化特性。Techniques that create compatibility between interfaces of different materials have the advantage of significant advantages. The polymer utilizes, inter alia, a plurality of inorganic materials as fillers to impart the desired electronic, thermal, mechanical and other physical properties to the final composition. The hydrocarbon composition of the polymer generally renders them incompatible with the inorganic composition of most filler systems. The polymers include aliphatic, olefinic, aromatic and heterofunctional systems (representative examples include polyethylene, polypropylene, polybutadiene, polyethers, polyimine, epoxides, acrylics, styrenes) , polysulfides, polyfluorenes, polycarbonates, polyesters, polyamines). Also included are various polymers such as glass, semicrystalline, crystalline, and elastomeric. (Representative fillers include, for example, multilayer tantalate, clay, calcium carbonate, talc, apatite, diatomaceous earth, kaolin, ATH (aluminum trihydrate), vermiculite, barite, glass, metal, metal oxide And wood filler). A typical embodiment utilizes a surface treatment agent and a decane coupling agent to treat the surface of the particulate filler to enhance surface compatibility between these different material types. This embodiment has been extended to use a decane and a surface treatment as a stripper for the channel layer of minerals and synthetic citrates. (Mineral and synthetic bismuth salts including bentonite, hectorite, montmorillonite) These internal and external surfaces have been modified to expand the space between adjacent citrate layers and to make their inner surfaces compatible with the polymer. , thus improving its dispersion characteristics and strengthening properties.

雖然已證明習知技術在多種工業應用上尚令人滿意，但是其對於使具有分散且輪廓分明之奈米結構形勢的表面之間相容的能力仍然有限。這種控制的好處在於它能對表面設計與功能產生合理的控制。再者，藉由輪廓分明之奈米結構形勢的存在，能提高表面的適應性，以獲得改良的連結性、准確性及對抗染色劑侵襲及對抗破壞的能力。希望得到的是宏觀層級的表面(百萬分之一米)在奈米層級(十億分之一米)的相容性，因為這能增加細部特徵、耐用性及各種長度規模的聚合物鏈的強化。這些表面改質劑當它們被放置在一填料上或一表面上時，由於無法控制其表面組裝及結構，直接限制了習知技術提供這種優點。再者，傳統表面處理的熱安定性有限乃是黏土性奈米複合材料熱機械性能降低的關鍵因素。While conventional techniques have proven to be satisfactory in a variety of industrial applications, their ability to make surfaces compatible with dispersed and well-defined nanostructures is still limited. The benefit of this control is that it provides reasonable control over surface design and function. Furthermore, by the presence of a well-defined nanostructure, the surface adaptability can be improved to achieve improved connectivity, accuracy, and resistance to stain intrusion and resistance to damage. What is expected is the compatibility of the macroscopic surface (millionths of a meter) at the nanometer level (one billionth of a meter), as this increases the detail characteristics, durability and polymer chains of various lengths. Strengthening. These surface modifying agents directly limit the prior art to provide such advantages when they are placed on a surface or on a surface because of the inability to control their surface assembly and structure. Furthermore, the limited thermal stability of conventional surface treatments is a key factor in the reduction of thermomechanical properties of clay nanocomposites.

本發明乃述及奈米結構之混合〝有機－無機〞化學品作為宏觀層級填料的內表面及外表面的處理及剝離劑。使用奈米結構之多面體寡聚倍半矽氧烷(POSS及圓球矽氧烷)之習知技術發表了其作為抗腐蝕材料之應用，但未層提及其應用在複合材料、奈米複合材料或填充材料技術中，利用其奈米尺寸、混合組成及界面相容性質來改良物理性質。見美國專利第5,888,544號。The present invention relates to a treatment and stripping agent for the inner surface and the outer surface of a macroscopic layered filler of a mixed organic/inorganic germanium chemical having a nanostructure. The use of nanostructured polyhedral oligomeric sesquioxanes (POSS and fluorosphere) has been published as an anti-corrosion material, but its application in composites and nanocomposites has not been mentioned. In materials or filler technology, its nanometer size, mixed composition, and interfacial compatibility properties are used to improve physical properties. See U.S. Patent No. 5,888,544.

從多面體寡聚倍半矽氧烷(POSS)試劑及樹脂已發展出具有改良疏水性、熱安定性、硬度及耐用性之奈米強化塗層。帶有POSS試劑之矽氧烷對於用來塗覆從礦物、金屬、玻璃及聚合材料所衍生之填充材料特別有用。POSS試劑之奈米尺寸及混合(有機/無機)組成對於改良宏觀層級及奈米層級顆粒填充材料與多種不同材料之間的相容性是高度有效的，這些材料包括聚合系統、生物系統、烴系統及水性系統。Nano-reinforced coatings with improved hydrophobicity, thermal stability, hardness and durability have been developed from polyhedral oligomeric sesquioxanes (POSS) reagents and resins. Oxane with POSS reagents is particularly useful for coating filler materials derived from minerals, metals, glass, and polymeric materials. The nano-size and mixed (organic/inorganic) composition of POSS reagents are highly effective in improving the compatibility between macro-level and nano-scale particle-filled materials and a variety of different materials, including polymerization systems, biological systems, hydrocarbons. System and water system.

