KR20140144663A - Alkoxysilyl compound having at least two alkoxysilyl groups, composition, cured product thereof, use thereof and preparing method of alkoxysilyl compound having at least two alkoxysilyl groups - Google Patents
Alkoxysilyl compound having at least two alkoxysilyl groups, composition, cured product thereof, use thereof and preparing method of alkoxysilyl compound having at least two alkoxysilyl groups Download PDFInfo
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The present invention relates to an alkoxysilyl compound having at least two alkoxysilyl groups (hereinafter referred to as "alkoxysilyl compounds") which exhibit excellent heat resistance in a composite, a composition containing the alkoxysilyl compound, a cured product thereof, a use thereof, and a process for producing an alkoxysilyl compound . More specifically, the present invention relates to a thermosetting resin composition which has excellent heat-resistant properties in a composite, in particular, a low coefficient of thermal expansion (CTE) and a high glass transition temperature synergistic effect (including a Tg- A composition containing the same, a cured product, a use thereof, and a process for producing an alkoxysilyl compound.
The coefficient of thermal expansion of a polymer material, specifically an epoxy cured product, is about 50 to 80 ppm / 占 폚, and the coefficient of thermal expansion (for example, the thermal expansion coefficient of silicon is 3 to 5 ppm / 占 폚 and the thermal expansion coefficient Is 17 ppm / [deg.] C), the coefficient of thermal expansion is very large, ranging from several times to several tens of times. Therefore, for example, when the polymer material is used together with an inorganic material or a metal material in a semiconductor, a display field, etc., the physical properties and processability of the polymer material remarkably increase due to the different thermal expansion coefficients of the polymer material and the inorganic material or metal material Is limited. Further, for example, in the case of semiconductor packaging or the like in which a silicon wafer and an epoxy substrate are used adjacent to each other, or when an inorganic barrier film is coated on a polymer film in order to impart gas barrier properties, (CTE-mismatch), cracking of the inorganic layer, bending of the substrate, peeling-off of the coating layer, and breakage of the substrate occur.
Due to the high CTE of the polymer material and the dimensional change of the polymer material due to the high CTE of the polymer material, it is possible to manufacture a next-generation semiconductor substrate, a PCB (printed circuit board), a packaging, an OTFT (Organic Thin Film Transistor) and flexible display substrates. Specifically, in the semiconductor and PCB fields, it is difficult to design the next-generation parts that require high integration, high fineness, flexibility, and high performance due to the epoxy material having an extremely high CTE as compared with metal / ceramic materials. Suffering. In other words, due to the high thermal expansion characteristics of the epoxy material at the component process temperature, defects occur in manufacturing the parts as well as the process is limited, and the design of the parts, workability and reliability are problematic. Therefore, in order to secure the workability and reliability of the electronic component, improved thermal expansion characteristics of the epoxy, that is, dimensional stability is required.
To date, in order to improve the thermal expansion characteristics (that is, a small thermal expansion coefficient) of an epoxy compound, a method of compounding an epoxy compound with inorganic particles (inorganic filler) and / or fibers has been widely used. In order to improve the thermal expansion characteristics, when the epoxy compound and the inorganic particles are combined as the filler, a CTE reduction effect can be obtained only by using a large amount of silica inorganic particles of about 2 to 30 μm in size. However, there is a problem that workability and physical properties of parts are deteriorated due to the filling of a large amount of inorganic particles. That is, a decrease in fluidity due to a large amount of inorganic particles and formation of voids in the interspace filling are problematic. Also, the viscosity of the material increases sharply due to the addition of the inorganic particles. Further, the size of the inorganic particles tends to decrease due to the miniaturization of the semiconductor structure. However, when the filler of 1 탆 or less is used, the problem of lowering the fluidity (viscosity increase) becomes more serious. When the inorganic particles having a large average particle diameter are used, the frequency of filling the application site of the composition containing the resin and the inorganic particles is increased. On the other hand, even when a composition containing fibers as an organic resin and a filler is used, the CTE is greatly reduced, but still shows a higher CTE as compared with a silicon chip or the like.
As described above, due to limitations of the present technology of compounding epoxy compounds, the manufacture of highly integrated high performance electronic components such as next-generation semiconductor substrates and PCBs is limited. Therefore, it is required to develop a new compound having improved CTE, that is, a low CTE and a high glass transition temperature property, in order to solve problems such as high CTE of the conventional thermosetting polymer composite and heat resistance and lack of processability.
According to one embodiment of the present invention, there is provided a novel alkoxysilyl compound exhibiting improved heat resistance characteristics, specifically low CTE and high glass transition temperature characteristics, and excellent flame retardancy in a cured product in a composite.
According to another embodiment of the present invention, there is provided an alkoxysilyl composition exhibiting improved heat resistance characteristics, specifically low CTE and high glass transition temperature characteristics, and excellent flame retardancy in a cured product in a complex of an alkoxysilyl compound.
Further, according to another embodiment of the present invention, an embodiment of the present invention, which exhibits improved heat resistance characteristics in a composite through blending with an epoxy compound, specifically low CTE and high glass transition temperature characteristics and excellent flame retardancy in a cured product A cured product of an alkoxysilyl composition is provided.
Further, according to another embodiment of the present invention, use of the alkoxysilyl composition according to an embodiment of the present invention is provided.
According to another embodiment of the present invention, there is provided a process for producing an alkoxysilyl group compound.
According to a first aspect of the present invention, there is provided an alkoxysilyl compound having at least two alkoxysilyl groups selected from the group consisting of the following formulas AI to II.
Substituents a and b of the above formulas AI to DI may be the following formula S1 or S2; hydrogen or an alkenyl group and the substituents c to f are selected from the group consisting of hydrogen, an alkyl group, an alkenyl group, aryl (aryl) can group, in the formula AI Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3) 2 -, -S- or -SO 2 - can be,
And the remainder may be hydrogen, an alkyl group, an alkenyl group or an aryl group, and in the formula (HI), M is -CH 2 - and, C1-C10 alkyl group in straight or branched chain wherein the formula II is in the meta position of the oxygen -, -C (CH 3) 2 -, -C (CF 3) 2 -, -S- or -SO 2 .
[Formula (S1)
- (CH 2 ) z -SiR 1 R 2 R 3
≪ RTI ID = 0.0 &
-CONH (CH 2 ) z -SiR 1 R 2 R 3
(In the formulas (S1) and (S2), R 1 to R 3 Is an alkyl group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, the alkyl group and the alkoxy group are linear or branched, and z is an integer of 3 to 10.)
According to a second aspect of the present invention,
In a first aspect, there is provided an alkoxysilyl composition comprising at least one alkoxysilyl compound.
According to a third aspect of the present invention,
In a second aspect, there is provided an alkoxysilyl composition further comprising at least one filler selected from the group consisting of inorganic particles and fibers.
According to a fourth aspect of the present invention,
In a third aspect, the inorganic particles include at least one metal oxide selected from the group consisting of silica, zirconia, titania, alumina, silicon nitride, and aluminum nitride; T-10 type silsesquioxane; Ladder type silsesquioxane; And cage-type silsesquioxane. The alkoxysilyl composition is at least one selected from the group consisting of cerium silsesquioxanes and cage silsesquioxanes.
According to a fifth aspect of the present invention,
In a third aspect, there is provided an alkoxysilyl composition wherein the inorganic particles are comprised between 5 wt% and 95 wt%, based on the total solids of the alkoxysilyl composition.
According to a sixth aspect of the present invention,
In a third aspect, there is provided an alkoxysilyl composition wherein the inorganic particles are contained in an amount of 30 wt% to 95 wt% based on the total solids of the alkoxysilyl composition.
According to a seventh aspect of the present invention,
In a third aspect, there is provided an alkoxysilyl composition wherein the inorganic particles are comprised between 5 wt% and 60 wt% based on the total solids of the alkoxysilyl composition.
According to an eighth aspect of the present invention,
In a third aspect, the fibers are selected from the group consisting of E glass fibers, T glass fibers, S glass fibers, NE glass fibers, H glass fibers, and quartz, and glass fiber and liquid crystal polyester fibers selected from the group consisting of polyethylene terephthalate fibers , A group consisting of wholly aromatic fibers, polybenzoxazole fibers, nylon fibers, polyethylene naphthalate fibers, polypropylene fibers, polyethersulfone fibers, polyvinylidene fluoride fibers, polyethylene sulfide fibers, and polyetheretherketone fibers And at least one organic fiber selected from the group consisting of organic fibers selected from the group consisting of organic fibers.
According to a ninth aspect of the present invention,
In a third aspect, there is provided an alkoxysilyl composition wherein said fibers are comprised between 10 wt% and 90 wt% of the total solids of the alkoxysilyl composition.
According to a tenth aspect of the present invention,
In a third aspect, there is provided an alkoxysilyl composition further comprising inorganic particles, wherein the inorganic particles comprise fibers.
According to an eleventh aspect of the present invention,
In a third aspect, there is provided an alkoxysilyl composition further comprising an alkoxysilyl group reaction catalyst.
According to a twelfth aspect of the present invention,
In an eleventh aspect, the alkoxysilyl group-containing catalyst comprises at least one inorganic acid selected from the group consisting of nitric acid, sulfuric acid, hydrochloric acid, acetic acid and phosphoric acid; ammonia; KOH; NH 4 OH; Amine; Metal alkoxides; Metal oxides; Metal organic acid salts; And a halide. The alkoxysilyl compound is at least one selected from the group consisting of a halide, a halide, and a halide.
According to a thirteenth aspect of the present invention,
In an eleventh aspect, the alkoxysilyl group-containing catalyst is used in an amount of 0.01 phr to 10 phr with respect to the alkoxysilyl compound.
According to a fourteenth aspect of the present invention,
In an eleventh aspect, there is provided an alkoxysilyl composition further comprising water.
According to a fifteenth aspect of the present invention,
In a second aspect, there is provided an epoxy resin composition comprising a glycidyl ether epoxy compound, a glycidyl epoxy compound, a glycidylamine epoxy compound, a glycidyl ester epoxy compound, a rubber modified epoxy compound, an aliphatic polyglycidyl epoxy compound, There is provided an alkoxysilyl composition further comprising at least one epoxy compound selected from the group consisting of aliphatic glycidylamine-based epoxy compounds.
According to a sixteenth aspect of the present invention,
In an aspect of the fifteenth aspect, the epoxy compound has a core structure in which a bisphenol A, bisphenol F, bisphenol S, biphenyl, naphthalene, benzene, thiodiphenol, fluorene, anthracene, isocyanurate, Alkoxysilyl compositions having 1,1,2,2-tetraphenylethane, tetraphenylmethane, 4,4'-diaminodiphenylmethane, aminophenol, cycloaliphatic, or novolac units are provided.
According to a seventeenth aspect of the present invention,
In a fifteenth aspect of the present invention, there is provided an epoxy resin composition comprising 1 to 99 wt% of the above alkoxy silyl compound, a glycidyl ether epoxy compound, a glycidyl epoxy compound, a glycidylamine epoxy compound, a glycidyl ester epoxy compound, There is provided an alkoxysilyl composition comprising 1 to 99 wt% of at least one epoxy compound selected from the group consisting of an epoxy compound, an aliphatic polyglycidyl-based epoxy compound and an aliphatic glycidylamine-based epoxy compound.
According to an eighteenth aspect of the present invention,
In a 15th aspect, there is provided an epoxy resin composition comprising 10 to 90% by weight of the alkoxy silyl compound and at least one epoxy resin selected from the group consisting of glycidyl ether epoxy compounds, glycidyl epoxy compounds, glycidylamine epoxy compounds, glycidyl ester epoxy compounds, An epoxy compound, an aliphatic polyglycidyl epoxy compound, and an aliphatic glycidylamine epoxy compound, based on the total weight of the alkoxysilyl compound.
According to a nineteenth aspect of the present invention,
In a fifteenth aspect, there is provided an alkoxysilyl composition further comprising a curing agent.
According to a twentieth aspect of the present invention,
There is provided an electronic material comprising an alkoxysilyl composition according to any one of the second to nineteenth aspects.
According to a twenty-first aspect of the present invention,
There is provided a substrate comprising an alkoxysilyl composition according to any one of the second to nineteenth aspects.
According to a twenty-second aspect of the present invention,
There is provided a film comprising an alkoxysilyl composition according to any one of the second to nineteenth aspects.
According to a twenty-third aspect of the present invention,
There is provided a laminate comprising a metal layer on a base layer made of an alkoxysilyl composition according to any one of the second to nineteenth aspects.
According to a twenty-fourth aspect of the present invention,
A printed wiring board comprising the laminate of the twenty-third aspect is provided.
According to a twenty-fifth aspect of the present invention,
A semiconductor device comprising a printed circuit board of the twenty-fourth aspect is provided.
According to a twenty-sixth aspect of the present invention,
There is provided a semiconductor packaging material comprising an alkoxysilyl composition according to any one of the second to nineteenth aspects.
According to a twenty-seventh aspect of the present invention,
A semiconductor device comprising a semiconductor packaging material of the 26th aspect is provided.
According to a twenty-eighth aspect of the present invention,
There is provided an adhesive comprising an alkoxysilyl composition according to any one of the second to nineteenth aspects.
According to a twenty-ninth aspect of the present invention,
There is provided a coating comprising an alkoxysilyl composition according to any one of the second to nineteenth aspects.
According to a thirtieth aspect of the present invention,
There is provided a composite material comprising an alkoxysilyl composition according to any one of the second to nineteenth aspects.
According to a thirty-first aspect of the present invention,
There is provided a prepreg comprising an alkoxysilyl composition according to any one of the second to nineteenth aspects.
According to a 32nd aspect of the present invention,
A laminated board having a metal layer disposed on a prepreg of the 31st perspective is provided.
According to a thirty-third aspect of the present invention,
There is provided a cured product of an alkoxysilyl composition according to any one of the second to nineteenth aspects.
According to a 34th aspect of the present invention,
In a 33 th aspect, a cured product of an alkoxysilyl composition having a coefficient of thermal expansion of 150 ppm / 占 폚 or less is provided.
According to a thirty fifth aspect of the present invention,
In a 34th aspect there is provided a cured product of an alkoxysilyl composition wherein the glass transition temperature is not greater than 80 占 폚 or does not exhibit a glass transition temperature.
According to a thirty sixth aspect of the present invention,
A process for producing an alkoxysilyl compound which is obtained by reacting any one of starting materials of the following formulas (AS) to (IS) with an isocyanate-based alkoxy silane of the following formula (M1) in the presence of an optional base and any solvent to obtain a final target of any one of the following formulas Method is provided.
[Starting material]
(A substituent and k and l in the formula AS to DS is hydrogen, m to p are hydrogen, an alkyl group, an alkenyl (alkenyl) group, or an aryl (aryl) AS Y in the formula is -CH 2 -., -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -
Formula ES to a more than one of the substituents of q to t IS is hydrogen and the other is alkyl, can be an alkenyl (alkenyl) group, or an aryl (aryl), in the formula HS M is -CH 2 -, -C ( CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -, and the formula IS may be substituted with a linear or branched C 1 -
≪ RTI ID =
OCN- (CH 2 ) z -SiR 1 R 2 R 3
(Wherein R 1 to R 3 At least one of them is a C1-C10 alkoxy group and the remainder is a linear or branched C1-C10 alkyl group, the alkoxy group and the alkyl group are linear or branched, and z is an integer of 3 to 10.)
[Final product]
(To have a substituent a and b of Formula DI and AI to formula S2, to f c is a substituent from hydrogen, an alkyl group, an alkenyl (alkenyl) Al group, or an aryl (aryl) can group, the general formula is -CH 2 Y AI -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -
And Formula EI to two or more of the substituents g to j of the formula (II) is S2, the rest from hydrogen, an alkyl group, an alkenyl (alkenyl) Al group, or an aryl (aryl) can group, the general formula HI M is -CH 2 - , -C (CH 3) 2 - , -C (CF 3) 2 -, -S- or -SO 2 -, and wherein formula (II) is optionally substituted in the meta position of the oxygen with C1-C10 alkyl group in straight or branched chain You can.
≪ RTI ID = 0.0 &
-CONH (CH 2 ) z -SiR 1 R 2 R 3
(In the above formula (S2), R 1 to R 3 Is an alkyl group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, the alkyl group and the alkoxy group are linear or branched, and z is an integer of 3 to 10.)
According to a thirty-seventh aspect of the present invention,
In the 36th aspect, the reaction is carried out so that the isocyanate-based alkoxy silane of formula (M1) is 1 to 5 equivalents based on 1 equivalent of the hydroxy group of any one of the starting materials AS to IS / RTI >
According to a 38th aspect of the present invention,
In a 36th aspect, there is provided a process for preparing an alkoxysilyl compound wherein the reaction is carried out at 15 ° C to 120 ° C for 1 to 72 hours.
According to a 39th aspect of the present invention,
Which comprises reacting a starting material of any one of the following formulas (AS) to (II) with an alkenyl compound of the following formula (M2) in the presence of a base and any solvent to obtain an intermediate (1)
And a step 1-2 of reacting the intermediate product (1) with an alkoxy silane of the formula (M3) in the presence of a metal catalyst and any solvent to obtain an end product of any one of the following formulas AI to II: Method is provided.
[Starting material]
(A substituent and k and l in the formula AS to DS is hydrogen, m to p are hydrogen, an alkyl group, an alkenyl (alkenyl) group, or an aryl (aryl) AS Y in the formula is -CH 2 -., -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -
Formula ES to a more than one of the substituents of q to t IS is hydrogen and the other is alkyl, can be an alkenyl (alkenyl) group, or an aryl (aryl), in the formula HS M is -CH 2 -, -C ( CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -, and the formula IS may be substituted with a linear or branched C 1 -
(M2)
X- (CH 2) z-2 -CH = CH 2
(Wherein, X is Cl, Br or halides of I, -O-SO 2 -CH 3 , -O-SO 2 -CF 3, -O-SO 2 -C 6 H 4 -CF 3, -O-SO 2 -C 6 H 4 -NO 2 or -O-SO 2 -C 6 H 4 -CH 3 , and z is an integer from 3 to 10.)
