Isocyanate silane composition and preparation method and application thereof

Abstract

The present invention relates to an isocyanate silane composition and a preparation method and application thereof. The isocyanate silane composition comprises isocyanate silane and a compound represented by formula (1) within 5-5000 ppm. The isocyanate silane composition provided by the present invention has excellent storage stability.

Description

Technical Field

[0001] The invention relates to the technical field of silane coupling agents, and in particular to an isocyanate silane composition and a preparation method and application thereof. Background Art

[0002] Isocyanate silane is an important silane coupling agent. It has been used as a raw material for silane-modified resins in various industrial products, especially in coatings, sealants, adhesives and elastomer materials, but is not limited to these application fields. Isocyanate silane can be obtained by thermal decomposition of carbamate silane.

[0003] However, isocyanate silanes are very active because they contain isocyanate groups and silane or siloxane groups. They often undergo side reactions such as polymerization and hydrolysis, which affect the quality of the product.

[0004] Therefore, there is an urgent need in the art to provide a storage-stable isocyanate silane raw material. Summary of the invention

[0005] In view of the shortcomings of the prior art, one of the purposes of the present invention is to provide an isocyanate silane composition having excellent storage stability.

[0006] To achieve this object, the present invention adopts the following technical solutions:

[0007] The present invention provides an isocyanate silane composition, which comprises isocyanate silane and 5ppm-5000ppm (for example, 6ppm, 10ppm, 12ppm, 15ppm, 20ppm, 40ppm, 50ppm, 60ppm, 100ppm, 150ppm, 200ppm, 210ppm, 250ppm, 300ppm, 320ppm, 350ppm, 400ppm, 450ppm, 500ppm, 1000ppm, 1500ppm, 2000ppm, 2500ppm, 3000ppm, 3500ppm, 4000ppm, 4500ppm, 4900ppm, etc.) of a compound represented by the following formula (1).

[0008]

[0009] Wherein, R1, R2, R4, R5 are saturated alkyl or alkoxy groups, the carbon chain length of the alkyl or alkoxy group is C1-C6, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy. R3, R6 are branched or straight chain alkylene or cycloalkylene or arylene or aralkylene, the branched or straight chain alkylene or cycloalkylene contains 1-12 carbon atoms, the arylene contains 6-10 carbon atoms, the aralkylene contains 7-10 carbon atoms, preferably substituted or unsubstituted -(CH2)n-, wherein n is a positive integer of 1-6, such as methyl, ethyl, propyl, butyl, pentyl, hexyl.

[0010] The researchers of the present invention have found that when the isocyanate silane composition contains less than 5000 ppm of the compound of formula (1), it has excellent storage stability. When the content is higher than 5000 ppm, the storage stability will be deteriorated, flocs will be generated during storage, and the purity of the product will be greatly reduced.

[0011] The isocyanate silane composition of the present invention is a substantially single compound (i.e., isocyanate silane) containing 95 wt.% or more of isocyanate silane as a main component, but is defined as an isocyanate silane composition because it contains the compound represented by the chemical formula (1) as a minor component.

[0012] In the present invention, the compound represented by the chemical formula (1) is referred to as SIDI.

[0013] Preferably, the isocyanate silane composition further comprises a chlorine-containing compound;

[0014] The chlorine content is measured by ICP-OES analysis based on the mass of chlorine, and the content of the chlorine-containing compound is less than 50ppm, for example, 0.6ppm, 1ppm, 2ppm, 3ppm, 4ppm, 5ppm, 6ppm, 7ppm, 8ppm, 9ppm, 10ppm, 11ppm, 12ppm, 13ppm, 14ppm, 15ppm, 16ppm, 17ppm, 18ppm, 19ppm, 20ppm, 21ppm, 22ppm, 23ppm, 24ppm, 25ppm, 26ppm, 27ppm, 28ppm, 29ppm, 30ppm, 31ppm, 32ppm, 33ppm, 34ppm, 35ppm, 36ppm, 37ppm, 38ppm, 39ppm, 40ppm, 41ppm, 42ppm, 43ppm, 44ppm, 45ppm, 46ppm, 47ppm, 48ppm, 49ppm and the like. There is no particular lower limit for the chlorine-containing compound, but in consideration of the time required for purification on an industrial scale, it is preferably 0.5 ppm or more. If the chlorine content is too high, the isocyanate silane will be highly active and polymerization will easily occur, thereby causing a decrease in product quality.

[0015] In the present invention, the contents of the compound represented by formula (1) and the chlorine-containing compound are based on the total mass of the composition.

[0016] The isocyanate silane is a compound represented by formula (2);

[0017]

[0018] Wherein, R, R1, R2 are saturated alkyl or alkoxy groups, the carbon chain length of the alkyl or alkoxy group is C1-C6, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy. R3 is a branched or straight chain alkylene or cycloalkylene or arylene or aralkylene, the branched or straight chain alkylene or cycloalkylene contains 1-12 carbon atoms, the arylene contains 6-10 carbon atoms, the aralkylene contains 7-10 carbon atoms, preferably substituted or unsubstituted -(CH2)n-, wherein n is a positive integer of 1-6, such as methyl, ethyl, propyl, butyl, pentyl, hexyl. Preferably, it includes any one or a combination of at least two of isocyanate propyl trimethoxy silane, isocyanate propyl triethoxy silane, isocyanate propyl dimethoxy methyl silane, isocyanate propyl diethoxy methyl silane, isocyanate methyl trimethoxy silane, isocyanate methyl triethoxy silane, isocyanate methyl dimethoxy methyl silane, and isocyanate methyl diethoxy methyl silane;

[0019] Preferably, the compound represented by formula (1) comprises any one or more combinations of the following compounds:

[0020]

[0021] In the present invention, SIDI is generated as a by-product in the production of isocyanate silane described below, and can, of course, be artificially added to obtain a desired content.

