Organosilicon compounds containing isocyanate groups and preparation methods of organosilicon compounds containing isocyanate groups

Abstract

The present invention provides an isocyanate group-containing organosilicon compound, which is an isocyanate group-containing organosilicon compound represented by the following general formula (1), characterized in that it has three or more R 2 base, and the viscosity at 25°C is 100mm 2 / s or less. Thus, an organosilicon compound having three or more isocyanate groups in one molecule, low viscosity and excellent handleability, which is suitable as a crosslinking agent, can be provided. 1 a R 2 b SiO (4‑a‑b) / 2 (1) In formula (1), R 1 is a monovalent alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group, a monovalent aryl group having 6 to 10 carbon atoms, or a monovalent aralkyl group having 7 to 10 carbon atoms, which is the same or different and does not have an aliphatic unsaturated group, and R 2 It is an organic group represented by the formula ‑CH2CH2Si(CH3)2OSi(CH3)2CH2CH2CH2NCO.

Description

Technical Field

[0001] The present invention relates to an organosilicon compound having three or more isocyanate groups in one molecule and having low viscosity. Background Art

[0002] Isocyanate groups can react with organic functional groups having active hydrogen, such as hydroxyl groups and amino groups, to form urethane bonds or urea bonds. Compounds having such functional groups are useful as synthetic raw materials for various polymers or as polymer modifiers.

[0003] Industrially, compounds containing isocyanate groups have long been produced by reacting amine compounds with phosgene. Currently, other synthetic methods that avoid the use of toxic phosgene include thermal decomposition of carbamates and the reaction of nitro compounds with carbon monoxide in the presence of a palladium catalyst.

[0004] When synthesizing polymers containing urethane bonds, a linear urethane polymer can be obtained from a diol compound having two hydroxyl groups per molecule and a compound having two isocyanate groups per molecule. The urethane bonds formed by this reaction can further react with isocyanate groups to form a crosslinked polymer.

[0005] Alternatively, a crosslinked polymer can be obtained by using a compound having three or more functional groups per molecule. For example, a prepolymer having isocyanate groups at the polymer terminals can be synthesized by reacting a polymer diol component with a diisocyanate component in a ratio where the isocyanate groups are in excess. This prepolymer can then be reacted with a compound having three or more hydroxyl groups per molecule as a crosslinking agent to obtain a crosslinked polymer. Alternatively, a crosslinked polymer can be obtained by reacting a compound having three or more isocyanate groups per molecule with a polymer diol component as a crosslinking agent.

[0006] One of the problems with synthesizing cross-linked polymers using these methods is the high viscosity of the composition before curing. For example, in the case of the former prepolymer method, the SANYO CHEMICAL INDUSTRIES, LTD. product catalog states that the viscosity of a prepolymer obtained from polytetramethylene ether glycol and 4,4'-diphenylmethane diisocyanate (trade name SANPRENE P-6090) at 80°C is 690 mPa·s, and the viscosity of a prepolymer obtained from polyester polyol and 4,4'-diphenylmethane diisocyanate (trade name SANPRENE P-7315) at 80°C is 1630 mPa·s. If the prepolymer has a high viscosity, degassing after mixing the cross-linking agent component is difficult.

[0007] Another problem with the method of obtaining a cross-linked polymer by reacting a prepolymer having isocyanate groups at the polymer terminals with a compound having three or more hydroxyl groups per molecule is that the isocyanate group is a functional group highly reactive with active hydrogen and, for example, also reacts with moisture in the air, so the prepolymer may gel during storage.

[0008] As an example of the latter cross-linking agent having three isocyanate groups in one molecule, the product catalog of Asahi Kasei Corporation states that the viscosity of the biuret-type product DURANATE24A-100 at 25°C, which is a hexamethylene diisocyanate derivative, is 1800 mPa·s, the viscosity of the isocyanurate-type product DURANATE TPA-100 at 25°C, is 1400 mPa·s, and the viscosity of the isocyanurate-type product DURANATE TKA-100 at 25°C, is 2600 mPa·s. The higher the viscosity, the more difficult it is to degas after mixing the cross-linking agent.

[0009] As a method for reducing the viscosity of isocyanate-containing compounds, it is believed that the method of converting them into organosilicon compound derivatives is effective. Such compounds having both isocyanate groups and polysiloxane groups are known to be useful as modifiers for organic compounds or polymers (Patent Documents 1 and 2).

[0010] Patent Document 1 describes an organosilicon compound having one isocyanate group and one vinyl group in one molecule. By subjecting the vinyl group to an addition reaction with a single-end hydrogen-containing polysiloxane, a polysiloxane having only one isocyanate group in the molecule can be obtained.

[0011] Patent Document 2 discloses γ-tris(trimethylsiloxy)silylpropyl isocyanate and a synthesis method thereof.