[Intermediate (1)]
Substituents k1 and l1 in the above formulas A1 to D1 are - (CH 2 ) Z-2 CH═CH 2 (Z is an integer of 3 to 10) and substituents m 1 to
Formula E1 to a substituent two or more of q1 to t1 of I1 is - (CH 2) Z-2 CH = CH 2 (Z 3 to 10 of an integer), and the other is hydrogen, an alkyl group, an alkenyl (alkenyl) group, or An aryl group,
In Formula H1 M is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3) 2 -, -S- or -SO 2 -, and wherein the formula I1 is a straight-chain or at the meta position of the oxygen And may be substituted with a branched C1-C10 alkyl group.
[Formula M3]
HSiR 1 R 2 R 3
(Wherein at least one of R 1 to R 3 is a C 1 -
[Final product]
(Wherein the substituents of formula AI to DI a and b the following formula S1, the substituent has the formula c to f S1, from hydrogen, an alkyl group, an alkenyl group or an aryl group (aryl) can group, the general formula AI Y is -CH 2 - , -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -
At least two of the substituents g to j in the above formulas (EI) to (II) are represented by the following formula (S1), and the remainder may be hydrogen, an alkyl group, an alkenyl group, or an aryl group,
Wherein M is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 - in the formula HI, May be substituted with a branched C1-C10 alkyl group.
[Formula (S1)
- (CH 2 ) z -SiR 1 R 2 R 3
(In the formula (S1), R 1 to R 3 Is an alkoxy group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group are branched or branched and z is an integer of 3 to 10.)
According to a fortieth aspect of the present invention,
In the 39th aspect, in the step 1-1, - (CH 2 ) Z-2 CH = CH 2 (Z is an alkyl group having 3 to 10 carbon atoms) of the alkenyl compound of the formula (M2) with respect to 1 equivalent of the hydroxy group of the starting material Is in the range of 0.5 to 10 equivalents based on the total amount of the alkoxysilyl compound.
According to a forty-first aspect of the present invention,
40. The method for producing an alkoxysilyl compound according to claim 39, wherein the step (1-1) is carried out at a temperature of 15 to 100 DEG C for 1 to 120 hours.
According to a 42nd aspect of the present invention,
According to a 39th aspect, in the step 1-2, an alkoxysilyl compound is prepared so that the alkoxy silane of the formula M3 is 1 to 5 equivalents based on 1 equivalent of the alkenyl group of the intermediate product (1) .
According to a fortieth aspect of the present invention,
In the 39th aspect, the above-mentioned step 1-2 is a method for producing an alkoxysilyl compound, which is carried out at 15 to 120 ° C for 1 to 72 hours.
According to a forty fourth aspect of the present invention,
In the 36th aspect, any one of EI to II having a hydroxy group which is not substituted with the above-described formula (S2) and an alkenyl compound of the following formula (M2) are reacted in the presence of an optional base and any solvent, (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10);
(CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) substituted in the step 1-3 is reacted with an alkoxy silane of the formula M 3 in the presence of a metal catalyst and any solvent to obtain a compound of the formula And a step of replacing the alkoxysilyl compound by S1.
(M2)
X- (CH 2) z-2 -CH = CH 2
(Wherein, X is Cl, Br or halides of I, -O-SO 2 -CH 3 , -O-SO 2 -CF 3, -O-SO 2 -C 6 H 4 -CF 3, -O-SO 2 -C 6 H 4 -NO 2 or -O-SO 2 -C 6 H 4 -CH 3 , and z is an integer from 3 to 10.)
[Formula M3]
HSiR 1 R 2 R 3
(Wherein at least one of R 1 to R 3 is a C 1 -
According to a forty-fifth aspect of the present invention,
In the forty-third aspect, the step (1-3) comprises reacting an alkenyl compound represented by - (CH 2 ) Z-2 CH = CH 2 (Z Is an integer of 3 to 10) is in the range of 0.5 to 10 equivalents.
According to a 46th aspect of the present invention,
In a 44th aspect, the step 1-3 is performed at a temperature of 15 to 100 캜 for 1 to 120 hours.
According to a forty-ninth aspect of the present invention,
45. The method of claim 44 aspect, the first stage 1-4 is substituted in Step 1-3 - (CH 2) Z- 2 CH = CH 2 (Z is an integer of 3 to 10) with respect to one equivalent of the formula M3 Wherein the alkoxysilyl compound is carried out in an amount of 1 to 5 equivalents.
According to a forty-ninth aspect of the present invention,
In the forty-fourth aspect, the above-mentioned step 1-4 is a method for producing an alkoxysilyl compound, which is carried out at a temperature of 15 to 120 캜 for 1 to 72 hours.
According to a 49th aspect of the present invention,
In the 39th aspect, any one of the above-mentioned formulas (EI) to (II) having a hydroxy group which is not substituted with an alkenyl group and the isocyanate-based alkoxy silane of the following formula (M1) To convert the hydroxy group into the formula (S2).
≪ RTI ID =
OCN- (CH 2 ) z -SiR 1 R 2 R 3
Wherein at least one of R 1 to R 3 is a C 1 -
According to a fiftieth aspect of the present invention,
In a 49th aspect, the present invention provides a process for producing an alkoxysilyl compound by reacting 1 to 5 equivalents of an isocyanate-based alkoxy silane of the above formula (M1) with respect to 1 equivalent of any one of the hydroxy groups of the formulas (EI) to .
According to a 51st aspect of the present invention,
In a 49th aspect, there is provided a process for preparing an alkoxysilyl compound wherein the reaction is carried out at 15 to 120 캜 for 1 to 72 hours.
According to a 52nd aspect of the present invention,
To to to any one of the starting materials of the formula AS to DS by reacting an alkenyl compound of the formula M2 under any base and any solvent present hydroxy groups are - (CH 2) Z-2 CH = CH 2 (Z is 3 to 10) to obtain an intermediate product (21);
A second step (2-2) of obtaining an intermediate product (22) having a hydroxy group by carrying out a rearrangement reaction with respect to the intermediate product (21);
Reacting the intermediate product (22) with an alkenyl compound of the following formula (M2) in the presence of an optional base and any solvent to obtain a compound wherein the hydroxy group is - (CH 2 ) Z-2 CH = CH 2 To obtain an intermediate product (23) which is substituted with a halogen atom; And
And a step (2-4) of reacting the intermediate product (23) with an alkoxy silane of the formula (M3) in the presence of a metal catalyst and any solvent to obtain an end product of any one of the following formulas AI to DI: Method is provided.
[Starting material]
(A substituent k to p of the above formula to AS DS is hydrogen, in formula AS Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3) 2 -, -S- or -SO 2 -.)
(M2)
X- (CH 2) z-2 -CH = CH 2
(Wherein, X is Cl, Br or halides of I, -O-SO 2 -CH 3 , -O-SO 2 -CF 3, -O-SO 2 -C 6 H 4 -CF 3, -O-SO 2 -C 6 H 4 -NO 2 or -O-SO 2 -C 6 H 4 -CH 3 , and z is an integer from 3 to 10.)
[Intermediate (21)]
(Substituent k1 and l1 of Formula A21 to D21 is - and (CH 2) Z-2 CH = CH 2 (Z is an integer of 3 to 10), m1 to p1 is hydrogen, in formula A21 Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -.
[Intermediate (22)]
(In the substituents k2 to p2 of the above formulas A22 to D22, any one of m2 and n2 and any of o2 and p2 is - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) and the other is hydrogen, in formula A22 Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3) 2 -, -S- or -SO 2 - a).
[Intermediate (23)]
(In the substituent k3 to p3 of Formula A23 to D23, k3; l3; m3, and any one of n3; any one, and o3 and p3 is - (CH 2) Z-2 CH = CH 2 (Z 3 to 10 is an integer), and the other is hydrogen, in formula A23 Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3) 2 -, -S- or -SO 2 - a. )
[Formula M3]
HSiR 1 R 2 R 3
(Wherein at least one of R 1 to R 3 is a C 1 -
[Final product]
(Wherein at least two of the substituents a to f of the formulas AI to DI have the following formula S1 and the rest are hydrogen or - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -.
[Formula (S1)
- (CH 2 ) z -SiR 1 R 2 R 3
(In the formula (S1), R 1 to R 3 Is an alkoxy group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group are branched or branched and z is an integer of 3 to 10.)
According to a 53rd aspect of the present invention,
In the 52nd aspect, the step (2-1) or (2-3) may be carried out by reacting the - (CH 2 ) Z- group of the alkenyl compound of the formula (M2) with one equivalent of the hydroxy group of the starting material or the intermediate product 2 CH = CH 2 (wherein Z is an integer of 3 to 10) is 0.5 to 10 equivalents based on the total amount of the alkoxysilyl compound.
According to a 54th aspect of the present invention,
In a 52nd aspect, the above-mentioned step 2-1 or step 2-3 is carried out at a temperature of from 15 캜 to 100 캜 for 1 to 120 hours.
According to a twenty-fifth aspect of the present invention,
In the 52nd aspect, step 2-4 further comprises reacting the intermediate product (23) with one equivalent of - (CH 2 ) Z-2 CH = CH 2 (Z is an integer from 3 to 10) There is provided a process for producing an alkoxysilyl compound which is performed so as to have 1 to 5 equivalents of a silane.
According to a 56th aspect of the present invention,
In a 52nd perspective, the above-mentioned Step 2-4 is a process for producing an alkoxysilyl compound which is carried out at 15 to 120 ° C for 1 to 72 hours.
According to a 57th aspect of the present invention,
In a 52nd aspect, the intermediate product (22) and A method for producing an alkoxysilyl compound, further comprising a step 2-5 of reacting an isocyanate-based alkoxy silane of the following formula (M1) in the presence of an optional base and any solvent to obtain an end product of any one of the following formulas AI to DI / RTI >
[Intermediate (22)]
(In the substituents k2 to p2 of the above formulas A22 to D22, any one of m2 and n2 and any of o2 and p2 is - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) and the other is hydrogen, in formula A22 Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3) 2 -, -S- or -SO 2 - a).
≪ RTI ID =
OCN- (CH 2 ) z -SiR 1 R 2 R 3
Wherein at least one of R 1 to R 3 is a C 1 -
[Final product]
Substituents a and b of the formulas AI to DI are represented by the following formula (S2), and either one of c and d, and either e or f is - (CH 2 ) Z-2 CH = CH 2 is an integer), and the other is hydrogen, in formula AI Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3) 2 -, -S- or -SO 2 - a).
≪ RTI ID = 0.0 &
-CONH (CH 2 ) z -SiR 1 R 2 R 3
(In the above formula (S2), R 1 to R 3 Is an alkoxy group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group are branched or branched and z is an integer of 3 to 10.)
According to a 58th aspect of the present invention,
In the 57th aspect of the present invention, the step 2-5 is a process for producing an alkoxysilyl compound by reacting 1 to 5 equivalents of the isocyanate-based alkoxy silane of the formula (M1) with respect to 1 equivalent of the hydroxy group of the intermediate product (22) / RTI >
According to a 59th aspect of the present invention,
In a 57th aspect, the step 2-5 is a method for producing an alkoxysilyl compound which is carried out at 15 to 120 DEG C for 1 to 72 hours.
According to a 60 th aspect of the present invention,
57. The process of any one of embodiments 57-26, wherein any one of the alkoxysilyl compounds is reacted with an alkoxy silane of the formula M3 in the presence of a metal catalyst and any solvent to obtain an end product of any one of the following formulas AI to DI: There is provided a process for preparing an alkoxysilyl compound which is further included.
[Formula M3]
HSiR 1 R 2 R 3
(Wherein at least one of R 1 to R 3 is a C 1 -
[Final product]
(To have a substituent a and b of Formula DI and AI to formula S2, any one of c and d, and one of e and f is the formula for S1, and the other is hydrogen, in formula Y is -CH 2 AI -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -.
[Formula (S1)
- (CH 2 ) z -SiR 1 R 2 R 3
≪ RTI ID = 0.0 &
-CONH (CH 2 ) z -SiR 1 R 2 R 3
(In the formulas (S1) and (S2), R 1 to R 3 Is an alkoxy group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group are branched or branched and z is an integer of 3 to 10.)
According to a 61st aspect of the present invention,
In a 60th aspect of the present invention, the step 2-6 is performed so that the alkoxysilyl compound of the formula M3 is 1 to 5 equivalents based on 1 equivalent of the alkenyl group of the alkoxysilyl compound.
According to a 62nd aspect of the present invention,
In a 60th aspect, the above step 2-6 provides a process for producing an alkoxysilyl compound which is carried out at 15 ° C to 120 ° C for 1 to 72 hours.
According to a 63rd aspect of the present invention,
52. The process of embodiment 52, wherein the intermediate product (23) is subjected to a rearrangement reaction to obtain an intermediate product (31) having a hydroxy group; And
Further comprising a step 3-2 of reacting the intermediate product (31) with an alkoxy silane of the formula (M3) in the presence of a metal catalyst and optionally in the presence of a solvent to obtain an end product of any one of the following formulas AI to DI: Is provided.
[Intermediate (31)]
(Substituent k1 and l1 of Formula A31 to D31 is hydrogen, m1 to p1 is - (CH 2) Z-2 CH = CH 2 (Z is an integer of 3 to 10), Y in the above formula A31 is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -.
[Formula M3]
HSiR 1 R 2 R 3
(Wherein at least one of R 1 to R 3 is a C 1 -
[Final product]
(Wherein the substituents a and b in the above formulas AI to DI are hydrogen, at least two of c to f are represented by the following formula S1, and the remainder are - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -.
[Formula (S1)
- (CH 2 ) z -SiR 1 R 2 R 3
(In the formula (S1), R 1 to R 3 Is an alkoxy group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group are branched or branched and z is an integer of 3 to 10.)
According to a 64th aspect of the present invention,
(CH 2 ) Z-2 CH = CH 2 (wherein Z is an alkyl group having 3 to 3 carbon atoms, and the like) in the presence of a base and optionally a solvent under the conditions of the intermediate product (31) To obtain an intermediate product (32) substituted with an integer of from 1 to 10; And
Further comprising a third step of reacting the intermediate product (32) with an alkoxy silane of the formula (M3) in the presence of a metal catalyst and optionally in the presence of a solvent to obtain an end product of any one of the following formulas AI to DI: Is provided.
(M2)
X- (CH 2) z-2 -CH = CH 2
(Wherein, X is Cl, Br or halides of I, -O-SO 2 -CH 3 , -O-SO 2 -CF 3, -O-SO 2 -C 6 H 4 -CF 3, -O-SO 2 -C 6 H 4 -NO 2 or -O-SO 2 -C 6 H 4 -CH 3 , and z is an integer from 3 to 10.)
[Intermediate (32)]
(The above formula A32 to D32 substituent of k2 to p2 is - (CH 2) Z-2 CH = CH 2 (Z is an integer of 3 to 10), and, Y in the above formula A32 is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -.
[Formula M3]
HSiR 1 R 2 R 3
(Wherein R 1 to R 3 At least one of them is a C1-C10 alkoxy group and the remainder is a straight or branched C1-C10 alkyl group, and the alkoxy group and the alkyl group are linear or branched.
[Final product]
(Wherein at least two of the substituents a to f of the formulas AI to DI have the following formula S1 and the remainder are - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) Is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -.
[Formula (S1)
- (CH 2 ) z -SiR 1 R 2 R 3
(In the formula (S1), R 1 to R 3 Is an alkoxy group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group are branched or branched and z is an integer of 3 to 10.)
According to a 65th aspect of the present invention,
(CH 2 ) Z-2 CH = CH 2 of the alkenyl compound of formula (M2) (Z is an integer of 3 to 5) relative to 1 equivalent of the hydroxy group of the intermediate product (22) To 10 equivalents) is in the range of 0.5 to 10 equivalents per mole of the alkoxysilyl compound.
According to a 66th aspect of the present invention,
In the 63rd aspect of the present invention, the step 3-1 is carried out at a temperature of from 15 캜 to 100 캜 for 1 to 120 hours to prepare an alkoxysilyl compound.
According to a 67th aspect of the present invention,
63. The method of embodiment 63 wherein said step 3-2 further comprises reacting said intermediate product (31) with one equivalent of - (CH 2 ) Z-2 CH = CH 2 (wherein Z is an integer from 3 to 10) There is provided a process for producing an alkoxysilyl compound which is performed so as to have 1 to 5 equivalents of a silane.
According to a 68th aspect of the present invention,
In the 63rd aspect, the step 3-2 is a method for producing an alkoxysilyl compound which is carried out at 15 ° C to 120 ° C for 1 to 72 hours.
According to a 69 th aspect of the present invention,
(CH 2 ) Z-2 CH = CH 2 of the alkenyl compound of formula (M2) (Z is an integer of 3 to 3 equivalents relative to 1 equivalent of the hydroxy group of the intermediate product (31) To 10 equivalents) is in the range of 0.5 to 10 equivalents per mole of the alkoxysilyl compound.
According to a seventy aspect of the present invention,
In a 64th aspect, the above-mentioned step 3-3 is a method for producing an alkoxysilyl compound which is carried out at 15 ° C to 100 ° C for 1 to 120 hours.
According to a 71st aspect of the present invention,
In a 64th perspective, the step 3-4 is a step of reacting the intermediate product (32) with 1 equivalent of - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) There is provided a process for producing an alkoxysilyl compound which is performed so as to have 1 to 5 equivalents of a silane.
According to a 72nd aspect of the present invention,
In a 64th perspective, the above-described step 3-4 is a method for producing an alkoxysilyl compound which is carried out at 15 to 120 ° C for 1 to 72 hours.
According to a 73rd aspect of the present invention,
63. The process of claim 63, wherein said intermediate product (31) and an isocyanate alkoxy silane of formula (M1) are reacted in the presence of any base and any solvent to obtain an end product of any one of formulas AI to DI: A method for producing an alkoxysilyl compound is provided.
≪ RTI ID =
OCN- (CH 2 ) z -SiR 1 R 2 R 3
Wherein at least one of R 1 to R 3 is a C 1 -
[Final product]
(Note that the formula AI to substituents of DI a and b have the following formula S2, c to f is - (CH 2) Z-2 CH = CH 2 (Z 3 to 10 of an integer), and, Y in the formula AI is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -.
≪ RTI ID = 0.0 &
-CONH (CH 2 ) z -SiR 1 R 2 R 3
(In the above formula (S2), R 1 to R 3 Is an alkoxy group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group are branched or branched and z is an integer of 3 to 10.)