較佳的塗覆劑使用了POSS－矽醇、POSS－烴氧化物、POSS－氯化物及POSS－鹽。最合適的是含有化學式為[(RSiO1 . 5 )n (RXSiO1 . 0 )m ]Σ# (m,n,#＝1－1,000的奇數及偶數；R＝烴、矽烷或矽氧基；X＝OH、Cl、OR)之官能基化異配位基組成物的POSS奈米結構。較佳之塗層方法包括無溶劑噴塗法、火焰噴塗法、熔融流動法及蒸氣沈積法。這些方法之所以有利，在於它們不產生也不使用揮發性有機化學物質，因此是無放射性的。或者，可使用傳統的含溶劑的塗覆法，包括旋塗、浸塗、刷塗及噴塗。Preferred coating agents use POSS-sterol, POSS-hydrocarbon oxides, POSS-chlorides and POSS-salts. Most suitable is an odd number and an even number containing the formula [(RSiO 1 . 5 ) n (RXSiO 1 . 0 ) m ] Σ # (m, n, #=1-1,000; R = hydrocarbon, decane or decyloxy; The POSS nanostructure of the functionalized hetero-coordination composition of X = OH, Cl, OR). Preferred coating methods include solventless spray coating, flame spray coating, melt flow processing, and vapor deposition. These methods are advantageous in that they do not produce or use volatile organic chemicals and are therefore non-radioactive. Alternatively, conventional solvent-containing coating methods can be used, including spin coating, dip coating, brush coating, and spray coating.

POSS試劑及樹脂系統亦適合用於多層矽酸鹽的剝離及用於填充材料包括黏土、碳酸鈣、滑石、矽灰石、矽藻土高嶺土之間的相容。ATH(三水合鋁)、蛭石、重晶石、玻璃、金屬、金屬氧化物及木材。所得到的POSS改質填充材料展現出改良的疏水性、改良之分散性及流變性質、防火性及防火係數。此種宏觀層級與奈米層級的填充材料能使其具有多重規模的強化(從宏觀到奈米)能力，因此能改良熱塑性或熱固性樹脂系統的熱性質、機械性質、透氣性及其它物理性質，這些熱塑性或熱固性樹脂系統的最終用途係在電子、醫藥裝置、運動器材及航空事業作為塗層或結構元件。POSS reagents and resin systems are also suitable for the stripping of multi-layer citrate and for compatibility between filler materials including clay, calcium carbonate, talc, apatite, and diatomaceous kaolin. ATH (aluminum trihydrate), vermiculite, barite, glass, metal, metal oxides and wood. The resulting POSS modified filler exhibits improved hydrophobicity, improved dispersibility and rheological properties, fire resistance and fire resistance. Such macro-level and nano-layered filler materials enable multi-scale strengthening (from macro to nano) capabilities, thereby improving the thermal, mechanical, gas and other physical properties of thermoplastic or thermoset resin systems. The end use of these thermoplastic or thermoset resin systems is in coatings or structural components in electronics, medical devices, sports equipment and aerospace applications.

本發明教示奈米結構POSS化學物質之使用作為表面處理，以對宏觀級及奈米級填充材料及表面提供奈米層級之表面特徵。由POSS試劑所提供之奈米級表面特徵更進一步用來使這些存在於聚合物系統中之具有奈米級長度之填充材料彼此相容，以在聚合塗層、複合物及奈米複合物中提供多重規模水平的強化作用。這種POSS表面改質劑可利用所有的習用塗覆技術來施加，包括漿液法、旋塗、刷塗、流動法及蒸氣沈積法。POSS表面改質劑現在已能從市售的矽烷原料中取得。較佳的結構及組成為對應於下式的官能基化組成：[(RSiO1 . 5 )n (RXSiO1 . 0 )m ]Σ# (m,n,#＝1－1,000的奇數及偶數；R＝烴、矽烷或矽氧基；X＝OH、Cl、OR)。The present invention teaches the use of nanostructured POSS chemistries as a surface treatment to provide nanoscale surface features for macroscopic and nanoscale fill materials and surfaces. The nanoscale surface features provided by the POSS reagent are further used to make these nanometer-sized filler materials present in the polymer system compatible with each other for use in polymeric coatings, composites, and nanocomposites. Provide multiple levels of reinforcement. Such POSS surface modifiers can be applied using all conventional coating techniques, including slurrying, spin coating, brushing, flow, and vapor deposition. POSS surface modifiers are now available from commercially available decane feedstocks. A preferred structure and composition is a functionalized composition corresponding to the formula: [(RSiO 1 . 5 ) n (RXSiO 1 . 0 ) m ] Σ # (m, n, #=1-1,000 odd and even numbers; R = hydrocarbon, decane or decyloxy; X = OH, Cl, OR).

圖式簡單說明Simple illustration

第1圖所示為一POSS奈米結構化學物質的構造。Figure 1 shows the structure of a POSS nanostructure chemical.

第2圖所示為作為單層施用在一表面的傳統矽烷(左圖)，與作為單層施用的奈米結構偶合劑的實際尺寸關係。Figure 2 shows the actual dimensional relationship of a conventional decane (left) applied as a single layer on a surface to a nanostructure coupling agent applied as a single layer.

第3圖所示為經由宏觀級表面的POSS表面改質所提供的多重長度規模強化作用(奈米級至宏觀級)。Figure 3 shows the multi-length scale enhancement (nano to macro) provided by POSS surface modification on a macro-scale surface.

第4圖所示為POSS矽醇偶合劑的結構模型，R可為適合與一聚合物偶合的官能基。Figure 4 shows a structural model of a POSS sterol coupler, R being a functional group suitable for coupling to a polymer.

第5圖所示為奈米結構表面改質劑的例子，包括POSS－一矽醇、二矽醇及三矽醇；POSS－矽氧化物、鹵化物；及POSS－樹脂。Figure 5 shows examples of nanostructured surface modifiers, including POSS-monosterol, dinonol and triterpene alcohol; POSS-quinone oxides, halides; and POSS-resins.