[0012] When used as a modifier for an organic compound or a modifier for a polymer, the organosilicon compounds described in Patent Documents 1 and 2 must have only one isocyanate group in the molecule in order to prevent cross-linking between reaction substrates.

[0013] An organosilicon compound having three or more isocyanate groups per molecule can be obtained by an addition reaction of an organopolysiloxane having three or more Si—H groups per molecule with an isocyanate compound having an aliphatic unsaturated group at the terminal, such as allyl isocyanate. However, allyl isocyanate has a low boiling point, is highly toxic, and has a strong pungent odor, requiring careful handling. Furthermore, due to its high price, it is not economically preferred.

[0014] Furthermore, aminopolysiloxanes can be obtained by subjecting an organopolysiloxane having three or more Si-H groups per molecule to an amine compound having an aliphatic unsaturated group at the terminal, such as allylamine, through an addition reaction. Alternatively, aminopolysiloxanes can be obtained by adding a compound in which the amino group is protected with a trialkylsilyl group, such as N,N-bistrimethylsilylallylamine, in place of allylamine, and then removing the protecting group.

[0015] The aminopolysiloxane obtained in this manner can then be reacted with a haloformate, such as phenyl chloroformate, to produce a phenyl carbamate derivative. The phenyl carbamate groups can then be converted to isocyanate groups through a thermal decomposition reaction. However, the thermal decomposition reaction of the phenyl carbamate typically requires high temperatures of 150-250°C, so gelation may sometimes occur during the reaction, preventing the desired product from being obtained. Furthermore, even when gelation does not occur, the product is highly viscous and is opaque, colored yellow or even brown, making it unsuitable for use as a crosslinking agent for resins.

[0016] Prior art literature

[0017] Patent Literature

[0018] Patent Document 1: Japanese Patent Application Laid-Open No. 08-104755

[0019] Patent Document 2: Japanese Patent Application Laid-Open No. 2001-026593 Summary of the Invention

[0020] Technical Problems to be Solved by the Invention

[0021] The present invention has been made in view of such circumstances, and an object of the present invention is to provide an organosilicon compound which has three or more isocyanate groups in one molecule and is suitable as a crosslinking agent, has low viscosity, and is excellent in handleability.

[0022] Technical means to solve technical problems

[0023] In order to solve the above technical problems, the present invention provides an isocyanate group-containing organosilicon compound, which is an isocyanate group-containing organosilicon compound represented by the following general formula (1), characterized in that it has three or more R 2 base, and the viscosity at 25°C is 100mm 2 / s or less,

[0024] R 1 a R 2 b SiO (4-a-b) / 2 (1)

[0025] In formula (1), R1 is a monovalent alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group, a monovalent aryl group having 6 to 10 carbon atoms, or a monovalent aralkyl group having 7 to 10 carbon atoms, which is the same or different and does not have an aliphatic unsaturated group, and R 2 It is an organic group represented by the formula -CH2CH2Si(CH3)2OSi(CH3)2CH2CH2CH2NCO, and a and b are positive numbers satisfying 0.9≤a≤1.9, 0.25≤b≤1.1, and 1.9≤a+b≤2.8, respectively.

[0026] Such a compound can provide an organosilicon compound suitable as a cross-linking agent, having three or more isocyanate groups in one molecule, low viscosity, and excellent handleability.

[0027] Furthermore, the present invention provides an isocyanate group-containing organosilicon compound, characterized in that the isocyanate group-containing organosilicon compound is a compound represented by the following general formula (2).

[0028] R 1 2R 3 SiO(SiR 1 2O) c (SiR 1 R 2 O) d SiR 1 2R 3 (2)

[0029] In formula (2), R 1 、R 2 With the R 1 、R 2 Same. 3 R 1 or R 2 Any one of , wherein c is an integer of 0 to 20, d is an integer of 1 to 10, and c+d is an integer of 1 to 30.

[0030] Such a compound can further enhance the effects of the present invention.

[0031] In addition, the present invention also provides an isocyanate group-containing organosilicon compound, characterized in that the isocyanate group-containing organosilicon compound is a compound represented by the following general formula (3).

[0032] R 1 e Si(OSiR 1 2R 2 ) f (3)

[0033] In formula (3), R 1 、R2 With the R 1 、R 2 Same, e is 0 or 1, f is 3 or 4, e+f is 4.

[0034] Such a compound can further enhance the effects of the present invention.

[0035] In addition, the present invention also provides an isocyanate group-containing organosilicon compound, characterized in that the isocyanate group-containing organosilicon compound is a compound represented by the following general formula (4).