According to a 74th aspect of the present invention,
In the 73rd aspect, the 3-5 step is a method for producing an alkoxysilyl compound by reacting 1 to 5 equivalents of the isocyanate alkoxy silane of the formula (M1) with respect to 1 equivalent of the hydroxy group of the intermediate product (31) / RTI >
According to a 75th aspect of the present invention,
In a 73rd aspect, the above-mentioned step 3-5 provides a method for producing an alkoxysilyl compound which is carried out at 15 to 120 ° C for 1 to 72 hours.
According to a seventy-sixth aspect of the present invention,
73. The method according to Claim 73, wherein said alkoxysilyl compound is reacted with an alkoxy silane of the formula M3 in the presence of a metal catalyst and optionally in the presence of a solvent to obtain an end product of any one of the following formulas AI to DI: There is provided a process for preparing an alkoxysilyl compound which is further included.
[Formula M3]
HSiR 1 R 2 R 3
(Wherein at least one of R 1 to R 3 is a C 1 -
[Final product]
(Wherein the substituents a and b in the formulas AI to DI are represented by the following formula (S2), at least two of c to f are represented by the following formula (S1), and the remainder are - (CH 2 ) Z-2 CH = CH 2 Wherein Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -.
[Formula (S1)
- (CH 2 ) z -SiR 1 R 2 R 3
≪ RTI ID = 0.0 &
-CONH (CH 2 ) z -SiR 1 R 2 R 3
(In the formulas (S1) and (S2), R 1 to R 3 Is an alkoxy group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group are branched or branched and z is an integer of 3 to 10.)
According to a 77th aspect of the present invention,
In the 76th aspect, the 3-6 step is a step of reacting the alkoxysilane of the above formula M3 with 1 equivalent of the alkoxysilyl compound - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) 1 to 5 equivalents of the alkoxysilyl compound.
According to a 78th aspect of the present invention,
In a 76th aspect, the third to sixth steps are performed at a temperature ranging from 15 to 120 캜 for 1 to 72 hours to produce an alkoxysilyl compound.
According to a 79th aspect of the present invention,
The process for producing an alkoxysilyl compound according to any one of the 52th to 78th aspects, wherein the transfer reaction is carried out at 140 ° C to 250 ° C for 1 to 200 hours.
According to an 80th aspect of the present invention,
The method for producing an alkoxysilyl compound according to any one of the 52th to 78th aspects, wherein the transfer reaction is carried out at 120 ° C to 250 ° C for 1 to 1000 minutes by injecting a microwave of 100W to 750W.
The alkoxysilyl composition comprising a novel alkoxysilyl compound according to the present invention is characterized in that the chemical bond formation between the alkoxysilyl group and the filler (fibers and / or particles) in the composite results in improved heat resistance characteristics, that is, the CTE of the alkoxysilyl composition is reduced (Hereinafter referred to as " Tg lease ") which does not exhibit a transition temperature rise or a glass transition temperature. Furthermore, the cured product containing the alkoxysilyl compound according to the present invention exhibits excellent flame retardancy due to the alkoxysilyl group.
Furthermore, when the alkoxysilyl composition according to the present invention is applied to a metal film of a substrate, it exhibits excellent adhesion to the metal film by chemical bonding of the functional group on the surface of the metal film and the alkoxysilyl group.
FIG. 1 is a graph showing the dimensional change of Example 1 and Comparative Example 1 according to the temperature change. FIG.
2 is a graph showing the dimensional change of Example 3 according to the temperature change.
3 is a photograph showing that the strip of the composite of Example 1 and Comparative Example 1 is burned.
Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, the embodiments of the present invention can be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below. Further, the embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art.
The present invention relates to a novel alkoxysilyl compound having improved heat resistance properties, particularly low CTE and high flame retardancy in a high Tg or Tg-free and / or cured product in a composite by curing the alkoxysilyl composition, A cured product thereof, a use thereof, and a process for producing the same.
"Composite" in the present invention refers to a cured product of a composition comprising an alkoxysilyl compound and a filler (fiber and / or particle). The term "cured product" in the present invention refers to a cured product of a composition containing an alkoxysilyl compound in a general sense, and includes a filler, an optional epoxy compound, a curing agent, a curing catalyst and other additives in addition to an alkoxysilyl compound and a curing catalyst Quot; refers to a cured product of a composition comprising any alkoxysilyl compound, including at least one selected from the group consisting of Further, the cured product may include a semi-finished product. Generally, since cured materials reinforced with inorganic particles or fibers are referred to as composites, cured materials have a wider meaning than composites, but composite materials with inorganic particles or fiber reinforced materials may be understood to have the same meaning.
When forming the composite by curing, the alkoxysilyl compound according to the present invention forms an interfacial bond with the surface of the filler (fiber and / or inorganic particle) and / or an alkoxysilyl term chemical bond with the alkoxysilyl group. Thus, it exhibits a chemical bond formation efficiency of a very good alkoxysilyl composite system, thus exhibiting a low CTE and a high glass transition temperature synergistic effect or Tg-less. Thus, the dimensional stability is improved. Further, the cured product containing the alkoxysilyl compound according to the present invention exhibits excellent flame retardancy.
In addition, the alkoxysilyl composition according to the present invention exhibits excellent adhesion with a metal film when chemically bonded to a chemically treated metal film, for example, a copper foil or the like, and is chemically bonded to a -OH group or the like on a metal surface by a metal surface treatment.
Hereinafter, an alkoxysilyl compound, an alkoxysilyl composition, a cured product, a use thereof, and a method for producing an alkoxysilyl compound provided in an embodiment of the present invention will be described in detail.
1. Alkoxysilyl compound
According to one embodiment of the present invention, there is provided an alkoxysilyl compound having at least two alkoxysilyl groups selected from the group consisting of the following formulas AI to II.
Substituents a and b of the above formulas AI to DI may be the following formula S1 or S2; hydrogen or an alkenyl group and the substituents c to f are selected from the group consisting of hydrogen, an alkyl group, an alkenyl group, aryl (aryl) can group, in the formula AI Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3) 2 -, -S- or -SO 2 -, and
And the remainder may be hydrogen, an alkyl group, an alkenyl group or an aryl group, and in the formula (HI), M is -CH 2 - and, C1-C10 alkyl group in straight or branched chain wherein the formula II is in the meta position of the oxygen -, -C (CH 3) 2 -, -C (CF 3) 2 -, -S- or -SO 2 . ≪ / RTI >
[Formula (S1)
- (CH 2 ) z -SiR 1 R 2 R 3
≪ RTI ID = 0.0 &
-CONH (CH 2 ) z -SiR 1 R 2 R 3
(In the formulas (S1) and (S2), R 1 to R 3 Is an alkyl group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, the alkyl group and the alkoxy group are linear or branched, and z is an integer of 3 to 10.)
As used herein, 'alkoxy' is a monovalent group that is -OR (R is alkyl), which may be linear or branched, cyclic or acyclic and may contain an N, O, S, or P heteroatom Or not.
As used herein, 'alkyl' refers to a monovalent hydrocarbon group having from 1 to 10 carbon atoms, which may be linear or branched, cyclic or acyclic, and may be N, O, S, or And may or may not have a P heteroatom.
As used herein, " alkenyl " refers to an alkyl group having one or more double carbon-carbon bonds, which may be linear or branched, cyclic or acyclic and may be N, O, S, And may or may not have an atom. Although not particularly limited, the number of carbon atoms may be C3 to C10, and - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10), which will be described later, may be included in the alkenyl.
As used herein, the term "aryl" refers to a residue obtained by removing one hydrogen atom from the nucleus of an aromatic hydrocarbon, and is not particularly limited. However, the number of carbon atoms may be C6-C30 and may be monocyclic or polycyclic have.
2. Alkoxysilyl compositions
According to still another embodiment of the present invention, there is provided a composition comprising at least one alkoxysilyl compound selected from the group consisting of the formulas AI to II according to any of the embodiments of the present invention.
Any of the compositions provided in the present invention can be used for electronic materials such as, but not limited to, semiconductor substrates, sealing materials (packaging materials), films, electronic parts applications such as printed wiring boards, adhesives, paints, And the like. Further, any of the compositions provided in the present invention may be a curable composition comprising a curable composition and / or an inorganic material.
The alkoxysilyl compound according to any of the above-mentioned and below-described embodiments of the present invention includes at least one alkoxysilyl compound selected from the group consisting of the above formulas AI to II provided by any embodiment of the present invention , Or alkoxysilyl compound of the present invention), it is understood that alkoxysilyl compositions of any kind and / or combination known in the art are included, and the catalyst constituting the alkoxysilyl composition, The kind of the inorganic material (filler) (for example, inorganic particles and / or fibers) and other additives and the blending ratio are not limited.
Further, according to one embodiment of the present invention, at least one kind of alkoxysilyl compound and inorganic material (filler) selected from the group consisting of the above formulas AI to II according to any embodiment of the present invention (for example, (Hereinafter, referred to as a " composite composition ") comprising the particles and / or fibers. As long as the composite composition contains at least one alkoxysilyl compound selected from the group consisting of the above formulas AI to II and a filler, It is understood that alkoxysilyl compositions of any kind and / or combination are included, and the type and proportion of the catalyst constituting the alkoxysilyl composition, the inorganic material (filler) (e.g., inorganic particles and / or fibers) But is not limited to.
The composite composition as well as the composition of any of the embodiments of the present invention described above and below may further contain inorganic particles and / or fibers as fillers which are inorganic materials.
As the inorganic particles, any inorganic particles known to be used for reducing the coefficient of thermal expansion of the organic resin can be used, including, but not limited to, silica (including fused silica and crystalline silica), zirconia, At least one metal oxide selected from the group consisting of titania, alumina, silicon nitride and aluminum nitride, and at least one metal oxide selected from the group consisting of T-10 type silsesquioxane, ladder type silsesquioxane, and cage type silsesquioxane At least one species selected from the group can be used. The inorganic particles may be used alone or as a mixture of two or more kinds.
When a particularly large amount of inorganic particles are blended, it is preferable to use fused silica. The fused silica can be used either in a crushed or spherical form, but it is preferable to use a spherical one in order to increase the blending amount of the fused silica and to suppress the increase of the melt viscosity of the molding material.
The inorganic particles include, but are not limited to, inorganic particles having a particle size of 0.5 nm to several tens of 탆 (for example, 50 탆 to 100 탆) in consideration of the use of the composite, specifically, the dispersibility of inorganic particles, Particles may be used. Since the inorganic particles are dispersed in the epoxy compound, it is preferable that the inorganic particles having the above-mentioned size are used together due to the difference in dispersibility depending on the particle size. In addition, in order to increase the blending amount of the inorganic particles, it is preferable to blend the inorganic particles with a wider particle distribution.
In the alkoxysilyl compound according to an embodiment of the present invention, the inorganic particles may be appropriately added to the alkoxysilyl compound according to the reduction of the CTE of the alkoxysilyl complex and the appropriate viscosity required for application, Such as from 5 wt% to 90 wt%, such as from 10 wt% to 90 wt%, such as from 30 wt% to 95 wt%, for example, based on the total solids of the alkoxysilyl composition, For example, from 30 wt% to 90 wt%, for example, from 5 wt% to 60 wt%, for example, from 10 wt% to 50 wt%.
More specifically, for example, in the case where the alkoxysilyl composition is used as a semiconductor encapsulant or the like, the content of the inorganic particles is not particularly limited, but the total amount of the alkoxysilyl composition, for example, For example, 30 wt% to 95 wt%, for example, 30 wt% to 90 wt%, based on the solid content. As an example, when the alkoxysilyl composition is used as a semiconductor substrate or the like, the content of the inorganic particles may be, for example, 5 wt% to 60 wt% based on the total solid content of the alkoxysilyl composition, %, For example, 10 wt% to 50 wt%.
On the other hand, when the fibers are used as an inorganic material, since the fibers are compounded in such a manner that the alkoxysilyl compound is wetted mainly on the fibers, the size of the fibers and the like are not particularly limited and fibers of any kind and size generally used in this technical field Can be used.
As the fiber, although not limited thereto, any conventional fiber used for improving the physical properties of the conventional organic resin cured product can be used. Specifically, glass fiber, organic fiber or a mixture thereof can be used. In addition, the term " glass fiber " as used herein is used in the meaning including not only glass fiber but also glass fiber fabric, glass fiber nonwoven fabric and the like. Examples of the glass fiber include glass fibers such as E glass fiber, T glass fiber, S glass fiber, NE glass fiber, D glass fiber and quartz glass fiber, and examples thereof include E or T And glass fibers. Examples of the organic fiber include, but are not limited to, liquid crystal polyester fibers, polyethylene terephthalate fibers, wholly aromatic fibers, polybenzoxazole fibers, nylon fibers, polyethylene naphthalate fibers, polypropylene fibers, polyethersulfone fibers, At least one kind selected from the group consisting of lidene fluoride fibers, polyethylene sulfide fibers and polyether ether ketone fibers may be used alone or in combination of two or more.
When fibers are used as fillers in any of the alkoxysilyl compositions according to the present invention, the content of fibers may be from 10 wt% to 90 wt%, for example from 30 wt% to 70 wt%, relative to the total solids content of the alkoxysilyl composition, , 35 wt% to 65 wt%. On the other hand, in an alkoxysilyl composition containing fibers, when the solid portion excluding the fibers is referred to as a resin component, in an alkoxysilyl composition containing fibers, the amount other than the fiber is an amount of the resin component. Thus, the resin content may be from 10 wt% to 90 wt%, for example from 30 wt% to 70 wt%, and for example from 35 wt% to 65 wt%. The content of the fibers in the above range is preferable from the viewpoint of heat resistance improvement and processability. The total solids content of the alkoxysilyl composition refers to the sum of the weights of the constituents of the alkoxysilyl composition excluding the solvent and other liquid substances in the components constituting the alkoxysilyl composition.
Furthermore, any alkoxysilyl compositions containing such fibers may further comprise inorganic particles, if desired. The inorganic particles may be blended in an amount ranging from 1 wt% to 70 wt%, based on the weight of the total resin content, in consideration of physical properties and fairness. At this time, the kind of the inorganic particles that can be used is not particularly limited, and any inorganic particles known in this technical field may be used. For example, the kind of the inorganic particles described above may be used.
According to another embodiment of the present invention, at least one alkoxysilyl compound and alkoxysilyl group reaction catalyst (hereinafter, referred to as 'reaction catalyst') selected from the group consisting of the above formulas AI to II according to any of the above- (Hereinafter referred to as a " reaction catalyst-containing composition "). The reaction-catalyst-containing composition is also understood to include alkoxysilyl compositions of any kind and / or combination, so long as it comprises at least one alkoxysilyl compound selected from the group consisting of the above formulas AI to II and a reaction catalyst, The type and proportion of the catalyst constituting the alkoxysilyl composition, the inorganic material (filler) (e.g., inorganic particles and / or fibers) and other additives are not limited.
The alkoxysilyl group-containing catalyst included in the composition according to any embodiment of the present invention includes, but is not limited to, at least one inorganic acid selected from the group consisting of nitric acid, sulfuric acid, hydrochloric acid, acetic acid, and phosphoric acid; ammonia; KOH; NH 4 OH; Amine; Metal alkoxide metal oxides; Metal organic acid salts; And a halide (e.g., dibutyltin dilaurate, and / or a tin salt of octylic acid, etc.) may be used. The blending amount of the alkoxysilyl group-containing catalyst is not particularly limited, but may include 0.01 phr to 10 phr of the alkoxysilyl group-containing catalyst for the alkoxysilyl compound.
To improve the efficiency of the alkoxysilyl group-containing catalyst, water may be further included in the composition including the alkoxysilyl group-containing catalyst. The amount of water is not particularly limited, but may be 0.01 to 100 equivalents of water based on 1 equivalent of the alkoxysilyl group.
Further, in this technical field, alkoxysilyl compositions, cured products and / or composites may be used together with various kinds of common epoxy compounds, depending on their applications and / or applications. Therefore, in the alkoxysilyl compositions according to any of the above-mentioned and later-described embodiments of the present invention, at least one alkoxysilyl compound selected from the group consisting of the above formulas AI to II according to any embodiment of the present invention, May also include any kind of epoxy compound known in the art (hereinafter, also referred to as a 'conventional epoxy compound').
The conventional epoxy compound is not particularly limited and may be any epoxy compound known in the art. For example, a glycidyl ether-based epoxy compound, a glycidyl-based epoxy compound, a glycidylamine-based epoxy compound , A glycidyl ester-based epoxy compound, a rubber-modified epoxy compound, an aliphatic polyglycidyl-based epoxy compound, and an aliphatic glycidylamine-based epoxy compound. Further, the conventional epoxy compound may have a core structure such as bisphenol A, bisphenol F, bisphenol S, biphenyl, naphthalene, benzene, thiodiphenol, fluorene, anthracene, isocyanurate, triphenylmethane, Glycidyl ether-based epoxy compounds having 1,2,4-tetraphenylmethane, 1,2,2-tetraphenylethane, tetraphenylmethane, 4.4'-diaminodiphenylmethane, aminophenocycloaliphatic or novolac units, glycidyl- A glycidyl ester-based epoxy compound, a rubber-modified epoxy compound, an aliphatic polyglycidyl-based epoxy compound, and an aliphatic glycidylamine-based epoxy compound.
For example, the conventional epoxy compound may include a glycidyl ether-based epoxy compound, a glycidyl-based epoxy compound, a glycidyl ether compound, a glycidyl ether-based epoxy compound, or a glycidyl ether-based epoxy compound having a core structure having bisphenol A, bisphenol F, bisphenol S, biphenyl, naphthalene, At least one member selected from the group consisting of amine-based epoxy compounds, glycidyl ester-based epoxy compounds, rubber-modified epoxy compounds, aliphatic polyglycidyl-based epoxy compounds and aliphatic glycidylamine-based epoxy compounds.
For example, but not by way of limitation, any alkoxysilyl composition according to one embodiment of the present invention may comprise from 1 to 99 wt% of an alkoxysilyl compound according to any embodiment of the present invention, based on the total weight of the alkoxysilyl compound, 1 to 99 wt% of an epoxy compound; For example, 10 to 90 wt% of the alkoxysilyl compound of the present invention and 10 to 90 wt% of a conventional epoxy compound; For example, 30 to 99 wt% of the alkoxysilyl compound of the present invention and 1 to 70 wt% of a conventional epoxy compound, such as 50 to 99 wt% of the alkoxysilyl compound of the present invention and 1 to 50 wt% of a conventional epoxy compound, For example, less than 10 to 100 wt% of the alkoxysilyl compounds of the present invention and more than 0 to 90 wt% of conventional epoxy compounds; For example, less than 30 to 100 wt% alkoxysilyl compounds of the present invention and more than 0 to 70 wt% of conventional epoxy compounds; For example, the alkoxysilyl compound of the present invention may contain less than 50 to 100 wt%, and more than 0 to 50 wt% of conventional epoxy compounds.