[0022] In the present invention, the content ratio of SIDI can be measured by gas chromatography analysis.

[0023] A second object of the present invention is to provide a method for preparing the isocyanate silane composition, the method comprising:

[0024] (1) a carbamate-forming step: subjecting aminosilane to a carbamate-forming reaction with carbonate in the presence of a catalyst to obtain a reaction product containing a carbamate-based silane;

[0025] (2) Carbamate termination step: adding a terminator to the reaction product obtained in step (1) to terminate the reaction of the reaction product obtained in step (1);

[0026] (3) Solvent separation and purification step: removing the solvent from the reaction product obtained in step (2), refining the solvent after removal to obtain a recycled solvent, and then returning it to the reaction system of step (1);

[0027] (4) Isocyanate formation step: thermally cracking the desolvation reaction product obtained in step (3), and separating and purifying it to obtain the isocyanate silane composition.

[0028] Specific examples of the urethanization step in step (1) include a method of directly reacting aminosilane with carbonate ester and a method of reacting allylsilane with carbamate ester. Preferably, a method of directly reacting aminosilane with carbonate ester is used.

[0029] Preferably, the aminosilane is a compound described by formula (3);

[0030]

[0031] Wherein, R, R1, R2 are saturated alkyl or alkoxy groups, the carbon chain length of the alkyl or alkoxy group is C1-C6, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy. R3 is a branched or straight chain alkylene or cycloalkylene or arylene or aralkylene, the branched or straight chain alkylene or cycloalkylene contains 1-12 carbon atoms, the arylene contains 6-10 carbon atoms, the aralkylene contains 7-10 carbon atoms, preferably substituted or unsubstituted -(CH2)n-, wherein n is a positive integer of 1-6, such as methyl, ethyl, propyl, butyl, pentyl, hexyl. Preferably, it includes any one or a combination of at least two of aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropyldimethoxymethylsilane, aminopropyldiethoxymethylsilane, aminomethyltrimethoxysilane, aminomethyltriethoxysilane, aminomethyldimethoxymethylsilane and aminomethyldiethoxymethylsilane.

[0032] The catalyst is a metal alkoxide. Preferably, the metal of the metal alkoxide is selected from Ca, K and Na, and the alkoxide is selected from methoxide, ethoxide, propoxide and butoxide.

[0033] Preferably, the carbonate is selected from dialkyl carbonates, such as any one or a combination of at least two of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate.

[0034] Preferably, the carbamate formation step specifically comprises: adding a catalyst to a carbonate solvent, then adding aminosilane, and then stirring and mixing the carbonate, catalyst and aminosilane reaction solution to perform a carbamate formation reaction to obtain the carbamate formation reaction solution.

[0035] The molar ratio of the aminosilane to the carbonate is greater than 1:0.6, for example, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1.0, 1:1.1, 1:1.5, 1:1.9, 1:2.1, 1:2.5, 1:2.9, 1:3.1, 1:4.1, 1:5.1, 1:6.0, 1:7.0, 1:8.0, 1:9.1, 1:10, etc., preferably greater than 1:1.0.

[0036] Preferably, the molar ratio of the aminosilane to the carbonate is 1:20 or less, preferably 1:15 or less.

[0037] Preferably, the temperature of the urethane-forming step is above 0°C, for example, 1°C, 5°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, etc., preferably above 10°C.

[0038] Preferably, the temperature of the urethanization step is 130° C. or lower, preferably 80° C. or lower, and more preferably 60° C. or lower.

[0039] Preferably, the urethane reaction time is 1 h or longer, for example 2 h, 3 h, 4 h, 6 h, 8 h, 10 h, 12 h, 14 h, 16 h, 18 h, 20 h, 22 h, 24 h, etc., preferably 3 h or longer.

[0040] Preferably, the urethanization reaction time is less than 25 hours, preferably less than 20 hours.

[0041] Preferably, the urethanization step is carried out under normal pressure or pressurized conditions.

[0042] Preferably, the urethanization process is a batch process or a continuous process, preferably a continuous process.

[0043] Preferably, the carbamate formation process can be an intermittent or continuous process. The continuous process is to continuously transport the aminosilane, the catalyst, and the carbonate to the carbamate formation reaction tank, react the aminosilane with the carbonate in the carbamate formation reaction tank, and continuously take out the carbamate reaction liquid (reactant) from the carbamate formation reaction tank. The present invention does not specifically limit the number of reactors in the continuous process, and illustratively, it can be two, three, four, five or more.

[0044] The carbamate termination process of step (2) is, specifically, adding an acid compound to the reaction solution of step (1), adjusting the pH of the reaction solution to 2-8, and terminating the reaction.

[0045] Preferably, the acid compound is an organic acid compound, more preferably a carboxylic acid compound having one or more carboxyl groups, for example, formic acid, acetic acid, propionic acid, butyric acid, hexanoic acid, succinic acid, benzenesulfonic acid, octanesulfonic acid, benzoic acid, nitrobenzoic acid, chlorobenzoic acid, maleic acid, sebacic acid, chloroacetic acid, citric acid, adipic acid, dimer fatty acid, dibutyl phosphate and di-(2-ethylhexyl)phosphoric acid.

