Organic-inorganic hybrid material, preparation process for the same and preparation process for its starting material

Abstract

To provide a highly stable organic-inorganic hybrid material with resistance to organic-inorganic phase separation.SOLUTION: An organic-inorganic hybrid material contains 5-50 wt.% of inorganic compounds and has a characteristic peak at a position of about 1050±50 cm-1 in Fourier transform infrared spectrum. Furthermore, the invention also provides a preparation process for the organic-inorganic hybrid material as well as a preparation process for its starting material "isocyanates". In particular, the preparation process for isocyanates involves producing isocyanates by converting carbonates.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an organic-inorganic mixed material, which contains an inorganic compound in an amount of 5 to 50 wt.% by weight and has a Fourier transform infrared spectrum of about 1050±50 cm. -1 The present invention provides a method for preparing the organic-inorganic mixed material and a composition of the starting material thereof. One of the compositions of the starting material is a condensate of isocyanate and phenols. In particular, the method for preparing the isocyanate is produced by converting carbonate esters, which can solve the waste problem of polycarbonate esters and does not release carbon dioxide during the conversion process, making it an economical and environmentally friendly production method. [Background technology]

[0002] Composite materials are widely used in high-tech industries, especially in applications involving organic-inorganic mixed materials. Due to their special high gas barrier properties, low moisture absorption and dispersibility, their material properties are significantly improved compared to conventional materials, making them indispensable materials for high-tech applications such as optics, medical materials, electronics and special coatings.

[0003] Composite materials are usually made by forming organic-inorganic mixed materials from organic polymers and inorganic substances. Compared with the molecular chains of organic polymers, inorganic particles or powders have a relatively large nanoscale size. Furthermore, when two-dimensional flat or sheet-like materials are introduced into the polymer after morphological change, separation of the organic-inorganic phase may occur, which will affect the properties and stability of the composite material.

[0004] Therefore, how to design the composition of additives to meet the requirements and promote the compatibility between organic and inorganic substances while improving the overall properties of the composite material, such as film-forming property, water absorption property, or gas barrier property, is an urgent problem to be overcome in this technical field. Summary of the Invention [Problem to be solved by the invention]

[0005] In view of the above background of the invention, in order to meet the industrial demand, the first objective of the present invention is to provide a new organic-inorganic mixed material. Innovatively, the organic-inorganic mixed material of the present invention is prepared by a new modifier and introduction method. Secondly, the organic-inorganic mixed material of the present invention is a green raw material that can be reused from carbonate ester or recycled carbonate ester, so that the purpose of recycling the material can be realized. [Means for solving the problem]

[0006] Specifically, the organic / inorganic mixed material is prepared by a sol-gel method from a compound represented by structural formula (1), a condensate of isocyanate and phenols, diphenyl carbonate, inorganic fine particles, and a polymer prepolymer, and the weight ratio of the inorganic compound contained in the organic / inorganic mixed material is 5 to 50 wt.% in the total weight of the organic / inorganic mixed material, and the Fourier transform infrared spectrum of about 1050 ± 50 cm -1 It has a characteristic peak at the position.

[0007] Specifically, the modifier of the present invention is a compound represented by the structural formula (1). JPEG2024170624000001.jpg16128

[0008] In the structural formula (1), BP is phenol, a polyphenol derivative, or a halogen-containing phenol, and X is (-CH2-). m or -O-, m is a positive integer of 1 to 10, and Y is (H). a , (-OH) b , (-OCH3) c , (-OCH2CH3) d or (-OCH2CH2CH3) e , and a+b+c+d+e=3.

[0009] Specifically, the phenol includes bisphenol A (2,2-bis(4-hydroxyphenyl) propane (bisphenol A)), bisphenol F (2,2-bis(4-hydroxyphenyl) methane (bisphenol F)), a compound represented by structural formula (2), a compound represented by structural formula (3), or a compound represented by structural formula (4).

[0010] The compound represented by the structural formula (2) is as follows. JPEG2024170624000002.jpg25153 The compound represented by the structural formula (3) is as follows. JPEG2024170624000003.jpg25149The compound represented by the structural formula (4) is as follows. JPEG2024170624000004.jpg25128

[0011] In the structural formulas (2), (3), and (4), R1 is a long carbon chain having 10 or less carbon atoms, a cycloalkane, a haloalkane, a carbonyl group, a sulfonyl group, a sulfinyl group, or a disubstituted polyphenol group; R2 is a hydrogen atom or a long carbon chain having 5 or less carbon atoms, a cycloalkane, a haloalkane, a carbonyl group, a sulfonyl group, a sulfinyl group, or a polyphenol group; each Z is independently an integer of 4 or less, and p≦20.

[0012] The organic / inorganic mixed material of the present invention contains the above-mentioned reactive composition of the modifier, thereby improving the compatibility between the organic substance and the inorganic substance, and an organic / inorganic mixed material with good physical properties can be prepared by the sol-gel method.

[0013] Specifically, the reaction compositions mainly consist of (1) the compound represented by the structural formula (1) and a polymer prepolymer; (2) a condensate of the isocyanate and a phenol and a polymer prepolymer; (3) the diphenyl carbonate and a polymer prepolymer, or (4) the inorganic fine particles and a polymer prepolymer.

[0014] Specifically, the polymer includes polyurethane, epoxy resin, or polyimide, and the molecular weight of the prepolymer is 5,000 to 50,000 Da.

[0015] The second object of the present invention is to provide a method for preparing an organic and inorganic mixed material according to the first object. Innovatively, the method provided by the present invention can solve the waste problem of polycarbonate, keep fixing carbon dioxide in the prepared organic and inorganic mixed material, extend the carbon cycle of carbon dioxide in the material, and is an economical and environmentally friendly manufacturing method.

