TW202111000A

TW202111000A - A organic-inorganic hybrid material, its fabricating process and its raw material's preparation

Info

Publication number: TW202111000A
Application number: TW109124312A
Authority: TW
Inventors: 戴憲弘; 吳建欣; 黃英治; 黃昱翔; 葉世傑; 鄭如忠
Original assignee: 詮達化學股份有限公司
Priority date: 2019-09-06
Filing date: 2019-09-06
Publication date: 2021-03-16

Abstract

The invention is related to an organic-inorganic hybrid material. The organic-inorganic hybrid material is a green material contains 5~50wt.% of inorganic compounds and have a peak at 1050±50 cm^-1 in the FTIR spectrum. Furthermore, the invention also provides a fabricating process of the organic-inorganic hybrid material as well as its starting material “isocyanates”. In particular, the isocyanates are prepared from carbonates.

Description

一種有機無機混成材料、其製備方法和其起始原料的製備方法 Organic-inorganic hybrid material, its preparation method and its starting material preparation method

本發明係關於一有機無機混成材料。該有機無機混成材料包含的無機化合物的重量百分比是5~50wt.%，且在傅立葉紅外光譜圖約1050±50cm^-1的位置有特徵峰。其次，本發明也提供該有機無機混成材料的製備方法及其起始原料組成；其中該起始原料組成之一是異氰酸鹽和酚類的縮合物。特別地，該異氰酸鹽的製備方法是從碳酸酯類轉化生成該異氰酸鹽，該方法能夠解決聚碳酸酯的廢棄物問題，且在轉化過程中不會釋放二氧化碳，是一具經濟價值的綠色環保製程。 The present invention relates to an organic-inorganic hybrid material. The weight percentage of the inorganic compound contained in the organic-inorganic hybrid material is 5-50wt.%, and there is a characteristic peak at a position of ^{about 1050±50cm -1 in the Fourier infrared spectrum.} Secondly, the present invention also provides a preparation method of the organic-inorganic hybrid material and its starting material composition; wherein one of the starting material composition is a condensate of isocyanate and phenols. In particular, the preparation method of the isocyanate is to convert the isocyanate from carbonates. This method can solve the problem of polycarbonate waste, and does not release carbon dioxide during the conversion process, which is an economical method. The value of green environmental protection process.

複合材料常應用在高科技產業，特別是有機無機混成材料的相關應用，因其特殊的高阻氣性、低吸濕性與分散性，相對於傳統材料，其材料性質提升明顯，目前已成為光學、醫材、電子和特殊塗料等高科技應用的必須材料。 Composite materials are often used in high-tech industries, especially related applications of organic-inorganic hybrid materials. Due to their special high gas barrier properties, low moisture absorption and dispersibility, compared with traditional materials, their material properties have been significantly improved. Required materials for high-tech applications such as optics, medical materials, electronics, and special coatings.

複合材料的往往由有機高分子與無機物形成有機-無機混城材料，然而想對於有機高分子的分子鏈，無機物粒子或粉末具有相對較大的奈米等級尺寸，加上型態變化後為二維平版或片狀材料導入高分子過程中，往往出現有機-無機相分離現象，影響複合材料的性質表現與材料的穩定性。 Composite materials are often composed of organic polymers and inorganic substances to form organic-inorganic hybrid materials. However, for the molecular chains of organic polymers, inorganic particles or powders have a relatively large nano-scale size, plus the change in shape. Dimensional plate or sheet material import high In the molecular process, organic-inorganic phase separation often occurs, which affects the properties and stability of composite materials.

綜上所述，如何設計一種添加劑配方與促進有機-無機物間相容性，同時提升複合材料的整體性質如成膜性、吸水性、或阻氣性滿足應用需求，一直是本技術領域亟需解決克服之問題。 In summary, how to design an additive formulation to promote the compatibility of organic-inorganic substances, while improving the overall properties of the composite material such as film-forming, water absorption, or gas barrier properties to meet application requirements, has always been an urgent need in this technical field. Solve the problems to overcome.

鑒於上述之發明背景，為了符合產業上之要求，本發明之第一目的在於提供一種新穎的有機無機混成材料。創新地，本發明的有機無機混成材料是一藉由一新穎的改質劑和導入方法所製成。第二，本發明的有機無機混成材料是一可來自碳酸酯或聚碳酸酯回收物重新使用的綠色原料，因此能夠達到材料循環使用的目的。 In view of the aforementioned background of the invention, in order to meet the requirements of the industry, the first object of the present invention is to provide a novel organic-inorganic hybrid material. Innovatively, the organic-inorganic hybrid material of the present invention is made by a novel modifier and introduction method. Second, the organic-inorganic hybrid material of the present invention is a green raw material that can be reused from recycled carbonate or polycarbonate, so it can achieve the purpose of recycling the material.

具體地，上述的有機無機混成材料是由結構式(1)所示之化合物或一異氰酸鹽和酚類反應的縮合物或碳酸二苯酯或一無機微球，和一高分子的預聚物藉由溶凝膠法所製備得到；以該有機無機混成材料的總重量計，其所包含的無機化合物的重量百分比是5~50wt.%，且在傅立葉紅外光譜圖中約1050±50cm^-1的位置有特徵峰。 Specifically, the above-mentioned organic-inorganic hybrid material is composed of a compound represented by the structural formula (1) or a condensate of a reaction between a monoisocyanate and a phenol, or diphenyl carbonate or an inorganic microsphere, and a polymer precursor. The polymer is prepared by the solvogel method; based on the total weight of the organic-inorganic hybrid material, the weight percentage of the inorganic compound contained in it is 5-50wt.%, and is about 1050±50cm in the Fourier Infrared Spectrogram There is a characteristic peak at the position of ^-1.

具體地，本發明所述的改質劑就是上述的結構式(1)所示之化合物。。 Specifically, the modifier of the present invention is the compound represented by the above-mentioned structural formula (1). .

該結構式(1)中所示的BP為苯酚、多苯酚衍生物或含鹵素的苯酚類；X可為(-CH₂-)_m或-O-；_m為1到10的正整數；Y為(H)_a、(-OH)_b、(-OCH₃)_c、(-OCH₂CH₃)_d或(-OCH₂CH₂CH₃)_e且a+b+c+d+e=3的任何組合。 The BP shown in the structural formula (1) is phenol, polyphenol derivatives or halogen-containing phenols; X can be (-CH ₂ -) _m or -O-; _m is a positive integer from 1 to 10; Y Is (H) _a , (-OH) _b , (-OCH ₃ ) _c , (-OCH ₂ CH ₃ ) _d or (-OCH ₂ CH ₂ CH ₃ ) _e and a+b+c+d+e=3 Any combination of.

具體地，上述的苯酚包含雙酚A(2,2-bis(4-hydroxyphenyl)propane(bisphenol A))、雙酚F(2,2-bis(4-hydroxyphenyl)methane(bisphenol F))、結構式(2)所示之化合物、結構式(3)所示之化合物或結構式(4)所示之化合物。 Specifically, the aforementioned phenol includes bisphenol A (2,2-bis(4-hydroxyphenyl)propane (bisphenol A)), bisphenol F (2,2-bis(4-hydroxyphenyl)methane (bisphenol F)), and the structure The compound represented by formula (2), the compound represented by structural formula (3), or the compound represented by structural formula (4).

該結構式(2)所示之化合物如下所示 The compound represented by the structural formula (2) is as follows

該結構式(3)所示之化合物如下所示 The compound represented by the structural formula (3) is as follows

該結構式(4)所示之化合物如下所示 The compound represented by the structural formula (4) is as follows

上述結構式(2)、(3)和(4)所示的R₁分別可為碳數10以下的長碳鏈，環烷烴、鹵代烷烴、羰基、磺醯基、亞磺醯基、或雙取代多酚基；R₂分別可為氫或碳數5以下的長碳鏈，環烷烴、鹵代烷烴、羰基、磺醯基、亞磺醯基、或多酚基；Z分別可為各自獨立出現的4以下整數、p≦20。 _{R 1} represented by the above structural formulas (2), (3) and (4) can be long carbon chains with carbon number 10 or less, cycloalkanes, halogenated alkanes, carbonyl groups, sulfonyl groups, sulfinyl groups, or double Substituted polyphenol group; R ₂ can be hydrogen or a long carbon chain with carbon number 5 or less, cycloalkane, halogenated alkane, carbonyl, sulfonyl, sulfinyl, or polyphenol group; Z can be each independently Integer of 4 or less, p≦20.

本發明的有機無機混成材料是採用上述的包含改質劑的反應配方，藉此增加有機物和無機物之間的相容性，並藉由溶凝膠法製成具有一良好物化性質的有機無機混成材料。 The organic-inorganic hybrid material of the present invention adopts the above-mentioned reaction formula containing modifiers to increase the compatibility between organic and inorganic substances, and is made into organic-inorganic hybrid materials with good physical and chemical properties by the solvogel method. material.

具體地，所述的反應配方的主要組成分別是：(1).上述結構式(1)所示之化合物和一高分子的預聚物；(2).上述異氰酸鹽和酚類反應的縮合物和一高分子的預聚物；(3).上述碳酸二苯酯(diphenyl carbonate)和一高分子的預聚物；或(4).上述的無機微球和一高分子的預聚物。 Specifically, the main components of the reaction formula are: (1) the compound represented by the above structural formula (1) and a polymer prepolymer; (2) the reaction between the above isocyanate and phenol (3). The above-mentioned diphenyl carbonate and a polymer prepolymer; or (4). The above-mentioned inorganic microsphere and a polymer prepolymer; Polymer.

具體地，該高分子包含聚氨酯、環氧樹脂或聚亞醯胺；其預聚物的分子量是5,000~50,000Da。 Specifically, the polymer contains polyurethane, epoxy resin or polyimide; the molecular weight of its prepolymer is 5,000-50,000 Da.