[0046] Preferably, the carboxylic acid compound has a water content of less than 1%, more preferably less than 5000 ppm. There is no particular lower limit for the water content, but in consideration of the time required for purification on an industrial scale, it is preferably greater than 0.5 ppm. If the water content is too high, excessive hydrolysis of the carbamate silane may occur, resulting in polymerization, which may lead to a decrease in product quality.

[0047] Preferably, the pH of the termination reaction solution is controlled to be above 1, such as 2, 3, 4, 5, 6, 7, 8, preferably above 5.

[0048] Preferably, the pH of the terminated reaction solution is controlled to be below 8, more preferably below 7.

[0049] Preferably, the reaction temperature in the carbamate termination step is 0°C or higher, for example, 5°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, etc., preferably 10°C or higher.

[0050] Preferably, the reaction temperature in the urethanization termination step is 180° C. or lower, preferably 150° C. or lower, and more preferably 110° C. or lower.

[0051] Preferably, the carbamate termination reaction is carried out under normal pressure or pressurized conditions.

[0052] Preferably, the carbamate termination step is a batch process or a continuous process, preferably a continuous process.

[0053] Preferably, the carbamate termination process can be an intermittent or continuous process. The continuous process is that the reaction liquid generated in the carbamate reaction tank is continuously transported to the carbamate termination reaction tank, the carbamate reaction liquid is reacted with the terminator in the termination reaction tank, and the termination reaction liquid (reaction material) is continuously taken out from the termination reaction tank. The present invention does not specifically limit the number of reactors in the continuous process, and illustratively, it can be two, three, four, five or more.

[0054] If necessary, the reaction product of the carbamate termination step may be subjected to a solvent separation and purification step, in which the reaction solvent (carbonate) is distilled off from the reaction solution using a known distillation column. Most of the solvent is returned to the carbamate formation step after purification.

[0055] If necessary, the desolvated reaction product may be subjected to a detarring step. The tar component may be removed from the reaction solution using a known detarring device such as a short-path evaporator. It should be noted that the reaction product from which the tar component has been removed by the detarring step is referred to as a carbamate silane intermediate.

[0056] Specifically, the isocyanate formation step (4) comprises mixing carbamate silane with a catalyst, subjecting the mixture to a heat treatment to cause a cracking reaction to deblock the alcohol, thereby obtaining isocyanate silane.

[0057] Preferably, the catalyst includes chlorides of zinc or tin and oxides of zinc, manganese, iron, calcium, copper and cobalt, such as zinc chloride, tin chloride, stannous chloride, zinc oxide, manganese oxide, iron oxide, calcium oxide, copper oxide and cobalt oxide, preferably tin chloride.

[0058] Preferably, the amount of the catalyst used is 1-500 ppm, preferably 10-100 ppm, based on the mass of the carbamate silane.

[0059] Preferably, the temperature of the cracking reactor is above 50°C, for example 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 150°C, 170°C, 190°C, 210°C, 250°C, 270°C, 300°C, etc., preferably above 120°C.

[0060] Preferably, the temperature of the cracking reactor is below 500°C, preferably below 350°C, more preferably below 300°C.

[0061] Preferably, the time in the cracking reactor is more than 0.1 h, for example, 0.2 h, 0.5 h, 1 h, 2 h, 3 h, 4 h, 6 h, 8 h, 10 h, 12 h, 14 h, 16 h, 18 h, 20 h, 22 h, 24 h, etc., preferably more than 0.5 h.

[0062] Preferably, the time in the cleavage reactor is less than 25 h, preferably less than 20 h.

[0063] Specific cracking reactors include kettle reactors, tubular reactors, fixed bed reactors, tower reactors, microchannel reactors, and evaporators, and more specifically, reactors, tubular furnaces, distillation towers, cracking towers, falling film evaporators, thin film evaporators, and short-path evaporators. Thin film evaporators, falling film evaporators, and short-path evaporators are preferred, or a combination of several of them.

[0064] The cleavage reaction is carried out under normal pressure or negative pressure, preferably negative pressure.

[0065] Preferably, the top pressure of the evaporator is above 0.1 kPa, for example, 0.2 kPa, 0.4 kPa, 0.6 kPa, 0.8 kPa, 1 kPa, 1.5 kPa, 2 kPa, 2.5 kPa, 3 kPa, 3.5 kPa, etc., preferably above 0.15 kPa.

[0066] Preferably, the top pressure of the evaporator is below 4 kPa, preferably below 2.5 kPa.

[0067] Preferably, the cleavage reaction is a batch process or a continuous process, preferably a continuous process.

[0068] Preferably, the carbamate termination process can be an intermittent or continuous process. The continuous process is to continuously transport the carbamate silane and the catalyst to the cracking reaction evaporator, react the carbamate silane in the cracking reaction evaporator, seal the alcoholysis, and continuously take out the alcohol produced by the cracking from the top of the evaporator, and continuously take out the isocyanate silane, SIDI and other by-products produced by the cracking from the bottom of the evaporator. The present invention does not specifically limit the number of evaporators in the continuous process, and illustratively, it can be two, three, four, five or more. It should be noted that the isocyanate silane, SIDI and other by-products produced by the cracking are recorded as isocyanate silane intermediate substances.

[0069] If necessary, the isocyanate silane intermediate product may be distilled and purified. The purification method is not particularly limited and can be carried out using industrial separation techniques such as distillation and crystallization.