[0036] [Chemical Formula 1]

[0037]

[0038] In formula (4), R 1 、R 2 With the R 1 、R 2 Similarly, g is an integer of 0 to 2, h is an integer of 3 to 5, and g+h is an integer of 3 to 7.

[0039] Such a compound can further enhance the effects of the present invention.

[0040] Furthermore, the present invention provides a method for preparing an isocyanate group-containing organosilicon compound, characterized in that an organohydrogen polysiloxane represented by the following general formula (5) is subjected to an addition reaction with CH2=CHSi(CH3)2OSi(CH3)2CH2CH2CH2NCO.

[0041] R 1 a H b SiO (4-a-b) / 2 (5)

[0042] In formula (5), R 1 , a and b and the R 1 , a and b are the same.

[0043] According to this method for producing a compound, an organosilicon compound suitable as a cross-linking agent, having three or more isocyanate groups in one molecule, low viscosity, and excellent handleability can be obtained.

[0044] Furthermore, the present invention provides a method for preparing an isocyanate group-containing organosilicon compound, characterized in that an organohydrogen polysiloxane represented by the following general formula (6) is subjected to an addition reaction with CH2=CHSi(CH3)2OSi(CH3)2CH2CH2CH2NCO.

[0045] R 1 2R 4 SiO(SiR1 2O) c (SiR 1 HO) d SiR 1 2R 4 (6)

[0046] In formula (6), R 1 , c and d and the R 1 , c and d are the same, R 4 R 1 or any of H.

[0047] According to this method for producing a compound, the isocyanate group-containing organosilicon compound represented by the general formula (2) can be produced efficiently.

[0048] Furthermore, the present invention provides a method for preparing an isocyanate group-containing organosilicon compound, characterized in that an organohydrogen polysiloxane represented by the following general formula (7) is subjected to an addition reaction with CH2=CHSi(CH3)2OSi(CH3)2CH2CH2CH2NCO.

[0049] R 1 e Si(OSiR 1 2H) f (7)

[0050] In formula (7), R 1 , e and f and the R 1 , e and f are the same.

[0051] By using this method for producing a compound, the isocyanate group-containing organosilicon compound represented by the general formula (3) can be produced efficiently.

[0052] Furthermore, the present invention provides a method for preparing an isocyanate group-containing organosilicon compound, characterized in that an organohydrogen polysiloxane represented by the following general formula (8) is subjected to an addition reaction with CH2=CHSi(CH3)2OSi(CH3)2CH2CH2CH2NCO.

[0053] [Chemical Formula 2]

[0054]

[0055] In formula (8), R 1 , g and h and the R 1 , g and h are the same.

[0056] By using this method for producing a compound, the isocyanate group-containing organosilicon compound represented by the general formula (4) can be produced efficiently.

[0057] Effects of the Invention

[0058] Even if the organosilicon compound of the present invention has three or more isocyanate groups that are highly reactive with hydroxyl groups or amino groups in one molecule, the viscosity at 25°C is 100 mm 2 The low viscosity of the polyol is less than 1 / s. Due to its low viscosity, it is easy to mix evenly with the polymeric polyol compound or the polymeric polyamine compound, and it is also easy to degas after mixing, so it is useful as a curing agent for obtaining a cured molded product. In addition, since it is transparent, the cured molded product will not become opaque. DETAILED DESCRIPTION

[0059] As described above, there has been a demand for the development of an organosilicon compound suitable as a crosslinking agent, having three or more isocyanate groups in one molecule, having low viscosity, and having excellent handleability.

[0060] The inventors of the present application have conducted intensive studies to achieve the above-mentioned object, and as a result, have discovered an isocyanate group-containing organosilicon compound having the following specific structure, thereby completing the present invention.

[0061] That is, the present invention is an isocyanate group-containing organosilicon compound, which is an isocyanate group-containing organosilicon compound represented by the following general formula (1), characterized in that it has three or more R 2 base, and the viscosity at 25°C is 100mm 2 / s or less.

[0062] R 1 a R 2 b SiO (4-a-b) / 2 (1)

[0063] In formula (1), R 1 is a monovalent alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group, a monovalent aryl group having 6 to 10 carbon atoms, or a monovalent aralkyl group having 7 to 10 carbon atoms, which is the same or different and does not have an aliphatic unsaturated group, and R 2 It is an organic group represented by the formula -CH2CH2Si(CH3)2OSi(CH3)2CH2CH2CH2NCO, and a and b are positive numbers satisfying 0.9≤a≤1.9, 0.25≤b≤1.1, and 1.9≤a+b≤2.8, respectively.

[0064] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0065] The isocyanate group-containing organosilicon compound of the present invention is represented by the following general formula (1), which has three or more R 2base, and the viscosity at 25°C is 100mm 2 / s or less isocyanate group-containing organic silicon compound.