本發明之第二目的在於提供第一目的所提供的有機無機混成材料的製備方法。創新地，本發明所提供的方法還能解決聚碳酸酯廢棄物的問題，同時也將二氧化碳繼續固定於所製備的有機無機混成材料中，延長了二氧化碳在材料中的碳循環，是一兼具環境友善和高經濟價值的方法。 The second object of the present invention is to provide a method for preparing the organic-inorganic hybrid material provided by the first object. Innovatively, the method provided by the present invention can also solve the problem of polycarbonate waste, while also continuing to fix carbon dioxide in the prepared organic-inorganic hybrid material, prolonging the carbon cycle of carbon dioxide in the material, and is both Environmentally friendly and high economic value method.

具體地，本發明所述的有機無機混成材料的製備方法包含下述步驟：(1).提供一如結構式(1)所示之化合物、一異氰酸鹽和酚類反應的縮合物、碳酸二苯酯或一無機微球；(2)加入上述之如結構式(1) 所示之化合物、異氰酸鹽和酚類反應的縮合物、碳酸二苯酯或無機微球至一分子量是5,000~50,000的高分子的預聚物，藉此得到一混合物，該高分子的預聚物的含量占該混合物的10~60質量%(wt.%)；和(3)r藉由溶凝膠法，使該混合物的組成份進行水解縮合反應，藉此形成所述之有機無機混成材料；以該有機無機混成材料的總重量計，其包含的無機化合物的重量百分比是5~50wt.%，且在傅立葉紅外光譜圖中約1050±50cm^-1位置有特徵峰。 Specifically, the preparation method of the organic-inorganic hybrid material of the present invention includes the following steps: (1). Provide a compound represented by the structural formula (1), a condensate of a reaction between an isocyanate and a phenol, Diphenyl carbonate or an inorganic microsphere; (2) Add the above-mentioned compound represented by the structural formula (1), the condensation product of the reaction of isocyanate and phenol, diphenyl carbonate or inorganic microsphere to one molecular weight Is a polymer prepolymer of 5,000 to 50,000, thereby obtaining a mixture, the content of the polymer prepolymer accounts for 10 to 60% by mass (wt.%) of the mixture; and (3) r by dissolving Gel method, the components of the mixture are subjected to a hydrolytic condensation reaction, thereby forming the organic-inorganic hybrid material; based on the total weight of the organic-inorganic hybrid material, the weight percentage of the inorganic compound contained is 5~50wt. %, and there is a characteristic peak at about 1050 ± 50 cm ^{-1 in the Fourier Infrared Spectrogram.}

具體地，上述的混合物還包含一溶劑，藉此使該混合物形成一均勻相。該溶劑包含四氫呋喃(Tetrahydrofuran)、二甲基亞碸(Dimethyl Sulfoxide)、二甲基甲醯胺Dimethylformamide、N-甲基吡咯烷酮(N-Methyl-2-Pyrrolidone)或苯甲醚(Anisole)。 Specifically, the above-mentioned mixture also contains a solvent, so that the mixture forms a homogeneous phase. The solvent includes Tetrahydrofuran, Dimethyl Sulfoxide, Dimethylformamide, N-Methyl-2-Pyrrolidone, or Anisole.

較佳地，該水解縮合反應的溫度範圍是20~60℃。 Preferably, the temperature range of the hydrolysis condensation reaction is 20-60°C.

本發明之第三目的是提供一種從碳酸酯類製備異氰酸鹽的方法。根據本方法製備得到的異氰酸鹽能夠作為本發明第一目的所述的有機無機混成材料的關鍵原料之一。特別地，該製備方法能夠使用廢聚碳酸酯作為反應進料之一，在經過兩階段的加熱步驟後，就能夠使其轉化成為異氰酸鹽。因此，本發明第三目的所提供的從碳酸酯類製備異氰酸鹽的方法還解決了聚碳酸酯廢棄物的處理問題。相較於傳統的光氣法製備異氰酸鹽，本方法是一非光氣法，在加熱步驟中不會釋放二氧化碳，因此，本發明第三目的所述的從碳酸酯類製備異氰酸鹽的方法兼具了安全和環境友善的優點，是一具有高度原子效益的異氰酸鹽製備方法。 The third object of the present invention is to provide a method for preparing isocyanate from carbonates. The isocyanate prepared according to the method can be used as one of the key raw materials of the organic-inorganic hybrid material according to the first object of the present invention. In particular, the preparation method can use waste polycarbonate as one of the reaction feeds, which can be converted into isocyanate after a two-stage heating step. Therefore, the method for preparing isocyanate from carbonates provided by the third object of the present invention also solves the problem of the disposal of polycarbonate waste. Compared with the traditional phosgene method for preparing isocyanate, this method is a non-phosgene method and does not release carbon dioxide during the heating step. Therefore, the third objective of the present invention is to prepare isocyanate from carbonates. The salt method combines the advantages of safety and environmental friendliness, and is an isocyanate preparation method with high atomic efficiency.

具體地，上述的從碳酸酯類製備異氰酸鹽的方法包含以下步驟：提供一混合物，該混合物包含一碳酸酯類、一胺類或含矽基之胺類的化合物和一溶劑；該碳酸酯類包含聚碳酸酯、碳酸二苯酯或其組合物；和進行一轉化程序，使上述混合物中的該碳酸酯類和該胺類或含矽基之胺類的化合物轉化生成所述的異氰酸鹽；該轉化程序包含第一加熱步驟和第二加熱步驟，該第一加熱步驟的操作溫度範圍是40~150℃；該第二加熱步驟的操作溫度範圍是100~250℃，且該第二加熱步驟的操作壓力範圍是在0.0001-400mmHg。 Specifically, the above-mentioned method for preparing isocyanate from carbonates includes the following steps: providing a mixture comprising a carbonate, an amine or a silyl-containing amine compound and a solvent; the carbonic acid The esters include polycarbonate, diphenyl carbonate or a combination thereof; and a conversion procedure is performed to convert the carbonate and the amine or silyl-containing amine compound in the above mixture to the isoform Cyanate; the conversion procedure includes a first heating step and a second heating step, the operating temperature range of the first heating step is 40~150°C; the operating temperature range of the second heating step is 100~250°C, and the The operating pressure range of the second heating step is 0.0001-400mmHg.

具體地，以該混合物的總重量計，該聚碳酸酯、碳酸二苯酯或其組合物的反應濃度是5~50wt.%。 Specifically, based on the total weight of the mixture, the reaction concentration of the polycarbonate, diphenyl carbonate, or a combination thereof is 5-50 wt.%.

綜上所述，本發明提供的一種有機無機混成材料、其製備方法和其起始原料的製備方法至少具備下述的創新性和優點：(1)本發明提供的有機無機混成材料是藉由添加特別設計的改質劑，藉此增加有機物和無機物的相容性，進一步提升其材料的整體性質，如防水性或成膜性；(2)本發明提供的有機無機混成材料的製備方法使用的反應配方的組成之一是來自廢棄的高分子，如聚碳酸酯，因此上述方法還解決了高分子材料的廢棄物問題；和(3)本發明的有機無機混成材料的其中一項起始原料是「異氰酸鹽」，其是使用碳酸酯類做起始物之一，經過加熱步驟就能轉化成異氰酸鹽，換言之，本發明還提供了一種無使用光氣製備異氰酸鹽的方法，且該方法在製備生產異氰酸鹽的過程中不會釋放碳酸酯類結構中的二氧化碳，大幅度延長了二氧化碳的碳循環，是一兼具安全和環保的綠色製程。 In summary, the organic-inorganic hybrid material provided by the present invention, its preparation method and the preparation method of its starting materials have at least the following innovations and advantages: (1) The organic-inorganic hybrid material provided by the present invention is made by The specially designed modifier is added to increase the compatibility of organic and inorganic substances, and further improve the overall properties of the material, such as water resistance or film forming; (2) The preparation method of organic-inorganic hybrid materials provided by the present invention is used One of the components of the reaction formula is from waste polymers, such as polycarbonate, so the above method also solves the waste problem of polymer materials; and (3) one of the organic-inorganic hybrid materials of the present invention The raw material is "isocyanate", which uses carbonates as one of the starting materials, which can be converted into isocyanate after a heating step. In other words, the present invention also provides a method for preparing isocyanate without using phosgene In addition, the method does not release carbon dioxide in the carbonate structure during the preparation and production of isocyanate, greatly prolongs the carbon cycle of carbon dioxide, and is a green manufacturing process that combines safety and environmental protection.

第1圖是示範例一的傅立葉紅外線(FTIR)光譜圖； Figure 1 is the Fourier Infrared (FTIR) spectrum of Example 1;

第2圖是示範例二的傅立葉紅外線(FTIR)光譜圖； Figure 2 is the Fourier Infrared (FTIR) spectrum of Example 2;

第3圖是示範例三的傅立葉紅外線(FTIR)光譜圖； Figure 3 is the Fourier Infrared (FTIR) spectrum of Example 3;

第4圖是示範例四的傅立葉紅外線(FTIR)光譜圖； Figure 4 is the Fourier Infrared (FTIR) spectrum of Example 4;

第5圖是示範例五的傅立葉紅外線(FTIR)光譜圖；和 Figure 5 is the Fourier Infrared (FTIR) spectrum of Example 5; and

第6圖是示範例十的傅立葉紅外線(FTIR)光譜圖。 Figure 6 is the Fourier Infrared (FTIR) spectrum of Exemplary Example 10.

有關本發明之前述及其他技術內容、特點與功效，在以下配合參考圖式之一較佳實施例的詳細說明中將可清楚的呈現。為了能徹底地瞭解本發明，將在下列的描述中提出詳盡的步驟及其組成。顯然地，本發明的施行並未限定於該領域之技藝者所熟習的特殊細節。另一方面，眾所周知的組成或步驟並未描述於細節中，以避免造成本發明不必要之限制。本發明的較佳實施例會詳細描述如下，然而除了這些詳細描述之外，本發明還可以廣泛地施行在其他的實施例中，且本發明的範圍不受限定，其以之後的專利範圍為準。 The foregoing and other technical content, features, and effects of the present invention will be clearly presented in the following detailed description of a preferred embodiment with reference to the drawings. In order to thoroughly understand the present invention, detailed steps and their composition will be proposed in the following description. Obviously, the implementation of the present invention is not limited to the specific details familiar to those skilled in the field. On the other hand, well-known components or steps are not described in details to avoid unnecessary limitation of the present invention. The preferred embodiments of the present invention will be described in detail as follows. However, in addition to these detailed descriptions, the present invention can also be widely implemented in other embodiments, and the scope of the present invention is not limited, which is subject to the following patent scope .