[0070] Preferably, the distillation is carried out in a distillation column.

[0071] Preferably, the distillation tower comprises a plate distillation tower or a packed distillation tower.

[0072] In the preferred technical solution of the present invention, the proportion of SIDI can be adjusted to the above range by controlling the reaction conditions and separation conditions. It should be noted that the proportion of SIDI in the isocyanate silane composition can also be adjusted by adding SIDI to the isocyanate silane composition.

[0073] Preferably, the distillation tower has a theoretical plate number of 1 or more, for example, 2, 4, 6, 8, 10, 14, 18, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, etc., preferably 5 or more.

[0074] Preferably, the distillation tower has a theoretical plate number of 60 or less, preferably 40 or less.

[0075] Preferably, the top pressure of the distillation tower is above 0.01 kPa, for example, 0.02 kPa, 0.05 kPa, 0.09 kPa, 0.1 kPa, 0.2 kPa, 0.4 kPa, 0.6 kPa, 0.8 kPa, 1 kPa, 1.5 kPa, 2 kPa, 2.5 kPa, 3 kPa, 3.5 kPa, etc., preferably above 0.02 kPa.

[0076] Preferably, the top pressure of the distillation tower is 4 kPa or less, preferably 2.5 kPa or less.

[0077] Preferably, the top reflux ratio of the distillation tower is greater than 0.01, for example, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 14, 18, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, etc., preferably greater than 0.1.

[0078] Preferably, the top reflux ratio of the distillation tower is 60 or less, preferably 40 or less.

[0079] The third object of the present invention is to provide a modified composition of an isocyanate silane composition, wherein the modified composition is a modified composition obtained by modifying the isocyanate silane composition described in the first object, wherein the modified isocyanate silane in the modified composition contains any one or a combination of at least two of the following (a)-(e) groups: (a) isocyanurate group, (b) uretdione group, (c) biuret group, (d) carbamate group, (e) urea group, (f) iminooxadiazinedione group, (g) allophanate group, (h) uretonimine group or (i) carbodiimide group.

[0080] A person skilled in the art can modify the isocyanate silane composition by a known method as needed to obtain an isocyanate silane-modified composition, and the isocyanate silane-modified composition can be suitably used as a raw material for a polyisocyanate component and a component containing an active hydrogen group as a polyurethane resin.

[0081] More specifically, the modified isocyanatosilane containing the functional group (isocyanurate group) described above (a) is a trimer of isocyanatosilane, and can be obtained, for example, by reacting an isocyanatosilane composition in the presence of a known isocyanurate-forming catalyst to isocyanurate the isocyanatosilane therein.

[0082] The modified isocyanatosilane containing the functional group (allophanate group) of (b) can be obtained by reacting an isocyanatosilane composition with an alcohol and then further reacting the mixture in the presence of a known allophanation catalyst.

[0083] The modified isocyanate silane containing the functional group (biuret group) described above (c) can be obtained by reacting an isocyanate silane composition with, for example, water, a tertiary alcohol (e.g., tert-butyl alcohol), a secondary amine (e.g., dimethylamine, diethylamine, etc.), and then further reacting the composition in the presence of a known biuret catalyst.

[0084] The modified isocyanate silane containing the functional group (urethane group) of (d) can be obtained by reacting an isocyanate silane composition with a polyol component (for example, trimethylolpropane, etc.).

[0085] The modified isocyanate silane containing the functional group (urea group) of (e) can be obtained by reacting an isocyanate silane composition with water, a polyamine component (described later), or the like.

[0086] The modified isocyanatosilane (asymmetric trimer) containing the functional group (f) (imidooxadiazinedione group) can be obtained by reacting an isocyanatosilane composition in the presence of a known iminooxadiazinedione catalyst to subject the isocyanatosilane to iminooxadiazinedione (e.g., trimerization).

[0087] The modified isocyanate silane containing the functional group (uretdione group) described above (g) can be obtained by heating the isocyanate silane composition at about 90°C to 200°C, or by reacting it in the presence of a known uretdione catalyst to uretdione the isocyanate silane (e.g., dimerize it).

[0088] The modified isocyanatosilane containing the functional group (h) (uretonimine group) can be obtained by reacting an isocyanatosilane composition in the presence of a known carbodiimide catalyst to form a carbodiimide group and then adding an isocyanatosilane to the carbodiimide group.

[0089] The modified isocyanate silane containing the functional group (carbodiimide group) of (i) above can be obtained by reacting an isocyanate silane composition in the presence of a known carbodiimide catalyst.

[0090] It should be noted that the isocyanate silane modified composition may contain at least one functional group of the above (a)-(i), or may contain two or more. Such an isocyanate silane modified composition may be generated by appropriately using the above reaction in combination. In addition, the isocyanate silane modified composition may be used alone or in combination of two or more.

[0091] A fourth object of the present invention is to provide a polyurethane resin, which is formed by reacting the isocyanate silane composition described in the first object with a substance containing an active hydrogen group, or by reacting the modified composition described in the third object with a substance containing an active hydrogen group.

[0092] Examples of substances containing active hydrogen groups include polyol components (components mainly containing polyols having two or more hydroxyl groups), polythiol components (components mainly containing polythiol having two or more mercapto groups (thiol groups)), and polyamine components (compounds mainly containing polyamines having two or more amino groups).

[0093] Examples of the polyol component include low molecular weight polyols and high molecular weight polyols.