The alkoxysilyl composition containing the epoxy compound may further include a curing agent. As the curing agent, any curing agent generally known as a curing agent for an epoxy compound may be used, and thus, for example, Amine-based resins, phenol-based resins, acid anhydride-based resins, and the like.
More specifically, although not limited thereto, as the amine-based curing agent, aliphatic amines, alicyclic amines, aromatic amines, other amines and modified polyamines can be used, and amine compounds containing two or more primary amine groups can be used. Specific examples of the amine curing agent include 4,4'-methylenedianiline (diamino diphenyl methane, DAM or DDM), diamino diphenyl sulfone (diamino diphenyl sulfone) DDS), m-phenylenediamine, diethylenetriamine (DETA), diethylene tetramine, triethylene tetramine (Triethylene tetramine), and the like. Tetramine, TETA), m-xylenediamine (MXDA), methanediamine (MDA), N, N'-Diethylenediamine (N, N'-DEDA) At least one aliphatic amine selected from the group consisting of ethylene tetramethylenetetraamine, ethylene tetramethylenetetramine, tetraethylenepentaamine (TEPA), and hexamethylenediamine, isophorone diamine (IPDI), N-aminoethyl piperazine , AEP), bis (4- One or more alicyclic amines selected from the group consisting of bis (4-amino-3-methylcyclohexyl) methane, Larominc 260), other amines such as dicyandiamide (DICY) , Epoxides, and the like.
Examples of the phenolic curing agent include, but are not limited to, phenol novolac resins, cresol novolac resins, bisphenol A novolac resins, xylenol novolac resins, triphenyl novolac resins, biphenyl novolak resins, dicyclopentadiene resins Novolac resins, phenol p-xylene, naphthalene-based phenol novolak resins, and triazine-based compounds.
Examples of the acid anhydride-based curing agent include, but are not limited to, aliphatic anhydrides such as dodecenyl succinic anhydride (DDSA) and poly azelaic poly anhydride, hexahydrophthalic anhydride Alicyclic anhydrides such as hexahydrophthalic anhydride (HHPA), methyl tetrahydrophthalic anhydride (MeTHPA), methylnadic anhydride (MNA), etc., trimellitic anhydride , Tetrabromophthalic anhydride (TBPA), tetrabromophthalic anhydride (TMA), pyromellitic acid dianhydride (PMDA), benzophenonetetracarboxylic dianhydride (BTDA) Halogen-based anhydrides such as chlorendic anhydride and the like Water and the like.
Generally, the degree of curing of the epoxy composite can be controlled by the degree of reaction between the curing agent and the epoxy group, and the content of the curing agent can be controlled based on the concentration of the epoxy group of the epoxy compound according to the desired degree of curing. For example, when an amine curing agent is used, the content of the curing agent is controlled so that the epoxy equivalent / amine equivalent ratio is 0.5 to 2.0 and equivalence ratio is, for example, 0.8 to 1.5 in the equivalent reaction of the amine curing agent and the epoxy group Is preferably used.
Although the amount of the curing agent is described taking the case of the amine-based curing agent as an example, any of the curing agents which can be used for curing the phenol-based curing agent, the acid anhydride-based curing agent and the epoxy compound not separately described in this specification, Can be suitably used in a stoichiometric amount according to the chemical reaction formula of the epoxy functional group and the reactive functional group of the curing agent based on the total epoxy group concentration in the alkoxysilyl composition.
Any curing accelerator (catalyst) may be further included as needed to facilitate the epoxy curing reaction described above. As the curing accelerator (catalyst), any catalyst which is generally known in the art for curing epoxy compositions can be used, including, but not limited to, imidazole, tertiary amine, A curing accelerator such as a quaternary ammonium-based, organic acid salt-based, Lewis acid, or phosphorus-based compound may be used.
More specifically, for example, there may be mentioned 2-methylimidazole (2MZ), 2-undecylimidazole, 2-ethyl-4-methylimidazole (2E4M) 2-cyanoethyl) -2-alkyl imidazole, 2-heptadecylimidazole (2HDI); Tertiary amine compounds such as benzyl dimethyl amine (BDMA), trisdimethylaminomethyl phenol (DMP-30) and triethylenediamine; Quaternary ammonium salts such as tetrabutylammonium bromide; Organic acid salts of diazabicyclo undecene (DBU) or DBU; Triphenylphosphine, a phosphoric acid ester of a phosphorus compound such as, BF 3 - may be made of Lewis acid such as, such as monoethylamine (BF 3 -MEA), thus not limited. These curing accelerators may be those which have been latent by their microcapsule coating and complex formation. These may be used alone depending on the curing conditions, or two or more kinds may be used in combination.
The blending amount of the curing accelerator is not particularly limited and may be blended in an amount generally used in this technical field. For example, it may be 0.1 to 10 phr (parts per hundred resin, parts by weight per 100 parts by weight of the epoxy compound), for example, 0.2 to 5 phr for the epoxy compound. The curing accelerator is preferably used in the above-mentioned contents in terms of the curing reaction promoting effect and the curing reaction rate control. By using the above curing accelerator in the above amount range, it is possible to accelerate curing and improve the throughput of the work.
The alkoxysilyl composition may be a releasing agent, a surface treatment agent, a flame retardant, a plasticizer, an antimicrobial agent, a leveling agent, a defoaming agent, a colorant, a stabilizer, a couple, or the like, which are conventionally compounded for controlling physical properties of the alkoxysilyl composition, Other additives such as a lixing agent, a viscosity adjusting agent, a diluent and the like may also be blended as required.
As described above, the term 'alkoxysilyl composition' as used herein refers to not only the alkoxysilyl compound of the present invention but also other components constituting the alkoxysilyl composition such as a catalyst, an inorganic material (filler) (For example, inorganic particles and / or fibers), other conventional epoxy compounds, and other additives that are blended as needed in the art, other than a solvent, and usually the solvent in the alkoxysilyl composition is an alkoxy The viscosity and the solids content of the alkoxysilyl composition may be arbitrarily adjusted in consideration of the processability of the silyl composition and the like.
Any of the alkoxysilyl compositions provided in any of the above embodiments of the present invention can be used for electronic materials. Although the electronic material is not limited to this, for example, a substrate for a semiconductor, a film, a prepreg, or a laminate in which a metal layer is disposed on a base layer made of the composition of the present invention, a substrate, a sealing material (packaging material) , A build-up substrate, and electronic parts such as a printed wiring board. It can also be applied to various applications such as adhesives, paints, and composite materials. According to another embodiment of the present invention, there is provided an electronic material comprising or consisting of any composition comprising the alkoxysilyl compound of the present invention. Furthermore, a semiconductor device comprising or consisting of the electronic material is also provided. Specifically, the semiconductor device is a semiconductor device including a semiconductor device and / or a semiconductor packaging material including (for example, mounting a semiconductor element) a printed wiring board comprising or consisting of a composition comprising the alkoxysilyl compound of the present invention . Also provided is a cured product, adhesive, paint or composite material comprising or consisting of any of the alkoxysilyl compositions provided in any of the embodiments of the present invention.
According to another embodiment of the present invention, there is provided a cured product comprising or consisting of the alkoxysilyl composition provided in any of the above-mentioned embodiments of the present invention. The alkoxysilyl composition provided in any of the above embodiments of the present invention is used as a cured product when it is actually applied, for example, when it is applied to an electronic material or the like. In this technical field, an alkoxysilyl compound and a filler Are generally referred to as complexes.
The alkoxysilyl compound provided in the embodiment of the present invention described above exhibits excellent heat resistance in a composite and / or flame retardancy in a cured product.
Specifically, the composite may have a low CTE, e.g., less than or equal to 15 ppm / C, such as less than or equal to 12 ppm / C, such as less than or equal to 10 ppm / C, such as less than or equal to 8 ppm / Lt; 0 > C or less, for example, 4 ppm / [deg.] C or less. The smaller the CTE value, the more excellent the physical properties, and the lower limit value of CTE is not particularly limited.
For example, any of the alkoxysilyl compounds according to the present invention, glass fibers such as E-glass and / or T-glass glass fibers as the inorganic material, and a resin content of 15 wt% to 60 wt% For example, not more than 10 ppm / ° C, such as not more than 8 ppm / ° C, such as not more than 6 ppm / ° C, for example, not more than 4 ppm / ° C Lt; / RTI >
For example, the composite containing 60 to 80 wt%, for example, 70 to 80 wt% of any alkoxysilyl compound and the inorganic particles, for example, silica particles, as the inorganic material according to the present invention is 20 ppm / For example less than or equal to 10 ppm / ° C, such as less than or equal to 8 ppm / ° C, such as less than or equal to 6 ppm / ° C, for example less than or equal to 4 ppm /
The composite according to the present invention (a cured product containing an inorganic material) has a Tg higher than 100 캜, for example, 130 캜 or higher, for example, 250 캜 or higher, or Tg-less. The larger the Tg value is, the better the physical properties are, and the upper limit value of Tg is not particularly limited.
On the other hand, the cured product of the alkoxysilyl compound itself (a cured product containing no inorganic material) according to the present invention has a CTE of 50 ppm / ° C to 150 ppm / ° C.
In this specification, ranges of values are meant to include any lower range between ranges and all numbers falling within that range, as well as lower and upper limits of range, unless specifically stated otherwise. For example, C1 to C10 are understood to include all of C1, C2, C3, C4, C5, C6, C7, C8, C9, Further, it is understood that the lower limit value or the upper limit value of the numerical range is not defined, it is understood that the smaller or larger the numerical value is, the more preferable it is, and particularly the limit thereof is not defined, and it includes any value. For example, a CTE of 4 ppm / ° C or less is understood to include all values in the range of 4, 3.5, 3, 2.7, 2, 1.4, 1, 0.5 ppm /
3. Method for producing alkoxysilyl compound
The alkoxysilyl compounds of the above formulas AI to II according to the present invention can be prepared by the following method, and each method will be described in detail.
end. A method for producing an alkoxysilyl compound having at least two substituents of -CONH (CH 2 ) z -SiR 1 R 2 R 3 and an unreacted substituent (Method 1)
The alkoxysilyl compounds of the formulas AI to II having substituents of two or more -CONH (CH 2 ) z -SiR 1 R 2 R 3 and unreacted substituents can be prepared by reacting a starting material of any one of the following formulas (AS) to Can be obtained by reacting an isocyanate-based alkoxy-silane in the presence of an optional base and any solvent.
[Starting material]
(A substituent and k and l in the formula AS to DS is hydrogen, m to p are hydrogen, an alkyl group, an alkenyl (alkenyl) group, or an aryl (aryl) AS Y in the formula is -CH 2 -., -C ( CH 3) 2 -, -C ( CF 3) 2 -, -S- or -SO 2 -, and
Formula ES to a more than one of the substituents of q to t IS is hydrogen and the other is alkyl, can be an alkenyl (alkenyl) group, or an aryl (aryl), in the formula HS M is -CH 2 -, -C ( CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -, and the formula IS may be substituted with a linear or branched C 1 -
≪ RTI ID =
OCN- (CH 2 ) z -SiR 1 R 2 R 3
Wherein at least one of R 1 to R 3 is a C 1 -
[Final product]
(Substituents a and b of the above formulas AI to DI are represented by the following formula (S2), substituents c to f may be hydrogen, an alkyl group, an alkenyl group or an aryl group,
In the formula (AI), Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -
At least two of the substituents g to j in the above formulas EI to II are represented by the following formula (S2), S2 is at least two hydrogen atoms of the above formulas (ES) to (IS), and the remainder is hydrogen, an alkyl group, an alkenyl group, (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -, and in the formula (II), M is -CH 2 - Lt; / RTI > may be substituted with a straight or branched C1-C10 alkyl group at the meta position of the oxygen.
≪ RTI ID = 0.0 &
-CONH (CH 2 ) z -SiR 1 R 2 R 3
(In the above formula (S2), R 1 to R 3 Is an alkyl group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, the alkyl group and the alkoxy group are linear or branched, and z is an integer of 3 to 10.)
In the
According to the
Examples of the base usable herein include, but are not limited to, K 2 CO 3 , Na 2 CO 3 , KHCO 3 , NaHCO 3 , triethylamine, and diisopropylethylamine. These bases may be used singly or in combination of two or more. It is preferable in terms of reaction efficiency that the base is used in an amount of 0.1 to 5 equivalents based on 1 equivalent of the hydroxy group of the starting material.
The solvent in the above reaction may be optionally used. For example, if the viscosity of the reactant is suitable for the reaction to proceed at the reaction temperature without additional solvent in the first step reaction, the solvent may not be used. That is, if the viscosity of the reactant is lowered to such an extent that the mixing and stirring of the reactants can proceed smoothly without a solvent, a separate solvent is not required, which can be easily determined by those skilled in the art. When a solvent is used, any organic solvent may be used as long as it is capable of dissolving the reactant well and can be easily removed after the reaction without any adverse effect on the reaction, and thus, for example, , Tetra hydrofuran (THF), methyl ethyl ketone (MEK), dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), and methylene chloride (MC). These solvents may be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited and may be appropriately selected so that the reactant is sufficiently dissolved and does not adversely affect the reaction, and a person skilled in the art can appropriately select it.
I. Method for producing an alkoxysilyl compound having at least two substituents of - (CH 2 ) z -SiR 1 R 2 R 3 and an unreacted substituent (Method 2)
Substituents of two or more - (CH 2 ) z -SiR 1 R 2 R 3 and an alkoxysilyl compound having an unreacted substituent may be prepared by reacting a starting material of any of the following formulas (AS) to ( II ) with an alkenyl compound of In the presence of a base and an optional solvent to obtain an intermediate (1) of any one of the following formulas (A1) to (I1); And a step (1-2) of reacting the intermediate product (1) with an alkoxy silane of the formula (M3) in the presence of a metal catalyst and optionally in the presence of a solvent to obtain an end product of any one of the following formulas AI to II .
[Starting material]
(A substituent and k and l in the formula AS to DS is hydrogen, m to p are hydrogen, an alkyl group, an alkenyl (alkenyl) group, or an aryl (aryl) AS Y in the formula is -CH 2 -., -C ( CH 3) 2 -, -C ( CF 3) 2 -, -S- or -SO 2 -, and
Formula ES to a more than one of the substituents of q to t IS is hydrogen and the other is alkyl, can be an alkenyl (alkenyl) group, or an aryl (aryl), in the formula HS M is -CH 2 -, -C ( CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -, and the formula IS may be substituted with a linear or branched C 1 -
(M2)
X- (CH 2) z-2 -CH = CH 2
(Wherein, X is Cl, Br or halides of I, -O-SO 2 -CH 3 , -O-SO 2 -CF 3, -O-SO 2 -C 6 H 4 -CF 3, -O-SO 2 -C 6 H 4 -NO 2 Or -O-SO 2 -C 6 H 4 -CH 3 , and z is an integer from 3 to 10.)
[Intermediate (1)]
Substituents k1 and l1 in the above formulas A1 to D1 are - (CH 2 ) Z-2 CH═CH 2 (Z is an integer of 3 to 10) and substituents m 1 to
Formula E1 to a substituent two or more of q1 to t1 of I1 is - (CH 2) Z-2 CH = CH 2 (Z 3 to 10 of an integer), and the - (CH 2) Z-2 CH = CH 2 (Z is an integer of 3 to 10) is the hydrogen of the above formula (ES to IS), and the remainder may be hydrogen, an alkyl group, an alkenyl group or an aryl group,
In Formula H1 M is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3) 2 -, -S- or -SO 2 -, and wherein the formula I1 is a straight-chain or at the meta position of the oxygen And may be substituted with a branched C1-C10 alkyl group.
[Formula M3]
HSiR 1 R 2 R 3
Wherein at least one of R 1 to R 3 is a C 1 -
[Final product]
(Substituents a and b of the above formulas AI to DI are represented by the following formula S1, and substituents c to f may be the formula S1, hydrogen, an alkyl group, an alkenyl group, or an aryl group,
In the formula (AI), Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -
At least two of the substituents g to j in the above formulas (EI) to (II) are represented by the following formula (S1), and the remainder may be hydrogen, an alkyl group, an alkenyl group, or an aryl group,
Wherein M is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 - in the formula HI, May be substituted with a branched C1-C10 alkyl group. )
[Formula (S1)
- (CH 2 ) z -SiR 1 R 2 R 3
(In the formula (S1), R 1 to R 3 Is an alkoxy group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group are branched or branched, and z is an integer of 3 to 10.)
In the above step 1-1, the starting material of any one of the above formulas (AS) to (IS) is reacted with the alkenyl compound of the above formula (M2) to prepare a starting material in which the hydroxy group is - (CH 2 ) Z-2 CH═CH 2 Is an integer of 3 to 10).
In the step 1-1, the - (CH 2 ) Z-2 CH = CH 2 (Z is an integer in the range of 3 to 10) of the alkenyl compound of the formula (M2) relative to 1 equivalent of the hydroxy group of the starting material is 0.5 to 10 And the reaction is carried out at 15 to 100 캜 for 1 to 120 hours to obtain an intermediate (1).
Examples of the base usable in the above step 1-1 include, but are not limited to, KOH, NaOH, K 2 CO 3 , Na 2 CO 3 , KHCO 3 , NaHCO 3 , NaH, pyridine, triethylamine, And diisopropylethylamine. These bases may be used singly or in combination of two or more. It is preferable in terms of reaction efficiency that the base is used in an amount of 0.1 to 5 equivalents based on 1 equivalent of the hydroxy group of the starting material.
In the step 1-1, the solvent may be optionally used. If the viscosity of the reactant at the reaction temperature is suitable for the reaction to proceed without any solvent, a solvent may not be used. That is, if the viscosity of the reactant is lowered to such an extent that the mixing and stirring of the reactants can proceed smoothly without a solvent, a separate solvent is not required, which can be easily determined by those skilled in the art. When a solvent is used, any organic solvent may be used as long as it is capable of dissolving the reactant well and can be easily removed after the reaction without any adverse effect on the reaction, and thus, for example, (Methyl ethyl ketone), DMF (dimethyl formamide), DMSO (dimethyl sulfoxide), methylene chloride (MC), H 2 O or alcohols (methanol, ethanol) Can be used. These solvents may be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited and may be appropriately selected so that the reactant is sufficiently dissolved and does not adversely affect the reaction, and a person skilled in the art can appropriately select it.