[0016] Specifically, the method for preparing the organic-inorganic mixed material of the present invention includes the following steps: (1) providing a compound represented by structural formula (1) or a condensation product of an isocyanate and a phenol, or diphenyl carbonate, or inorganic fine particles; (2) adding the compound represented by the structural formula (1), or a condensate of an isocyanate and a phenol, or diphenyl carbonate, or inorganic fine particles to a prepolymer having a molecular weight of 5,000 to 50,000 to obtain a mixture, the content of the prepolymer being 10 to 60% by mass of the mixture; (3) The mixture is hydrolyzed and condensed by a sol-gel method to form the organic / inorganic mixed material, and the weight ratio of the inorganic compound contained in the organic / inorganic mixed material is 5 to 50 wt.% in the total weight of the organic / inorganic mixed material, and the Fourier transform infrared spectrum of about 1050 ± 50 cm -1 It has a characteristic peak at the position.

[0017] Specifically, the mixture further includes a solvent, which makes the mixture homogenous, and the solvent includes tetrahydrofuran, dimethyl sulfoxide, dimethyl formamide, N-methyl-2-pyrrolidone, or anisole.

[0018] Preferably, the temperature range of the hydrolysis condensation reaction is 20 to 60°C.

[0019] The third object of the present invention is to provide a method for preparing isocyanates from carbonates. The isocyanates prepared by the method of the present invention are one of the important raw materials for the organic-inorganic mixed material of the first object of the present invention. In particular, the preparation method uses waste polycarbonates as one of the reaction raw materials, and can be converted into isocyanates by simply carrying out a two-stage heating process. Therefore, the preparation method of isocyanates from carbonates provided by the third aspect of the present invention can solve the problem of treating waste polycarbonates. Compared with the conventional preparation method of isocyanates using the phosgene method, the method of the present invention is a non-phosgene method and does not release carbon dioxide in the heating process, so the preparation method of isocyanates from carbonates in the third aspect of the present invention has the advantages of being safe and environmentally friendly, and is an effective preparation method of isocyanates.

[0020] Specifically, the method for preparing isocyanate from carbonate esters includes the following steps: providing a mixture, the mixture includes a compound of carbonate esters, amines or silicon-containing amines and a solvent, the carbonate esters include polycarbonate, diphenyl carbonate or a combination thereof; and performing a conversion process, converting the compound of carbonate esters and the compound of amines or silicon-containing amines in the mixture to produce the isocyanate, the conversion process includes a first heating step and a second heating step, the operation temperature of the first heating step is 40-150°C, the operation temperature of the second heating step is 100-250°C, and the operation pressure of the second heating step is 0.0001-400mmHg.

[0021] Specifically, the reaction concentration of the polycarbonate or diphenyl carbonate or a combination thereof is 5 to 50 wt. % in the total weight of the mixture. Effect of the Invention

[0022] From the above, the organic-inorganic mixed material provided by the present invention, its preparation method, and its starting material preparation method have at least the following innovations and advantages. (1) The organic-inorganic mixed material provided by the present invention improves the compatibility between organic and inorganic substances by adding a special modifier, and further improves the overall physical properties of the material, such as waterproofness and film-forming ability. (2) One of the reaction components used in the preparation method of the organic-inorganic mixed material provided by the present invention is a waste polymer such as polycarbonate, so the method can solve the waste problem of polymer materials. (3) One of the starting materials of the organic-inorganic mixed material of the present invention is "isocyanate", which uses carbonate esters as one of the starting materials and can be converted into isocyanate simply by carrying out a heating process. In other words, the present invention also provides a non-phosgene method for preparing isocyanate, which does not release carbon dioxide of the carbonate ester structure during the production process of isocyanate, greatly extending the oxygen circulation of carbon dioxide, and is a safe and environmentally friendly preparation method. [Brief description of the drawings]

[0023] [Figure 1] FIG. 2 is a Fourier transform infrared (FTIR) spectrum of Example 1. [Diagram 2] FIG. 1 is a Fourier transform infrared (FTIR) spectrum of Example 2. [Diagram 3] FIG. 1 is a Fourier transform infrared (FTIR) spectrum of Example 3. [Figure 4] FIG. 1 is a Fourier transform infrared (FTIR) spectrum of Example 4. [Diagram 5] FIG. 1 is a Fourier transform infrared (FTIR) spectrum of Example 5. [Figure 6] FIG. 1 is a Fourier transform infrared (FTIR) spectrum of Example 10. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024] The above and other technical contents, features and effects of the present invention will be clearly described below in detail with reference to the drawings for preferred embodiments. In order to fully understand the present invention, the following description will show detailed steps and their configurations. Of course, the present invention is not limited to specific details well known to those skilled in the art in its implementation. Meanwhile, detailed descriptions of known compositions and steps will be omitted to avoid unnecessary limitations of the present invention. Hereinafter, preferred embodiments of the present invention will be described in detail, but in addition to these detailed descriptions, the present invention can be widely implemented in other embodiments, and the scope of the present invention is not limited by the scope of the patents described below.

[0025] According to the first embodiment of the present invention, the present invention provides a new organic inorganic mixed material. Innovatively, the organic inorganic mixed material of the present invention is prepared by a new modifier and introduction method. Secondly, the organic inorganic mixed material of the present invention is a green raw material that can be reused from carbonate ester or recycled carbonate ester, so that the purpose of recycling materials can be realized.

[0026] In a specific embodiment, the organic-inorganic mixed material is prepared by a sol-gel method using a compound represented by structural formula (1), a condensate of isocyanate and phenols, diphenyl carbonate or inorganic fine particles, and a polymer prepolymer. In the total weight of the organic-inorganic mixed material, the weight ratio of the inorganic compound contained is 5 to 50 wt.%, and the Fourier transform infrared spectrum of about 1050 ± 50 cm -1 It has a characteristic peak at the position.