根據本發明的第一實施例，本發明提供一種新穎的有機無機混成材料。創新地，本發明的有機無機混成材料是一藉由一新穎的改質劑和導入方法所製成。第二，本發明的有機無機混成材料是一可來自碳酸酯或聚碳酸酯回收物重新使用的綠色原料，因此能夠達到材料循環使用的目的。 According to the first embodiment of the present invention, the present invention provides a novel organic-inorganic hybrid material. Innovatively, the organic-inorganic hybrid material of the present invention is made by a novel modifier and introduction method. Second, the organic-inorganic hybrid material of the present invention is a green raw material that can be reused from recycled carbonate or polycarbonate, so it can achieve material Purpose of recycling.

於一具體實施例，上述的有機無機混成材料是由結構式(1)所示之化合物、一異氰酸鹽和酚類反應的縮合物、碳酸二苯酯或一無機微球，和一高分子的預聚物藉由溶凝膠法所製成；以該有機無機混成材料的總重量計，其包含的無機化合物的重量百分比是5~50wt.%，且在傅立葉紅外光譜圖中約1050±50cm^-1的位置具有特徵峰。 In a specific embodiment, the above-mentioned organic-inorganic hybrid material is composed of a compound represented by the structural formula (1), a condensate of a reaction between an isocyanate and a phenol, diphenyl carbonate or an inorganic microsphere, and a high The molecular prepolymer is made by the solvogel method; based on the total weight of the organic-inorganic hybrid material, the weight percentage of the inorganic compound contained in it is 5-50wt.%, and it is about 1050 in the Fourier infrared spectrum. The position of ±50 cm ^-1 has a characteristic peak.

具體地，所述的改質劑是結構式(1)所示之化合物。 Specifically, the modifier is a compound represented by structural formula (1).

該結構式(1)中所示的BP為苯酚、多苯酚衍生物或含鹵素的苯酚類；X可為(-CH₂-)_m或-O-；m為1到10的正整數；Y為(H)_a、(-OH)_b、(-OCH₃)_c、(-OCH₂CH₃)_d或(-OCH₂CH₂CH₃)_e，且a+b+c+d+e=3；即a,b,c,d,e的加總係等於3，較佳地，其中b,c,d或e是1~3的整數。 The BP shown in the structural formula (1) is phenol, polyphenol derivatives or halogen-containing phenols; X can be (-CH ₂ -) _m or -O-; m is a positive integer from 1 to 10; Y Is (H) _a , (-OH) _b , (-OCH ₃ ) _c , (-OCH ₂ CH ₃ ) _d or (-OCH ₂ CH ₂ CH ₃ ) _e , and a+b+c+d+e= 3; That is, the sum of a, b, c, d, and e is equal to 3. Preferably, b, c, d or e is an integer from 1 to 3.

具體地，該結構式(2)所示之化合物如下所示。 Specifically, the compound represented by the structural formula (2) is shown below.

具體地，該結構式(3)所示之化合物如下所示。 Specifically, the compound represented by the structural formula (3) is shown below.

具體地，該結構式(4)所示之化合物如下所示。 Specifically, the compound represented by the structural formula (4) is shown below.

上述結構式(2)、(3)和(4)所示的R₁分別可為碳數10以下的長碳鏈，環烷烴、鹵代烷烴、羰基、磺醯基、亞磺醯基、或雙取代多酚基；R₂分別可為氫或碳數5以下的長碳鏈，環烷烴、鹵代烷烴、羰基、磺醯基、亞磺醯基、或多酚基；Z分別可為各自獨立出現的4以下整數；和p≦20。 _{R 1} represented by the above structural formulas (2), (3) and (4) can be long carbon chains with carbon number 10 or less, cycloalkanes, halogenated alkanes, carbonyl groups, sulfonyl groups, sulfinyl groups, or double Substituted polyphenol group; R ₂ can be hydrogen or a long carbon chain with carbon number 5 or less, cycloalkane, halogenated alkane, carbonyl, sulfonyl, sulfinyl, or polyphenol group; Z can be each independently An integer below 4; and p≦20.

於一較佳實施例，具有結構式(1)的化合物是4-(2-(4-苯酚基)丙烷-2-基)苯基(3-(三甲氧基硅烷基)丙基)胺酯(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl(3-(trimethoxysilyl)propyl)carbamate；該化合物另一名稱是三甲基甲硅烷氧基氨端聚二甲基硅氧烷或3-伯胺丙基三乙氧硅烷；其中硅氧烷上的胺端基團是伯胺基團，其特性使得上述的有機硅聚合物能夠在水性體系中較寬的pH範圍內形成淨正電荷。 In a preferred embodiment, the compound of structural formula (1) is 4-(2-(4-phenolyl)propan-2-yl)phenyl(3-(trimethoxysilyl)propyl)amine ester (4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl(3-(trimethoxysilyl)propyl)carbamate; the other name of this compound is trimethylsilyloxy amino-terminated polydimethylsiloxane Or 3-primary amine propyl triethoxysilane; wherein the amine end group on the siloxane is a primary amine group, and its characteristics enable the above-mentioned organosilicon polymer to form a net in a wide pH range in an aqueous system positive charge.

於一具體實施例，該異氰酸鹽包含脂肪族異氰酸鹽、異氰酸己酯(hexyl isocyanate)、1-異氰酸辛酯(octyl isocyanate)、十二烷基異氰酸酯(dodecyl isocyanate)、十八烷基異氰酸酯(octadecyl isocyanate)、環己基異氰酸酯(cyclohexyl isocyanate)、三甲基矽烷異氰酸酯(trimethylsilyl isocyanate)、異氰酸丙基三乙氧基矽烷(3-(triethoxysilyl)propyl isocyanate)，異氰酸丙基三甲氧基矽烷(3-(trimethoxysilyl)propyl isocyanate)、異丙基異氰酸酯phenylethyl isocyanate，甲基異氰酸酯(methyl isocyanate)、乙基異氰酸酯(ethyl isocyanate)、丙基異氰酸酯(propyl isocyanate)、二十烷基異氰酸酯(eicosyl isocyanate)或二十四烷基異氰酸酯(tetracosyl isocyanate)。 In a specific embodiment, the isocyanate includes aliphatic isocyanate, isocyanate Hexyl isocyanate, octyl isocyanate, dodecyl isocyanate, octadecyl isocyanate, cyclohexyl isocyanate, trimethyl silane Trimethylsilyl isocyanate, 3-(triethoxysilyl)propyl isocyanate, 3-(trimethoxysilyl)propyl isocyanate, phenylethyl isocyanate isocyanate, methyl isocyanate, ethyl isocyanate, propyl isocyanate, eicosyl isocyanate or tetracosyl isocyanate.

於一具體實施例，該無機微球是由結構式(1)所示之化合物或該異氰酸鹽和酚類反應的縮合物包覆一無機粒子的表面所構成。 In a specific embodiment, the inorganic microspheres are formed by covering the surface of an inorganic particle with the compound represented by the structural formula (1) or the condensate of the isocyanate and phenols.

於一具體實施例，該無機粒子包含矽氧化物或硫化物、鋁氧化物或硫化物、鈦氧化物或硫化物、鍺氧化物或硫化物、鐵氧化物或硫化物、鋇氧化物或硫化物、鋅氧化物或硫化物、銅氧化物或硫化物、鉻氧化物或硫化物、鈮氧化物或硫化物、錳氧化物或硫化物、錫氧化物或硫化物、鋰氧化物或硫化物、鈰氧化物或硫化物、鈷氧化物或硫化物、二氧化矽、二氧化鈦、氧化鋅、氧化鋯、氧化鐵、鈦酸鋇、鈮酸鋰、硒化鎘、氧化銅、鋯酸鋇、三氧化二鉻、五氧化二鈮、二氧化鈰、鈦酸鐵、矽化鐵、氧化鋁/氧化鈦混合層、氧化鋁/氧化鋯混合層、氧化錳、氧化錫、或硫化鋅。 In a specific embodiment, the inorganic particles include silicon oxide or sulfide, aluminum oxide or sulfide, titanium oxide or sulfide, germanium oxide or sulfide, iron oxide or sulfide, barium oxide or sulfide Compound, zinc oxide or sulfide, copper oxide or sulfide, chromium oxide or sulfide, niobium oxide or sulfide, manganese oxide or sulfide, tin oxide or sulfide, lithium oxide or sulfide , Cerium oxide or sulfide, cobalt oxide or sulfide, silicon dioxide, titanium dioxide, zinc oxide, zirconium oxide, iron oxide, barium titanate, lithium niobate, cadmium selenide, copper oxide, barium zirconate, three Chromium oxide, niobium pentoxide, ceria, iron titanate, iron silicide, aluminum oxide/titania mixed layer, aluminum oxide/zirconia mixed layer, manganese oxide, tin oxide, or zinc sulfide.

於一具體實施例，該無機粒子的粒徑範圍是20~1,000nm。 In a specific embodiment, the size of the inorganic particles ranges from 20 nm to 1,000 nm.

於一具體實施例，該高分子包含聚氨酯、環氧樹脂或聚亞醯胺。 In a specific embodiment, the polymer comprises polyurethane, epoxy resin or polyarylene amine.

於一具體實施例，該高分子的預聚物之分子量是5,000~50,000Da。 In a specific embodiment, the molecular weight of the polymer prepolymer is 5,000-50,000 Da.