In the step 1-2, the intermediate product (1) and the alkoxy silane of the formula (M3) are reacted in the presence of a metal catalyst and optionally in the presence of a solvent to obtain an intermediate compound (1) Lt; RTI ID = 0.0 > II. ≪ / RTI > The alkenyl group of the intermediate product (1) includes not only the alkenyl group present in the starting material but also - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) substituted by the above formula do. Since the alkenyl group of the intermediate product (1) and the alkoxysilane react with each other in an equivalent ratio according to the stoichiometry in the step 1-2, the alkoxy silane of the formula M3 is reacted with the alkenyl group of the intermediate product (1) 5 equivalents, and the reaction is carried out at 15 to 120 DEG C for 1 to 72 hours.
As the metal catalyst in the first-step reaction, for example, platinum catalyst of PtO 2 or H 2 PtCl 6 (chloroplatinic acid) may be used. From the viewpoint of the reaction efficiency, it is preferable to use the platinum catalyst in an amount of 0.005 to 0.05 equivalent based on 1 equivalent of the alkenyl group of the intermediate product (1).
In the first-step reaction, the solvent can be optionally used. For example, if the viscosity of the reactant at the reaction temperature is suitable for the reaction to proceed without any additional solvent in the first to second reaction steps, the solvent may not be used. That is, if the viscosity of the reactant is lowered to such an extent that the mixing and stirring of the reactants can proceed smoothly without a solvent, a separate solvent is not required, which can be easily determined by those skilled in the art. When a solvent is used, any solvent can be used to dissolve the reactant well, and any aprotic solvent can be used as long as it can be easily removed after the reaction without any adverse effect on the reaction. But are not limited to, toluene, acetonitrile, tetrahydrofuran (THF), methyl ethyl ketone (MEK), dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), methylene chloride have. These solvents may be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited and may be appropriately selected so that the reactant is sufficiently dissolved and does not adversely affect the reaction, and a person skilled in the art can appropriately select it.
All. A method for producing an alkoxysilyl compound having at least one substituent of -CONH (CH 2 ) z -SiR 1 R 2 R 3 and at least one substituent and unreacted substituent of - (CH 2 ) z -SiR 1 R 2 R 3 (Method 3)
The alkoxysilyl compound having at least one substituent of two or more -CONH (CH 2 ) z -SiR 1 R 2 R 3 and at least one substituent and unreacted substituent of - (CH 2 ) z -SiR 1 R 2 R 3 can be prepared by the method In addition to any one of the formulas EI to II, which may have a substituent of two or more -CONH (CH 2 ) z -SiR 1 R 2 R 3 and an alkoxysilyl compound having an unreacted substituent, (CH 2 ) z -SiR 1 R 2 R 3 .
Specifically, among the alkoxysilyl compounds prepared in the
(M2)
X- (CH 2) z-2 -CH = CH 2
(Wherein, X is Cl, Br or halides of I, -O-SO 2 -CH 3 , -O-SO 2 -CF 3, -O-SO 2 -C 6 H 4 -CF 3, -O-SO 2 -C 6 H 4 -NO 2 Or -O-SO 2 -C 6 H 4 -CH 3 , and z is an integer from 3 to 10.)
[Formula M3]
HSiR 1 R 2 R 3
(Wherein at least one of R 1 to R 3 is a C 1 -
[Formula (S1)
- (CH 2 ) z -SiR 1 R 2 R 3
(In the formula (S1), R 1 to R 3 Is an alkoxy group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group are branched or branched and z is an integer of 3 to 10.)
The first one of the hydroxy to the formula II EI to 1-3 stage, reacting the alkenyl compound of formula II EI to any one of the above general formula M2 having a hydroxy group, a group - (CH 2) Z-2 CH = CH 2 (Z is an integer of 3 to 10).
(CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) of the alkenyl compound of the formula (M2) per equivalent of the hydroxy group of any one of the formulas (EI) to (II) ) Is added in an amount of 0.5 to 10 equivalents, and the reaction is carried out at 15 to 100 ° C for 1 to 120 hours.
Examples of the base usable in the second step 1-3, without limitation, for example, KOH, NaOH, K 2 CO 3, Na 2 CO 3, KHCO 3, NaHCO 3, NaH, pyridine, triethylamine, And diisopropylethylamine. These bases may be used singly or in combination of two or more. It is preferable in terms of reaction efficiency that the base is used in an amount of 0.1 to 5 equivalents based on 1 equivalent of the hydroxy group of the starting material.
In the step 1-3, the solvent may be optionally used. If the viscosity of the reactant at the reaction temperature is suitable for the reaction to proceed without any solvent, a solvent may not be used. That is, if the viscosity of the reactant is lowered to such an extent that the mixing and stirring of the reactants can proceed smoothly without a solvent, a separate solvent is not required, which can be easily determined by those skilled in the art. When a solvent is used, any organic solvent may be used as long as it is capable of dissolving the reactant well and can be easily removed after the reaction without any adverse effect on the reaction, and thus, for example, (Methyl ethyl ketone), DMF (dimethyl formamide), DMSO (dimethyl sulfoxide), methylene chloride (MC), H 2 O or alcohols (methanol, ethanol) Can be used. These solvents may be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited and may be appropriately selected so that the reactant is sufficiently dissolved and does not adversely affect the reaction, and a person skilled in the art can appropriately select it.
(CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) substituted in the step 1-3 and the alkoxy silane of the formula M 3 are reacted with a metal catalyst by reacting in the presence of a solvent, wherein - (CH 2) z-2 CH = CH 2 is replaced by the formula S1 is (z is an integer of 3 to 10), at least two -CONH (CH 2) z -SiR 1 R 2 substituent and at least one of R 3 - can be obtained an alkoxysilyl compound having a (CH 2) z -SiR substituent of the 1 R 2 R 3 and unreacted substituents. In the step 1-4, - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) substituted in the step 1-3 is reacted with an alkoxysilane at an equivalent ratio according to stoichiometry, 1 to 5 equivalents of the alkoxysilane of Formula M3 is added to 1 equivalent of - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) substituted in Step 1-3, , And may be carried out at 15 캜 to 120 캜 for 1 to 72 hours.
As the metal catalyst in the first-step reaction, for example, PtO 2 or platinum catalyst of H 2 PtCl 6 (chloroplatinic acid) may be used. It is preferable that the platinum catalyst is used in an amount of 0.005 to 0.05 equivalent based on 1 equivalent of - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) substituted in the step 1-3 Do.
In the first-step reaction, the solvent can be optionally used as needed. For example, if the viscosity of the reactant is suitable for the reaction to proceed at the reaction temperature without additional solvent in step 1-4, the solvent may not be used. That is, if the viscosity of the reactant is lowered to such an extent that the mixing and stirring of the reactants can proceed smoothly without a solvent, a separate solvent is not required, which can be easily determined by those skilled in the art. When a solvent is used, any solvent can be used to dissolve the reactant well, and any aprotic solvent can be used as long as it can be easily removed after the reaction without any adverse effect on the reaction. But are not limited to, toluene, acetonitrile, tetrahydrofuran (THF), methyl ethyl ketone (MEK), dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), methylene chloride have. These solvents may be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited and may be appropriately selected so that the reactant is sufficiently dissolved and does not adversely affect the reaction, and a person skilled in the art can appropriately select it.
la. A process for producing an alkoxysilyl compound having at least one substituent of at least one (CH 2 ) z -SiR 1 R 2 R 3 and at least one substituent and unreacted substituent of -CONH (CH 2 ) z -SiR 1 R 2 R 3 ( Method 4)
The alkoxysilyl compound having at least one substituent of two or more - (CH 2 ) z -SiR 1 R 2 R 3 and at least one substituent of the -CONH (CH 2 ) z -SiR 1 R 2 R 3 and an unreacted substituent can be prepared by the method In addition to any one of the formulas EI to II which may have a substituent of two or more - (CH 2 ) z -SiR 1 R 2 R 3 prepared in 2 and a hydroxy group in the alkoxysilyl compound having an unreacted substituent, -CONH (CH 2 ) z -SiR 1 R 2 R 3 .
Specifically, among the alkoxysilyl compounds prepared in Method 2, any one of the formulas (EI) to (II) which may have a hydroxy group which is not substituted with an alkenyl group in the above-mentioned Step 1-1 and the isocyanate alkoxy- In the presence of a base and optionally in the presence of a solvent to obtain an alkoxysilyl compound in which the hydroxy group is substituted by the formula (S2).
≪ RTI ID =
OCN- (CH 2 ) z -SiR 1 R 2 R 3
Wherein at least one of R 1 to R 3 is a C 1 -
In Method 4, an alkoxysilyl compound is prepared by reacting the isocyanate-based alkoxy silane of Formula M1 in an amount of 1 to 5 equivalents based on 1 equivalent of the hydroxy group of any one of the formulas EI to II in the presence of an optional base and any solvent can do. Further, this reaction can be carried out at 15 캜 to 120 캜 for 1 to 72 hours.
According to the above method 4, the hydroxy group of any one of formulas (EI) to (II) is substituted with -CONH (CH 2 ) z -SiR 1 R 2 R 3 to form two or more (CH 2 ) z -SiR 1 R 2 R 3 And the remaining unreacted substituents having at least one substituent of -CONH (CH 2 ) z -SiR 1 R 2 R 3 and being optionally hydrogen, an alkyl group, an alkenyl group or an aryl group, Silyl compounds can be prepared.
Examples of usable bases include, but are not limited to, K 2 CO 3 , Na 2 CO 3 , KHCO 3 , NaHCO 3 , triethylamine, and diisopropylethylamine. These bases may be used singly or in combination of two or more. It is preferable in terms of reaction efficiency that the base is used in an amount of 0.1 to 5 equivalents based on 1 equivalent of the hydroxy group of the starting material.
The solvent in the above reaction may be optionally used. For example, if the viscosity of the reactant is suitable for the reaction to proceed at the reaction temperature without any solvent in the reaction, the solvent may not be used. That is, if the viscosity of the reactant is lowered to such an extent that the mixing and stirring of the reactants can proceed smoothly without a solvent, a separate solvent is not required, which can be easily determined by those skilled in the art. When a solvent is used, any organic solvent may be used as long as it is capable of dissolving the reactant well and can be easily removed after the reaction without any adverse effect on the reaction, and thus, for example, , Tetra hydrofuran (THF), methyl ethyl ketone (MEK), dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), and methylene chloride (MC). These solvents may be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited and may be appropriately selected so that the reactant is sufficiently dissolved and does not adversely affect the reaction, and a person skilled in the art can appropriately select it.
hemp. (CH 2 ) z -SiR 1 R 2 R 3 is substituted by 2 to 4 substituents selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, (Method 5) < RTI ID = 0.0 >
(CH 2 ) z -SiR 1 R 2 R 3 is alkenylated with starting materials (AS to DS) in which all the substituents are hydrogen, and the rearrangement reaction is carried out once , Realkenylated and linking a substituent of (CH 2 ) z -SiR 1 R 2 R 3 .
The Specifically, reacting an alkenyl compound of the formula M2, and any one of the starting materials of the formula AS to DS under any base and any solvent present hydroxy group - (CH 2) Z-2 CH = CH 2 To obtain an intermediate product (21) substituted with a halogen atom (Z is an integer of 3 to 10); A second step (2-2) of obtaining an intermediate product (22) having a hydroxy group by carrying out a rearrangement reaction with respect to the intermediate product (21); Reacting the intermediate product (22) with an alkenyl compound of the following formula (M2) in the presence of an optional base and any solvent to obtain a compound wherein the hydroxy group is - (CH 2 ) Z-2 CH = CH 2 To obtain an intermediate product (23) which is substituted with a halogen atom; And performing the step 2-4 of reacting the intermediate product (23) with an alkoxy silane of the formula (M3) in the presence of a metal catalyst and any solvent to obtain an end product of any one of the following formulas AI to DI: Can be obtained.
[Starting material]
(A substituent k to p of the above formula to AS DS is hydrogen, in formula AS Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3) 2 -, -S- or -SO 2 -.)
(M2)
X- (CH 2) z-2 -CH = CH 2
(Wherein, X is Cl, Br or halides of I, -O-SO 2 -CH 3 , -O-SO 2 -CF 3, -O-SO 2 -C 6 H 4 -CF 3, -O-SO 2 -C 6 H 4 -NO 2 or -O-SO 2 -C 6 H 4 -CH 3 , and z is an integer from 3 to 10.)
[Intermediate (21)]
(Substituent k1 and l1 of Formula A21 to D21 is - and (CH 2) Z-2 CH = CH 2 (Z is an integer of 3 to 10), m1 to p1 is hydrogen, in formula A21 Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -.
[Intermediate (22)]
(In the substituents k2 to p2 of the above formulas A22 to D22, any one of m2 and n2 and any of o2 and p2 is - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) and the other is hydrogen, in formula A22 Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3) 2 -, -S- or -SO 2 - a).
[Intermediate (23)]
(In the substituent k3 to p3 of Formula A23 to D23, k3; l3; m3 or any one of n3; any one, and o3 or p3 is - (CH 2) Z-2 CH = CH 2 (Z 3 to 10 is an integer), and the other is hydrogen, in formula A23 Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3) 2 -, -S- or -SO 2 - a. )
[Formula M3]
HSiR 1 R 2 R 3
(Wherein at least one of R 1 to R 3 is a C 1 -
[Final product]
(Wherein at least two of the substituents a to f of the formulas AI to DI have the following formula S1 and the rest are hydrogen or - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -.
[Formula (S1)
- (CH 2 ) z -SiR 1 R 2 R 3
(In the formula (S1), R 1 to R 3 Is an alkoxy group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group are branched or branched and z is an integer of 3 to 10.)
In the step 2-1, any one of the starting materials of the above formulas (AS) to (DS) wherein all the substituents are hydrogen is reacted with the alkenyl compound of the above formula (M2) in the presence of any base and any solvent to prepare a compound wherein the hydroxy group is - 2 ) an intermediate product (21) substituted with Z-2 CH = CH 2 (Z is an integer of 3 to 10) can be obtained.
(CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) of the alkenyl compound of the formula (M2) per equivalent of the hydroxy group of any one of the formulas (AS) to ) Is added in an amount of 0.5 to 10 equivalents, and the reaction is carried out at 15 to 100 ° C for 1 to 120 hours.
Examples of the base usable in the second step 2-1, without limitation, for example, KOH, NaOH, K 2 CO 3, Na 2 CO 3, KHCO 3, NaHCO 3, NaH, pyridine, triethylamine, And diisopropylethylamine. These bases may be used singly or in combination of two or more. It is preferable in terms of reaction efficiency that the base is used in an amount of 0.1 to 5 equivalents based on 1 equivalent of the hydroxy group of the starting material.
In the step 2-1, the solvent may be optionally used. If the viscosity of the reactant at the reaction temperature is suitable for the reaction to proceed without any solvent, a solvent may not be used. That is, if the viscosity of the reactant is lowered to such an extent that the mixing and stirring of the reactants can proceed smoothly without a solvent, a separate solvent is not required, which can be easily determined by those skilled in the art. When a solvent is used, any organic solvent may be used as long as it is capable of dissolving the reactant well and can be easily removed after the reaction without any adverse effect on the reaction, and thus, for example, (Methyl ethyl ketone), DMF (dimethyl formamide), DMSO (dimethyl sulfoxide), methylene chloride (MC), H 2 O or alcohols (methanol, ethanol) Can be used. These solvents may be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited and may be appropriately selected so that the reactant is sufficiently dissolved and does not adversely affect the reaction, and a person skilled in the art can appropriately select it.
Step 2-2 may be carried out in which the intermediate product 22 having a hydroxy group is obtained by performing a rearrangement reaction with respect to the alkenylated intermediate product 21 in the step 2-1.
Since the transfer reaction is a unimolecular reaction, there is no restriction on the equivalents. The reaction is carried out at 140 to 250 ° C for 1 to 200 hours, or at a temperature of 120 to 250 ° C for 1 to 1000 minutes ≪ / RTI >
The solvent may not be used if the viscosity of the reactant is suitable for the reaction to proceed as the temperature is increased during the transposition reaction. That is, if the viscosity of the reactant is lowered to such an extent that the mixing and stirring of the reactants can proceed smoothly without a solvent, a separate solvent is not required, which can be easily determined by those skilled in the art. However, it may be carried out in the presence of a solvent, if necessary, and is not particularly limited, but xylene, 1,2-dichlorobenzene, N, N-diethylaniline and the like can be used. The postponing reaction to be described later can be performed in the same manner as in the step 2-2.
In the step 2-3, the intermediate product (22) having the hydroxy group prepared in the step 2-2 and the alkenyl compound of the formula (M2) are reacted in the presence of an optional base and any solvent to form a hydroxy group An intermediate product (23) substituted with - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) can be obtained.
Step 2-3 is alkenylation of the intermediate product 22, and may be carried out under the same conditions as the alkenylation reaction performed in Step 2-1.
In the step 2-4, the intermediate product 23 in which the alkenylation has been performed in the step 2-3 is reacted with the alkoxy silane of the formula M3 in the presence of a metal catalyst and any solvent to obtain a final product of the following formulas AI to DI The alkoxysilyl compound having 2 to 4 substituents of (CH 2 ) z -SiR 1 R 2 R 3 can be obtained. In step (2-4), - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) substituted in step 2-3 is reacted with an alkoxysilane at an equivalent ratio according to stoichiometry, 1 to 5 equivalents of the alkoxysilane of Formula M3 is added to 1 equivalent of - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) substituted in Step 2-3, , And may be carried out at 15 캜 to 120 캜 for 1 to 72 hours.
The metal catalyst used in the step 2-4 may be, for example, PtO 2 or platinum catalyst of H 2 PtCl 6 (chloroplatinic acid). In view of the reaction efficiency, it is preferable to use the platinum catalyst in an amount of 0.005 to 0.05 equivalent based on 1 equivalent of the alkenyl group substituted in the step 1-3.