第6圖所示為兩矽酸鹽片間藉由POSS的嵌插/剝離作用模型。Figure 6 shows the intercalation/peeling effect model of the two bismuth silicate sheets by POSS.

第7圖所示為鉀蒙脫土(MMT)與經過POSST M －矽醇剝離的MMT的X光繞射最大值(截選)。Figure 7 shows the X-ray diffraction maximum (truncated) of potassium montmorillonite (MMT) and MMT stripped by POSS T M -sterol.

較佳實施例之詳細說明Detailed description of the preferred embodiment 奈米結構的化學式表示法的定義Definition of the chemical formula of the nanostructure

為了瞭解本發明的奈米結構化學組成，對多面體寡聚倍半矽氧烷(POSS)及多面體寡聚矽酸鹽奈米結構的化學式表示法定義如下：[(RSiO1 . 5 )n (R’XSiO1 . 5 )m ]Σ# 表示異配位基組成物(其中R≠R’)[(RSiO1 . 5 )n (RXSiO1 . 0 )m ]Σ# 表示官能化異配位基組成物(其中R可為相同或不相同)In order to understand the chemical composition of the nanostructure of the present invention, the chemical formula for the polyhedral oligomeric sesquioxane (POSS) and polyhedral oligomeric phthalate nanostructures is defined as follows: [(RSiO 1 . 5 ) n (R 'XSiO 1 . 5 ) m ]Σ # represents a hetero-coordination group composition (wherein R≠R')[(RSiO 1 . 5 ) n (RXSiO 1 . 0 ) m ]Σ # represents a functionalized hetero-coordination composition (where R can be the same or different)

在上述定義中，R＝有機取代基(H、甲矽氧烷基、環狀或線性脂肪族、芳香族，或額外含有反應性官能基如醇類、酯類、胺類、酮類、烯烴、醚或鹵化物之矽氧基)。X包括但不限於OH、Cl、Br、I、烷氧基(OR)、醋酸酯基(OOCR)、過氧化物基(OOR)、胺基(NR2)、異氰酸酯基(NCO)及R。符號m與n代表組成物之化學計量。符號Σ是表示該組成形成一奈米結構，而符號#係指該奈米結構中所含的矽原子數目。#的數值通常為m＋n的和。應注意的是，Σ#不應被誤認為決定化學計量的因數，它僅用來系統的描述整體奈米結構的特性(aka cage size)。In the above definition, R = organic substituent (H, methyl oxoalkyl, cyclic or linear aliphatic, aromatic, or additionally reactive functional groups such as alcohols, esters, amines, ketones, olefins) , an ether or a halide of a decyloxy group). X includes, but is not limited to, OH, Cl, Br, I, alkoxy (OR), acetate (OOCR), peroxide (OOR), amine (NR2), isocyanate (NCO), and R. The symbols m and n represent the stoichiometry of the composition. The symbol Σ means that the composition forms a nanostructure, and the symbol # refers to the number of ruthenium atoms contained in the nanostructure. The value of # is usually the sum of m+n. It should be noted that Σ# should not be mistaken for determining the stoichiometry factor, it is only used to systematically describe the aka cage size.

奈米結構化學物質係由下列特徵來定義。它們乃是單獨的分子，而非分子的組成物型態流動的組合。它們具有輪廓分明的三維形狀多面體幾何。適當的例子是簇體，而平面烴類、樹枝狀聚合物(dendrimers)及顆粒則非適當例子。它們具有奈米層級的尺寸，範圍從大約0.7nm至5.0nm。因此，它們比小分子大，但小於宏觀級分子。它們具有系統性的化學，能控制幾何化學、反應性及它們的物理性質。Nanostructured chemical substances are defined by the following characteristics. They are separate molecules, not a combination of molecular form flow. They have well-defined three-dimensional shape polyhedral geometry. Suitable examples are clusters, while planar hydrocarbons, dendrimers and particles are not suitable examples. They have a size on the nanometer scale ranging from about 0.7 nm to 5.0 nm. Therefore, they are larger than small molecules but smaller than macroscopic molecules. They have systemic chemistry that controls geometric chemistry, reactivity, and their physical properties.

較佳實施例之詳細說明Detailed description of the preferred embodiment

第1圖所示為多面體寡聚半倍矽氧烷(POSS)類的奈米結構化學物質的構造模型。Figure 1 shows the structural model of a polyhedral oligomeric hemi-oxynitride (POSS) nanostructure chemical.

它們的特徵包括一獨特的混合(有機－無機)組成物，具有許多有利的物理特性，包括陶瓷(熱安定性與氧化安定性)和聚合物(加工性及韌性)的物理特性。此外，它們具有一無機的骨架，外面包覆的是相容性有機基團R及反應基X，其中R＝有機取代基(H、甲矽氧烷基、環狀或線性脂肪或芳香基，可能額外含有反應性官能基例如醇類、酯類、胺類、酮類、烯烴類、醚類或鹵化物)。X包括但不限於OH、Cl、Br、I、烷氧基(OR)、醋酸酯基(OOCR)、過氧基(OOR)、胺基(NR2 )、異氰酸酯基(NCO)及R。此無機的骨架與其週邊連結的基團共同形成化學精確的立方形建構塊，這些建構塊當施加於一表面上時，能提供規則且輪廓分明的表面形勢。Their characteristics include a unique hybrid (organic-inorganic) composition with many advantageous physical properties including ceramic (thermal stability and oxidation stability) and physical properties of the polymer (processability and toughness). In addition, they have an inorganic skeleton coated with a compatible organic group R and a reactive group X, wherein R = an organic substituent (H, a methoxyalkyl group, a cyclic or linear aliphatic or aromatic group, It may additionally contain reactive functional groups such as alcohols, esters, amines, ketones, olefins, ethers or halides). X includes, but is not limited to, OH, Cl, Br, I, alkoxy (OR), acetate (OOCR), peroxy (OOR), amine (NR 2 ), isocyanate (NCO), and R. This inorganic backbone, together with its peripherally bonded groups, forms chemically accurate cuboid building blocks that, when applied to a surface, provide a regular and well-defined surface condition.