[0027] Specifically, the modifier is a compound represented by structural formula (1). JPEG2024170624000005.jpg16128

[0028] In the structural formula (1), BP is phenol, a polyphenol derivative, or a halogen-containing phenol, and X is (-CH2-CH2-). m or -O-, m is a positive integer of 1 to 10, and Y is (H). a , (OH) b , (-OCH3) c , (-OCH2CH3) d or (-OCH2CH2CH3) e and a+b+c+d+e=3. That is, the sum of a, b, c, and d is 3. Preferably, b, c, d, or e is an integer of 1 to 3.

[0029] Specifically, the phenol includes bisphenol A (2,2-bis(4-hydroxyphenyl) propane (bisphenol A), bisphenol F (2,2-bis(4-hydroxyphenyl) methane (bisphenol F), a compound represented by structural formula (2), a compound represented by structural formula (3), or a compound represented by structural formula (4).

[0030] Specifically, the compound represented by the structural formula (2) is as follows. JPEG2024170624000006.jpg25153

[0031] Specifically, the compound represented by the structural formula (3) is as follows. JPEG2024170624000007.jpg25155

[0032] Specifically, the compound represented by the structural formula (4) is as follows. JPEG2024170624000008.jpg25128

[0033] In the structural formulas (2), (3), and (4), R1 may be a long carbon chain having 10 or less carbon atoms, a cycloalkane, a haloalkane, a carbonyl group, a sulfonyl group, a sulfinyl group, or a di-substituted polyphenol group; R2 may be hydrogen or a long carbon chain having 5 or less carbon atoms, a cycloalkane, a haloalkane, a carbonyl group, a sulfonyl group, a sulfinyl group, or a polyphenol group; each Z is independently an integer of 4 or less, and p≦20.

[0034] In a preferred embodiment, the compound having structural formula (1) is 4-(2-(4-hydroxyphenyl)propane-2-yl)phenyl(3-(trimethoxysilyl)propyl)carbamate, another name for this compound is trimethylsiloxyamino terminated polydimethylsiloxane or 3-primaryaminopropyltriethoxysilane. The amine end groups of the siloxane are primary amine groups, which allows the silicone polymer to form a net positive charge in aqueous solutions over a wide pH range.

[0035] In a specific embodiment, the isocyanate is an aliphatic isocyanate, hexyl isocyanate, 1-octyl isocyanate, dodecyl isocyanate, octadecyl isocyanate, cyclohexyl isocyanate, trimethylsilyl isocyanate, 3-(triethoxysilyl)propyl isocyanate, 3-(trimethoxysilyl)propyl isocyanate, isopropyl isocyanate, phenylethyl isocyanate, methyl isocyanate, ethyl isocyanate, propyl isocyanate, eicosyl isocyanate, or the like. isocyanate or tetracosyl isocyanate.

[0036] In a specific embodiment, the inorganic fine particles are formed by covering the surfaces of inorganic particles with the compound represented by structural formula (1) or a condensation product of the reaction of the isocyanate with a phenol.

[0037] In specific embodiments, 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 or sulfide, lithium oxide or sulfide, cerium oxide or sulfide, cobalt oxide or sulfide, silicon dioxide, titanium dioxide, zinc oxide, zirconia, iron oxide, barium titanate, lithium niobate, cadmium selenide, copper oxide, barium zirconate, chromium trioxide, niobium pentoxide, cerium dioxide, iron titanate, iron silicide, aluminum oxide / titanium oxide mixed layer, aluminum oxide / zirconia mixed layer, manganese oxide, tin oxide, or zinc sulfide.

[0038] In a specific embodiment, the particle size range of the inorganic particles is 20 to 1,000 nm.

[0039] In specific embodiments, the polymer includes polyurethane, epoxy, or polyimide.

[0040] In a specific embodiment, the molecular weight of the polymer prepolymer is 5,000 to 50,000 Da.

[0041] In a specific embodiment, the sol-gel process is a hydrolysis condensation reaction.

[0042] In specific embodiments, 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, 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, zirconia, iron oxide, barium titanate, lithium niobate, cadmium selenide, copper oxide, barium zirconate, chromium trioxide, niobium pentoxide, cerium dioxide, iron titanate, iron silicide, aluminum oxide / titanium oxide mixed layer, aluminum oxide / zirconia mixed layer, manganese oxide, tin oxide, or zinc sulfide.

[0043] According to a second embodiment of the present invention, the present invention provides a method for preparing an organic-inorganic mixed material, the method for preparing the organic-inorganic mixed material includes the steps of: providing a compound represented by structural formula (1), a condensate of isocyanate and phenols, diphenyl carbonate, or inorganic fine particles; adding the compound represented by structural formula (1), the condensate of isocyanate and phenols, diphenyl carbonate, or inorganic fine particles to a prepolymer having a molecular weight of 5,000 to 50,000 to obtain a mixture, the content of the prepolymer being 10 to 60 mass% of the mixture; and forming the organic-inorganic mixed material by hydrolysis and condensation reaction of the composition of the mixture by a sol-gel method, the weight ratio of the inorganic compound contained in the organic-inorganic mixed material being 5 to 50 wt.% in the total weight of the organic-inorganic mixed material, the structure being capable of a covalent bond recombination reaction, and a Fourier transform infrared spectrum of about 1050±50 cm. -1 and having a characteristic peak at the position.