In the step 2-4, the solvent may optionally be used as required. For example, if the viscosity of the reactant at the reaction temperature is suitable for the reaction to proceed without additional solvent in step 2-4, the solvent may not be used. That is, if the viscosity of the reactant is lowered to such an extent that the mixing and stirring of the reactants can proceed smoothly without a solvent, a separate solvent is not required, which can be easily determined by those skilled in the art. When a solvent is used, any solvent can be used to dissolve the reactant well, and any aprotic solvent can be used as long as it can be easily removed after the reaction without any adverse effect on the reaction. But are not limited to, toluene, acetonitrile, tetrahydrofuran (THF), methyl ethyl ketone (MEK), dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), methylene chloride have. These solvents may be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited and may be appropriately selected so that the reactant is sufficiently dissolved and does not adversely affect the reaction, and a person skilled in the art can appropriately select it.
bar. Alkenyl substituent is biotinylated all the starting material (Formula AS to DS) hydrogen, and after performing once the seat shifting reaction, having two -CONH (CH 2) z -SiR substituents and alkenyl of 1 R 2 R 3 Method for producing alkoxysilyl compound (Method 6)
The alkoxysilyl compounds having two substituents and alkenyl groups of two -CONH (CH 2 ) z -SiR 1 R 2 R 3 are alkenylated with starting materials (AS to DS) wherein all substituents are hydrogen, (CH 2 ) z -SiR 1 R 2 R 3 .
Specifically, the intermediate product (22) obtained by subjecting the starting materials (AS to DS) in which all the substituents are hydrogen in the
[Intermediate (22)]
(In the substituents k2 to p2 of the above formulas A22 to D22, any one of m2 and n2 and any of o2 and p2 is - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) and the other is hydrogen, in formula A22 Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3) 2 -, -S- or -SO 2 - a).
≪ RTI ID =
OCN- (CH 2 ) z -SiR 1 R 2 R 3
Wherein at least one of R 1 to R 3 is a C 1 -
[Final product]
Substituents a and b of the formulas AI to DI are represented by the following formula (S2), and any one of c and d and either e or f is - (CH 2 ) Z-2 CH = CH 2 is an integer), and the other is hydrogen, in formula AI Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3) 2 -, -S- or -SO 2 - a).
≪ RTI ID = 0.0 &
-CONH (CH 2 ) z -SiR 1 R 2 R 3
(In the above formula (S2), R 1 to R 3 Is an alkoxy group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group are branched or branched and z is an integer of 3 to 10.)
In the step 2-5, an alkoxysilyl compound is reacted in an amount of 1 to 5 equivalents based on 1 equivalent of the hydroxy group of the intermediate product (22) in the presence of an optional base and any solvent so that an isocyanate- Can be manufactured. Further, this reaction can be carried out at 15 캜 to 120 캜 for 1 to 72 hours.
Examples of the base usable in step 2-5 include, but are not limited to, K 2 CO 3 , Na 2 CO 3 , KHCO 3 , NaHCO 3 , NaH, pyridine, triethylamine, diisopropylethyl Amines. These bases may be used singly or in combination of two or more. It is preferable in terms of reaction efficiency that the base is used in an amount of 0.1 to 5 equivalents based on 1 equivalent of the hydroxy group of the intermediate product (22).
In the step 2-5, the solvent may be optionally used. If the viscosity of the reactant at the reaction temperature is suitable for the reaction to proceed without any solvent, a solvent may not be used. That is, if the viscosity of the reactant is lowered to such an extent that the mixing and stirring of the reactants can proceed smoothly without a solvent, a separate solvent is not required, which can be easily determined by those skilled in the art. When a solvent is used, any organic solvent may be used as long as it is capable of dissolving the reactant well and can be easily removed after the reaction without any adverse effect on the reaction, and thus, for example, , Tetra hydrofuran (THF), methyl ethyl ketone (MEK), dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), and methylene chloride (MC). These solvents may be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited and may be appropriately selected so that the reactant is sufficiently dissolved and does not adversely affect the reaction, and a person skilled in the art can appropriately select it.
four. Alkenyl substituent is biotinylated all the starting material (Formula AS to DS) hydrogen, and after performing once the seat shifting reaction, 2 -CONH (CH 2) substituent and at least one or more of the z -SiR 1 R 2 R 3 - (CH 2 ) z -SiR 1 R 2 R 3 (Method 7) A method for producing an alkoxysilyl compound having a substituent of -
The alkoxysilyl compound having two substituents of -CONH (CH 2 ) z -SiR 1 R 2 R 3 and at least one substituent of - (CH 2 ) z -SiR 1 R 2 R 3 is the compound 2 -CONH (CH 2) z -SiR addition to the compound having an alkoxysilyl 1 R 2 R 3 substituent groups and alkenyl can be prepared by coupling a substituent (CH 2) z -SiR 1 R 2 R 3 .
Specifically, a method for producing the final product of any one of the following formulas AI to DI by reacting any one of the alkoxysilyl compounds prepared in the above method 6 with an alkoxy silane of the following formula M3 in the presence of a metal catalyst and any solvent, The alkoxysilyl compound is prepared.
[Formula M3]
HSiR 1 R 2 R 3
Wherein at least one of R 1 to R 3 is a C 1 -
[Final product]
Wherein any one of c and d, e and f is a group represented by the following formula (S1) and the remainder is hydrogen, and Y in the formula (AI) is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -.
[Formula (S1)
- (CH 2 ) z -SiR 1 R 2 R 3
≪ RTI ID = 0.0 &
-CONH (CH 2 ) z -SiR 1 R 2 R 3
(In the formulas (S1) and (S2), R 1 to R 3 Is an alkoxy group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group are branched or branched and z is an integer of 3 to 10.)
In step 2-6, - (CH 2 ) Z-2 CH═CH 2 (Z is an integer of 3 to 10) of the alkoxysilyl compound prepared in step 2-5 and the alkoxysilane are reacted in an equivalent ratio The alkoxy silane of formula M3 is reacted with 1 equivalent of - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) of the alkoxysilyl compound prepared in step 2-5, To 5 equivalents, and the reaction is carried out at 15 to 120 DEG C for 1 to 72 hours.
The metal catalyst used in the step 2-6 may include, but is not limited to, PtO 2 or platinum catalyst of H 2 PtCl 6 (chloroplatinic acid). It is preferable that the platinum catalyst is used in an amount of 0.005 to 0.05 equivalent based on 1 equivalent of - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) of the alkoxysilyl compound prepared in Step 2-5 It is preferable from the viewpoint of efficiency.
In the step 2-6, the solvent may optionally be used as required. For example, if the viscosity of the reactant is suitable for the reaction to proceed at the reaction temperature without any solvent in Step 2-6, the solvent may not be used. That is, if the viscosity of the reactant is lowered to such an extent that the mixing and stirring of the reactants can proceed smoothly without a solvent, a separate solvent is not required, which can be easily determined by those skilled in the art. When a solvent is used, any solvent can be used to dissolve the reactant well, and any aprotic solvent can be used as long as it can be easily removed after the reaction without any adverse effect on the reaction. But are not limited to, toluene, acetonitrile, tetrahydrofuran (THF), methyl ethyl ketone (MEK), dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), methylene chloride have. These solvents may be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited and may be appropriately selected so that the reactant is sufficiently dissolved and does not adversely affect the reaction, and a person skilled in the art can appropriately select it.
Ah. Alkenyl substituent is biotinylated all the starting material (Formula AS to DS) hydrogen, and then subjected twice to place moving the reaction, 4 - (CH 2) z -SiR 2 R 3 and the substituents of R 1 having a hydroxy group, Method for producing alkoxysilyl compound (Method 8)
The alkoxysilyl compound having a substituent group and a hydroxy group of 4 - (CH 2 ) z --SiR 1 R 2 R 3 is further subjected to the rearrangement reaction to the intermediate product (23) prepared in the
Specifically, step 3-1 is carried out to obtain an intermediate product (31) having a hydroxy group by carrying out a rearrangement reaction to the intermediate product (23) prepared in the
[Intermediate (23)]
(In the substituent k3 to p3 of Formula A23 to D23, k3; l3; m3 or any one of n3; any one, and o3 or p3 is - (CH 2) Z-2 CH = CH 2 (Z 3 to 10 is an integer), and the other is hydrogen, in formula A23 Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3) 2 -, -S- or -SO 2 - a. )
[Intermediate (31)]
(K1 and l1 is the substituent of Formula A31 to D31 is hydrogen, m1 to p1 is - (CH 2) Z-2 CH = CH 2 (Z is an integer of 3 to 10), and, Y in the above formula A31 is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -.
[Formula M3]
HSiR 1 R 2 R 3
(Wherein at least one of R 1 to R 3 is a C 1 -
[Final product]
(Wherein the substituents a and b in the above formulas AI to DI are hydrogen, at least two of c to f are represented by the following formula S1, and the remainder are - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -.
[Formula (S1)
- (CH 2 ) z -SiR 1 R 2 R 3
(In the formula (S1), R 1 to R 3 Is an alkoxy group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group are branched or branched, and z is an integer of 3 to 10.)
The position transfer reaction in the step 3-1 may be carried out in the same manner as the position transfer reaction in the step 2-2 of the
In the step 3-2, the intermediate product (31) prepared in the above step 3-1 and the alkoxy silane of the formula (M3) are reacted in the presence of a metal catalyst and any solvent to obtain an end product of the above formulas AI to DI have.
In step 3-2, - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) and alkoxysilane of the intermediate product (31) (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) of the intermediate product (31) prepared in the above-mentioned Step 3-1, To 1 to 5 equivalents of the alkoxy silane, and the reaction is carried out at 15 ° C to 120 ° C for 1 to 72 hours.
The metal catalyst used in the step 3-2 may be, for example, PtO 2 or platinum catalyst of H 2 PtCl 6 (chloroplatinic acid). The platinum catalyst is used in an amount of 0.005 to 0.05 equivalent based on 1 equivalent of - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) of the intermediate product (31) Is preferable in terms of reaction efficiency.
In the step 3-2 reaction, the solvent can be optionally used as needed. For example, if the viscosity of the reactant is suitable for the reaction to proceed at the reaction temperature without additional solvent in Step 3-2, the solvent may not be used. That is, if the viscosity of the reactant is lowered to such an extent that the mixing and stirring of the reactants can proceed smoothly without a solvent, a separate solvent is not required, which can be easily determined by those skilled in the art. When a solvent is used, any solvent can be used to dissolve the reactant well, and any aprotic solvent can be used as long as it can be easily removed after the reaction without any adverse effect on the reaction. But are not limited to, toluene, acetonitrile, tetrahydrofuran (THF), methyl ethyl ketone (MEK), dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), methylene chloride have. These solvents may be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited and may be appropriately selected so that the reactant is sufficiently dissolved and does not adversely affect the reaction, and a person skilled in the art can appropriately select it.
character. Alkenyl substituent is biotinylated all the starting material hydrogen (Formula AS to DS), and subjected twice to place shifting reaction, 6-a (CH 2) z -SiR have a substituent 1 R 2 R 3 hydroxy groups (Method 9) < RTI ID = 0.0 >
The alkoxysilyl compound having a substituent of 6 - (CH 2 ) z --SiR 1 R 2 R 3 and having no hydroxy group can be obtained by alkenylation of the intermediate product (31) of the
Specifically, the intermediate product (31) prepared in step 3-1 of the
[Intermediate (31)]
(K1 and l1 is the substituent of Formula A31 to D31 is hydrogen, m1 to p1 is - (CH 2) Z-2 CH = CH 2 (Z is an integer of 3 to 10), and, Y in the above formula A31 is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -.
(M2)
X- (CH 2) z-2 -CH = CH 2
(Wherein, X is Cl, Br or halides of I, -O-SO 2 -CH 3 , -O-SO 2 -CF 3, -O-SO 2 -C 6 H 4 -CF 3, -O-SO 2 -C 6 H 4 -NO 2 or -O-SO 2 -C 6 H 4 -CH 3 , and z is an integer from 3 to 10.)
[Intermediate (32)]
(The above formula A32 to D32 substituent of k2 to p2 is - (CH 2) Z-2 CH = CH 2 (Z is an integer of 3 to 10), and, Y in the above formula A31 is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -.
[Formula M3]
HSiR 1 R 2 R 3
(Wherein R 1 to R 3 At least one of them is a C1-C10 alkoxy group and the remainder is a straight or branched C1-C10 alkyl group, and the alkoxy group and the alkyl group are linear or branched.
[Final product]
(Wherein at least two of the substituents a to f of the formulas AI to DI have the following formula S1 and the remainder are - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) Is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -.
[Formula (S1)
- (CH 2 ) z -SiR 1 R 2 R 3
(In the formula (S1), R 1 to R 3 Is an alkoxy group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group are branched or branched and z is an integer of 3 to 10.)
In the step 3-3, the intermediate product (31) prepared in the step 3-1 and the alkenyl compound of the formula (M2) are reacted in the presence of an optional base and optionally in the presence of a solvent to form a - (CH 2 ) Z -2 & gt ; CH = CH 2 (Z is an integer of 3 to 10).
(CH 2 ) Z-2 CH = CH 2 (Z) of the alkenyl compound of the formula (M2) with respect to 1 equivalent of the hydroxy group of the intermediate product (31) Is an integer of 3 to 10) is added in an amount of 0.5 to 10 equivalents, and the reaction is carried out at 15 to 100 캜 for 1 to 120 hours.
Examples of the base usable in the second step 3-3, without limitation, for example, KOH, NaOH, K 2 CO 3, Na 2 CO 3, KHCO 3, NaHCO 3, NaH, pyridine, triethylamine, And diisopropylethylamine. These bases may be used singly or in combination of two or more. It is preferable in terms of reaction efficiency that the base is used in an amount of 0.1 to 5 equivalents based on 1 equivalent of the hydroxy group of the intermediate product (31) prepared in the above-mentioned Step 3-1.
In the step 3-3, the solvent may be optionally used. If the viscosity of the reactant at the reaction temperature is suitable for the reaction to proceed without any solvent, a solvent may not be used. That is, if the viscosity of the reactant is lowered to such an extent that the mixing and stirring of the reactants can proceed smoothly without a solvent, a separate solvent is not required, which can be easily determined by those skilled in the art. When a solvent is used, any organic solvent may be used as long as it is capable of dissolving the reactant well and can be easily removed after the reaction without any adverse effect on the reaction, and thus, for example, (Methyl ethyl ketone), DMF (dimethyl formamide), DMSO (dimethyl sulfoxide), methylene chloride (MC), H 2 O or alcohols (methanol, ethanol) Can be used. These solvents may be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited and may be appropriately selected so that the reactant is sufficiently dissolved and does not adversely affect the reaction, and a person skilled in the art can appropriately select it.
In the step 3-4, the intermediate product (32) prepared in the step 3-3 is reacted with the alkoxy silane of the formula (M3) in the presence of a metal catalyst and any solvent to obtain an end product of the following formulas AI to DI have.
(CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) of the intermediate product (32) prepared in the step 3-3 is reacted with the alkoxysilane in the stoichiometry (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) of the intermediate product (32) prepared in the above Step 3-3, To 1 to 5 equivalents of the alkoxy silane, and the reaction is carried out at 15 ° C to 120 ° C for 1 to 72 hours.
The metal catalyst used in the step 3-4 may be, for example, PtO 2 or platinum catalyst of H 2 PtCl 6 (chloroplatinic acid). The platinum catalyst is used in an amount of 0.005 to 0.05 equivalent based on 1 equivalent of - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) of the intermediate product (31) Is preferable in terms of reaction efficiency.
In the third-step reaction, the solvent can be optionally used as needed. For example, if the viscosity of the reactant at the reaction temperature is suitable for the reaction to proceed without additional solvent in step 3-4, the solvent may not be used. That is, if the viscosity of the reactant is lowered to such an extent that the mixing and stirring of the reactants can proceed smoothly without a solvent, a separate solvent is not required, which can be easily determined by those skilled in the art. When a solvent is used, any solvent can be used to dissolve the reactant well, and any aprotic solvent can be used as long as it can be easily removed after the reaction without any adverse effect on the reaction. But are not limited to, toluene, acetonitrile, tetrahydrofuran (THF), methyl ethyl ketone (MEK), dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), methylene chloride have. These solvents may be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited and may be appropriately selected so that the reactant is sufficiently dissolved and does not adversely affect the reaction, and a person skilled in the art can appropriately select it.
car. The starting materials (AS to DS) wherein all the substituents are hydrogen are alkenylated and the displacement reaction is carried out twice to obtain the substituents of two -CONH (CH 2 ) z -SiR 1 R 2 R 3 and four alkenyl (Method 10) < RTI ID = 0.0 >
An alkoxysilyl compound having two substituents of -CONH (CH 2 ) z -SiR 1 R 2 R 3 and four - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) in the first intermediate product produced in step 3-1 (31) can be prepared by combining additionally a substituent, -CONH (CH 2) z -SiR 1 R 2 R 3.
Specifically, the intermediate product (31) prepared in the step 3-1 of the
[Intermediate (31)]
(K1 and l1 is the substituent of Formula A31 to D31 is hydrogen, m1 to p1 is - (CH 2) Z-2 CH = CH 2 (Z is an integer of 3 to 10), and, Y in the above formula A31 is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -.
≪ RTI ID =
OCN- (CH 2 ) z -SiR 1 R 2 R 3
Wherein at least one of R 1 to R 3 is a C 1 -
[Final product]
(Note that the formula AI to substituents of DI a and b have the following formula S2, c to f is - (CH 2) Z-2 CH = CH 2 (Z 3 to 10 of an integer), and, Y in the formula AI is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -.
≪ RTI ID = 0.0 &
-CONH (CH 2 ) z -SiR 1 R 2 R 3
(In the above formula (S2), R 1 to R 3 Is an alkoxy group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group are branched or branched and z is an integer of 3 to 10.)
In the step 3-5, the alkoxysilyl compound is reacted in an amount of 1 to 5 equivalents based on 1 equivalent of the hydroxy group of the intermediate product (31) in the presence of an optional base and any solvent so that the isocyanate- Can be manufactured. Further, this reaction can be carried out at 15 캜 to 120 캜 for 1 to 72 hours.