[0066] R 1 a R 2 b SiO (4-a-b) / 2 (1)

[0067] In formula (1), R 1 is a monovalent alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group, a monovalent aryl group having 6 to 10 carbon atoms, or a monovalent aralkyl group having 7 to 10 carbon atoms, which is the same or different and does not have an aliphatic unsaturated group, and R 2 It is an organic group represented by the formula -CH2CH2Si(CH3)2OSi(CH3)2CH2CH2CH2NCO, and a and b are positive numbers satisfying 0.9≤a≤1.9, 0.25≤b≤1.1, and 1.9≤a+b≤2.8, respectively.

[0068] The above-mentioned viscosity is a viscosity measured at 25° C. using a modified Ostwald capillary viscometer.

[0069] R 1 It can be any of linear, branched, and cyclic. Specific examples include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; saturated alicyclic hydrocarbon groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl and tolyl; aralkyl groups such as benzyl and phenethyl; fluorine-substituted alkyl groups such as trifluoropropyl and nonafluorohexyl, etc., preferably methyl and phenyl.

[0070] a is 0.9 to 1.9, preferably 1.0 to 1.8, b is 0.25 to 1.1, preferably 0.4 to 1.0, and a+b is 1.9 to 2.8, preferably 2.0 to 2.6. This is because if a is less than 0.9, the cost of the silicon unit forming the present compound is high, which is not economically preferable. If it is greater than 1.9, it is difficult to make R 2 The number of bases is 3 or more, and it is difficult to make the viscosity at 25°C 100mm 2 If b is less than 0.25, it is difficult to make R 2 The number of bases is 3 or more, and it is difficult to make the viscosity at 25°C 100mm 2 / s or less. If it is greater than 1.1, the silicon unit of the present compound is not economically preferred. If a+b is less than 1.9, the silicon unit of the present compound is not economically preferred. If it is greater than 2.8, it is difficult to make R 2 The number of bases is 3 or more, and it is difficult to make the viscosity at 25°C 100mm 2 / s or less.

[0071] The isocyanate group-containing organosilicon compound of the present invention is preferably any one of the compounds represented by the following general formulae (2) to (4).

[0072] The isocyanate group-containing organosilicon compound of the present invention is preferably a linear isocyanate group-containing organosilicon compound represented by the following general formula (2), and its viscosity at 25° C. is 100 mm 2 / s or less.

[0073] R 1 2R 3 SiO(SiR 1 2O) c (SiR 1 R 2 O) d SiR 1 2R 3 (2)

[0074] In formula (2), R 1 、R 2 With the R 1 、R 2 Same. 3 R 1 or R 2 Any one of the following, and one molecule has 3 or more R 2 The base is a radical, c is an integer from 0 to 20, d is an integer from 1 to 10, and c+d is an integer from 1 to 30.

[0075] c is 0 to 20, preferably 0 to 10, d is 1 to 10, preferably 1 to 5, and c+d is 1 to 30, preferably 1 to 10. When c is 20 or less, it is easy to make R 2 The number of bases is 3 or more, and the viscosity at 25°C is easily adjusted to 100 mm 2 / s or less, if d is less than 10 and c+d is less than 30, it is easy to make the viscosity at 25°C to 100mm 2 / s or less. In addition, R may be contained as needed 1 SiO 1.5 Units or SiO2 units are used as units constituting siloxane.

[0076] Furthermore, the isocyanate group-containing organosilicon compound of the present invention is preferably a branched isocyanate group-containing organosilicon compound represented by the following general formula (3), which has 3 to 4 R 2 base, and the viscosity at 25°C is 100mm 2 / s or less.

[0077] R 1e Si(OSiR 1 2R 2 ) f (3)

[0078] In formula (3), R 1 、R 2 With the R 1 、R 2 Same, e is 0 or 1, f is 3 or 4, e+f is 4.

[0079] Furthermore, the isocyanate group-containing organosilicon compound of the present invention is preferably an isocyanate group-containing organosilicon compound having a cyclic structure represented by the following general formula (4), which has three or more R 2 base, and the viscosity at 25°C is 100mm 2 / s or less.

[0080] [Chemical Formula 3]

[0081]

[0082] In formula (4), R 1 、R 2 With the R 1 、R 2 Similarly, g is an integer of 0 to 2, h is an integer of 3 to 5, and g+h is an integer of 3 to 7.

[0083] According to the present invention, an isocyanate group-containing organosilicon compound represented by the above-mentioned general formulae (2) to (4) having a desired linear, branched, or cyclic structure can be provided.

[0084] Hereinafter, methods for producing the compounds represented by the above-mentioned general formulae (1) to (4) will be described.