於一具體實施例，該溶凝膠法是一水解縮合反應。 In a specific embodiment, the lytic gel method is a hydrolysis condensation reaction.

於一具體實施例，該無機化合物包含矽氧化物或硫化物、鋁氧化物或硫化物、鈦氧化物或硫化物、鍺氧化物或硫化物、鐵氧化物或硫化物、鋇氧化物或硫化物、鋅氧化物或硫化物、銅氧化物或硫化物、鉻氧化物或硫化物、鈮氧化物或硫化物、錳氧化物或硫化物、錫氧化物或硫化物、鋰氧化物或硫化物、鈰氧化物或硫化物、鈷氧化物或硫化物、二氧化矽、二氧化鈦、氧化鋅、氧化鋯、氧化鐵、鈦酸鋇、鈮酸鋰、硒化鎘、氧化銅、鋯酸鋇、三氧化二鉻、五氧化二鈮、二氧化鈰、鈦酸鐵、矽化鐵、氧化鋁/氧化鈦混合層、氧化鋁/氧化鋯混合層、氧化錳、氧化錫、或硫化鋅。 In a specific embodiment, the inorganic compound includes silicon oxide or sulfide, aluminum oxide or sulfide, titanium oxide or sulfide, germanium oxide or sulfide, iron oxide or sulfide, barium oxide or sulfide Compound, zinc oxide or sulfide, copper oxide or sulfide, chromium oxide or sulfide, niobium oxide or sulfide, manganese oxide or sulfide, tin oxide or sulfide, lithium oxide or sulfide , Cerium oxide or sulfide, cobalt oxide or sulfide, silicon dioxide, titanium dioxide, zinc oxide, zirconium oxide, iron oxide, barium titanate, lithium niobate, cadmium selenide, copper oxide, barium zirconate, three Chromium oxide, niobium pentoxide, ceria, iron titanate, iron silicide, aluminum oxide/titania mixed layer, aluminum oxide/zirconia mixed layer, manganese oxide, tin oxide, or zinc sulfide.

根據本發明的第二實施例，本發明提供一種有機無機混成材料的製備方法，其步驟包含：提供一如結構式(1)所示之化合物、一異氰酸鹽和酚類反應的縮合物、碳酸二苯酯或一無機微球；加入上述之如結構式(1)所示之化合物、異氰酸鹽和酚類反應的縮合物、碳酸二苯酯或無機微球至一分子量是5,000~50,000的高分子的預聚物，藉此得到一混合物，該預聚物的含量占該混合物的10~60質量%；和進行溶凝膠法，使該混合物的組成份進行水解縮合反應，藉此形成所述之有機無機混成材料，以該有機無機混成材料的總重量計，其包含的無機化合物的重量百分比是5~50wt.%，且其結構能進行共價鍵重組反應和在傅立葉紅外光譜圖中約1050±50cm^-1位置具有特徵峰。 According to the second embodiment of the present invention, the present invention provides a method for preparing an organic-inorganic hybrid material, the steps of which include: providing a compound represented by structural formula (1), a condensate reacted with an isocyanate and a phenol , Diphenyl carbonate or an inorganic microsphere; adding the above compound as shown in structural formula (1), isocyanate and phenol reaction condensate, diphenyl carbonate or inorganic microsphere to a molecular weight of 5,000 ~50,000 high molecular weight prepolymer, thereby obtaining a mixture, the content of the prepolymer accounts for 10-60% by mass of the mixture; and carrying out the solvogel method to make the components of the mixture undergo a hydrolysis condensation reaction, Thus, the organic-inorganic hybrid material is formed. Based on the total weight of the organic-inorganic hybrid material, the weight percentage of the inorganic compound contained in it is 5-50wt.%, and its structure can undergo covalent bond recombination reaction and in Fourier There is a characteristic peak at about 1050±50cm ^{-1 in the infrared spectrum.}

於一具體實施例，該結構式(1)如下所示。 In a specific embodiment, the structural formula (1) is as follows.

該結構式(1)中所示的BP為苯酚、多苯酚衍生物或含鹵素的苯酚類；X可為(-CH₂-)_m或-O-；m為1到10的正整數；Y為(H)_a、(-OH)_b、(-OCH₃)_c、(-OCH₂CH₃)_d或(-OCH₂CH₂CH₃)_e且a+b+c+d+e=3的任何組合。 The BP shown in the structural formula (1) is phenol, polyphenol derivatives or halogen-containing phenols; X can be (-CH ₂ -) _m or -O-; m is a positive integer from 1 to 10; Y Is (H) _a , (-OH) _b , (-OCH ₃ ) _c , (-OCH ₂ CH ₃ ) _d or (-OCH ₂ CH ₂ CH ₃ ) _e and a+b+c+d+e=3 Any combination of.

於一具體實施例，該異氰酸鹽包含脂肪族異氰酸鹽、異氰酸己酯(hexyl isocyanate)、1-異氰酸辛酯(octyl isocyanate)、十二烷基異氰酸酯(dodecyl isocyanate)、十八烷基異氰酸酯(octadecyl isocyanate)、環己基異氰酸酯(cyclohexyl isocyanate)、三甲基矽烷異氰酸酯(trimethylsilyl isocyanate)、異氰酸丙基三乙氧基矽烷 (3-(triethoxysilyl)propyl isocyanate)，異氰酸丙基三甲氧基矽烷(3-(trimethoxysilyl)propyl isocyanate)、異丙基異氰酸酯phenylethyl isocyanate，甲基異氰酸酯(methyl isocyanate)、乙基異氰酸酯(ethyl isocyanate)、丙基異氰酸酯(propyl isocyanate)、二十烷基異氰酸酯(eicosyl isocyanate)或二十四烷基異氰酸酯(tetracosyl isocyanate)。 In a specific embodiment, the isocyanate includes aliphatic isocyanate, hexyl isocyanate, 1-octyl isocyanate, dodecyl isocyanate, Octadecyl isocyanate, cyclohexyl isocyanate, trimethylsilyl isocyanate, propyl triethoxy silane (3-(triethoxysilyl)propyl isocyanate), 3-(trimethoxysilyl)propyl isocyanate, phenylethyl isocyanate, methyl isocyanate, ethyl isocyanate ), propyl isocyanate, eicosyl isocyanate or tetracosyl isocyanate.

於一具體實施例，該無機粒子包含矽氧化物或硫化物、鋁氧化物或硫化物、鈦氧化物或硫化物、鍺氧化物或硫化物、鐵氧化物或硫化物、鋇氧化物或硫化物、鋅氧化物或硫化物、銅氧化物或硫化物、鉻氧化物或硫化物、鈮氧化物或硫化物、錳氧化物或硫化物、錫氧化物或硫化物、鋰氧化物或硫化物、鈰氧化物或硫化物、鈷氧化物或硫化物、二氧化矽、二氧化鈦、氧化鋅、氧化鋯、氧化鐵、鈦酸鋇、鈮酸鋰、硒化鎘、氧化銅、鋯酸鋇、三氧化二鉻、五氧化二鈮、二氧化鈰、鈦酸鐵、矽化鐵、氧化鋁/氧化鈦混合層、氧化鋁/氧化鋯混合層、氧化錳、氧化錫、或硫化鋅 In a specific embodiment, the inorganic particles include silicon oxide or sulfide, aluminum oxide or sulfide, titanium oxide or sulfide, germanium oxide or sulfide, iron oxide or sulfide, barium oxide or sulfide Compound, zinc oxide or sulfide, copper oxide or sulfide, chromium oxide or sulfide, niobium oxide or sulfide, manganese oxide or sulfide, tin oxide or sulfide, lithium oxide or sulfide , Cerium oxide or sulfide, cobalt oxide or sulfide, silicon dioxide, titanium dioxide, zinc oxide, zirconium oxide, iron oxide, barium titanate, lithium niobate, cadmium selenide, copper oxide, barium zirconate, three Chromium oxide, niobium pentoxide, ceria, iron titanate, iron silicide, aluminum oxide/titanium oxide mixed layer, aluminum oxide/zirconia mixed layer, manganese oxide, tin oxide, or zinc sulfide

於一具體實施例，該高分子包含聚氨酯、環氧樹脂或聚亞醯胺。 In a specific embodiment, the polymer includes polyurethane, epoxy resin, or polyimide.

於一具體實施例，該混合物還包含一溶劑或一添加劑。 In a specific embodiment, the mixture further includes a solvent or an additive.

於一具體實施例，該溶劑包含四氫呋喃(Tetrahydrofuran)、二甲基亞碸(Dimethyl Sulfoxide)、二甲基甲醯胺Dimethylformamide、N-甲基吡咯烷酮(N-Methyl-2-Pyrrolidone)或苯甲醚(Anisole)。 In a specific embodiment, the solvent includes Tetrahydrofuran, Dimethyl Sulfoxide, Dimethylformamide, N-Methyl-2-Pyrrolidone, or anisole (Anisole).

於一具體實施例，該添加劑包含硼酸、磷酸、鹽酸、硫酸、硝酸、亞硫酸、乙酸、甲酸、丙酸、鹼金屬氫氧化物、磷酸鈉鹽、脂肪族胺類、哌啶及其衍生物、咪唑及其衍生物或含氮雜環狀化合物。 In a specific embodiment, the additive includes boric acid, phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid, sulfurous acid, acetic acid, formic acid, propionic acid, alkali metal hydroxide, sodium phosphate, aliphatic amines, piperidine and its derivatives , Imidazole and its derivatives or nitrogen-containing heterocyclic compounds.

於一具體實施例，該水解縮合反應的溫度範圍是20~60℃。 In a specific embodiment, the temperature range of the hydrolysis condensation reaction is 20-60°C.