奈米結構表面改質劑所提供的一特別有利的特徵在於，其單一分子能提供五倍的表面積覆蓋，相較於以假想單層形態施加的等同的矽烷偶合劑所能提供者。第2圖中之實施所採用的尺寸乃是取自R為環己基的系統的單晶X光數據，並能支持這項陳述。A particularly advantageous feature provided by the nanostructured surface modifier is that its single molecule provides five times the surface area coverage compared to equivalent decane coupling agents applied in the imaginary monolayer form. The dimensions used in the implementation of Figure 2 are single crystal X-ray data from a system in which R is a cyclohexyl group and can support this statement.

POSS化學物質當施加於宏觀級表面(纖維、填充材料、顆粒等等)或奈米級表面(奈米顆粒、填充材料)時，皆能提供一種確為奈米層級的表面幾何。依據表面結合位的數目，POSS骨架在該表面將其自身組合成一規則形態，以提供規則形態的奈米建構塊。我們發現使用POSS矽醇來作為表面改質劑最為節省成本。POSS矽醇尚有一優點，在於它們易於與其它極性表面基反應(例如Si－OH)以與該表面之間形成熱安定的矽－氧連結。POSS－硫醇與POSS矽烷在各種不同表面之組合已被發表。POSS chemistries provide a surface geometry that is indeed nanoscale when applied to macroscopic surfaces (fibers, fillers, particles, etc.) or nanoscale surfaces (nanoparticles, fillers). Depending on the number of surface binding sites, the POSS skeleton combines itself into a regular morphology on the surface to provide a regular building of nanostructured blocks. We have found that using POSS sterols as a surface modifier is the most cost effective. POSS sterols also have the advantage that they readily react with other polar surface groups (e.g., Si-OH) to form a thermally stable 矽-oxygen linkage with the surface. The combination of POSS-thiol and POSS decane on various surfaces has been published.

使用POSS系統之表面改質已被顯示為有利的，不僅在於能提高填充材料的分散性，還能改良其界面相容性。當施加於表面時，奈米結構之化學物質亦能提供各種長度規模的強化作用的優點。第3圖所示之例子為經過10－ 9 米之奈米尺寸的POSS表面改質劑改質的一宏觀級填充材料表面(毫米至微米尺寸(10－ 3 至10－ 6 米))。以此方式改質之一填充材料(或纖維)能經由POSS表面改質而同時提供宏觀級強化作用(經由顆粒大小)與奈米級強化作用。Surface modification using a POSS system has been shown to be advantageous not only to improve the dispersibility of the filler material, but also to improve its interfacial compatibility. When applied to a surface, the chemical structure of the nanostructure can also provide the advantage of strengthening in various length scales. The example shown in Figure 3 is a macroscopic filler surface (mm to micron size (10 - 3 to 10 - 6 m)) modified with a 10 - 9 meter nanometer-sized POSS surface modifier. In this way one of the filler materials (or fibers) can be modified via the POSS surface while providing macroscopic strengthening (via particle size) and nanoscale strengthening.

POSS矽醇作為表面改質劑的另一優點在於它們是無發散性的。奈米層級尺寸的POSS矽醇使得它們相較於習用矽烷及有機性表面處理劑而言，較不具揮發性。POSS矽烷本質上的安定性是獨特的，因此不會就地產生及釋出揮發性有機成份如醇類或酸類，而習用矽烷偶合劑在連接及黏結至一表面之前則必定會發生。因此，POSS矽烷的可燃性亦較低，因為它們的揮發性較低且具有無揮發性的加工優點。Another advantage of POSS sterols as surface modifiers is that they are non-dispersive. Nano-sized POSS sterols make them less volatile than conventional decane and organic surface treatments. The inherent stability of POSS decane is unique and therefore does not produce and release volatile organic components such as alcohols or acids in situ, whereas conventional decane coupling agents must occur before joining and bonding to a surface. Therefore, POSS decanes are also less flammable because of their lower volatility and processing advantages without volatility.

POSS矽烷亦可經由將反應性基團(例如乙烯基、氨基、環氧基、甲基丙烯酸基等等)直接結合至其骨架上(第4圖)，而以化學方式將兩不同類型的材料連結在一起。這種能力與已知的矽烷偶合劑的能力相似。POSS decane can also chemically combine two different types of materials by directly bonding a reactive group (eg, vinyl, amino, epoxy, methacrylic, etc.) to its backbone (Fig. 4). Linked together. This ability is similar to the ability of known decane coupling agents.

以奈米結構POSS矽醇進行表面改質Surface modification with nanostructured POSS sterol

奈米結構化學物質是全球奈米技術趨勢的一部份(更小、更便宜、分子控制)，直接影響各行各業及各行業的產品。Nanostructured chemicals are part of the global nanotechnology trend (smaller, cheaper, molecularly controlled) that directly affects products from all walks of life and industries.