[0085] The isocyanate group-containing organosilicon compound of the present invention can be obtained by subjecting an organohydrogen polysiloxane corresponding to the compound represented by the following general formulae (5) to (8) to a hydrosilylation reaction with an alkenyl group-containing isocyanate compound CH2=CHSi(CH3)2OSi(CH3)2CH2CH2CH2NCO.

[0086] The isocyanate group-containing organosilicon compound represented by the general formula (1) of the present invention can be obtained by hydrosilylation of an organohydrogenpolysiloxane represented by the following general formula (5) with the alkenyl group-containing isocyanate compound in the presence of a platinum catalyst or the like.

[0087] R 1 a H b SiO (4-a-b) / 2(5)

[0088] In formula (5), R 1 , a and b and the R 1 , a and b are the same.

[0089] Similarly, when the target compound is a linear compound represented by the general formula (2), it can be obtained by subjecting an organohydrogen polysiloxane represented by the following general formula (6) to an addition reaction with the alkenyl group-containing isocyanate compound.

[0090] R 1 2R 4 SiO(SiR 1 2O) c (SiR 1 HO) d SiR 1 2R 4 (6)

[0091] In formula (6), R 1 , c and d and the R 1 , c and d are the same, R 4 R 1 or any of H.

[0092] When the target compound is a branched compound represented by the general formula (3), it can be obtained by subjecting an organohydrogen polysiloxane represented by the following general formula (7) to an addition reaction with the alkenyl group-containing isocyanate compound.

[0093] R 1 e Si(OSiR 1 2H) f (7)

[0094] In formula (7), R 1 , e and f and the R 1 , e and f are the same.

[0095] When the target compound is a compound having a cyclic structure represented by the general formula (4), it can be obtained by subjecting an organohydrogen polysiloxane represented by the following general formula (8) to an addition reaction with the alkenyl group-containing isocyanate compound.

[0096] [Chemical Formula 4]

[0097]

[0098] In formula (8), R 1 、R 2 , g and h and the R 1 、R 2 , g and h are the same.

[0099] The addition reaction of the above-mentioned organohydrogenpolysiloxane and the alkenyl isocyanate compound can be carried out according to a conventionally known method. For example, with respect to 1 mole of hydrogen atoms directly bonded to silicon atoms in the organohydrogenpolysiloxane represented by general formulas (5) to (8), more than 1 mole equivalent of the alkenyl isocyanate compound is added and reacted. The reaction temperature is not particularly limited, but is preferably a temperature that does not exceed the boiling point of the solvent used. For example, it can be carried out at a temperature of about 0°C to about 120°C. The reaction can be carried out in the presence of a solvent, a hydrosilylation catalyst or a stabilizer. The solvent, the hydrosilylation catalyst and the stabilizer can use conventionally known solvents, hydrosilylation catalysts and stabilizers without particular limitation.

[0100] In this reaction, preferably at least 1 molar equivalent of the alkenyl group-containing isocyanate compound is added per 1 mole of hydrogen atoms directly bonded to silicon atoms in the organohydrogenpolysiloxane, more preferably 1.0 to 3.0 molar equivalents, even more preferably 1.1 to 2.0 molar equivalents, and particularly preferably 1.2 to 1.5 molar equivalents.

[0101] The hydrosilylation catalyst is preferably a noble metal catalyst, particularly preferably a platinum catalyst derived from chloroplatinic acid. In particular, the stability of the platinum catalyst can be improved by completely neutralizing the chloride ions of chloroplatinic acid with sodium bicarbonate. For example, a complex of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane and a sodium bicarbonate-neutralized product of chloroplatinic acid (Karstedt catalyst) is more preferred.

[0102] The amount of the hydrosilylation catalyst added may be a catalytic amount sufficient to cause the above reaction to proceed. For example, a complex of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane and a sodium bicarbonate neutralized product of chloroplatinic acid may be used in an amount of 1 ppm to 80 ppm, calculated as platinum, relative to the mass of the hydrosiloxane compound represented by formulae (5) to (8).

[0103] The addition reaction carried out in the presence of a platinum catalyst can be carried out in the absence of a solvent, or using hydrocarbon solvents such as isooctane, toluene, and xylene, ether solvents such as tetrahydrofuran, dibutyl ether, ethylene glycol dimethyl ether (monoglyme), and diethylene glycol dimethyl ether (diglyme), and aprotic solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and dimethylimidazolidinone.

[0104] The isocyanate compound CH2=CHSi(CH3)2OSi(CH3)2CH2CH2CH2NCO used in the addition reaction can be synthesized by the following known methods (A) to (C).