[0094] The low molecular weight polyol is a compound having two or more hydroxyl groups and having a number average molecular weight of 60 or more and less than 400.

[0095] Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, alkane (7-22) diol, diethylene glycol, triethylene glycol, dipropylene glycol, 3-methyl-1,5-pentanediol, alkane-1,2-diol (C (carbon number, hereinafter the same) 17-20), isosorbide, 1,3- or 1,4-cyclohexanedimethanol, and mixtures thereof. compounds, 1,4-cyclohexanediol, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, diols such as bisphenol A, triols such as glycerol and trimethylolpropane, tetraols such as tetramethylolmethane (pentaerythritol), diglycerol, pentahydric alcohols such as xylitol, hexahydric alcohols such as sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, dipentaerythritol, heptahydric alcohols such as avocado, octahydric alcohols such as sucrose, etc.

[0096] The low molecular weight polyols also include polyalkylene oxides having a number average molecular weight of 60 or more and less than 400 (including random and / or block copolymers of two or more alkylene oxides) obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to the above alcohols as initiators.

[0097] The high molecular weight polyol is a compound having two or more hydroxyl groups and having a number average molecular weight of 400 or more, for example, 10000 or less, and preferably 5000 or less. Examples of the high molecular weight polyol include polyether polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols, polysiloxane polyols, fluorine polyols, and vinyl monomer-modified polyols.

[0098] Examples of polyether polyols include polyoxy (C2-C3) alkylene polyols, polytetramethylene ether glycol, polytrimethylene ether glycol, etc. Examples of polyoxy (C2-C3) alkylene polyols include addition polymers of C2-3 alkylene oxides such as ethylene oxide and propylene oxide (random and / or block copolymers of two or more alkylene oxides) using the above-mentioned low molecular weight polyols as initiators. In addition, specific examples of polyoxy (C2-3) alkylene include polyethylene glycol, polypropylene glycol, polyethylene polypropylene copolymers, etc.

[0099] Examples of the polytetramethylene ether glycol include a ring-opening polymer (polytetramethylene ether glycol) obtained by cationic polymerization of tetrahydrofuran and an amorphous polytetramethylene ether glycol obtained by copolymerizing a polymerization unit of tetrahydrofuran with the above-mentioned diol.

[0100] In addition, plant-derived polytetramethylene ether glycol produced using tetrahydrofuran produced from plant-derived raw materials such as furfural as a starting material may be mentioned.

[0101] Examples of polytrimethylene ether glycol include polyols produced by polycondensation of plant-derived 1,3-propanediol.

[0102] Examples of the polyester polyol include polycondensates obtained by reacting the above-mentioned low molecular weight polyol (preferably diol) and polybasic acid (preferably dibasic acid) under known conditions.

[0103] Examples of the polybasic acid include saturated aliphatic dicarboxylic acids (C11-C13) such as oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, 3-methyl-3-ethylglutaric acid, azelaic acid, and sebacic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, and phthalic acid; Aromatic dicarboxylic acids, alicyclic dicarboxylic acids such as hexahydrophthalic acid, other carboxylic acids such as dimer acid, hydrogenated dimer acid, HET acid, and acid anhydrides derived from these carboxylic acids, such as oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 2-alkyl (C12-C18) succinic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, and acid halides derived from these carboxylic acids, such as oxalyl dichloride, adipoyl dichloride, sebacoyl dichloride, etc.

[0104] Examples of the polyester polyol include plant oil-based polyester polyols obtained by condensing the above-mentioned low molecular weight polyols with hydroxycarboxylic acids such as plant oil fatty acids containing hydroxy groups (e.g., castor oil fatty acids containing ricinoleic acid, hydrogenated castor oil fatty acids containing 12-hydroxystearic acid, etc.) under known conditions.

[0105] In addition, examples of polyester polyols include polycaprolactone polyols, polyvalerolactone polyols obtained by ring-opening polymerization of lactones such as ε-caprolactone and γ-valerolactone using the above-mentioned low molecular weight polyols (preferably diols) as initiators, and lactone polyester polyols obtained by copolymerizing these with the above-mentioned diols.

[0106] Examples of the polycarbonate polyol include a ring-opening polymer of ethylene carbonate using the above-mentioned low molecular weight polyol (preferably a diol) as an initiator, and an amorphous polycarbonate polyol obtained by copolymerizing the above-mentioned diol with a ring-opening polymer.

[0107] In addition, regarding the polyurethane polyol, there can be mentioned polyester polyurethane polyol, polyether polyol, polycarbonate polyurethane polyol, or polyester polyether polyurethane polyol obtained by reacting the polyester polyol, polyether polyol and / or polycarbonate polyol obtained by the above method with the above-mentioned polyisocyanate (including isocyanate silane. The same applies hereinafter) in a ratio where the equivalent ratio of hydroxyl group to isocyanate group (OH / NCO) is greater than 1, obtained by reacting.

[0108] Examples of the epoxy polyol include epoxy polyols obtained by reaction of the above-mentioned low molecular weight polyols with polyfunctional halohydrins such as epichlorohydrin and β-methylepichlorohydrin.

[0109] Examples of the vegetable oil polyol include hydroxyl group-containing vegetable oils such as castor oil and coconut oil, and examples thereof include castor oil polyol and ester-modified castor oil polyol obtained by reacting castor oil polyol with polypropylene polyol.

[0110] Examples of the polyolefin polyol include polybutadiene polyol and partially saponified ethylene-vinyl acetate copolymer.