要改良纖維及礦物粒子的一個簡單又節省成本的方式乃是將奈米構造化學物質施加到這些宏觀級強化物的表面。這種方式乃類似於在該表面上塗覆有機矽烷、偶合劑、鋁鹽或其它表面改質劑。但是，以奈米構造化學物質進行表面改質能更有效地提高相容性、阻隔溼氣及控制塗層構造，這最終會改良塗層的耐用性及可靠性。A simple and cost-effective way to improve fiber and mineral particles is to apply nanostructured chemicals to the surface of these macroscale reinforcements. This approach is similar to coating the surface with an organic decane, coupling agent, aluminum salt or other surface modifying agent. However, surface modification with nanostructured chemicals can improve compatibility, block moisture, and control coating construction, which ultimately improves the durability and reliability of the coating.

一些POSS單體及試劑已被發展成作表面改質之用。此系統可被認為是傳統矽烷偶合劑的奈米結構相似物(第5圖)。Some POSS monomers and reagents have been developed for surface modification. This system can be considered as a nanostructure similarity to a conventional decane coupling agent (Fig. 5).

POSS表面改質劑可經由溶液加工法、熔融噴塗法或蒸氣沈積法而被施加於礦物、玻璃、金屬、陶瓷及聚合表面。每一POSS系統上的極性基團(例如矽醇、矽烷、烷氧基等)都對填充材料表面提供了一個化學接合點，而奈米結構上的其它有機基團則使得該表面具有疏水性，並且在填充材料與聚合物基質之間提供相容性(見第2、3圖)。又，此種經處理的填充材料的表面此時則適於與一聚合物基質在奈米層級上交互作用，因此對聚合物鏈提供奈米級及宏觀級的強化作用。所得到的多重規模的強化作用能對傳統宏觀級強化作用提供更寬廣的功能及價值。The POSS surface modifier can be applied to mineral, glass, metal, ceramic, and polymeric surfaces via solution processing, meltblowing, or vapor deposition. Polar groups on each POSS system (eg, decyl alcohol, decane, alkoxy, etc.) provide a chemical bond to the surface of the filler material, while other organic groups on the nanostructure make the surface hydrophobic. And provide compatibility between the filler material and the polymer matrix (see Figures 2 and 3). Moreover, the surface of such treated filler material is now adapted to interact with a polymer matrix at the nano-layer level, thereby providing nano- and macro-level strengthening of the polymer chain. The resulting multi-scale reinforcement can provide a broader range of functions and value for traditional macro-level reinforcement.

目前已顯示，以POSS技術處理金屬表面，即使在高溫下仍能提供優越的抗腐蝕性，而以POSS處理礦物則顯示能降低水氣的吸收及改良其分散性。It has been shown that the treatment of metal surfaces with POSS technology provides superior corrosion resistance even at high temperatures, while treatment of minerals with POSS has been shown to reduce moisture absorption and improve dispersion.

傳統的矽烷偶合劑(例如RSiX3 )通常具有一個R基，並且含有三個容易水解的官能基(例如X＝Cl、OCH3 )。一偶合劑的表面塗層通常被描述為一個單層，雖然目前已顯示，由稀釋為0.25%的溶液來塗覆的偶合劑能夠沈積的表面塗層達到了8層的厚度。亦已知，此種偶合劑在連結至欲被塗覆的表面之前必須經由水解成中間體矽醇物種(例如RSi(OH)3 )而被活化。此種活化過程使得危險的有機成份如HCl及甲醇被去除。奈米結構偶合劑提供了明顯優於傳統“小分子”技術的優點。第2圖提供了一“矽烷單層”與一奈米結構偶合劑的物理尺寸的比較。從其各自覆蓋的面積的比較可以清楚的看出，奈米結構的偶合劑提供了比傳統矽烷單層更強的疏水性及更大的表面塗層。Traditional Silane coupling agent (e.g., RSiX 3) typically has a group R, and contains three readily hydrolyzable functional group (e.g., X = Cl, OCH 3). The surface coating of a coupling agent is generally described as a single layer, although it has been shown that a surface coating of a coupling agent coated with a solution diluted to 0.25% can achieve a thickness of eight layers. It is also known that such coupling agents must be activated via hydrolysis to intermediate sterol species (e.g., RSi(OH) 3 ) prior to attachment to the surface to be coated. This activation process removes hazardous organic components such as HCl and methanol. Nanostructure couplers offer advantages that are significantly superior to traditional "small molecule" technologies. Figure 2 provides a comparison of the physical dimensions of a "decane monolayer" with a nanostructure coupler. It is clear from the comparison of the areas covered by the respective layers that the coupling agent of the nanostructure provides a stronger hydrophobicity and a larger surface coating than the conventional decane monolayer.

其它的優點還包括：可獲致更加規則的表面塗層，即使奈米結構具有輪廓分明的多面體結構，相對於多官能性矽烷的多層所產生的無規結構。Other advantages include the ability to obtain a more regular surface coating, even if the nanostructure has a well-defined polyhedral structure, relative to the random structure produced by the multilayer of polyfunctional decane.