[0105] (A) Isocyanation based on the reaction of CH2=CHSi(CH3)2OSi(CH3)2CH2CH2CH2NH2 with phosgene

[0106] (B) Isocyanation based on the reaction of CH2=CHSi(CH3)2OSi(CH3)2CH2CH2CH2I with potassium cyanate

[0107] (C) Phenyl carbamate represented by CH2=CHSi(CH3)2OSi(CH3)2CH2CH2CH2NH2 is obtained by reacting CH2=CHSi(CH3)2OSi(CH3)2CH2CH2CH2NH2 with phenyl chloroformate, or CH2=CHSi(CH3)2OSi(CH3)2CH2CH2CH2NH2 with diphenyl carbonate, and then isocyanating is carried out by thermal decomposition reaction.

[0108] Among the above methods, the synthesis method (C) disclosed in Patent Document 1 is preferred, which is a method of thermally decomposing phenyl carbamate in the presence of trialkylchlorosilane and an acid-binding agent.

[0109] As described above, the isocyanate group-containing organosilicon compound of the present invention can be produced by using an organohydrogenpolysiloxane having a desired structure as a raw material, and structures such as linear, branched, and cyclic structures can be readily distinguished and produced.

[0110] Example

[0111] Hereinafter, the present invention will be described in detail using Examples and Comparative Examples, but the present invention is not limited thereto.

[0112] In addition, the viscosity was measured at a temperature of 25°C using a modified Ostwald capillary viscometer.

[0113] [Synthesis example]

[0114] 331.2 g of potassium carbonate and 300.0 g of water were added to the flask and uniformly dissolved. 180.0 g of ethyl acetate and 150.0 g of toluene were then added, and the flask was ice-cooled before adding 217.0 g of the following aminovinyldisiloxane.

[0115] [Chemical Formula 5]

[0116]

[0117] Next, 156.5 g of phenyl chloroformate was added dropwise at a rate that did not cause the internal temperature to exceed 10°C. The internal temperature was maintained below 10°C and the reaction was continued for a further 2 hours. Then, 800 g of water was added to dissolve the generated salt. The aqueous layer was separated, and the organic layer was washed with water and dried over anhydrous sodium sulfate. After filtration, the resulting solution was concentrated under reduced pressure to obtain 336.1 g of the following phenyl carbamate derivative.

[0118] [Chemical Formula 6]

[0119]

[0120] Next, 336.1 g of the synthesized phenyl carbamate derivative and 300.0 g of xylene were added to the flask. 131.0 g of triethylamine was added, and after heating to an internal temperature of 80°C, 129.9 g of trimethylsilyl chloride was added dropwise. After the addition was complete, the mixture was heated and stirred at 100°C for 1 hour, and then at 120°C for 6 hours. After cooling to room temperature, the generated salt was filtered, and the filtrate was washed with 300 g of water and dried over anhydrous sodium sulfate. After filtration, the mixture was distilled under reduced pressure to obtain 155.3 g of the target product, 1-(3-isocyanatepropyl)-1,1,3,3-tetramethyl-3-vinyldisiloxane [A].

[0121] [Chemical Formula 7]

[0122]

[0123] The boiling point is 64.0-65.0°C / 300Pa, and the purity measured by gas chromatography is 99.9%.

[0124] [Example 1]

[0125] 121.5 g of isocyanate vinyl disiloxane [A] obtained in Synthesis Example was added to a flask. After replacing the flask with argon atmosphere, the internal temperature was heated to 70°C. After adding 0.04 g of a Custer catalyst (platinum concentration: 3%), 27.3 g of the organohydrogenpolysiloxane represented by the following formula [H-1] was added dropwise. After completion of the dropwise addition, the reaction was allowed to proceed at 110°C for 5 hours.

[0126] [Chemical Formula 8]

[0127]

[0128] After the reaction, unreacted products were distilled off by heating under reduced pressure to obtain 126.1 g of isocyanate siloxane of the following formula [I-1].

[0129] [Chemical Formula 9]

[0130]

[0131] In general formula (1), a=1, b=1. In general formula (4), g=0, h=4, R 1 =Methyl. Appearance is colorless and transparent liquid, viscosity at 25℃ is 41.6mm 2 / s, and the isocyanate equivalent is 318 g / mole.

[0132] [Example 2]

[0133] 126.0 g of isocyanate vinyl disiloxane [A] obtained in Synthesis Example was added to a flask. After replacing the flask with argon atmosphere, the internal temperature was heated to 70°C. After adding 0.06 g of a Custer catalyst (platinum concentration: 3%), 40.3 g of the organohydrogenpolysiloxane represented by the following formula [H-2] was added dropwise. After completion of the dropwise addition, the reaction was allowed to proceed at 110°C for 5 hours.

[0134] [Chemical Formula 10]

[0135]

[0136] After the reaction, unreacted products were distilled off by heating under reduced pressure to obtain 140.4 g of isocyanate siloxane of the following formula [I-2].