[0044] In a specific embodiment, the structural formula (1) is as follows: JPEG2024170624000009.jpg16128

[0045] In the structural formula (1), BP is phenol, a polyphenol derivative, or a halogen-containing phenol, and X is (-CH2-). m Or -O- where m is a positive integer from 1 to 10, and Y is (H) a , (-OH) b , (-OCH3) c , (-OCH2CH3) d Or, it may be any combination of (-OCH2CH2CH3)e and a+b+c+d+e=3.

[0046] Specifically, the phenol includes bisphenol A (2,2-bis(4-hydroxyphenyl)propane (bisphenol A)), bisphenol F (2,2-bis(4-hydroxyphenyl)methane (bisphenol F)), a compound represented by structural formula (2), a compound represented by structural formula (3), or a compound represented by structural formula (4).

[0047] Specifically, the compound represented by the structural formula (2) is as follows. JPEG2024170624000010.jpg25153

[0048] Specifically, the compound represented by the structural formula (3) is as follows. JPEG2024170624000011.jpg25150

[0049] Specifically, the compound represented by the structural formula (4) is as follows. JPEG2024170624000012.jpg25128

[0050] In the structural formulas (2), (3), and (4), R1 may be a long carbon chain having 10 or less carbon atoms, a cycloalkane, a haloalkane, a carbonyl group, a sulfonyl group, a sulfinyl group, or a di-substituted polyphenol group; R2 may be hydrogen or a long carbon chain having 5 or less carbon atoms, a cycloalkane, a haloalkane, a carbonyl group, a sulfonyl group, a sulfinyl group, or a polyphenol group; each Z is independently an integer of 4 or less, and p≦20.

[0051] In a preferred embodiment, the compound having structural formula (1) is 4-(2-(4-hydroxyphenyl)propane-2-yl)phenyl(3-(trimethoxysilyl)propyl)carbamate, another name for this compound is trimethylsiloxyamino terminated polydimethylsiloxane or 3-primaryaminopropyltriethoxysilane. The amine end groups of the siloxane are primary amine groups, which allows the silicone polymer to form a net positive charge in aqueous solutions over a wide pH range.

[0052] In a specific embodiment, the isocyanate is an aliphatic isocyanate, hexyl isocyanate, 1-octyl isocyanate, dodecyl isocyanate, octadecyl isocyanate, cyclohexyl isocyanate, trimethylsilyl isocyanate, 3-(triethoxysilyl)propyl isocyanate, 3-(trimethoxysilyl)propyl isocyanate, isopropyl isocyanate, phenylethyl isocyanate, methyl isocyanate, ethyl isocyanate, propyl isocyanate, eicosyl isocyanate, isocyanate or tetracosyl isocyanate.

[0053] In a specific embodiment, the inorganic fine particles are formed by covering the surface of the inorganic particles with the compound represented by the structural formula (1) or a condensation product of the reaction of the isocyanate with a phenol.

[0054] 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, 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, zirconia, iron oxide, barium titanate, lithium niobate, cadmium selenide, copper oxide, barium zirconate, chromium trioxide, niobium pentoxide, cerium dioxide, iron titanate, iron silicide, aluminum oxide / titanium oxide mixed layer, aluminum oxide / zirconia mixed layer, manganese oxide, tin oxide, or zinc sulfide.

[0055] In a specific embodiment, the inorganic particles have a particle size ranging from 20 to 1,000 nm.

[0056] In specific embodiments, the polymer comprises polyurethane, epoxy, or polyimide.

[0057] In a specific embodiment, the molecular weight of the polymer prepolymer is 5,000 to 50,000 Da.

[0058] In a specific embodiment, the mixture further comprises a solvent or an additive.

[0059] In specific embodiments, the solvent includes Tetrahydrofuran, Dimethyl Sulfoxide, Dimethyl Formamide, N-Methyl-2-Pyrrolidone, or Anisole.

[0060] In specific embodiments, the additives include boric acid, phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid, sulfurous acid, acetic acid, formic acid, propionic acid, alkali metal hydroxides, sodium phosphate, aliphatic amines, piperidine and its derivatives, imidazole and its derivatives, or nitrogen heterocycle-containing compounds. In a specific embodiment, the temperature range of the hydrolysis condensation reaction is 20-60°C.

[0061] According to a third embodiment of the present invention, the present invention provides a method for preparing an isocyanate from a carbonate ester. The method includes the steps of providing a mixture and performing a conversion process. The mixture includes a carbonate ester, an amine or a silicon-containing amine-like compound, and a solvent. The carbonate ester includes polycarbonate, diphenyl carbonate, or a combination thereof. The conversion process converts the carbonate ester and the amine or silicon-containing amine-like compound of the mixture to produce the isocyanate. The conversion process includes a first heating step and a second heating step, the operating temperature of the first heating step is 40-150°C, the operating temperature of the second heating step is 100-250°C, and the operating pressure of the second heating step is 0.0001-400mmHg.

[0062] In a specific embodiment, the amine compound includes benzylamine, n-ethylamine, phenethylamine, n-propylamine, 3-phenylpropylamine, n-butylamine, 4-phenylbutylamine, n-pentylamine, 5-phenylpentylamine, n-hexylamine, 6-phenylhexylamine, isobutylamine, aminoethyl-1,4-diazepine, 1-methylpiperazine, N-aminopropylmorpholine, or aminoethyl-1,4-diazepine.

[0063] In a specific embodiment, the silicon-containing amine compound is 3-aminopropyltriethoxysilane or 3-aminopropyltrimethoxysilane.

[0064] In a specific embodiment, the reactant concentration of the polycarbonate, diphenyl carbonate or a combination thereof is 5-50 wt.% in the total weight of the mixture.