根據本發明的第三實施例，本發明提供一種從碳酸酯類製備異氰酸鹽的方法，其步驟包含：提供一混合物，該混合物包含一碳酸酯類、一胺類或含矽基之胺類的化合物和一溶劑；該碳酸酯類包含聚碳酸酯、碳酸二苯酯或其組合物；和進行一轉化程序，使上述混合物中的該碳酸酯類和該胺類或含矽基之胺類的化合物轉化生成所述的異氰酸鹽；該轉化程序包含第一加熱步驟和第二加熱步驟，該第一加熱步驟的操作溫度是40~150℃，和該第二加熱步驟的操作溫度是100~250℃，且該第二加熱步驟的操作壓力在0.0001-400mmHg。 According to a third embodiment of the present invention, the present invention provides a method for preparing isocyanates from carbonates, the steps of which include: providing a mixture comprising a carbonate, an amine, or a silicon-containing amine And a solvent; the carbonate contains polycarbonate, diphenyl carbonate or a combination thereof; and a conversion process is performed to make the carbonate and the amine or the amine containing silicon group in the above mixture Compounds of this type are converted to the isocyanate; the conversion procedure includes a first heating step and a second heating step, the operating temperature of the first heating step is 40~150°C, and the operating temperature of the second heating step It is 100~250°C, and the operating pressure of the second heating step is 0.0001-400mmHg.

於一具體實施例，該胺類化合物包含苯甲胺(Benzylamine)、正乙胺(Ethylamine)、苯乙胺(Phenethylamine)、正丙胺(Propylamine)、3-苯基丙胺(3-Phenylpropylamine)、正丁胺(Butylamine)、4-苯基丁胺(4-Phenylbutylamine)、正戊胺(Pentylamine)、5-苯基戊胺(5-Phenylpentylamine)、正己胺(Hexylamine)、6-苯基己胺(6-Phenylhexylamine)、異丁胺(Isobutylamine)胺乙基-1,4-二氮己圜(Aminoethylpiperazine)、甲基六氫吡嗪(1-Methylpiperazine)、N-氨丙基嗎啉(3-Morpholinopropylamine)或胺乙基-1,4-二氮己圜(Aminoethylpiperazine)。 In a specific embodiment, the amine compound includes Benzylamine, Ethylamine, Phenethylamine, Propylamine, 3-Phenylpropylamine, and Butylamine, 4-Phenylbutylamine, Pentylamine, 5-Phenylpentylamine, Hexylamine, 6-Phenylhexylamine 6-Phenylhexylamine), Isobutylamine, Aminoethyl-1,4-Aminoethylpiperazine, 1-Methylpiperazine, N-Aminopropyl 3-Morpholinopropylamine or Aminoethylpiperazine.

於一具體實施例，該含矽基之胺類化合物包含3-氨基丙基三乙氧基矽烷((3-Aminopropyl)triethoxysilane)或3-氨基丙基三甲氧基矽烷((3-Aminopropyl)trimethoxysilane)。 In a specific embodiment, the silicon-containing amine compound includes 3-aminopropyl triethoxysilane ((3-Aminopropyl) triethoxysilane) or 3-aminopropyl trimethoxysilane ((3-Aminopropyl) trimethoxysilane ).

於一具體實施例，以該混合物的總重量計，該聚碳酸酯、碳酸二苯酯或其組合物的反應濃度是5~50wt.%。 In a specific embodiment, based on the total weight of the mixture, the reaction concentration of the polycarbonate, diphenyl carbonate or the combination thereof is 5-50 wt.%.

於一具體實施例，該溶劑包含二***(Diethyl ether)、二丙醚(Di-n-propyl ether)、異丙醚(Isopropyl ether)苯甲醚(Anisole)、苯***(Ethoxybenzene)、苯丙醚(Propoxybenzene)、苯丁醚(Butoxybenzene)、鄰甲基苯甲醚(2-Methoxytoluene)、間甲基苯甲醚(3-Methoxytoluene)、對甲基苯甲醚(4-Methoxytoluene)、苄基乙基醚(Benzyl ethyl ether)、二苯醚(Diphenyl ether)、二苄醚(Dibenzyl ether)、四氫呋喃(Tetrahydrofuran)、二氫吡喃(2,3-Dihydropyran)、四氫吡喃(Tetrahydropyran)、2-甲基四氫吡喃(2-Methyl Tetrahydropyran)、苯(Benzene)、甲苯(Toluene)、二甲苯(Xylene)、乙苯(Ethylbenzene)、二乙苯(Diethylbenzene)或環己苯(Cyclohexylbenzene) In a specific embodiment, the solvent includes diethyl ether, di-n-propyl ether, isopropyl ether, anisole, ethoxybenzene, and styrene-acrylic ether. Propoxybenzene, Butoxybenzene, 2-Methoxytoluene, 3-Methoxytoluene, 4-Methoxytoluene, Benzyl Ethyl ether (Benzyl ethyl ether), diphenyl ether (Diphenyl ether), dibenzyl ether (Dibenzyl ether), tetrahydrofuran (Tetrahydrofuran), dihydropyran (2,3-Dihydropyran), tetrahydropyran (Tetrahydropyran), 2-Methyl Tetrahydropyran, Benzene, Toluene, Xylene, Ethylbenzene, Diethylbenzene or Cyclohexylbenzene

綜上所述，本發明所提供的有機無機混成材料及其製備方法，藉由使用新穎的改質劑和導入方式，大幅增加有機物和無機物的相容性，再利用溶凝膠法製成本發明所述的有機無機混成材料。其次，本發明所述的有機無機混成材料可來自碳酸酯或聚碳酸酯回收物重新使用的綠色原料，因此能夠達到材料循環使用的目的。第三，本發明提供的從碳酸酯類製備生成異氰酸鹽的方法是一非光氣法，且在製備異氰酸鹽的過程中不會釋放二氧化碳，因此延長了二氧化碳的碳循環，是一兼具安全和環保的製備方法。 In summary, the organic-inorganic hybrid material and its preparation method provided by the present invention greatly increase the compatibility of organic and inorganic substances by using novel modifiers and introduction methods, and then use the solvogel method to make the compound of the present invention. The organic-inorganic hybrid materials. Secondly, the organic-inorganic hybrid materials of the present invention can be derived from recycled green raw materials from carbonate or polycarbonate recycling, so that the purpose of material recycling can be achieved. Third, the present invention The provided method for preparing isocyanate from carbonates is a non-phosgene method, and does not release carbon dioxide during the process of preparing isocyanate, thus prolonging the carbon cycle of carbon dioxide, which is both safe and Environmentally friendly preparation method.

以下實驗例和示範例係依據上述之發明內容和實施例所述之內容所進行的實驗，並據此做為本發明的詳細說明。 The following experimental examples and demonstration examples are based on the above-mentioned contents of the invention and the contents described in the examples, and are used as detailed descriptions of the invention accordingly.

本發明所述的具有結構式(1)之化合物/改質劑的通用製備步驟The general preparation steps of the compound/modifier with structural formula (1) according to the present invention

取適量的異氰酸酯和苯酚類溶解在非極性溶劑形成一均勻的混合物，於60~100℃之間進行反應，為了加速反應進行可加入微量有機錫、胺、鉍或鋅等觸媒加速反應。經過十二小時觀測苯酚類消耗完畢後，再經過純化並除去溶劑，然後得到如結構式(1)所示之化合物。 Dissolve an appropriate amount of isocyanate and phenols in a non-polar solvent to form a uniform mixture, and react at 60~100°C. In order to accelerate the reaction, a small amount of organotin, amine, bismuth or zinc can be added to accelerate the reaction. After 12 hours of observing the consumption of phenols, it is purified and the solvent is removed to obtain the compound represented by the structural formula (1).

改質劑代表實驗例：3-伯胺丙基三乙氧硅烷；(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl(3-(trimethoxysilyl)propyl)carbamate的製備方式 Representative experimental example of modifier: 3-primary amine propyl triethoxysilane; Preparation method of (4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl(3-(trimethoxysilyl)propyl)carbamate

異氰酸丙基三乙氧基硅烷5g與雙酚A(BPA)4.17g溶在甲苯50毫升，於80~100℃之間進行反應，並加入微量有機錫觸媒加速反應。經過十二小時使用薄層層析(thin layer chromatography)觀測雙酚A消耗完畢後，經過純化並除去溶劑，然後得到3-伯胺丙基三乙氧硅烷7.8g(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl(3-(trimethoxysilyl)propyl)carbamate，反應過程以FT-IR監測1716cm^-1的胺基甲酸酯(carbamate)之碳氧雙鍵官能基吸收峰生成，最後利用減壓蒸餾除去溶劑後得到產物，並進行¹H-NMR分析。 5g of isocyanate propyltriethoxysilane and 4.17g of bisphenol A (BPA) were dissolved in 50ml of toluene, and the reaction was carried out at 80~100℃, and a small amount of organotin catalyst was added to accelerate the reaction. After twelve hours of observing the consumption of bisphenol A by thin layer chromatography, after purification and removal of the solvent, 7.8 g of 3-primary aminopropyltriethoxysilane (4-(2-(4 -hydroxyphenyl)propan-2-yl)phenyl(3-(trimethoxysilyl)propyl)carbamate, the reaction process was monitored by FT-IR to monitor the formation of the carbon-oxygen double bond functional group absorption peak of the ^{1716cm -1 carbamate,} Finally, the solvent was removed by distillation under reduced pressure to obtain the product, which was ^{analyzed by 1} H-NMR.

FTIR(KBr)：1716cm^-1,3350cm^-1(NH,urethane),950cm^-1(Si-O)；¹H-NMR(400MHz,d-DMSO)：δ(ppm)=0.5(t,6H),1.2(t,27H),1.5(t,18H),3.0(m,6H),3.8(m,18H),6.7(m,6H),7.0(m,12H),7.2(m,6H),7.7(t,3H),9.2(s,3H)。 FTIR (KBr): 1716cm ^-1 , 3350cm ^-1 (NH,urethane), 950cm ^-1 (Si-O); ¹ H-NMR (400MHz, d-DMSO): δ(ppm)=0.5(t,6H) ,1.2(t,27H),1.5(t,18H),3.0(m,6H),3.8(m,18H),6.7(m,6H),7.0(m,12H),7.2(m,6H), 7.7 (t, 3H), 9.2 (s, 3H).