[0137] [Chemical Formula 11]

[0138]

[0139] In general formula (1), a=1.75, b=0.75. In general formula (3), e=1, f=3, R 1 =Methyl. Appearance is colorless and transparent liquid, viscosity at 25℃ is 20.7mm 2 / s, and the isocyanate equivalent is 359 g / mole.

[0140] [Example 3]

[0141] 91.9 g of isocyanate vinyl disiloxane [A] obtained in Synthesis Example was added to a flask. After replacing the flask with argon atmosphere, the internal temperature was heated to 70°C. After adding 0.04 g of a Custer catalyst (platinum concentration: 3%), 38.2 g of the organohydrogenpolysiloxane represented by the following formula [H-3] was added dropwise. After completion of the dropwise addition, the reaction was allowed to proceed at 110°C for 5 hours.

[0142] [Chemical Formula 12]

[0143]

[0144] After the reaction, unreacted products were distilled off by heating under reduced pressure to obtain 103.4 g of isocyanate siloxane of the following formula [I-3].

[0145] [Chemical Formula 13]

[0146]

[0147] In general formula (1), a=1.75, b=0.75. In general formula (3), e=1, f=3, R 1 = methyl, decyl. Appearance is colorless and transparent liquid, viscosity at 25°C is 29.6mm 2 / s, and the isocyanate equivalent is 382 g / mole.

[0148] [Example 4]

[0149] 78.4 g of isocyanate vinyl disiloxane [A] obtained in Synthesis Example was added to a flask. After replacing the flask with argon atmosphere, the internal temperature was heated to 70°C. After adding 0.04 g of a Custer catalyst (platinum concentration: 3%), 27.3 g of the organohydrogenpolysiloxane represented by the following formula [H-4] was added dropwise. After completion of the dropwise addition, the reaction was allowed to proceed at 110°C for 5 hours.

[0150] [Chemical Formula 14]

[0151]

[0152] After the reaction, unreacted products were distilled off by heating under reduced pressure to obtain 83.0 g of isocyanate siloxane of the following formula [I-4].

[0153] [Chemical Formula 15]

[0154]

[0155] In general formula (1), a=1.75, b=0.75. In general formula (3), e=1, f=3, R 1 = methyl, phenyl. Appearance is colorless and transparent liquid, viscosity at 25℃ is 28.6mm 2 / s, and the isocyanate equivalent is 374 g / mole.

[0156] [Example 5]

[0157] 79.7 g of isocyanate vinyl disiloxane [A] obtained in Synthesis Example was added to a flask. After replacing the flask with argon atmosphere, 20 ml of toluene was added and the internal temperature was heated to 70°C. After adding 0.06 g of a Custer catalyst (platinum concentration: 3%), 16.4 g of the organohydrogenpolysiloxane represented by the following formula [H-5] was added dropwise. After completion of the dropwise addition, the reaction was allowed to proceed at 110°C for 5 hours.

[0158] [Chemical Formula 16]

[0159]

[0160] After the reaction, the solvent and unreacted products were distilled off by heating under reduced pressure to obtain 77.8 g of isocyanate siloxane of the following formula [I-5].

[0161] [Chemical Formula 17]

[0162]

[0163] In general formula (1), a=1, b=1. In general formula (4), g=0, h=5, R 1 =Methyl. Appearance is light yellow transparent liquid, viscosity at 25℃ is 70.6mm 2 / s, and the isocyanate equivalent is 369 g / mole.

[0164] [Example 6]

[0165] 90.4 g of isocyanate vinyl disiloxane [A] obtained in Synthesis Example was added to a flask. After replacing the flask with argon atmosphere, 15 ml of toluene was added and the internal temperature was heated to 70°C. After adding 0.04 g of a Custer catalyst (platinum concentration: 3%), 25.4 g of the organohydrogenpolysiloxane represented by the following formula [H-6] was added dropwise. After completion of the dropwise addition, the reaction was allowed to proceed at 110°C for 5 hours.

[0166] [Chemical Formula 18]

[0167]

[0168] After the reaction, the solvent and unreacted products were distilled off by heating under reduced pressure to obtain 94.7 g of isocyanate siloxane of the following formula [I-6].

[0169] [Chemical Formula 19]

[0170]

[0171] In general formula (1), a=1.6, b=0.8. In general formula (3), e=0, f=4, R 1 =Methyl. Appearance is colorless and transparent liquid, viscosity at 25℃ is 29.2mm 2 / s, and the isocyanate equivalent is 375 g / mole.