[0065] In a specific embodiment, the solvent is diethyl ether, dipropyl ether, isopropyl ether, anisole, ethoxybenzene, propoxybenzene, butoxybenzene, O-methylanisole (2-MethoxyToluene), m-methylanisole (3-MethoxyToluene), p-methylanisole (4-MethoxyToluene), benzyl ethyl ether, diphenyl ether, dibenzyl ether, tetrahydrofuran, dihydropyran, tetrahydropyran, 2-methyltetrahydropyran, ... Tetrahydropyran, Benzene, Toluene, Xylene, Ethylbenzene, Diethylbenzene, or Cyclohexylbenzene.

[0066] From the above, the organic-inorganic mixed material and the preparation method thereof provided by the present invention greatly improve the compatibility of organic and inorganic substances by using a new modifier and introduction method, and the organic-inorganic mixed material of the present invention is prepared by using a sol-gel method. And the organic-inorganic mixed material of the present invention is a green raw material that can be reused from recycling carbonate ester or polycarbonate ester, so the purpose of recycling materials can be realized. Furthermore, the method of preparing isocyanate from carbonate esters provided by the present invention is a non-phosgene method, and no carbon dioxide is released in the process of preparing isocyanate, so the carbon circulation of carbon dioxide is extended, and it is a safe and environmentally friendly preparation method.

[0067] The following experimental examples and examples are based on the above-mentioned invention and the contents described in the examples, and are used to explain the present invention in detail.

[0068] General Process for Preparing Compounds / Modifiers Having Formula (1) of the Present Invention An appropriate amount of isocyanate and phenols are dissolved in a non-polar solvent to form a homogeneous mixture, which is then reacted at 60 to 100°C. To promote the reaction, a small amount of a catalyst such as organotin, amine, bismuth, or zinc may be added. After 12 hours of observation, when the phenols are completely consumed, the solvent is removed by purification to obtain a compound represented by structural formula (1).

[0069] Representative experimental example of modifier: 3-primary aminopropyltriethoxysilane; (4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl(3-(trimethoxysilyl)propyl)carbamate preparation method 5 g of isocyanatopropyltriethoxysilane and 4.17 g of bisphenol A (BPA) were dissolved in 50 ml of toluene and reacted at 80 to 100°C. A small amount of organotin catalyst was added to accelerate the reaction. After 12 hours of observation by thin layer chromatography, when bisphenol A was completely consumed, the reaction was purified and the solvent was removed to obtain 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, and the peak peak was observed at 1716 cm. -1 The carbon-oxygen double bond functional group absorption peak of the carbamate is generated, and finally the solvent is removed by vacuum distillation to obtain the product. 1 H-NMR analysis was carried out.

[0070] (FTIR)(KBr):1716 cm -1 , 3350 cm -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).

[0071] The isocyanates used in the normal preparation process of the compound having the above-mentioned structural formula (1) include aliphatic isocyanates, either alone or in mixture, such as aliphatic isocyanates, hexyl isocyanate, 1-octyl isocyanate, dodecyl isocyanate, octadecyl isocyanate, cyclohexyl isocyanate, trimethylsilyl isocyanate, 3-(triethoxysilyl)propyl isocyanate, 3-(trimethoxysilyl)propyl isocyanate, isopropyl isocyanate, phenylethyl isocyanate, methyl isocyanate, ethyl isocyanate, propyl isocyanate, propyl silane ... isocyanate, eicosyl isocyanate or tetracosyl isocyanate is used.

[0072] The phenols used in the normal preparation process of the compound having the above-mentioned structural formula (1) are 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).

[0073] Conventional preparation process of the inorganic particles of the present invention The siloxane functional group-containing compound of structural formula (1) undergoes a condensation reaction with the hydroxyl group (-OH), amine group (-NH2) or thiol group (-SH) on the surface of the inorganic particles, whereby the compound of structural formula (1) containing a carbamate functional group is bonded and fixed to the surface of the inorganic particles, forming the inorganic fine particles of the present invention. The inorganic fine particles are surface-functionalized inorganic particles. The particle size range of the inorganic particles is 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 or sulfide, lithium oxide or sulfide, cerium oxide or sulfide, cobalt oxide or sulfide, silicon dioxide, titanium dioxide, zinc oxide, zirconia, iron oxide, barium titanate, lithium niobate, cadmium selenide, copper oxide, barium zirconate, chromium trioxide, niobium pentoxide, cerium dioxide, iron titanate, iron silicide, aluminum oxide / titanium oxide mixed layer, aluminum oxide / zirconia mixed layer, manganese oxide, tin oxide, or zinc sulfide.

[0074] Typical preparation steps of the organic-inorganic mixed material of the present invention The present invention provides a compound represented by the structural formula (1), a condensate of the isocyanate and a phenol, diphenyl carbonate, or the inorganic fine particles. In particular, a raw material having a carbamate functional group and a polymer containing a carbonyl group have good compatibility. The present invention provides a polymer prepolymer. The polymer prepolymer includes a prepolymer of a polymer having a molecular weight of 5,000 to 50,000, such as polyurethanes, epoxy resins, polyimide, or polyamic acid (PAA). The compound represented by the structural formula (1) is directly added to the polymer prepolymer, and monitored with an infrared spectrometer to obtain a 950 cm -1 Absorption peaks can be observed on the left and right of the Si-OR functional group. After diluting the mixed solution containing the compound represented by structural formula (1) and the polymer prepolymer with a solvent, an acid catalyst such as hydrochloric acid, nitric acid, or acetic acid in a weight ratio of 0.1 to 5.0 is added and stirred uniformly, a film is formed, dried, and placed in a 60°C oven to complete the sol-gel reaction for 24 to 48 hours. Then, the film is dried in a vacuum oven to remove excess solvent. After the reaction is completed, the film is dried at 950cm. -1 The Si-OR functional group disappears and the peak appears again at 1000–1100cm -1 The Si-O-Si functional group was formed, completing the preparation of the organic / inorganic hybrid material of the present invention.