[0111] Examples of the acrylic polyol include copolymers obtained by copolymerizing a hydroxyl group-containing acrylic acid ester and a copolymerizable vinyl monomer copolymerizable with the hydroxyl group-containing acrylic acid ester.

[0112] Examples of the hydroxyl group-containing acrylate include 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, 2,2-dihydroxymethylbutyl (meth)acrylate, polyhydroxyalkyl maleate, polyhydroxyalkyl fumarate, etc. Preferably, 2-hydroxyethyl (meth)acrylate is used.

[0113] Examples of the copolymerizable vinyl monomer include alkyl (meth)acrylates (having 1 to 12 carbon atoms) such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, isononyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl acrylate, and isobornyl (meth)acrylate, and examples of alkyl (meth)acrylates (having 1 to 12 carbon atoms) such as styrene, vinyltoluene, and α-methylstyrene.

[0114] Aromatic vinyl monomers, for example, vinyl cyanides such as (meth)acrylonitrile, vinyl monomers containing carboxyl groups such as (meth)acrylic acid, fumaric acid, maleic acid, itaconic acid, or their alkyl esters, for example, ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, oligoethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and other alkane polyol poly(meth)acrylates, for example, 3-(2-isocyanate-2-propyl)-α-methylstyrene, etc.

[0115] The acrylic polyol can be obtained by copolymerizing these hydroxyl group-containing acrylic acid esters and copolymerizable vinyl monomers in the presence of a suitable solvent and a polymerization initiator.

[0116] In addition, acrylic polyols include, for example, silicone polyols and fluorine polyols.

[0117] Examples of the polysiloxane polyol include acrylic polyols obtained by blending a polysiloxane compound containing a vinyl group such as γ-methacryloxypropyltrimethoxysilane as a copolymerizable vinyl monomer during the copolymerization of the above-mentioned acrylic polyols.

[0118] Examples of the fluorine polyol include acrylic polyols obtained by blending a fluorine compound containing a vinyl group such as tetrafluoroethylene or chlorotrifluoroethylene as a copolymerizable vinyl monomer during the copolymerization of the above-mentioned acrylic polyols.

[0119] The vinyl monomer-modified polyol can be obtained by reacting the above-mentioned high molecular weight polyol with a vinyl monomer such as the above-mentioned alkyl (meth)acrylate.

[0120] The above-mentioned polyol components can be used alone or in combination of two or more.

[0121] In addition, in the reaction of the polyisocyanate component and the component containing the active hydrogen group, when the equivalent ratio of the active hydrogen group to the isocyanate group is less than 1, an isocyanate group-terminated polymer having an isocyanate group at the molecular end is generated, and when the equivalent ratio of the active hydrogen group to the isocyanate group is greater than 1, an active hydrogen group-terminated polymer having an active hydrogen group at the molecular end is generated. Both the isocyanate group-terminated polymer and the active hydrogen group-terminated polymer are contained in the resin (polyurethane resin). The isocyanate group-terminated polymer is a one-component curing type resin.

[0122] As the use of polyurethane resin, specifically, it can be suitably applied to ink, transfer foil, adhesive, binder, gel, elastomer, foam, adhesive, liquid curing type sealing material, RIM molded product, micro foam polyurethane, various microcapsules, optical materials, water-based resin, thermosetting resin, active energy ray (for example, electron beam, ultraviolet light, etc.) curing resin, artificial and synthetic leather, coagulation powder, robot components, mobile components, medical care materials, carbon fiber reinforced plastic (CFRP) base resin, transparent rubber, transparent hard resin, waterproof material, film , sheets, tubes, plates, speakers, sensors, organic electroluminescent components, solar power generation components, robot components, wearable components, sporting goods, leisure goods, medical supplies, nursing supplies, residential components, audio components, lighting components, chandeliers, outdoor lights, packaging, vibration-proof / anti-seismic / shock-absorbing components, sound-proof components, daily necessities, groceries, buffers, bedding, stress absorbing materials, stress relaxation materials, interior and exterior decorative parts of automobiles, conveyor components, components for office automation equipment, surface protection components for groceries, self-repairing materials, health appliances, etc.

[0123] Compared with the prior art, the present invention has the following beneficial effects:

[0124] The isocyanate silane composition provided by the present invention contains the compound of formula (1) in an amount of less than 5000 ppm and has excellent storage stability. DETAILED DESCRIPTION

[0125] (I) The determination method of the relevant test in the present invention is as follows:

[0126] 1. Content ratio of compound SIDI

[0127] First, analysis was performed by gas chromatography under the following conditions, and area normalization was performed using the area value of the obtained gas chromatogram.

[0128] 2. Content ratio of isocyanate silane

[0129] The analysis was performed by gas chromatography under the following conditions using an isocyanate silane having a purity of 99 mol % as a standard substance by an internal standard method.

[0130] Instrument: Agilent 7890

[0131] (1) Chromatographic column: DB-5 (30m×0.25mm×0.25μm); (2) Injection volume: 0.5μL; (3) Split ratio: 1 / 30; (4) Inlet temperature: 260℃; (5) Column flow rate: 1.5mL / min; (6) Program temperature: 100℃ for 1min, then increase the temperature to 280℃ at 10℃ / min and hold for 20min; (7) FID detector temperature: 280℃; (8) Hydrogen flow rate: 40mL / min, air flow rate: 400mL / min.

[0132] 3. The chlorine content in isocyanate silane is determined by ICP-OES analysis;

[0133] Instrument: Thermo Scientific ICAP 7200ICP-OES.