[0172] [Example 7]

[0173] 25.0 g of the organohydrogenpolysiloxane represented by the following formula [H-7] was added to a flask. After replacing the flask with argon atmosphere, 15 ml of toluene was added and the internal temperature was heated to 70°C. After adding 0.06 g of a Custer catalyst (platinum concentration: 3%), 34.8 g of the isocyanate vinyl disiloxane [A] obtained in the synthesis example was added dropwise. After completion of the dropwise addition, the reaction was allowed to proceed at 110°C for 5 hours.

[0174] [Chemical Formula 20]

[0175]

[0176] After the reaction, the solvent and unreacted products were distilled off by heating under reduced pressure to obtain 47.9 g of isocyanate siloxane of the following formula [I-7].

[0177] [Chemical Formula 21]

[0178]

[0179] In general formula (1), a=1.82, b=0.29. In general formula (2), c=10, d=5, R 1 =R 3 =Methyl. Appearance is yellow transparent liquid, viscosity at 25℃ is 84.1mm 2 / s, and the isocyanate equivalent is 553 g / mole.

[0180] [Example 8]

[0181] 51.2 g of isocyanate vinyl disiloxane [A] obtained in Synthesis Example was added to a flask. After replacing the flask with argon atmosphere, the internal temperature was heated to 70°C. After adding 0.06 g of a Custer catalyst (platinum concentration: 3%), 15.0 g of the organohydrogenpolysiloxane represented by the following formula [H-8] was added dropwise. After completion of the dropwise addition, the reaction was allowed to proceed at 110°C for 5 hours.

[0182] [Chemical Formula 22]

[0183]

[0184] After the reaction, unreacted products were distilled off by heating under reduced pressure to obtain 51.1 g of isocyanate siloxane of the following formula [I-8].

[0185] [Chemical Formula 23]

[0186]

[0187] In general formula (1), a=1.25, b=0.75. In general formula (4), g=1, h=3, R 1= methyl, propyl. Appearance is light yellow transparent liquid, viscosity at 25 ° C is 34.0mm 2 / s, and the isocyanate equivalent is 383 g / mole.

[0188] According to the present invention, an organosilicon compound having three or more isocyanate groups in one molecule, low viscosity, and excellent handleability, suitable as a crosslinking agent, can be obtained. An example of a crosslinking agent is the commercially available DURANATE TKA-100, an isocyanurate-type derivative of hexamethylene diisocyanate. Assuming a density of 1 g / cm 3 , then its viscosity is 2600mm 2 / s, in contrast, the viscosity of the present invention is 100mm 2 Furthermore, since the organosilicon compound of the present invention has a low viscosity, it is easy to mix uniformly with the polymeric polyol compound or the polymeric polyamine compound, and it is also easy to degas after mixing, so it is useful as a curing agent for obtaining a cured molded product.

[0189] The present invention is not limited to the above-mentioned embodiments, which are merely examples, and any technical solution having substantially the same structure and effect as the technical concept described in the claims of the present invention is within the scope of protection of the present invention.

Claims

1. An isocyanate group-containing organosilicon compound, which is an isocyanate group-containing organosilicon compound represented by the following general formula (3) or (4), characterized in that: There are more than 3 R in one molecule 2 base, and the viscosity at 25°C is 100mm 2 / s or less, R 1 e Si(OSiR 1 2R 2 ) f (3) In formula (3), R 1 is a monovalent alkyl group having 1 to 10 carbon atoms, a monovalent aryl group having 6 to 10 carbon atoms, or a monovalent aralkyl group having 7 to 10 carbon atoms, which is the same or different and does not have an aliphatic unsaturated group, and R 2 An organic group represented by the formula -CH2CH2Si(CH3)2OSi(CH3)2CH2CH2CH2NCO, e is 0 or 1, f is 3 or 4, e+f is 4, In formula (4), R 1 is a monovalent alkyl group having 1 to 10 carbon atoms and not having an aliphatic unsaturated group, of the same or different types, 2 It is an organic group represented by the formula -CH2CH2Si(CH3)2OSi(CH3)2CH2CH2CH2NCO, g is an integer of 0 to 2, h is an integer of 3 to 5, and g+h is an integer of 3 to 7.

2. A method for preparing an isocyanate group-containing organosilicon compound according to claim 1, characterized in that: The organohydrogen polysiloxane represented by the following general formula (7) is subjected to an addition reaction with CH2=CHSi(CH3)2OSi(CH3)2CH2CH2CH2NCO. R 1 e Si(OSiR 1 2H) f (7) In formula (7), R 1 , e and f and the R 1 , e and f are the same.

3. A method for preparing an isocyanate group-containing organosilicon compound according to claim 1, characterized in that: The organohydrogen polysiloxane represented by the following general formula (8) is subjected to an addition reaction with CH2=CHSi(CH3)2OSi(CH3)2CH2CH2CH2NCO. [Chemical Formula 2] In formula (8), R 1 , g and h and the R 1 , g and h are the same.

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