額外的優點包括：可達到一更規則的表面塗層，即使該奈米結構有輪廓分明的多面體結構，而非多層多官能性矽烷所產生的無規結構。再者，因為POSS矽烷是空氣穩定的，POSS奈米結構不需要經由水解來活化，具有無限期的保存壽命，並可直接與欲被處理的表面反應。其它因使用奈米結構POSS矽烷偶合劑所獲得的良好性質包括能修改奈米結構上的相容性R基團使配合樹脂基質的溶解度特性。此外，POSS矽烷系統可以無溶劑的方式塗覆，因此，不含揮發性有機成份(VOCs)，因此，可免去傳統偶合劑所存在的發散性及曝露於VOCs的問題。Additional advantages include the ability to achieve a more regular surface coating, even if the nanostructure has a well-defined polyhedral structure rather than the random structure produced by the multilayer polyfunctional decane. Furthermore, since POSS decane is air-stable, the POSS nanostructure does not need to be activated by hydrolysis, has an indefinite shelf life, and can directly react with the surface to be treated. Other good properties obtained by using a nanostructured POSS decane coupling agent include the ability to modify the compatible R groups on the nanostructure to impart solubility characteristics to the resin matrix. In addition, the POSS decane system can be applied in a solvent-free manner and, therefore, does not contain volatile organic compounds (VOCs), thus eliminating the divergence and exposure to VOCs of conventional coupling agents.

以POSS化學物質作嵌插或剝離Insertion or stripping with POSS chemicals

POSS試劑與分子二氧化矽亦常用於塗覆礦物特別是多層矽酸鹽的內表面。當作為塗層塗覆在礦物或其它多孔材料上時，POSS實體能夠有效地將較高的礦物相容性傳至選定的氣體入口及出口，以及其它分子例如溶劑、單體及聚合物。由於通行能力相似，POSS矽烷與非反應性分子二氧化矽都能進入多層矽酸鹽的內部通道，並且同時作為通道之分隔件及相容物，以藉由可聚合之單體及聚合物鏈來傳遞此種親和力較高之材料，以供嵌插及剝離(第6圖)。POSS reagents and molecular cerium oxide are also commonly used to coat the inner surface of minerals, particularly multilayer silicates. When applied as a coating on mineral or other porous materials, the POSS entity is effective in transferring higher mineral compatibility to selected gas inlets and outlets, as well as other molecules such as solvents, monomers, and polymers. Due to similar transport capacity, POSS decane and non-reactive molecular cerium oxide can enter the internal channels of the multi-layer citrate, and at the same time serve as a separator and a compatible substance for the channel, by polymerizable monomers and polymer chains. This material with a high affinity is transmitted for insertion and peeling (Fig. 6).

位在POSS籠的各角落處的有機R基團對相容性的影響乃直接造成相容性的提高。這些R基造成相容的能力乃直接源自於同類相溶的理論。這一基礎理論僅陳述了相似組成(或化學勢)的物質比起不相似組成(或化學勢)的物質更易相容。因此，藉由POSS籠上的R取代基與一聚合物鏈的碳氫化合物組成的適當配合，POSS能以有機方式改質矽酸鹽及其它類似的材料，因此使它們與有機組成物相容。The effect of the organic R groups at various corners of the POSS cage on compatibility is directly responsible for improved compatibility. The ability of these R groups to cause compatibility is directly derived from the theory of homogeneous compatibility. This basic theory only states that substances of similar composition (or chemical potential) are more compatible than substances of dissimilar composition (or chemical potential). Thus, by appropriate coordination of the R substituents on the POSS cage with the hydrocarbon composition of a polymer chain, POSS can organically modify the phthalate and other similar materials, thus making them compatible with the organic composition.

POSS矽烷能有效嵌插且最終剝離多層矽酸鹽的能力已經由X光繞射實驗得到證實。X光繞射技術提供了一個能夠敏銳測量層疊矽酸鹽片之間的層間隔的方式。第7圖顯示鉀蒙脫土的入射X光角度對強度水平作圖，此蒙脫土乃塗覆有兩種不同的POSS－三矽醇。The ability of POSS decane to effectively intercalate and ultimately strip multi-layer citrate has been demonstrated by X-ray diffraction experiments. X-ray diffraction technology provides a means to sharply measure the layer spacing between stacked tantalum sheets. Figure 7 shows the incident X-ray angle of potassium montmorillonite plotted against the intensity level, which is coated with two different POSS-triterols.

蒙脫土(MMT)的未處理的繞射最大值，相當於2θ值7.14，對應的通道間隔為12.4。使用式[(EtSiO1 . 5 )4 (Et(OH)SiO1 . 0 )3 ]Σ7 (乙基T7)或[(I－BuSiO1 . 5 )4 (I－Bu(OH)SiO1 . 0 )3 ]Σ7 (異丁基T7)的POSS矽醇來處理MMT則造成了此最大值偏移至較低的2θ值，使乙基T7的2θ值成為5.94而異丁基T7的2θ值5.86，其等對應之通道內間隔分別為14.96與15.10。The untreated diffraction maximum of montmorillonite (MMT) is equivalent to a 2θ value of 7.14, corresponding to a channel spacing of 12.4. . The formula [(EtSiO 1 . 5 ) 4 (Et(OH)SiO 1 . 0 ) 3 ] Σ 7 (ethyl T7) or [(I-BuSiO 1 . 5 ) 4 (I-Bu(OH)SiO 1 . 0 ) 3 ]Σ 7 (isobutyl T7) POSS sterol to treat MMT caused this maximum shift to a lower 2θ value, making the 2θ value of ethyl T7 5.94 and the 2θ of isobutyl T7 The value is 5.86, and the corresponding channel spacing is 14.96. With 15.10 .