[0075] Typical Preparation Process for Polyurethane Prepolymer The polyurethane prepolymer is prepared by a polymer polymerization reaction. Specifically, diisocyanates such as diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI) or 1,6-hexylene diisocyanate (HDI) and polyols such as polyether glycol (PEG), polytetramethylene ether glycol (PTMEG), polycaprolactone polyol (PCL) or polycarbonate diol (PCPO) are condensation polymerized at 60 to 80 ° C., and a small amount of a solvent such as dimethylformamide (DMF), N-methylpyrrolidone (NMP), tetrahydrofuran, dimethyl sulfoxide or anisole may be added during the reaction. After about 30 minutes, the prepolymerization reaction is completed, and at this time, a characteristic peak of a carbamate functional group can be observed in the FT-IR spectrum.

[0076] The various carbamate-containing organic inorganic mixed materials prepared by the conventional preparation process of the polyurethane prepolymer and organic inorganic mixed material are shown in Table 1. Diisocyanate and polyol are the reaction composition of polyurethane prepolymer. Silica is the content of inorganic compounds in the prepared organic inorganic mixed material.

[0077] Table 1 JPEG2024170624000013.jpg222148 a) The number after the polyol indicates the molecular weight, and polyether polyol 2000 indicates a polyether polyol having a molecular weight of 2000 g / mol. b) Silica (%) indicates the weight ratio of the inorganic compound in the entire organic / inorganic mixed material. c) The water contact angle on the flat surface of the organic-inorganic composite material is shown. X indicates poor film-forming properties. O indicates average film-forming properties. ◎ indicates excellent film-forming properties.

[0078] Example 1 is a polyurethane obtained by prepolymerizing diphenylmethane diisocyanate MDI and polyester polyol PCL2000. Example 1 is a control experiment in which structural formula (1) was not added. According to the FT-IR spectrum shown in FIG. 1, -1 A characteristic peak of the carbamate functional group can be observed at a position near the center of the graph. Example 2 is a polyurethane prepolymer obtained by polymerizing MDI and polyester polyol PCL2000. Then, the compound represented by structural formula (1) or the compound produced in the representative experimental example is added to the polyurethane prepolymer obtained by polymerizing MDI and polyester polyol PCL2000 to form a mixed solution, which is diluted with a solvent, and then an acid catalyst such as hydrochloric acid, nitric acid or acetic acid in a weight ratio of 0.1 to 5.0 is added and stirred uniformly, a film is formed, dried, and placed in a 60°C oven to complete the sol-gel reaction for 24 to 48 hours, and then dried in a vacuum oven to remove excess solvent. After the reaction is completed, the sol-gel reaction is performed at 950 cm -1 The Si-OR functional group disappears and the Si-O-Si functional group is generated again. (FTIR spectrum 1041 cm -1 The spectrum of the organic / inorganic mixed material of the present invention was thus completed. Example 3 is a polyurethane obtained by prepolymerizing MDI and polycarbonate polyol PCPO2000, and structural formula (1) is not added to Example 3. As shown in FIG. 3, the (FTIR) spectrum of the polyurethane has a characteristic peak at 1742 cm -1 In Example 4, a polyurethane was prepared by prepolymerizing MDI and polycarbonate polyol PCPO2000. The polyurethane was prepared by adding a compound represented by the structural formula (1) or a compound produced in a representative experimental example, and then passing through the same sol-gel reaction process and preparation process as in Example 2. The polyurethane was then subjected to a 1085 cm FTIR spectrum. -1 The newly generated Si-O-Si functional groups can be observed in the vicinity, and the (FTIR) spectrum of the resulting organic / inorganic hybrid material is shown in Figure 4.

[0079] Example 5 is a polyurethane obtained by polymerizing MDI and polyether polyol PTMEG2000, and in Example 5, structural formula (1) is not added. -1 A characteristic peak of the carbamate functional group can be observed around the 950 cm position, and the (FTIR) spectrum is shown in FIG. 5. In Examples 6 to 10, after diluting the mixed solution of the compound represented by structural formula (1) or the compound of the representative experimental example and the polymer prepolymer with a solvent, silica-based nano-microspheres having a size of 20 to 1,000 nm are further added, and an acid catalyst is added in a weight ratio of 0.1 to 5.0, and the mixture is stirred uniformly, formed into a film, dried, and placed in a 60°C oven to complete the sol-gel reaction for 24 to 48 hours, and then dried in a vacuum oven to remove excess solvent. After the reaction is completed, the (FTIR) spectrum position is 950 cm -1 The Si-OR functional group disappears, and then at 1095cm -1 The Si-O-Si functional group was generated (Example 10) to obtain the organic-inorganic mixed material of the present invention, and its (FTIR) spectrum is shown in FIG.

[0080] The above-mentioned Examples 1, 3, and 5 are experimental control groups to which the compound represented by the structural formula (1) or the compound of the representative experimental example was not added. The above-mentioned Examples 2, 4, and 6 to 10 show organic-inorganic mixed materials obtained by preparing polyurethane prepolymers formed from various diisocyanates and polyols and the compound represented by the structural formula (1) or the compound of the representative experimental example (3-primary aminopropyltriethoxysilane; (4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl (3-(trimethoxysilyl)propyl)carbamate) by the above-mentioned normal process.

[0081] From the above, the compound having a carbamate functional group of the present invention effectively assists compatibility between inorganic substances and polymer prepolymers, and the weight ratio of the inorganic compounds contained in the organic-inorganic mixed material of the present invention obtained by preparing by the sol-gel method is 5-50wt.%. Secondly, the water contact angle on a flat surface of the organic-inorganic mixed material of the present invention is usually 80-90 degrees, and the technical significance is that the water resistance or wet resistance of the organic-inorganic mixed material of the present invention is greatly improved, so that the organic-inorganic mixed material provided by the present invention is particularly advantageous as an insulating, sealing, waterproofing or structural material.