上述的製備具有結構式(1)之化合物的通用步驟所使用的異氰酸酯包含脂肪族的異氰酸酯、單獨或混合使用脂肪族異氰酸鹽、異氰酸己酯(hexyl isocyanate)、1-異氰酸辛酯(octyl isocyanate)、十二烷基異氰酸酯(dodecyl isocyanate)、十八烷基異氰酸酯(octadecyl isocyanate)、環己基異氰酸酯(cyclohexyl isocyanate)、三甲基矽烷異氰酸酯(trimethylsilyl isocyanate)、異氰酸丙基三乙氧基矽烷(3-(triethoxysilyl)propyl isocyanate)，異氰酸丙基三甲氧基矽烷(3-(trimethoxysilyl)propyl isocyanate)、異丙基異氰酸酯phenylethyl isocyanate，甲基異氰酸酯(methyl isocyanate)、乙基異氰酸酯(ethyl isocyanate)、丙基異氰酸酯(propyl isocyanate)、二十烷基異氰酸酯(eicosyl isocyanate)或二十四烷基異氰酸酯(tetracosyl isocyanate)。 The isocyanate used in the above-mentioned general steps for the preparation of the compound of structural formula (1) contains aliphatic isocyanate, aliphatic isocyanate, hexyl isocyanate, 1-isocyanate octyl isocyanate, singly or in combination. Octyl isocyanate, dodecyl isocyanate, octadecyl isocyanate, cyclohexyl isocyanate, trimethylsilyl isocyanate, propyl isocyanate 3-(triethoxysilyl)propyl isocyanate, 3-(trimethoxysilyl)propyl isocyanate, phenylethyl isocyanate, methyl isocyanate, ethyl Ethyl isocyanate, propyl isocyanate, eicosyl isocyanate or tetracosyl isocyanate.

上述的製備具有結構式(1)之化合物的通用步驟所使用的苯酚類可來自雙酚或多酚類，該苯酚包含雙酚A(2,2-bis(4-hydroxyphenyl)propane(bisphenol A))、雙酚F(2,2-bis(4-hydroxyphenyl)methane(bisphenol F))、結構式(2)所示之化合物、結構式(3)所示之化合物或結構式(4)所示之化合物。 The phenols used in the above-mentioned general steps for preparing compounds of structural formula (1) can be derived from bisphenols or polyphenols, and the phenols include bisphenol A (2,2-bis(4-hydroxyphenyl)propane (bisphenol A) ), bisphenol F (2,2-bis(4-hydroxyphenyl)methane(bisphenol F)), the compound represented by structural formula (2), the compound represented by structural formula (3), or the compound represented by structural formula (4) The compound.

本發明所述的無機微球之通用製備步驟General preparation steps of the inorganic microspheres of the present invention

使結構式(1)之含矽氧烷官能基的化合物與無機物顆粒表面的氫氧基(-OH)、胺基(-NH₂)或硫醇基(-SH)進行縮合反應，藉此將含氨基甲酸酯官能基之結構式(1)之化合物鍵結固定在無機粒子的表面上，藉此形成本發明所述的無機微球，該無機微球是一表面官能基化的無機粒子。其次，該無機粒子的粒徑範圍20~1,000nm；具體地，該無機粒子包含矽氧化物或硫化物、鋁氧化物或硫化物、鈦氧化物或硫化物、鍺氧化物或硫化物、鐵氧化物或硫化物、鋇氧化物或硫化物、鋅氧化物或硫化物、銅氧化物或硫化物、鉻氧化物或硫化物、鈮氧化物或硫化物、錳氧化物或硫化物、錫氧化物或硫化物、鋰氧化物或硫化物、鈰氧化物或硫化物、鈷氧化物或硫化物、二氧化矽、二氧化鈦、氧化鋅、氧化鋯、氧化鐵、鈦酸鋇、鈮酸鋰、硒化鎘、氧化銅、鋯酸鋇、三氧化二鉻、五氧化二鈮、二氧化鈰、鈦酸鐵、矽化鐵、氧化鋁/氧化鈦混合層、氧化鋁/氧化鋯混合層、氧化錳、氧化錫、或硫化鋅。 The siloxane functional group-containing compound of structural formula (1 _{) is condensed with the hydroxyl group (-OH), amine group (-NH 2} ) or thiol group (-SH) on the surface of the inorganic particles, thereby The compound of structural formula (1) containing carbamate functional group is bonded and fixed on the surface of the inorganic particle, thereby forming the inorganic microsphere of the present invention, which is a surface functionalized inorganic particle . Secondly, the particle size of the inorganic particles ranges from 20 to 1,000 nm; specifically, the inorganic particles include silicon oxide or sulfide, aluminum oxide or sulfide, titanium oxide or sulfide, germanium oxide or sulfide, iron Oxide or sulfide, barium oxide or sulfide, zinc oxide or sulfide, copper oxide or sulfide, chromium oxide or sulfide, niobium oxide or sulfide, manganese oxide or sulfide, tin oxide Compound or sulfide, lithium oxide or sulfide, cerium oxide or sulfide, cobalt oxide or sulfide, silicon dioxide, titanium dioxide, zinc oxide, zirconium oxide, iron oxide, barium titanate, lithium niobate, selenium Cadmium, copper oxide, barium zirconate, chromium trioxide, niobium pentoxide, ceria, iron titanate, iron silicide, aluminum oxide/titanium oxide mixed layer, aluminum oxide/zirconia mixed layer, manganese oxide, Tin oxide, or zinc sulfide.

本發明所述的有機無機混成材料之通用製備步驟The general preparation steps of the organic-inorganic hybrid material of the present invention

提供如上述的結構式(1)所示之化合物、該異氰酸鹽和酚類反應的縮合物、碳酸二苯酯或上述之無機微球；，特別地，上述之具有胺基甲酸酯官能基(carbamate)的原料與含羰基(carbonyl)的高分子具有良好相容性；提供一高分子預聚物；該高分子預聚物包含聚氨酯(polyurethanes)、環氧樹酯(epoxy resins)、聚亞醯胺或聚醯胺酸(Polyamic acid；PAA)等分子量5,000~50,000的高分子的預聚物；將上述結構式(1)之化合物直接加入上述之高分子預聚物當中，並透過紅外線光譜儀監控，可在950cm^-1觀察到Si-O-R的官能基左右的吸收鋒出現，將上述包含結構式(1)所示之化合物與上述之高分子預聚物的混合溶液以溶劑進行稀釋後，加入0.1~5.0重量比的鹽酸、硝酸或醋酸等酸性觸媒並攪拌至均勻，成膜烘乾並置入60℃的烘箱，24~48小時完成溶膠凝膠反應，然後在真空烘箱中進行乾燥去除剩下多餘的溶劑。反應完成後950cm^-1的Si-O-R官能基消失，重新生成1000-1100cm^-1的Si-O-Si官能基，藉此完成本發明所述的有機/無機混成材料的製備。 Provide the compound represented by the above-mentioned structural formula (1), the condensate of the reaction between the isocyanate and phenols, diphenyl carbonate or the above-mentioned inorganic microspheres; in particular, the above-mentioned having urethane Carbamate raw materials have good compatibility with carbonyl-containing polymers; a polymer prepolymer is provided; the polymer prepolymer includes polyurethanes and epoxy resins , Polyimide or polyamide acid (Polyamic acid; PAA) and other polymer prepolymers with a molecular weight of 5,000 to 50,000; add the compound of the above structural formula (1) directly to the above polymer prepolymer, and Through infrared spectrometer monitoring, ^{the absorption front around the functional group of Si-OR can be observed at 950cm -1} . The mixed solution containing the compound represented by the structural formula (1) and the polymer prepolymer mentioned above is used as a solvent. After dilution, add acidic catalysts such as hydrochloric acid, nitric acid or acetic acid at a weight ratio of 0.1 to 5.0 and stir until uniform, dry the film and put it in an oven at 60°C, complete the sol-gel reaction within 24 to 48 hours, and then in a vacuum oven Drying to remove the remaining excess solvent. After completion of the reaction 950cm Si-OR functional group ^-1 disappeared regenerate Si-O-Si ^-1 1000-1100 functional group, to prepare an organic / inorganic hybrid material, thereby completing the present invention.

聚氨酯預聚物之通用製備步驟General preparation steps of polyurethane prepolymer

上述之聚氨酯的預聚物的是利用高分子聚合反應製備而成。具體地，將各種的二異氰酸酯酸酯，如二苯基甲烷二異氰酸酯(MDI)、異佛爾酮二異氰酸酯(IPDI)或1,6-己二異氰酸酯(HDI)；和聚多元醇如聚醚二醇(PEG)、聚四氫呋喃二醇(PTMEG)、聚己內酯多元醇(PCL)、或聚碳酸酯二醇(PCPO)在60-80℃之間進行縮合聚合反應，反應過程可加入少量溶劑如二甲基甲醯胺(DMF)、N-甲基吡咯烷酮(NMP)、四氫呋喃(Tetrahydrofuran)、二甲基亞碸(Dimethyl Sulfoxide)或苯甲醚(Anisole)幫助反應進行，約半小時後完成預聚反應，此時可在FT-IR光譜圖上看到胺基甲酸酯官能基的特徵峰。 The above-mentioned polyurethane prepolymer is prepared by polymer polymerization. Specifically, various diisocyanate esters, such as diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI) or 1,6-hexamethylene diisocyanate (HDI); and polyols such as polyether Glycol (PEG), polytetrahydrofuran glycol (PTMEG), polycaprolactone polyol (PCL), or polycarbonate diol (PCPO) undergo condensation polymerization at 60-80°C, and a small amount can be added during the reaction Solvents such as dimethylformamide (DMF), N-methylpyrrolidone (NMP), tetrahydrofuran (Tetrahydrofuran), dimethyl sulfoxide (Dimethyl Sulfoxide) or anisole (Anisole) help the reaction proceed, about half an hour later After the prepolymerization reaction is completed, the characteristic peak of the urethane functional group can be seen on the FT-IR spectrum.