考慮到[(EtSiO1 . 5 )4 (Et(OH)SiO1 . 0 )3 ]Σ7 與/或[(i－BuSiO1 . 5 )4 (i－Bu(OH)SiO1 . 0 )3 ]Σ7 奈米結構的尺寸約為14，可確認蒙脫土矽酸鹽層間之通道間隔會因該通道中存在有POSS而增加。位在該通道中之POSS係連結至含有矽酸鹽及鉀/鈉平衡陽離子的內表面上。要注意，一旦通道層分開到這程度，則不帶有矽醇的POSS實體在物理上也能進入該通道而不與內表面連結。式[(RSiO1 . 5 )n ]Σ # 的POSS分子二氧化矽與POSS單體為此種非鍵結的穿入物/剝離物的實例。另一繞射最大值，位在2θ＝8.72(乙基T7)與2θ＝8.65(異丁基T7)，表示這些POSS矽醇亦存在於蒙脫土片的表面與外緣。Consider [(EtSiO 1 . 5 ) 4 (Et(OH)SiO 1 . 0 ) 3 ]Σ 7 and/or [(i-BuSiO 1 . 5 ) 4 (i-Bu(OH)SiO 1 . 0 ) 3 ]Σ 7 nanometer structure size is about 14 It can be confirmed that the channel spacing between the montmorillonite layers will increase due to the presence of POSS in the channel. The POSS located in the channel is attached to the inner surface containing the citrate and potassium/sodium balance cations. It is to be noted that once the channel layer is separated to this extent, a POSS entity without sterol can physically enter the channel without being attached to the inner surface. The POSS molecular cerium oxide and POSS monomer of the formula [(RSiO 1 . 5 ) n ] Σ # are examples of such non-bonded penetrants/releases. Another diffraction maximum, located at 2θ = 8.72 (ethyl T7) and 2θ = 8.65 (isobutyl T7), indicates that these POSS sterols are also present on the surface and outer edge of the montmorillonite sheet.

塗覆與加工方法Coating and processing method

POSS矽醇、分子二氧化矽與POSS樹脂乃是以低熔點及高熔點固體及油料天然的存在。它們在多種常見的溶劑中呈現高度的溶解度，這些溶劑包括芳香族、烴類、鹵化系統及各種有機單體包括苯乙烯、丙烯酸類、環狀拉伸與未拉伸之烯烴、縮水甘油、酯類、醇類及醚類。它們熔化及溶解的能力使其得以利用所有習用的塗覆技術來塗覆，包括漿液法、旋塗、刷塗、噴塗、流塗及蒸氣沈積法。POSS sterols, molecular cerium oxide and POSS resins are naturally present in low melting and high melting solids and oils. They exhibit high levels of solubility in a variety of common solvents including aromatics, hydrocarbons, halogenated systems and various organic monomers including styrene, acrylics, cyclically stretched and unstretched olefins, glycidol, esters. Classes, alcohols and ethers. Their ability to melt and dissolve allows them to be coated using all conventional coating techniques, including slurrying, spin coating, brushing, spraying, flow coating, and vapor deposition.

典型的藉助溶劑的塗覆方法包括將POSS實體溶於一所要的溶劑中，濃度為0.1重量%至99重量%，然後將此溶液與欲被塗覆之材料或表面接觸。之後通常藉由蒸發將溶劑移除，再藉由機械式抹擦或外加溶劑清洗以去除過量的POSS。吸收在該表面上的材料的量將視POSS組成、表面型態及塗覆方法而有變化。POSS三矽醇在不同材料表面上的典型負載量顯示於下表2。A typical solvent-based coating process involves dissolving the POSS entity in a desired solvent at a concentration of from 0.1% to 99% by weight and then contacting the solution with the material or surface to be coated. The solvent is typically removed by evaporation and then washed by mechanical wiping or an additional solvent to remove excess POSS. The amount of material absorbed on the surface will vary depending on the POSS composition, surface morphology and coating method. Typical loadings of POSS triterpene on the surface of different materials are shown in Table 2 below.

表面塗層及萃取研究Surface coating and extraction research

POSS矽醇已被證實，一旦被塗在一材料表面上，會展現優異的黏著性及耐用性。而藉由溫和地加熱剛經處理的材料或表面則能再提高該黏著性。例如，在120℃這樣低的溫度下加熱能提高POSS矽醇之連結，可能是經由加速極性表面基團與POSS矽醇的反應性矽－氧基之間的鍵結。表3含有一些塗覆有各種POSS矽醇的選出的材料在處理前後的萃取資料。POSS sterols have been shown to exhibit excellent adhesion and durability once applied to a surface of a material. This adhesion can be further enhanced by gently heating the freshly treated material or surface. For example, heating at such low temperatures as 120 ° C can increase the linkage of POSS sterols, possibly by accelerating the bond between the polar surface groups and the reactive 矽-oxy groups of POSS sterols. Table 3 contains extracts from selected materials coated with various POSS sterols before and after treatment.

例example

溶劑輔助塗覆法將異辛基POSS三矽醇(100克)溶於400mL的二氯甲烷中。在此混合物中加入500克蒙脫土。在室溫下攪拌此混合物30分鐘。然後在真空下移除揮發性溶劑並將它收集。應注意，可利用超臨界流體例如CO2 來取代易燃的碳氫化合物溶劑。所得到的自由流動的固體可以直接使用或者在使用前再在120℃下溫和地熱處理。Solvent-assisted coating was carried out by dissolving isooctyl POSS triterpene alcohol (100 g) in 400 mL of dichloromethane. To this mixture was added 500 g of montmorillonite. The mixture was stirred at room temperature for 30 minutes. The volatile solvent was then removed under vacuum and it was collected. It should be noted that a supercritical fluid such as CO 2 may be utilized in place of the flammable hydrocarbon solvent. The resulting free-flowing solid can be used directly or heat-treated at 120 ° C before use.