[0082] Representative Experimental Examples for Preparing Isocyanates from Carbonates of the Present Invention 3-Aminopropyltrimethoxysilane and polycarbonate ester are mixed in a solvent, and the solvent is selected from the group consisting of diethyl ether, dipropyl ether, isopropyl ether, anisole, ethoxybenzene, propoxybenzene, butoxybenzene, O-methylanisole (2-MethoxyToluene), m-methylanisole (3-MethoxyToluene), p-methylanisole (4-MethoxyToluene), benzyl ethyl ether, diphenyl ether, and dibenzyl ether. ether, tetrahydrofuran, dihydropyran, tetrahydropyran, 2-methyl tetrahydropyran, benzene, toluene, xylene, ethylbenzene, diethylbenzene or cyclohexylbenzene. First, the reaction is carried out by heating to 80-90°C, and then the temperature is increased to 200-250°C, while the operating pressure to control the high temperature is under vacuum, and the pressure range is 0.0001-400mmHg. Finally, the isocyanate of isocyanatopropyltriethoxysilane is obtained, and the isocyanate of the (FTIR) spectrum at 2260cm is obtained. -1 A characteristic absorption peak of isocyanate was observed.

[0083] Instead of 3-aminopropyltrimethoxysilane used in the representative experimental example for preparing isocyanates from carbonate esters, other amine compounds may be used, which allows the preparation of isocyanates with various alkyl or functional groups. The other amine compounds include benzylamine, n-ethylamine, phenethylamine, n-propylamine, 3-phenylpropylamine, n-butylamine, 4-phenylbutylamine, n-pentylamine, 5-phenylpentylamine, n-hexylamine, 6-phenylhexylamine, isobutylamine, aminoethyl-1,4-diazepine, 1-methylpiperazine, N-aminopropylmorpholine (3-morpholinopropylamine), and aminoethyl-1,4-diazepine. These include aliphatic amines such as piperazine, and silicon-containing amine compounds such as 3-aminopropyltriethoxysilane.

[0084] Although specific experimental examples are used to explain the present invention, they are not intended to limit the scope of the present invention, and those skilled in the art will understand that various modifications or changes can be made without departing from the gist of the present invention. And the abstract and title of the invention are intended to assist in patent search, and are not intended to limit the scope of the rights of the present invention.

Claims

1. An organic / inorganic mixed material in which a condensate covers the surfaces of inorganic particles, The condensate is prepared by a sol-gel method from a reaction product of the compound represented by structural formula (1) with a phenol and a polymer prepolymer, The weight ratio of the inorganic compound contained in the organic-inorganic mixed material is 5 to 50 wt. % in the total weight of the organic-inorganic mixed material, and the Fourier transform infrared spectrum of the inorganic compound is 1050 ± 50 cm -１ The organic-inorganic mixed material has a characteristic peak at the position of (BP is phenol, a polyphenol derivative, or a halogen-containing phenol; X is (-CH ２ -) m or -O-, where 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.

2. The organic-inorganic mixed material according to claim 1, characterized in that the compound represented by the structural formula (1) is 4-(2-(4-phenol)propan-2-yl)phenyl(3-(trimethoxysilyl)propyl)amine ester.

3. The organic-inorganic mixed material according to claim 1, characterized in that the phenol includes bisphenol A, bisphenol F, a compound represented by structural formula (2), a compound represented by structural formula (3), or a compound represented by structural formula (4). (R １ each represents a long carbon chain having 10 or less carbon atoms, a cycloalkane, a haloalkane, a carbonyl group, a sulfonyl group, a sulfinyl group, or a disubstituted polyphenol group, R ２ are each hydrogen, a long carbon chain having 5 or less carbon atoms, a cycloalkane, a haloalkane, a carbonyl group, a sulfonyl group, a sulfinyl group, or a polyphenol group, Each Z is independently an integer of 4 or less, and p≦20.

4. The inorganic particles are 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 or sulfide, lithium oxide or sulfide, cerium oxide or sulfide, cobalt oxide or sulfide, silicon dioxide, titanium dioxide, zinc oxide, zirconia, iron oxide, barium titanate, lithium niobate, cadmium selenide, copper oxide, barium zirconate, chromium trioxide, niobium pentoxide, cerium dioxide, iron titanate, iron silicide, aluminum oxide / titanium oxide mixed layer, aluminum oxide / zirconia mixed layer, manganese oxide, tin oxide, or zinc sulfide. The organic-inorganic mixed material according to claim 5, characterized in that it contains.

5. 6. The organic-inorganic mixed material according to claim 5, wherein the inorganic particles have a particle size range of 20 to 1,000 nm.

6. The organic-inorganic hybrid material according to claim 1 , wherein the polymer comprises polyurethane, epoxy resin or polyimide.

7. 2. The organic-inorganic mixed material according to claim 1, wherein the molecular weight of the high molecular prepolymer is 5,000 to 50,000 Da.

8. The organic-inorganic mixed material according to claim 1 , wherein the sol-gel method is a hydrolysis-condensation reaction.

9. The inorganic compound is 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 or sulfide, lithium oxide or sulfide, cerium oxide or sulfide, cobalt oxide or sulfide, silicon dioxide, titanium dioxide, zinc oxide, zirconia, iron oxide, barium titanate, lithium niobate, cadmium selenide, copper oxide, barium zirconate, chromium trioxide, niobium pentoxide, cerium dioxide, iron titanate, iron silicide, aluminum oxide / titanium oxide mixed layer, aluminum oxide / zirconia mixed layer, manganese oxide, tin oxide, or zinc sulfide. The organic-inorganic mixed material according to claim 1.