[0134] 4. The water content of the terminator is measured by Karl Fischer titrator;

[0135] Instrument: Swiss Metrohm 915KF Ti-Touch

[0136] 5. pH test is measured by pH meter;

[0137] Instrument: Mettler-Toledo S210

[0138] (II) Raw materials and sources

[0139] Reagent name factory purity Aminopropyltrimethoxysilane Inokay ＞99.0％ Dimethyl carbonate Inokay ＞99.0％ 30% Sodium methoxide methanol solution Inokay ＞99.0％ Stannous chloride Inokay ＞99.0％ Acetic acid Inokay ＞99.0％

[0140] For the convenience of understanding the present invention, the present invention lists the following embodiments. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0141] It should be noted that, unless otherwise specified, "parts" and "%" are based on mass.

[0142] Examples 1-7, Comparative Example 1

[0143] The above-mentioned embodiments and comparative examples respectively provide an isocyanate silane composition, and the specific composition thereof is shown in Table 1.

[0144] The preparation method of the isocyanate propyl trimethoxy silane (IPMS) composition is as follows:

[0145] Specifically, 1150 parts by mass of APMS (aminopropyltrimethoxysilane), 810 parts by mass of DMC (dimethyl carbonate), and 12 parts by mass of a 30% methanol solution of sodium methoxide were placed in a carbamate reaction vessel. Next, the temperature in the carbamate reaction vessel was adjusted to 60° C., and the pressure (gauge pressure) in the vessel was adjusted to normal pressure, and the reaction was carried out under this condition for 6 hours.

[0146] Next, acetic acid was added to the carbamate reaction kettle and reacted for 0.5 h to terminate the carbamate reaction. Thus, a carbamate silane reaction solution was prepared. The amount of acetic acid used, the pH of the terminated reaction solution, and the water content of acetic acid are shown in Table 1.

[0147] Next, the carbamate reaction liquid was evaporated by thin film evaporation at 140°C / 20 KPa to remove light components such as methanol and dimethyl carbonate, and then by thin film evaporation at 185°C / 0.5 KPa to remove heavy components, thereby obtaining 1475 parts by mass of a carbamate silane (UPMS) intermediate.

[0148] Next, the UPMS intermediate was mixed with 50 ppm of stannous chloride and continuously transported to a thin film evaporator at a rate of 250 parts by mass / h, and the UPMS was cracked at 195°C / 20 KPa. The methanol gas produced by the cracking was condensed by a condenser above the evaporator and continuously taken out, and the components containing isocyanate silane (IPMS), SIDI and other by-products produced by the cracking were continuously taken out from the bottom of the evaporator, thereby obtaining 1270 parts by mass of IPMS intermediate. The content ratios of UPMS, IPMS, SIDI and chlorine element in the IPMS intermediate are shown in Table 1.

[0149] Next, the intermediate material is continuously fed to the distillation tower at a supply rate of 100 parts by mass / h. The distillation tower is filled with a filler equivalent to 10 theoretical plates. Then, in the distillation tower, the light component is removed from the top of the tower, and the IPMS composition product is extracted from the tower.

[0150] The distillation conditions in the distillation tower are as follows:

[0151] Tower bottom temperature: 100-160℃

[0152] Tower top temperature: 60-130℃

[0153] Tower top pressure: 0-500Pa

[0154] Duration: 1-10h

[0155] The extraction rate and top reflux ratio of the distillation process are shown in Table 1.

[0156] Table 1 shows the content ratios of IPMS, SIDI, and chlorine element in the IPMS composition.

[0157] Table 1 Conditions and results of Examples 1-7 and Comparative Examples 1-2

[0158]

[0159]

[0160] Storage stability test

[0161] The IPMS compositions of the above examples and comparative examples were subjected to storage stability test and evaluation, as follows:

[0162] The IPMS compositions of the above-mentioned examples and comparative examples were placed in a transparent glass bottle, filled with nitrogen and sealed, and then stored at 50° C. for 6 months to obtain the stored compositions, and the content of the stored IPMS compositions was measured in the same gas phase test method as above. The appearance changes of the compositions were observed with the naked eye. The results are shown in Table 2 below.

[0163] Table 2 Application effect data of IPMS composition

[0164]

[0165] As can be seen from Table 2, the present invention controls the content of SIDI in the isocyanate silane composition within 5000ppm, and the composition has excellent storage stability. After being stored at 50°C for 6 months, the purity of the composition still meets the commercial standard requirements. The content of SIDI is higher than 5000ppm (Comparative Examples 1 and 2), and the stability performance is not as good as that of the present invention. The isocyanate silane composition provided by the present invention has better stability.

[0166] The applicant declares that the present invention illustrates the detailed method of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed method, that is, it does not mean that the present invention must rely on the above-mentioned detailed method to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. An isocyanate silane composition, comprising isocyanate silane and 5 ppm to 5000 ppm or less of a compound represented by formula (1); in, R1, R2, R4, and R5 are saturated alkyl or alkoxy groups, wherein the carbon chain length of the alkyl or alkoxy group is C1 to C6; R3 and R6 are branched or straight chain alkylene or cycloalkylene or arylene or aralkylene, wherein the branched or straight chain alkylene or cycloalkylene contains 1 to 12 carbon atoms, the arylene contains 6 to 10 carbon atoms, and the aralkylene contains 7 to 10 carbon atoms; The isocyanate silane is a compound represented by formula (2); Among them, R, R1, and R2 are saturated alkyl or alkoxy groups, and the carbon chain length of the alkyl or alkoxy group is C1 to C6; R3 is a branched or straight-chain alkylene group or cycloalkylene group or arylene group or aralkylene group, and the branched or straight-chain alkylene group or cycloalkylene group contains 1 to 12 carbon atoms, the arylene group contains 6 to 10 carbon atoms, and the aralkylene group contains 7 to 10 carbon atoms.