Examples of the base usable in step 3-5 include, but are not limited to, K 2 CO 3 , Na 2 CO 3 , KHCO 3 , NaHCO 3 , NaH, pyridine, triethylamine, diisopropylethyl Amines. These bases may be used singly or in combination of two or more. It is preferable in terms of reaction efficiency that the base is used in an amount of 0.1 to 5 equivalents based on 1 equivalent of the hydroxy group of the intermediate product (31).
In the step 3-5, the solvent may be optionally used. If the viscosity of the reactant at the reaction temperature is suitable for the reaction to proceed without any solvent, a solvent may not be used. That is, if the viscosity of the reactant is lowered to such an extent that the mixing and stirring of the reactants can proceed smoothly without a solvent, a separate solvent is not required, which can be easily determined by those skilled in the art. When a solvent is used, any organic solvent may be used as long as it is capable of dissolving the reactant well and can be easily removed after the reaction without any adverse effect on the reaction, and thus, for example, , Tetra hydrofuran (THF), methyl ethyl ketone (MEK), dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), and methylene chloride (MC). These solvents may be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited and may be appropriately selected so that the reactant is sufficiently dissolved and does not adversely affect the reaction, and a person skilled in the art can appropriately select it.
Car. The starting materials (AS to DS) in which all the substituents are hydrogen are alkenylated and the rearrangement reaction is carried out twice to obtain the substituents of two -CONH (CH 2 ) z -SiR 1 R 2 R 3 and at least two - (CH 2 ) z -SiR 1 R 2 R 3 (Method 11)
The alkoxysilyl compound having two substituents of -CONH (CH 2 ) z -SiR 1 R 2 R 3 and at least two substituents of - (CH 2 ) z -SiR 1 R 2 R 3 is the To an alkoxysilyl compound in addition to a substituent of - (CH 2 ) z -SiR 1 R 2 R 3 .
Specifically, Step 3-6 in which any one of the alkoxysilyl compounds prepared in
[Formula M3]
HSiR 1 R 2 R 3
(Wherein at least one of R 1 to R 3 is a C 1 -
[Final product]
(Wherein the substituents a and b in the formulas AI to DI are represented by the following formula (S2), at least two of c to f are represented by the following formula (S1), and the remainder are - (CH 2 ) Z-2 CH = CH 2 Wherein Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -.
[Formula (S1)
- (CH 2 ) z -SiR 1 R 2 R 3
≪ RTI ID = 0.0 &
-CONH (CH 2 ) z -SiR 1 R 2 R 3
(In the formulas (S1) and (S2), R 1 to R 3 Is an alkoxy group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group are branched or branched and z is an integer of 3 to 10.)
In the step 3-6, the alkoxysilyl compound - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) of the alkoxysilyl compound produced in the
As the metal catalyst in the step 3-6, for example, but not limited thereto, a platinum catalyst of PtO 2 or H 2 PtCl 6 (chloroplatinic acid) may be used. It is preferable that the platinum catalyst is used in an amount of 0.005 to 0.05 equivalent based on 1 equivalent of - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) of the alkoxysilyl compound prepared in the above-mentioned
In the third to sixth step reaction, the solvent can be optionally used as needed. For example, if the viscosity of the reactant at the reaction temperature is suitable for the reaction to proceed without additional solvent in the 3-6 reaction step, the solvent may not be used. That is, if the viscosity of the reactant is lowered to such an extent that the mixing and stirring of the reactants can proceed smoothly without a solvent, a separate solvent is not required, which can be easily determined by those skilled in the art. When a solvent is used, any solvent can be used to dissolve the reactant well, and any aprotic solvent can be used as long as it can be easily removed after the reaction without any adverse effect on the reaction. But are not limited to, toluene, acetonitrile, tetrahydrofuran (THF), methyl ethyl ketone (MEK), dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), methylene chloride have. These solvents may be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited and may be appropriately selected so that the reactant is sufficiently dissolved and does not adversely affect the reaction, and a person skilled in the art can appropriately select it.
Hereinafter, the present invention will be described more specifically by way of specific examples. The following examples are provided to aid understanding of the present invention, and the scope of the present invention is not limited thereto.
Synthesis Example 1 : Synthesis of bisphenol A-based alkoxysilyl compound (AI) (Hydrosilyation, A-1) (Method 2)
(1)
25 g of bisphenol A (A), 39.7 g of allyl bromide and 400 ml of tetrahydrofuran (THF) were placed in a two-necked flask and stirred at room temperature. Thereafter, a solution obtained by dissolving 10.5 g of NaOH in 400 ml of H 2 O was slowly added at room temperature for 1 hour, and then stirred for 4 hours. Then, THF was removed using an evaporator, 400 ml of ethyl acetate was added, and the workpiece was worked up with H 2 O to remove the inorganic matter. MgSO 4 was added to the organic layer to remove remaining H 2 O, filtered through a celite filter, and evaporated to dryness to obtain an intermediate product.
(2) Step 2
The flask was charged with 10 g of the intermediate product, PtO 2 , 11.7 g of triethoxysilane, and 150 ml of toluene were placed, and the mixture was stirred at room temperature for 5 minutes. Then, the mixture was heated and stirred at 80 캜 for 12 hours. Thereafter, the mixture was cooled to room temperature and filtered with a Celite filter to remove the inorganic matter. The toluene was removed by evaporation and completely dried using a vacuum pump to obtain the final object (A-1).
- The synthesis reaction of Synthesis Example 1 is as follows.
Synthesis Examples 2 to 7 : Hydrosilylation (B-1 to G-1) (Method 2)
The alkoxysilyl compounds of Formulas B-1 to G-1 were synthesized by proceeding the first step and the second step reaction in the same manner as in Synthesis Example 1 except for the amount of the reactants used. The amounts of the reactants used in the first and second steps are shown in Tables 1 and 2 below.
- Synthesis reaction of Synthesis Example 2
- Synthesis reaction of Synthesis Example 3
- Synthesis reaction of Synthesis Example 4
- Synthesis reaction of Synthesis Example 5
- Synthesis reaction of Synthesis Example 6
- Synthesis reaction of Synthesis Example 7
Synthesis Example 8 : Diamino diphenyl methane-based alkoxysilyl compound (Hydrosilyation, H-1) (Method 2)
(1)
20 g of diaminomiphenylmethane (I) and 400 ml of CH 3 CN were added to a two-necked flask at room temperature and stirred, and then 73.2 g of allyl bromide was added at 0 ° C. Then, 47.9 g of pyridine was added slowly for 1 hour, and reacted at 80 DEG C for 2 hours with stirring. After completion of the reaction, the solvent was removed using an evaporator, and the reaction mixture was worked up with 400 ml of ethyl acetate and 1M NaOH solution. The organic layer was separated, and MgSO 4 was added to the organic layer to remove remaining H 2 O, Intermediate product was obtained.
(2) Step 2
The flask was charged with 10 g of the above intermediate product and PtO 2 , 20.2 g of triethoxysilane and 150 ml of toluene were placed, and the mixture was stirred at room temperature for 5 minutes. Then, the mixture was heated and stirred at 80 캜 for 12 hours. Thereafter, the mixture was cooled to room temperature and filtered with a Celite filter to remove the inorganic matter. The toluene was evaporated to dryness and completely dried using a vacuum pump to give the final product (H-1).
- The synthesis reaction of Synthesis Example 8 is as follows.
Synthesis Example 9 : Aminophenol-based alkoxysilyl compound (Hydrosilyation, I-1) (Method 2)
(1)
25 g of aminophenol (I), 124.7 g of allyl bromide and 400 ml of tetrahydrofuran (THF) were placed in a two-necked flask and stirred at room temperature. Then, a solution obtained by dissolving 33.0 g of NaOH in 400 ml of H 2 O was added slowly at room temperature for 1 hour and further stirred for 4 hours. Thereafter, THF was removed using an evaporator, 400 ml of ethyl acetate was added, and work up was performed with H 2 O to remove the inorganic matter. MgSO 4 was added to the organic layer to remove the remaining H 2 O, followed by filtration with a celite filter and drying by evaporation to obtain an intermediate product.
(2) Step 2
The flask was charged with 10 g of the above intermediate product and PtO 2 , 23.6 g of triethoxysilane, and 150 ml of toluene were placed, and the mixture was stirred at room temperature for 5 minutes. Then, the mixture was heated and stirred at 80 캜 for 12 hours. Thereafter, the mixture was cooled to room temperature and filtered with a Celite filter to remove the inorganic matter. The toluene was evaporated to dryness and completely dried using a vacuum pump to give the final object (I-3).
- The synthetic reaction used in Synthesis Example 9 is as follows.
Synthesis Example 10 : Bisphenol A-based alkoxysilyl compound (carbamate, A-2) (Method 1)
25 g of bisphenol A (A), 34.0 g of diisopropylethylamine (DIPEA) and 200 ml of methylene chloride were added to the flask, and the mixture was stirred at room temperature for 5 minutes. Thereafter, 54.2 g of triethoxysilylpropyl isocyanate was added at room temperature, and the mixture was heated to 60 DEG C and reacted for 12 hours. After completion of the reaction, the solution cooled to room temperature was worked up with H 2 O, the organic layer was separated, and MgSO 4 was added to remove the remaining H 2 O, followed by filtration with a celite filter and evaporation drying to obtain the final object A- ).
The synthetic reaction used in Synthesis Example 10 is as follows.
Synthesis Examples 11 to 16 : Synthesis of alkoxysilyl compounds (carbamate, B-2 to G-2) (Method 1)
The reaction was carried out in the same manner as in Synthesis Example 10 except for the amount of the reactant used to synthesize the alkoxysilyl compounds of Formulas B-2 to G-2. The amount of reactants used in each synthesis step is shown in the table below.
The synthetic reaction used in Synthesis Example 11 is as follows.
The synthetic reaction used in Synthesis Example 12 is as follows.
The synthesis reaction used in Synthesis Example 13 is as follows.
The synthesis reaction used in Synthesis Example 14 is as follows.
- The synthetic reaction used in Synthesis Example 15 is as follows.
- The synthetic reaction used in Synthesis Example 16 is as follows.
Synthesis Example 17 : Diaminodiphenylmethane-based alkoxysilyl compound (carbamate, H-2) (Method 1)
25 g of diaminodiphenylmethane (H), 97.8 g of diisopropylethylamine (DIPEA) and 500 ml of methylene chloride were added to the flask and stirred at room temperature. Thereafter, 374.3 g of triethoxysilylpropyl isocyanate was added at room temperature for 30 minutes, and then the mixture was further reacted at room temperature for 30 minutes. Then, the solvent was removed using an evaporator, and the reaction was carried out at a temperature of 80 ° C. for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and then worked up using H 2 O. The organic layer was separated, and MgSO 4 was added to the organic layer to remove remaining H 2 O. The organic layer was then filtered with a Celite filter, 2).
- The synthetic reaction used in Synthesis Example 17 is as follows.
Synthesis Example 18 : Aminophenolic alkoxysilyl compound (carbamate, I-2) (Method 1)
10 g of aminophenol (I), 28.4 g of diisopropylethylamine (DIPEA) and 400 ml of methylene chloride were put in a flask and stirred at room temperature. Thereafter, 45.3 g of triethoxysilylpropyl isocyanate was added at room temperature for 30 minutes, and further reacted at room temperature for 30 minutes. Thereafter, the temperature was heated to 60 DEG C and the reaction was carried out for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and then worked up with H 2 O. The organic layer was separated, and MgSO 4 was added to the organic layer to remove remaining H 2 O. The organic layer was then filtered through a Celite filter, 2).
The synthetic reaction used in Synthesis Example 18 is as follows.
Synthesis Example 19 : Bisphenol A-based alkoxysilyl compound (Hydrosilylation, A-3) (Method 5)
(1)
An intermediate product was obtained by the same reaction as the one-step reaction of Synthesis Example 1.
(2) Step 2
10 g of 4,4 '- (propane-2,2-diyl) bis (allyloxybenzene) as the intermediate product of the first step was added to the flask and reacted at 180 ° C for 8 hours to perform 4,4 - (propane-2,2-diyl) bis (2-allylphenol).
(3) Step 3
A reflux condenser was attached to a two-necked flask, and 9 g of 4,4 '- (propane-2,2-diyl) bis (2-allylphenol) intermediate product in the second stage was dissolved in acetone at 80 ° C. That, 6.4ml allyl bromide and K 2 CO 3 and then And the mixture was stirred at 80 ° C for 24 hours, cooled to room temperature, filtered through a Celite filter, and evaporated to remove the solvent to obtain a reaction product. The reaction product was dissolved in ethyl acetate, washed with water and washed with brine solution. The organic solvent layer was dried over MgSO 4 , filtered and the solvent was removed using an evaporator to obtain 4,4'- (propane-2,2-diyl) bis (2-allyl-1- (allyloxy) benzene ).
(4) Step 4
The flask was charged with 10 g of the intermediate product of the third step and PtO 2 , 22.1 ml of triethoxysilane, and 150 ml of toluene were placed and stirred for 5 minutes at room temperature, followed by stirring at 85 ° C for 36 hours. Thereafter, the mixture was cooled to room temperature and filtered with a Celite filter to remove the inorganic matter. The toluene was evaporated to dryness and completely dried using a vacuum pump to obtain the final object (A-3).
- The synthetic reaction used in Synthesis Example 19 is as follows.
Synthesis Examples 20 to 22 : Hydrosilylation (B-3 to D-3) (method 5)
The reaction of the first to fourth steps was carried out in the same manner as in Synthesis Example 19 except for the amount of the reactant used to synthesize an alkoxysilyl compound of the formulas B3 to D3 having four alkoxysilyl groups. The amounts of the reactants used in the third and fourth steps are shown in Tables 4 and 5 below.
The synthetic reaction used in Synthesis Example 20 is as follows.
The synthetic reaction used in Synthesis Example 21 is as follows.
- The synthetic reaction used in Synthesis Example 22 is as follows.
Synthesis Example 23 : Bisphenol A-based alkoxysilyl compound having allyl group (Carbamate, A-4) (Method 6)
(1) The first stage and the second stage
The reaction proceeded in the same manner as in the first step and the second step reaction in Synthesis Example 19 to obtain 4,4 '- (propane-2,2-diyl) bis (2-allylphenol) intermediate product having two allyl groups.
(2) Step 3
10 g of 4,4 '- (propane-2,2-diyl) bis (2-allylphenol), 10.1 g of sodium diisopropylethylamine (DIPEA) and 300 ml of methylene chloride were added to the flask and stirred at room temperature. Thereafter, 16.0 g of triethoxysilylpropyl isocyanate (OCN (CH 2 ) 3 Si (OEt) 3 ) was added at room temperature for 5 minutes, and the mixture was heated to 80 ° C and reacted for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and then worked up using H 2 O. The organic layer was separated, and MgSO 4 was added to the organic layer to remove remaining H 2 O. The organic layer was then filtered through a Celite filter, 4).
The synthesis reaction used in Synthesis Example 23 is as follows.
Synthesis Examples 24 to 26 : Synthesis of alkoxysilyl compounds having two allyl groups (Carbamate, B-4 to D-4) (Method 6)
The alkoxysilyl compounds of Formulas B-4 to D-4 having two allyl groups were synthesized in the same manner as in Synthesis Example 23 except for the amount of the reactants used. The amount of reactants used in each synthesis step is shown in Table 6 below.
The synthesis reaction used in Synthesis Example 24 is as follows.
The synthesis reaction used in Synthesis Example 25 is as follows.
The synthesis reaction used in Synthesis Example 26 is as follows.
Synthesis Example 27 : Bisphenol A-based alkoxysilyl compound (A-5) having two kinds of alkoxysilyl groups (Method 7)
10 g of 4,4 '- (propane-2,2-diyl) bis (2-allyl-4,1-phenylene) bis (3- (triethoxysilyl) propylcarbamate) compound A-4 synthesized in Synthesis Example 23 0.06 g of PtO 2 , 4.5 g of triethoxysilane and 100 ml of toluene were placed, stirred for 5 minutes at room temperature, and then heated and stirred at 80 ° C for 12 hours. Thereafter, the mixture was cooled to room temperature and filtered with a Celite filter to remove the inorganic matter. The toluene was evaporated to dryness and completely dried using a vacuum pump to obtain the final object (A-5).
- The synthetic reaction used in Synthesis Example 27 is as follows.
Synthesis Example 28 to Synthesis Example 30 : Synthesis of alkoxysilyl compounds (B-5 to D-5) having two alkoxysilyl groups (Method 7)
The reaction was carried out in the same manner as in Synthesis Example 27 except for the amount of the reactant used to synthesize alkoxysilyl compounds of the formulas B-5 to D-5 having two kinds of alkoxysilyl groups. The amount of reactants used in each synthesis step is shown in Table 7 below.
The synthetic reaction used in Synthesis Example 28 is as follows.
- The synthetic reaction used in Synthesis Example 29 is as follows.
The synthesis reaction used in Synthesis Example 30 is as follows.
Synthesis Example 31 : alkoxysilyl compound (A-6) having two kinds of alkoxysilyl groups (Method 8)
(1)
To the flask was added 8.57 g of diisopropylethylamine (DIPEA), 16.40 g of triethoxysilylpropyl isocyanate and 60 ml of methylene chloride at room temperature. Then, a solution of 25 g of bisphenol A (A) dissolved in 60 ml of methylene chloride was added slowly at 60 DEG C for 6 hours. Thereafter, it was further stirred for 9 hours. After completion of the reaction, the solution cooled to room temperature was worked up with H 2 O, the organic layer was separated, and MgSO 4 was added to remove remaining H 2 O, followed by filtration and evaporation to dryness to obtain an intermediate product.
(2) Step 2
25 g of the intermediate product of the first step, 9.69 g of allyl bromide and 50 ml of tetrahydrofuran (THF) were added to a two-necked flask, and the mixture was stirred at room temperature. Thereafter, a solution obtained by dissolving 3.20 g of NaOH in 50 ml of H 2 O was slowly added at room temperature for 1 hour, and then stirred for 4 hours. Then, THF was removed by using an evaporator, 200 ml of ethyl acetate was added, and the workpiece was worked up with H 2 O to remove the inorganic matter. MgSO 4 was added to the organic layer to remove remaining H 2 O, filtered through a celite filter, and evaporated to dryness to obtain an intermediate product.