10. A method for preparing an organic-inorganic mixed material, comprising the steps of: (1) providing a condensation product obtained by reacting a compound represented by structural formula (1) with a phenol and inorganic fine particles; (BP is phenol, a polyphenol derivative, or a halogen-containing phenol; X is (-CH ２ -) m or -O-, where 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. (2) adding a condensate obtained by reacting the compound represented by the structural formula (1) with a phenol to a prepolymer having a molecular weight of 5,000 to 50,000 to obtain a mixture, the content of the prepolymer being 10 to 60% by mass of the mixture; (3) performing a sol-gel process to subject the mixture to a hydrolysis and condensation reaction to obtain a condensate; (4) covering the surfaces of the inorganic fine particles with the condensate, thereby forming the organic-inorganic mixed material; The weight ratio of the inorganic compound contained in the organic-inorganic mixed material is 5 to 50 wt. % in the total weight of the organic-inorganic mixed material, and the Fourier transform infrared spectrum of the inorganic compound is 1050 ± 50 cm -１ having a characteristic peak at position

11. The compound represented by the structural formula (1) is 4-(2-(4-phenol)propan-2-yl)phenyl(3-(trimethoxysilyl)propyl)amine ester, the preparation method of the organic-inorganic mixed material according to claim 10.

12. The preparation method of organic-inorganic mixed material according to claim 10, characterized in that the phenol comprises bisphenol A, bisphenol F, a compound represented by structural formula (2), a compound represented by structural formula (3) or a compound represented by structural formula (4). (R １ each represents a long carbon chain having 10 or less carbon atoms, a cycloalkane, a haloalkane, a carbonyl group, a sulfonyl group, a sulfinyl group, or a disubstituted polyphenol group, R ２ are each hydrogen, a long carbon chain having 5 or less carbon atoms, a cycloalkane, a haloalkane, a carbonyl group, a sulfonyl group, a sulfinyl group, or a polyphenol group, Each Z is independently an integer of 4 or less, and p≦20.

13. The method for preparing organic-inorganic composite material according to claim 10, characterized in that 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 or sulfide, lithium oxide or sulfide, cerium oxide or sulfide, cobalt oxide or sulfide, silicon dioxide, titanium dioxide, zinc oxide, zirconia, iron oxide, barium titanate, lithium niobate, cadmium selenide, copper oxide, barium zirconate, chromium trioxide, niobium pentoxide, cerium dioxide, iron titanate, iron silicide, aluminum oxide / titanium oxide mixed layer, aluminum oxide / zirconia mixed layer, manganese oxide, tin oxide, or zinc sulfide.

14. The method for preparing an organic-inorganic mixed material according to claim 10, characterized in that the particle size range of the inorganic particles is 20 to 1,000 nm.

15. The method for preparing an organic-inorganic hybrid material according to claim 10, wherein the polymer comprises polyurethane, epoxy resin or polyimide.

16. The method for preparing an organic-inorganic mixed material according to claim 10, characterized in that the mixture further comprises a solvent or an additive.

17. 17. The method for preparing an organic-inorganic hybrid material according to claim 16, wherein the solvent comprises tetrahydrofuran, dimethylsulfoxide, dimethylformamide, N-methylpyrrolidone or anisole.

18. 17. The method for preparing organic-inorganic mixed material according to claim 16, characterized in that said additive comprises 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 heterocycle-containing compound.

19. The method for preparing an organic-inorganic mixed material according to claim 10, wherein the temperature of the hydrolysis and condensation reaction is 20 to 60°C.

20. A process for preparing isocyanates from carbonates, comprising the steps of: (1) providing a mixture, the mixture comprising compounds of carbonates, amines or silicon-containing amines and a solvent, the carbonates comprising polycarbonates, diphenyl carbonate or a combination thereof; (2) A step of performing a conversion process, in which the compounds of the carbonates and the amines or silicon-containing amines in the mixture are converted to produce the isocyanates, the conversion process includes a first heating step and a second heating step, the operation temperature of the first heating step is 40-150°C, the operation temperature of the second heating step is 100-250°C, and the operation pressure of the second heating step is 0.0001-400 mmHg.

21. The method for preparing an isocyanate according to claim 20, wherein the amine compound comprises benzylamine, n-ethylamine, phenethylamine, n-propylamine, 3-phenylpropylamine, n-butylamine, 4-phenylbutylamine, n-pentylamine, 5-phenylpentylamine, n-hexylamine, 6-phenylhexylamine, isobutylamine aminoethyl-1,4-diazepine, methylhexahydropyrazine, N-aminopropylmorpholine or aminoethyl-1,4-diazepine.

22. The method for preparing an isocyanate according to claim 20, characterized in that the silicon-containing amine compound comprises 3-aminopropyltriethoxysilane or 3-aminopropyltrimethoxysilane.

23. The method for preparing an isocyanate according to claim 20, characterized in that the reactive concentration of the polycarbonate or diphenyl carbonate or a combination thereof in the total weight of the mixture is 5 to 50 wt.%.

24. 21. The process for preparing an isocyanate according to claim 20, wherein the solvent comprises diethyl ether, dipropyl ether, isopropyl ether anisole, ethoxybenzene, propoxybenzene, butoxybenzene, O-methyl anisole, m-methyl anisole, p-methyl anisole, benzyl ethyl ether, diphenyl ether, dibenzyl ether, tetrahydrofuran, dihydropyran, tetrahydropyran, 2-methyltetrahydropyran, benzene, toluene, xylene, ethylbenzene, diethylbenzene or cyclohexylbenzene.

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