2. The isocyanate silane composition according to claim 1, characterized in that The isocyanate silane composition further includes a chlorine-containing compound; the content of the chlorine-containing compound is less than 50 ppm, but not 0, based on the mass of the chlorine element.

3. The isocyanate silane composition according to claim 1, characterized in that In the compound shown in formula (2), R, R1, and R2 are methyl, ethyl, propyl, butyl, pentyl, hexyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, and hexyloxy; and / or, in the compound shown in formula (2), R3 is substituted or unsubstituted -(CH2)n-, where n is a positive integer from 1 to 6.

4. The isocyanate silane composition according to claim 3, characterized in that In the compound represented by formula (2), R3 is methylene, ethylene, propylene, butylene, pentylene or hexylene.

5. The isocyanate silane composition according to any one of claims 1 to 4, characterized in that The compound represented by formula (1) includes any one or more combinations of the following compounds:

6. A method for preparing the isocyanate silane composition according to any one of claims 1 to 5, the method comprising the following steps: (1) a carbamate-forming step: subjecting aminosilane to a carbamate-forming reaction with carbonate in the presence of a catalyst to obtain a reaction product containing a carbamate-based silane; (2) Carbamate termination step: adding a terminator to the reaction product obtained in step (1) to terminate the reaction of the reaction product obtained in step (1); (3) Solvent separation and purification step: removing the solvent from the reaction product obtained in step (2), refining the solvent after removal to obtain a recycled solvent, and then returning it to the reaction system of step (1); (4) Isocyanate formation step: thermally cracking the desolvation reaction product obtained in step (3), and separating and purifying it to obtain the isocyanate silane composition.

7. The preparation method according to claim 6, characterized in that: The aminosilane in step (1) is a compound described by formula (3); Among them, R, R1, and R2 are saturated alkyl or alkoxy groups, and the carbon chain length of the alkyl or alkoxy group is C1 to C6; R3 is a branched or straight-chain alkylene group or cycloalkylene group or arylene group or aralkylene group, and the branched or straight-chain alkylene group or cycloalkylene group contains 1 to 12 carbon atoms, the arylene group contains 6 to 10 carbon atoms, and the aralkylene group contains 7 to 10 carbon atoms.

8. The preparation method according to claim 7, characterized in that: R, R1, and R2 are methyl, ethyl, propyl, butyl, pentyl, hexyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, and hexyloxy; and / or, R3 is substituted or unsubstituted -(CH2)n-, wherein n is a positive integer of 1 to 6.

9. The preparation method according to claim 8, characterized in that: R3 is methylene, ethylene, propylene, butylene, pentylene or hexylene.

10. The preparation method according to any one of claims 6 to 9, characterized in that: The catalyst in step (1) is a metal alkoxide; and / or the carbonate is selected from dialkyl carbonate; and / or the terminator in step (2) is selected from acid compounds.

11. The preparation method according to claim 10, characterized in that: The catalyst in step (1) is methoxide, ethoxide, propoxide and butoxide; and / or the carbonate is any one or a combination of at least two of dimethyl carbonate, diethyl carbonate, dipropyl carbonate and dibutyl carbonate; and / or the terminator in step (2) is an organic acid compound.

12. The preparation method according to claim 10, characterized in that: The terminator in step (2) is selected from carboxylic acid compounds having one or more carboxyl groups; the water content of the carboxylic acid compounds is less than 1%.

13. The preparation method according to claim 12, characterized in that: The carboxylic acid compound having one or more carboxyl groups in step (2) is formic acid, acetic acid, propionic acid, butyric acid, caproic acid, succinic acid, benzoic acid, nitrobenzoic acid, chlorobenzoic acid, maleic acid, sebacic acid, chloroacetic acid, citric acid, adipic acid, and dimer fatty acid.

14. A modified composition of an isocyanate silane composition, wherein the modified composition is a modified composition obtained by modifying the isocyanate silane composition according to any one of claims 1 to 5 or the isocyanate silane composition prepared by the preparation method according to any one of claims 6 to 13, wherein the modified isocyanate silane in the modified composition contains any one or a combination of at least two of the following (a)-(e) groups: (a) isocyanurate group, (b) uretdione group, (c) biuret group, (d) carbamate group, (e) urea group, (f) iminooxadiazinedione group, (g) allophanate group, (h) uretonimine group or (i) carbodiimide group.

15. A polyurethane resin, characterized in that: The polyurethane resin is formed by reacting the isocyanate silane composition according to any one of claims 1 to 5 or the isocyanate silane composition prepared by the preparation method according to any one of claims 6 to 13 with a substance containing an active hydrogen group; or by reacting a modified composition of the isocyanate silane composition according to claim 14 with a substance containing an active hydrogen group.

16. The polyurethane resin according to claim 15, characterized in that The substance containing an active hydrogen group is selected from one or more of a polyol component (a component containing a polyol having two or more hydroxyl groups), a polythiol component (a component containing a polythiol having two or more thiol groups (thiol groups)), and a polyamine component (a compound containing a polyamine having two or more amino groups).

Images