根據上述的聚氨酯的預聚物和有機無機混成材料之通用製備步驟所製備而成的各種含胺基甲酸酯有機無機混成材料如表一所示；其中所列二異氰酸酯和多元醇是聚氨酯預聚物的反應配方；矽(Silica)是代表製備所得到的有機無機混成材料的無機化合物含量。 The various urethane-containing organic-inorganic hybrid materials prepared according to the general preparation steps of the above-mentioned polyurethane prepolymers and organic-inorganic hybrid materials are shown in Table 1. The listed diisocyanates and polyols are polyurethane prepolymers. Polymer reaction formula; Silica is the inorganic compound content that represents the organic-inorganic hybrid material prepared.

表一Table I

示範例一為MDI與聚酯類多元醇PCL2000預聚合的聚氨酯，示範例一是未添加結構式(1)的實驗對照組，根據第1圖所示的FT-IR圖譜，在1737cm^-1左右位置觀察到胺基甲酸酯官能基的特徵峰。示範例二為MDI與聚酯類多元醇PCL2000聚合的聚氨酯預聚物，然後將結構式(1)所示之化合物或代表實驗例所合成的化合物加入上述之MDI與聚酯類多元醇PCL2000聚合的聚氨酯預聚物，藉此形成一混合溶液，並以溶劑進行稀釋後，加入0.1~5.0重量比的鹽酸、硝酸或醋酸等酸性觸媒並攪拌至均勻，成膜烘乾並置入60℃的烘箱，24~48小時完成溶膠凝膠反應，然後在真空烘箱中進行乾燥去除剩下多餘的溶劑。反應完成後950cm^-1的Si-O-R官能基消失，重新生成Si-O-Si官能基，在FTIR光譜1041cm^-1的位置具有特徵峰，其光譜圖如第2圖所示，藉此完成本發明所述的有機/無機混成材料的製備。示範例三為MDI與聚碳酸酯多元醇PCPO2000預聚合的聚氨酯，示範例三未添加結構式(1)，如第3圖所示，其FTIR圖譜在1742cm^-1左右觀察到胺基甲酸酯和碳酸酯重疊的C=O(carbonyl)官能基。示範例四係為MDI與聚碳酸酯多元醇PCPO2000預聚合的聚氨酯，加入結構式(1)所示之化合物或代表實驗例所合成的化合物，經由和上述示範例二相同的溶膠凝膠反應步驟和製備程序，可以在FTIR圖譜觀察到1085cm^-1左右觀察到新生成的Si-O-Si官能基，所得到的有機/無機混成材料的FTIR圖譜如第4圖所示。 Example 1 is a polyurethane prepolymerized with MDI and polyester polyol PCL2000. Example 1 is an experimental control group without structural formula (1). According to the FT-IR spectrum shown in Figure ^{1, it is} about 1737cm -1 A characteristic peak of the urethane functional group was observed at the position. The second example is a polyurethane prepolymer polymerized by MDI and polyester polyol PCL2000, and then the compound represented by structural formula (1) or the compound synthesized in the representative experimental example is added to the above-mentioned MDI and polyester polyol PCL2000 to polymerize Polyurethane prepolymer, to form a mixed solution, and after diluting with a solvent, add 0.1~5.0 weight ratio of acidic catalyst such as hydrochloric acid, nitric acid or acetic acid and stir until uniform, dry the film and place it at 60℃ In the oven, the sol-gel reaction is completed within 24 to 48 hours, and then dried in a vacuum oven to remove the remaining excess solvent. After the reaction is completed, ^{the Si-OR functional group at 950 cm -1} disappears, and the Si-O-Si functional group is regenerated. It has a characteristic peak at the position of ^{1041 cm -1 in the FTIR spectrum.} The preparation of the organic/inorganic hybrid material described in the invention. Example 3 is a polyurethane pre-polymerized with MDI and polycarbonate polyol PCPO2000. Example 3 does not add structural formula (1). As shown in Figure 3, the FTIR spectrum is about 1742cm ^-1 and urethane is observed. C=O(carbonyl) functional group overlapping with carbonate. The fourth example is a polyurethane pre-polymerized with MDI and polycarbonate polyol PCPO2000. The compound represented by the structural formula (1) or the compound synthesized in the representative experimental example is added, and the sol-gel reaction step is the same as that of the second example above. And the preparation procedure, the newly formed Si-O-Si functional groups can be observed in the FTIR spectrum at about 1085 cm ^{-1. The} FTIR spectrum of the obtained organic/inorganic hybrid material is shown in Figure 4.

示範例五為MDI與聚醚類多元醇PTMEG2000聚合的聚氨酯，示範例五未添加結構式(1)，在FTIR圖譜1732cm^-1左右看到胺基甲酸酯官能基的特徵峰，其FTIR圖譜如第5圖所示。示範例六至十係為加入結構式(1)所示之化合物或代表實驗例之化合物與上述之高分子預聚物的混合溶液以溶劑進行稀釋後，再加入尺寸為20~1,000nm的無機粒子，該無機粒子是矽氧化物，加入0.1~5.0重量比的等酸性觸媒並攪拌至均勻，成膜烘乾並置入60℃的烘箱，24~48小時完成溶膠凝膠反應，然後在真空烘箱中進行乾燥去除剩下多餘的溶劑。反應完成後FTIR圖譜位置950cm^-1的Si-O-R官能基消失，然後生成(示範例十)1095cm^-1的Si-O-Si官能基，藉此得到本發明所述的有機無機混成材料，其FTIR圖譜如第6圖所示。 Exemplary example 5 is a polyurethane polymerized by MDI and polyether polyol PTMEG2000. In example 5, structural formula (1) is not added. The characteristic peak of the urethane functional group is seen ^{in the FTIR spectrum at about 1732 cm -1, and its FTIR spectrum} As shown in Figure 5. Exemplary examples six to ten are to add the compound represented by the structural formula (1) or the mixed solution of the compound of the representative experimental example and the above-mentioned polymer prepolymer after diluting with a solvent, and then adding an inorganic with a size of 20~1,000nm Particles, the inorganic particles are silicon oxides, add 0.1~5.0 weight ratio of acidic catalyst and stir until uniform, film formation and drying and put in a 60℃ oven, 24~48 hours to complete the sol-gel reaction, and then Dry in a vacuum oven to remove excess solvent. After completion of the reaction FTIR spectra functional position 950cm ^Si-OR-1 disappeared, and then generates (exemplary embodiment ten) 1095cm ^Si-O-Si-1 functional group, thereby obtaining an organic-inorganic hybrid material according to the present invention, which The FTIR spectrum is shown in Figure 6.

上述示範例一、三、五是沒有加入結構式(1)所示之化合物或代表實驗例之化合物的實驗對照組；上述示範例二、四、六至十四是各種的二異氰酸酯和多元醇所形成的聚氨酯的預聚物和結構式(1) 所示化合物或代表實驗例之化合物(3-伯胺丙基三乙氧硅烷；(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl(3-(trimethoxysilyl)propyl)carbamate)根據上述的通用步驟所製備得到的有機無機混成材料。 The above example 1, 3, and 5 are experimental control groups without adding the compound represented by the structural formula (1) or the compound representing the experimental example; the above example 2, 4, 6 to 14 are various diisocyanates and polyols The formed polyurethane prepolymer and structural formula (1) The compound shown or the compound representing the experimental example (3-primary amine propyl triethoxysilane; (4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl(3-(trimethoxysilyl)propyl)carbamate) according to The organic-inorganic hybrid material prepared by the above-mentioned general steps.

據此，本發明所述的具有胺基甲酸酯官能基(carbamate)的化合物能夠有效地協助無機物與高分子預聚物相容，然後藉由溶凝膠法製備得到本發明所述的有機無機混成材料，其所包含的無機化合物的重量百分比是5~50wt.%；第二，本發明的有機無機混成材料的平面上水接觸角通常在80~90度之間，其具體意義是本發明的有機無機混成材料的抗水性或抗濕潤性大幅提升，因此本發明所提供的有機無機混成材料特別利於作為絕緣、密封防水或結構性材料。 Accordingly, the compound with carbamate function of the present invention can effectively assist the compatibility of inorganic substances with polymer prepolymers, and then the organic compound of the present invention can be prepared by the lyogel method. Inorganic hybrid materials, the weight percentage of inorganic compounds contained in it is 5-50wt.%; second, the water contact angle on the plane of the organic-inorganic hybrid materials of the present invention is usually between 80-90 degrees, and its specific meaning is this The water resistance or moisture resistance of the organic-inorganic hybrid material of the invention is greatly improved. Therefore, the organic-inorganic hybrid material provided by the present invention is particularly advantageous as an insulating, sealing, waterproof, or structural material.