第1圖所示為一POSS奈米結構化學物質的構造。Figure 1 shows the structure of a POSS nanostructure chemical.

第2圖所示為作為單層施用在一表面的傳統矽烷(左圖)，與作為單層施用的奈米結構偶合劑的實際尺寸關係。Figure 2 shows the actual dimensional relationship of a conventional decane (left) applied as a single layer on a surface to a nanostructure coupling agent applied as a single layer.

第3圖所示為經由宏觀級表面的POSS表面改質所提供的多重長度規模強化作用(奈米級至宏觀級)。Figure 3 shows the multi-length scale enhancement (nano to macro) provided by POSS surface modification on a macro-scale surface.

第4圖所示為POSS矽醇偶合劑的結構模型，R可為適合與一聚合物偶合的官能基。Figure 4 shows a structural model of a POSS sterol coupler, R being a functional group suitable for coupling to a polymer.

第5圖所示為奈米結構表面改質劑的例子，包括POSS－一矽醇、二矽醇及三矽醇；POSS－矽氧化物、鹵化物；及POSS－樹脂。Figure 5 shows examples of nanostructured surface modifiers, including POSS-monosterol, dinonol and triterpene alcohol; POSS-quinone oxides, halides; and POSS-resins.

第6圖所示為兩矽酸鹽片間藉由POSS的嵌插/剝離作用模型。Figure 6 shows the intercalation/peeling effect model of the two bismuth silicate sheets by POSS.

第7圖所示為鉀蒙脫土(MMT)與經過POSST M －矽醇剝離的MMT的X光繞射最大值(截選)。Figure 7 shows the X-ray diffraction maximum (truncated) of potassium montmorillonite (MMT) and MMT stripped by POSS T M -sterol.

Claims (12)

一種用以改質一基材之物理特性的方法，該基材係選自於下列所組成之組群中：沸石、合成及天然矽酸鹽、矽石、鋁土、礦物、天然及人造纖維、玻璃及金屬纖維，包含：在該基材上塗覆一層奈米結構化學物質，該奈米結構化學物質係選自於多面體寡聚倍半矽氧烷之群組，且該多面體寡聚倍半矽氧烷係具有[(RSiO1.5 )n (RXSiO1.0 )m ]Σ# 之結構，其中m、n及#係為由1至1000的整數，R為線性脂族烴且X=OH，及其中該奈米結構化學物質改質該基材之一物理性質，該性質係選自於由(a)降低經由該基材的濕氣吸收力及(b)當該基材被使用作為一填充材料時，提升其與一聚合物的相容性所構成之組群。A method for modifying the physical properties of a substrate selected from the group consisting of zeolites, synthetic and natural citrates, vermiculite, alumina, minerals, natural and man-made fibers And glass and metal fibers, comprising: coating a layer of a nanostructure chemical on the substrate, wherein the nanostructure chemical is selected from the group of polyhedral oligomeric sesquioxanes, and the polyhedral oligomeric half The siloxane has a structure of [(RSiO 1.5 ) n (RXSiO 1.0 ) m ] Σ # , wherein m, n and # are integers from 1 to 1000, R is a linear aliphatic hydrocarbon and X = OH, and The nanostructure chemical modifies one of the physical properties of the substrate selected from (a) reducing moisture absorption through the substrate and (b) when the substrate is used as a filler material At the same time, the group formed by the compatibility with a polymer is improved. 如申請專利範圍第1項之方法，其中該基材係以一奈米結構化學物質的混合物來塗覆。 The method of claim 1, wherein the substrate is coated with a mixture of one nanostructured chemical. 如申請專利範圍第1項之方法，其中該奈米結構化學物質係嵌入該基材。 The method of claim 1, wherein the nanostructure chemical is embedded in the substrate. 如申請專利範圍第1項之方法，其中該奈米結構化學物質將該基材剝離。 The method of claim 1, wherein the nanostructure chemical detaches the substrate. 如申請專利範圍第1項之方法，其中該基材係使用一種無溶劑技術來塗覆。 The method of claim 1, wherein the substrate is coated using a solventless technique. 如申請專利範圍第5項之方法，其中該無溶劑技術為一種熔融加工法。 The method of claim 5, wherein the solventless technique is a melt processing method. 如申請專利範圍第1項之方法，其中該基材係使用一種 溶劑輔助技術來塗覆。 The method of claim 1, wherein the substrate is a type Solvent assisted technology to coat. 如申請專利範圍第7項之方法，其中該溶劑輔助技術係選自於下列所組成的組群中：噴塗、流塗及混合加工技術。 The method of claim 7, wherein the solvent assisting technique is selected from the group consisting of: spray coating, flow coating, and hybrid processing techniques. 如申請專利範圍第1項之方法，其中該基材係使用一種超臨界流體輔助技術來塗覆。 The method of claim 1, wherein the substrate is coated using a supercritical fluid assist technique. 如申請專利範圍第9項之方法，其中該超臨界流體輔助技術包含噴塗、流塗及混合加工技術。 The method of claim 9, wherein the supercritical fluid assisting technique comprises spraying, flow coating, and mixing processing techniques. 如申請專利範圍第1項之組成物，其中該奈米結構化學物質係反應性地連結至該基材上。 The composition of claim 1, wherein the nanostructure chemical is reactively attached to the substrate. 如申請專利範圍第1項之組成物，其中該奈米結構化學物質係非反應性地連結至該基材上。 The composition of claim 1, wherein the nanostructure chemical is non-reactively bonded to the substrate.
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