本發明所述的由碳酸酯類製備異氰酸酯之代表實驗例The representative experimental example of preparing isocyanate from carbonates according to the present invention

3-氨基丙基三甲氧基矽烷((3-Aminopropyl)trimethoxysilane)和聚碳酸酯混合在一溶劑中，該溶劑包含二***(Diethyl ether)、二丙醚(Di-n-propyl ether)、異丙醚(Isopropyl ether)苯甲醚(Anisole)、苯***(Ethoxybenzene)、苯丙醚(Propoxybenzene)、苯丁醚(Butoxybenzene)、鄰甲基苯甲醚(2-Methoxytoluene)、間甲基苯甲醚(3-Methoxytoluene)、對甲基苯甲醚(4-Methoxytoluene)、苄基乙基醚(Benzyl ethyl ether)、二苯醚(Diphenyl ether)、二苄醚(Dibenzyl ether)、四氫呋喃(Tetrahydrofuran)、二氫吡喃(2,3-Dihydropyran)、四氫吡喃(Tetrahydropyran)、2-甲基四氫吡喃(2-Methyl Tetrahydropyran)、苯(Benzene)、甲苯(Toluene)、二甲苯(Xylene)、乙苯(Ethylbenzene)、二乙苯(Diethylbenzene)或環己苯(Cyclohexylbenzene)。先加熱至80~90℃反應，然後再升溫至200~250℃，同時控制高溫的操作壓力是在真空下，其壓力區間是0.0001-400mmHg，最後得到異氰酸丙基三乙氧基硅烷之異氰酸酯，其FTIR圖譜在2260cm^-1觀察到異氰酸酯的特徵吸收峰。 3-Aminopropyl trimethoxysilane ((3-Aminopropyl) trimethoxysilane) and polycarbonate are mixed in a solvent containing diethyl ether, di-n-propyl ether, isopropyl ether and isopropyl ether. Isopropyl ether Anisole, Ethoxybenzene, Propoxybenzene, Butoxybenzene, 2-Methoxytoluene, m-methyl anisole Ether (3-Methoxytoluene), 4-Methoxytoluene, Benzyl ethyl ether, Diphenyl ether, Dibenzyl ether, Tetrahydrofuran , Dihydropyran (2,3-Dihydropyran), Tetrahydropyran (Tetrahydropyran), 2-Methyl Tetrahydropyran (2-Methyl Tetrahydropyran), Benzene, Toluene, Xylene ), Ethylbenzene, Diethylbenzene or Cyclohexylbenzene. First heat to 80~90℃ to react, and then heat to 200~250℃, while controlling the high temperature operating pressure under vacuum, the pressure range is 0.0001-400mmHg, and finally get the isocyanate propyl triethoxy silane For isocyanate, the characteristic absorption peak of isocyanate is observed ^{at 2260 cm -1} in the FTIR spectrum.

上述之由碳酸酯類製備異氰酸酯之代表實驗例所使用的3-氨基丙基三甲氧基矽烷((3-Aminopropyl)trimethoxysilane)可以使用其他的胺類化合物替代，藉此製成具有各種烷基或官能基的異氰酸酯，上述的其他的胺類化合物包含脂肪族胺類，如苯甲胺(Benzylamine)、正乙胺(Ethylamine)、苯乙胺(Phenethylamine)、正丙胺(Propylamine)、3-苯基丙胺(3-Phenylpropylamine)、正丁胺(Butylamine)、4-苯基丁胺(4-Phenylbutylamine)、正戊胺(Pentylamine)、5-苯基戊胺(5-Phenylpentylamine)、正己胺(Hexylamine)、6-苯基己胺(6-Phenylhexylamine)、異丁胺(Isobutylamine)胺乙基-1,4-二氮己圜(Aminoethylpiperazine)、甲基六氫吡嗪(1-Methylpiperazine)、N-氨丙基嗎啉(3-Morpholinopropylamine)或胺乙基-1,4-二氮己圜(Aminoethylpiperazine)或含矽基胺類化合物，如3-氨基丙基三乙氧基矽烷((3-Aminopropyl)triethoxysilane)。 The 3-aminopropyl trimethoxysilane ((3-Aminopropyl)trimethoxysilane) used in the above-mentioned representative experiment of preparing isocyanates from carbonates can be replaced by other amine compounds to produce various alkyl or Functional isocyanate, the above-mentioned other amine compounds include aliphatic amines, such as Benzylamine, Ethylamine, Phenethylamine, Propylamine, 3-phenyl 3-Phenylpropylamine, Butylamine, 4-Phenylbutylamine, Pentylamine, 5-Phenylpentylamine, Hexylamine , 6-Phenylhexylamine, Isobutylamine, Aminoethylpiperazine, 1-Methylpiperazine, N-Ammonia Propylmorpholine (3-Morpholinopropylamine) or Aminoethyl-1,4-Diazahexylamine (Aminoethylpiperazine) or silylamine compounds such as 3-Aminopropyltriethoxysilane ((3-Aminopropyl) triethoxysilane).

以上雖以特定實驗例說明本發明，但並不因此限定本發明之範圍，只要不脫離本發明之要旨，熟悉本技藝者瞭解在不脫離本發明的意圖及範圍下可進行各種變形或變更。此外，摘要部分和標題僅是用來輔助專利文件搜尋之用，並非用來限制本發明之權利範圍。 Although specific experimental examples are used to illustrate the present invention above, the scope of the present invention is not limited thereby. As long as the spirit of the present invention is not deviated, those skilled in the art will understand that various modifications or changes can be made without departing from the intent and scope of the present invention. In addition, the abstract part and title are only used to assist in searching for patent documents, and are not used to limit the scope of rights of the present invention.

Claims

一種從碳酸酯類製備異氰酸鹽的方法，其包含以下步驟： A method for preparing isocyanate from carbonates, which comprises the following steps:

(1)提供一混合物，該混合物包含一碳酸酯類、一胺類或含矽基之胺類的化合物和一溶劑；該碳酸酯類包含聚碳酸酯、碳酸二苯酯或其組合物；和 (1) Providing a mixture, the mixture comprising a carbonate, an amine or a silyl-containing amine compound and a solvent; the carbonate comprising polycarbonate, diphenyl carbonate or a combination thereof; and

(2)進行一轉化程序，使上述混合物中的該碳酸酯類和該胺類或含矽基之胺類的化合物轉化生成所述的異氰酸鹽；該轉化程序包含第一加熱步驟和第二加熱步驟，該第一加熱步驟的操作溫度是40~150℃，和該第二加熱步驟的操作溫度是100~250℃，且該第二加熱步驟的操作壓力是在0.0001-400mmHg。 (2) Perform a conversion procedure to convert the carbonate and the amine or silyl-containing amine compound in the above mixture to the isocyanate; the conversion procedure includes a first heating step and a second In the second heating step, the operating temperature of the first heating step is 40-150°C, and the operating temperature of the second heating step is 100-250°C, and the operating pressure of the second heating step is 0.0001-400 mmHg.

如申請專利範圍第1項所述之異氰酸鹽的製備方法，該胺類化合物包含苯甲胺(Benzylamine)、正乙胺(Ethylamine)、苯乙胺(Phenethylamine)、正丙胺(Propylamine)、3-苯基丙胺(3-Phenylpropylamine)、正丁胺(Butylamine)、4-苯基丁胺(4-Phenylbutylamine)、正戊胺(Pentylamine)、5-苯基戊胺(5-Phenylpentylamine)、正己胺(Hexylamine)、6-苯基己胺(6-Phenylhexylamine)、異丁胺(Isobutylamine)胺乙基-1,4-二氮己圜(Aminoethylpiperazine)、甲基六氫吡嗪(1-Methylpiperazine)、N-氨丙基嗎啉(3-Morpholinopropylamine)或胺乙基-1,4-二氮己圜(Aminoethylpiperazine)。 As the method for preparing isocyanate described in item 1 of the scope of patent application, the amine compound includes Benzylamine, Ethylamine, Phenethylamine, Propylamine, 3-Phenylpropylamine, Butylamine, 4-Phenylbutylamine, Pentylamine, 5-Phenylpentylamine, N-hexyl Hexylamine, 6-Phenylhexylamine, Isobutylamine, Aminoethyl-1,4-Aminoethylpiperazine, 1-Methylpiperazine , N-Aminopropylmorpholine (3-Morpholinopropylamine) or Aminoethyl-1,4-diazepine (Aminoethylpiperazine).

如申請專利範圍第1項所述之異氰酸鹽的製備方法，該含矽基之胺類化合物包含3-氨基丙基三乙氧基矽烷((3-Aminopropyl)triethoxysilane)或3-氨基丙基三甲氧基矽烷((3-Aminopropyl)trimethoxysilane)。 As the method for preparing isocyanate described in item 1 of the scope of patent application, the amine containing silicon group is The compound includes 3-Aminopropyl triethoxysilane ((3-Aminopropyl) triethoxysilane) or 3-Aminopropyl trimethoxysilane ((3-Aminopropyl) trimethoxysilane).

如申請專利範圍第1項所述之異氰酸鹽的製備方法，以該混合物的總重量計，該聚碳酸酯或碳酸二苯酯或其組合物的反應濃度是5~50wt.%。 According to the method for preparing isocyanate described in item 1 of the scope of patent application, based on the total weight of the mixture, the reaction concentration of the polycarbonate or diphenyl carbonate or the combination thereof is 5-50 wt.%.

如申請專利範圍第1項所述之異氰酸鹽的製備方法，該溶劑包含二***(Diethyl ether)、二丙醚(Di-n-propyl ether)、異丙醚(Isopropyl ether)苯甲醚(Anisole)、苯***(Ethoxybenzene)、苯丙醚(Propoxybenzene)、苯丁醚(Butoxybenzene)、鄰甲基苯甲醚(2-Methoxytoluene)、間甲基苯甲醚(3-Methoxytoluene)、對甲基苯甲醚(4-Methoxytoluene)、苄基乙基醚(Benzyl ethyl ether)、二苯醚(Diphenyl ether)、二苄醚(Dibenzyl ether)、四氫呋喃(Tetrahydrofuran)、二氫吡喃(2,3-Dihydropyran)、四氫吡喃(Tetrahydropyran)、2-甲基四氫吡喃(2-Methyl Tetrahydropyran)、苯(Benzene)、甲苯(Toluene)、二甲苯(Xylene)、乙苯(Ethylbenzene)、二乙苯(Diethylbenzene)或環己苯(Cyclohexylbenzene)。 According to the method for preparing isocyanate described in item 1 of the scope of patent application, the solvent includes diethyl ether, di-n-propyl ether, and isopropyl ether (Isopropyl ether). (Anisole), Ethoxybenzene, Propoxybenzene, Butoxybenzene, 2-Methoxytoluene, 3-Methoxytoluene, p-methylanisole 4-Methoxytoluene, Benzyl ethyl ether, Diphenyl ether, Dibenzyl ether, Tetrahydrofuran, Dihydropyran (2,3) -Dihydropyran, Tetrahydropyran, 2-Methyl Tetrahydropyran, Benzene, Toluene, Xylene, Ethylbenzene, Two Diethylbenzene or Cyclohexylbenzene.