(3) Step 3
To the flask was added 25 g of the intermediate product of the second stage, PtO 2 0.18 g of triethoxysilane, and 150 ml of toluene were placed, and the mixture was stirred at room temperature for 5 minutes. Then, the mixture was heated and stirred at 80 캜 for 12 hours. Thereafter, the mixture was cooled to room temperature and filtered with a Celite filter to remove the inorganic matter. The toluene was removed by evaporation and completely dried using a vacuum pump to obtain the final object (A-6).
The synthetic reaction used in Synthesis Example 31 is as follows.
Synthesis Example 32 to Synthesis Example 34 : An alkoxysilyl compound having two alkoxysilyl groups (B-6 to D-6) (Method 8)
The reaction was carried out in the same manner as in Synthesis Example 31 except for the amount of the reactant used to synthesize an alkoxysilyl compound of the formulas B-6 to D-6 having two kinds of alkoxysilyl groups. The amount of reactants used in each synthesis step is shown in the table below.
(1)
profile
Isocyanate
(2) Step 2
(3) Step 3
- The synthetic reaction used in Synthesis Example 32 is as follows.
- The synthetic reaction used in Synthesis Example 33 is as follows.
- The synthesis reaction used in Synthesis Example 34 is as follows.
Synthesis Example 35: alkoxysilyl compound (A-7) having two kinds of alkoxysilyl groups (Method 9)
(1)
25 g of bisphenol A (A), 8.02 g of allyl bromide and 83 ml of tetrahydrofuran (THF) were placed in a two-necked flask and stirred at room temperature. Thereafter, a solution obtained by dissolving 2.65 g of NaOH in 83 ml of H 2 O was added slowly at room temperature for 3 hours, and then stirred for further 4 hours. Then, THF was removed by using an evaporator, 200 ml of ethyl acetate was added, and the workpiece was worked up with H 2 O to remove the inorganic matter. MgSO 4 was added to the organic layer to remove remaining H 2 O, filtered through a celite filter, and evaporated to dryness to obtain an intermediate product.
(2) Step 2
To the flask was added 25 g of the intermediate product of the first step, PtO 2 0.14 g of triethoxysilane, 10.59 g of triethoxysilane, and 277 ml of toluene, and the mixture was stirred at room temperature for 5 minutes. Then, the mixture was heated and stirred at 80 캜 for 12 hours. Thereafter, the mixture was cooled to room temperature and filtered with a Celite filter to remove the inorganic matter. The toluene was removed by evaporation and completely dried using a vacuum pump to obtain an intermediate product.
(3) Step 3
To the flask was added 5.55 g of diisopropylethylamine (DIPEA), 10.63 g of triethoxysilylpropyl isocyanate and 86 ml of methylene chloride at room temperature. Then, a solution of 25 g of the intermediate product of the second step in 64 ml of methylene chloride was added slowly at 60 DEG C for 6 hours. Thereafter, it was further stirred for 9 hours. After completion of the reaction, the solution cooled to room temperature was worked up with H 2 O, the organic layer was separated, and MgSO 4 was added to remove remaining H 2 O, followed by filtration and evaporation to dryness to obtain the final product (A-7).
- The synthetic reaction used in Synthesis Example 35 is as follows.
Synthesis Example 36 to Synthesis Example 38 : alkoxysilyl compounds (B-7 to D-7) having two kinds of alkoxysilyl groups (Method 9)
The reaction was carried out in the same manner as in Synthesis Example 35 except for the amount of the reactant used to synthesize alkoxysilyl compounds of the formulas B-7 to D-7 having two types of alkoxysilyl groups. The amount of reactants used in each synthesis step is shown in the table below.
(1)
Bromide
(2) Step 2
(3) Step 3
Isocyanate
- The synthetic reaction used in Synthesis Example 36 is as follows.
- The synthetic reaction used in Synthesis Example 37 is as follows.
The synthetic reaction used in Synthesis Example 38 is as follows.
Synthesis Example 39 : alkoxysilyl compound (A-8) having four alkoxysilyl groups (Method 10)
(1)
25 g of bisphenol A (A), 16.25 g of allyl bromide and 83 ml of tetrahydrofuran (THF) were placed in a two-necked flask and stirred at room temperature. Then, a solution obtained by dissolving 5.37 g of NaOH in 83 ml of H 2 O was slowly added at room temperature for 3 hours, and then stirred for 4 hours. Then, THF was removed by using an evaporator, 200 ml of ethyl acetate was added, and the workpiece was worked up with H 2 O to remove the inorganic matter. MgSO 4 was added to the organic layer to remove remaining H 2 O, filtered through a celite filter, and evaporated to dryness to obtain an intermediate product.
(2) Step 2
25 g of 4,4 '- (propane-2,2-diyl) bis ((allyloxy) benzene) as the intermediate product of the first step was added to the flask, and the reaction was carried out at 180 ° C. for 8 hours to perform a rearrangement (Claisen rearrangement) To obtain 4,4 '- (propane-2,2-diyl) bis (2-allylphenol).
(3) Step 3
25 g of 4,4 '- (propane-2,2-diyl) bis (2-allylphenol), 13.18 g of allyl bromide and 68 ml of tetrahydrofuran (THF) were placed in a two-necked flask, Lt; / RTI > Thereafter, a solution obtained by dissolving 4.36 g of NaOH in 68 ml of H 2 O was slowly added at room temperature for 3 hours, and then stirred for 4 hours. Then, THF was removed by using an evaporator, 200 ml of ethyl acetate was added, and the workpiece was worked up with H 2 O to remove the inorganic matter. MgSO 4 was added to the organic layer to remove remaining H 2 O, filtered through a celite filter, and evaporated to dryness to obtain an intermediate product.
(4) Step 4
25 g of 4,4 '- (propane-2,2-diyl) bis (2-allyl-1- (allyloxy) benzene) as the intermediate product in the third step was added to the flask and reacted at 180 ° C. for 8 hours 4,4 '- (propane-2,2-diyl) bis (2,6-diallylphenol) is obtained with Claisen rearrangement.
(5)
To the flask was added 25 g of the intermediate product of the fourth step, PtO 2 0.10 g of triethoxysilane, 30.36 g of triethoxysilane and 214 ml of toluene, and the mixture was stirred at room temperature for 5 minutes. Then, the mixture was heated and stirred at 80 캜 for 12 hours. Thereafter, the mixture was cooled to room temperature and filtered with a Celite filter to remove the inorganic matter. The toluene was removed by evaporation and completely dried using a vacuum pump to obtain the final object (A-8).
The synthetic reaction used in Synthesis Example 39 is as follows.
Synthesis Examples 40 to 42: Compounds (B-8 to D-8) having four alkoxysilyl groups (Method 10)
The reaction was carried out in the same manner as in Synthesis Example 39 except for the amount of the reactant used, to synthesize an alkoxysilyl compound of the formulas B-8 to D-8 having four alkoxysilyl groups. The amount of reactants used in each synthesis step is shown in the table below.
(1)
Bromide
(2) Step 2
In the second step reaction for the synthesis of the compounds B-8 to D-8, the reaction proceeds only with the product of the first step.
(3) Step 3
Bromide
(4) Step 4
In the second step reaction for synthesis of the compounds B-8 to D-8, the reaction proceeds only with the product of the third step.
(5)
The synthetic reaction used in Synthesis Example 40 is as follows.
- The synthetic reaction used in Synthesis Example 41 is as follows.
- The synthetic reaction used in Synthesis Example 42 is as follows.
Synthesis Example 43: Compound (A-9) having 6 alkoxysilyl groups (Method 11)
(1)
25 g of the intermediate product after the fourth step reaction of Synthesis Example 39, 11.18 g of allyl bromide and 58 ml of tetrahydrofuran (THF) were added to a two-necked flask, and the mixture was stirred at room temperature. Thereafter, a solution obtained by dissolving 3.70 g of NaOH in 58 ml of H 2 O was added slowly at room temperature for 3 hours, and then stirred for further 4 hours. Then, THF was removed by using an evaporator, 200 ml of ethyl acetate was added, and the workpiece was worked up with H 2 O to remove the inorganic matter. MgSO 4 was added to the organic layer to remove remaining H 2 O, filtered through a celite filter, and evaporated to dryness to obtain an intermediate product.
(2) Step 2
To the flask was added 25 g of the intermediate product of the first step, PtO 2 0.09 g of triethoxysilane, 39.54 g of triethoxysilane, and 186 ml of toluene, and the mixture was stirred at room temperature for 5 minutes. Then, the mixture was heated and stirred at 80 캜 for 12 hours. Thereafter, the mixture was cooled to room temperature and filtered with a Celite filter to remove the inorganic matter. The toluene was removed by evaporation and completely dried using a vacuum pump to obtain the final product (A-9).
The synthetic reaction used in Synthesis Example 43 is as follows.
Synthesis Examples 44 to 46: Compounds having six alkoxysilyl groups (B-9 to D-9) (Method 11)
The reaction was carried out in the same manner as in Synthesis Example 43 except for the amount of the reactant used to synthesize alkoxysilyl compounds of the formulas B-9 to D-9 having six alkoxysilyl groups. The amount of reactants used in each synthesis step is shown in the table below.
(1)
Bromide
(2) Step 2
- The synthetic reaction used in Synthesis Example 44 is as follows.
- The synthetic reaction used in Synthesis Example 45 is as follows.
The synthetic reaction used in Synthesis Example 46 is as follows.
Synthesis Example 47: Compound (carbamate, A-10) having 4 allyl groups and 2 alkoxysilyl groups (Method 12)
To the flask was added 11.94 g of diisopropylethylamine (DIPEA), 22.85 g of triethoxysilylpropyl isocyanate and 46 ml of methylene chloride at room temperature. Then, a solution of 25 g of the intermediate product after the fourth step reaction of Synthesis Example 39 in 46 ml of methylene chloride was added slowly at 60 DEG C for 6 hours. Thereafter, it was further stirred for 9 hours. After completion of the reaction, the solution cooled to room temperature was worked up with H 2 O, the organic layer was separated, and MgSO 4 was added to remove remaining H 2 O, followed by filtration and evaporation to dryness to obtain an intermediate product.
The synthetic reaction used in Synthesis Example 47 is as follows.
Synthesis Examples 48 to 50: Compounds having four allyl groups and two alkoxysilyl groups (carbamate, B-10 to D-10) (Method 12)
The reaction was carried out in the same manner as in Synthesis Example 47 except for the amount of the reactant used to synthesize an alkoxysilyl compound of the formulas B-10 to D-10 having four allyl groups and two alkoxysilyl groups. The amount of reactants used in each synthesis step is shown in the table below.
Isocyanate
The synthetic reaction used in Synthesis Example 48 is as follows.
The synthetic reaction used in Synthesis Example 49 is as follows.
The synthetic reaction used in Synthesis Example 50 is as follows.
Synthesis Example 51: Compound (A-11) having two kinds of alkoxysilyl groups (Method 13)
(1)
To the flask was added 25 g of the intermediate product after the fourth step reaction of Synthesis Example 39, PtO 2 0.10 g of triethoxysilane, 30.36 g of triethoxysilane and 214 ml of toluene, and the mixture was stirred at room temperature for 5 minutes. Then, the mixture was heated and stirred at 80 캜 for 12 hours. Thereafter, the mixture was cooled to room temperature and filtered with a Celite filter to remove the inorganic matter. The toluene was removed by evaporation and completely dried using a vacuum pump to obtain an intermediate product.
(2) Step 2
5.39 g of diisopropylethylamine (DIPEA), 10.32 g of triethoxysilylpropyl isocyanate and 20 ml of methylene chloride were stirred at room temperature. Then, a solution of 25 g of the intermediate product of the first stage in 20 ml of methylene chloride was added slowly at 60 DEG C for 6 hours. Thereafter, it was further stirred for 9 hours. After completion of the reaction, the solution cooled to room temperature was worked up with H 2 O, the organic layer was separated, and MgSO 4 was added to remove remaining H 2 O, followed by filtration and evaporation to dryness to obtain an intermediate product.
The synthetic reaction used in Synthesis Example 51 is as follows.
Synthesis Examples 52 to 54: Compounds (B-11 to D-11) having two alkoxysilyl groups (Method 13)
The reaction was carried out in the same manner as in Synthesis Example 51 except for the amount of the reactant used to synthesize alkoxysilyl compounds of the formulas B-11 to D-11 having two types of alkoxysilyl groups. The amount of reactants used in each synthesis step is shown in the table below.
(1)
(2) Step 2
Isocyanate
- The synthetic reaction used in Synthesis Example 52 is as follows.
- The synthetic reaction used in Synthesis Example 53 is as follows.
The synthetic reaction used in Synthesis Example 54 is as follows.
Property evaluation
1. Manufacture of glass fiber composites
Glass fiber (glass fabric of Nittobo, E-glass or T-glass 2116) was added to the mixture obtained by dissolving the compounding composition of Table 8 in methyl ethyl ketone to have a solid content of 40 wt% To prepare a glass fiber composite. Thereafter, the composite was placed in a vacuum oven heated at 100 캜 to remove the solvent, and then cured by hot pressing to obtain a glass fiber composite film (4 mm x 16 mm x 0.1 mm (thickness)) of Examples 1 to 8 and Comparative Examples 1 and 2 ). In preparing the composite film, the resin content of the composite film was controlled according to the pressure of the press and the viscosity of the resin, and the content of the resin in the composite film was as shown in Table 8 below.
2. Epoxy
filler
Complex
Cured goods
)
An epoxy compound and silica slurry (solids content 70 wt%, 2-methoxyethanol solvent, silica
3. Evaluation of heat resistance
The dimensional changes of the composites obtained in the above Examples and Comparative Examples according to the temperature were evaluated using a thermo-mechanical analyzer and are shown in Table 22 below. Specimens of the glass fiber composite film of the alkoxysilyl compound were prepared in a size of 4 × 16 × 0.1 (㎣) and 5 × 5 × 3 (㎣) of the epoxy filler composite specimen. Tg-less in Table 22 below means that the glass transition temperature is not shown. Fig. 1 shows a dimensional change according to the temperature of Example 1 and Comparative Example 1, and Fig. 2 shows a dimensional change according to the temperature of Example 3.
(1) DGEBA: bisphenol A epoxy (Aldrich)
(2) TMTE: triphenylmethane-based epoxy (Aldrich)
(3) HF-1M: phenol novolac type curing agent (Meiwa Plastic Industries)
(4) TPP: triphenylphosphine (Aldrich)
(5) tin-OC: Tin (II) 2-ethylhexanoate (Aldrich)
As shown in Table 22, the glass fiber composites of Examples 1 and 2 including the tetraalkoxysilyl bisphenol A, which is an alkoxysilyl compound according to the present invention, had the glass fibers of Comparative Example 1 containing no alkoxysilyl compound of the present invention CTE was lower than that of the composite. Specifically, as shown in Fig. 1, the glass fiber composite of the alkoxysilyl compound of Example 1 produced using E-glass had a constant dimensional change with a small temperature change and a small variation width, The CTE was significantly reduced compared to the CTE of the.
When the alkoxysilyl compound of the present invention was compounded with T-glass, it was observed to be 2.9 ppm / DEG C lowered to a level similar to the CTE of the silicon wafer as shown in Fig.
A strip of the composite of Example 1 and Comparative Example 1 of Table 22 above was ignited and a photograph of these streams burned is shown in FIG. As shown in Fig. 3, the strips of the alkoxysilyl composite according to the present invention all spontaneously extinguished within 1 second to 2 seconds. However, the composite strip of Comparative Example 1, which did not have an alkoxysilyl group, burned to completion and was completely burned. From these results, it was found that the cured product containing the alkoxysilyl compound according to the present invention had excellent flame retardancy.
The present invention is not limited to the above-described embodiments and the accompanying drawings. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims, .
Claims (80)
Substituents a and b of the above formulas AI to DI may be the following formula S1 or S2; hydrogen or an alkenyl group and the substituents c to f are selected from the group consisting of hydrogen, an alkyl group, an alkenyl group, aryl (aryl) can group, in the formula AI Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3) 2 -, -S- or -SO 2 - can be,
And the remainder may be hydrogen, an alkyl group, an alkenyl group or an aryl group, and in the formula (HI), M is -CH 2 - and, C1-C10 alkyl group in straight or branched chain wherein the formula II is in the meta position of the oxygen -, -C (CH 3) 2 -, -C (CF 3) 2 -, -S- or -SO 2 .
[Formula (S1)
- (CH 2 ) z -SiR 1 R 2 R 3
≪ RTI ID = 0.0 &
-CONH (CH 2 ) z -SiR 1 R 2 R 3
(In the formulas (S1) and (S2), R 1 to R 3 Is an alkyl group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, the alkyl group and the alkoxy group are linear or branched, and z is an integer of 3 to 10.)
[Starting material]
(A substituent and k and l in the formula AS to DS is hydrogen, m to p are hydrogen, an alkyl group, an alkenyl (alkenyl) group, or an aryl (aryl) AS Y in the formula is -CH 2 -., -C ( CH 3) 2 -, -C ( CF 3) 2 -, -S- or -SO 2 -, and
Formula ES to a more than one of the substituents of q to t IS is hydrogen and the other is alkyl, can be an alkenyl (alkenyl) group, or an aryl (aryl), in the formula HS M is -CH 2 -, -C ( CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -, and the formula IS may be substituted with a linear or branched C 1 -C 10 alkyl group at the meta position of oxygen.
≪ RTI ID =
OCN- (CH 2 ) z -SiR 1 R 2 R 3
Wherein at least one of R 1 to R 3 is a C 1 -C 10 alkoxy group and the remainder is a straight or branched C 1 -C 10 alkyl group, the alkoxy group and the alkyl group are linear or branched, and z is 3 to 10 .
[Final product]
(Substituents a and b of the above formulas AI to DI are represented by the following formula (S2), substituents c to f may be hydrogen, an alkyl group, an alkenyl group or an aryl group,
In the formula (AI), Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -
And Formula EI to two or more of the substituents g to j of the formula (II) is S2, the rest from hydrogen, an alkyl group, an alkenyl (alkenyl) Al group, or an aryl (aryl) can group, the general formula HI M is -CH 2 - , -C (CH 3) 2 - , -C (CF 3) 2 -, -S- or -SO 2 -, and wherein formula (II) is optionally substituted in the meta position of the oxygen with C1-C10 alkyl group in straight or branched chain You can.
≪ RTI ID = 0.0 &
-CONH (CH 2 ) z -SiR 1 R 2 R 3
(In the above formula (S2), R 1 to R 3 Is an alkyl group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, the alkyl group and the alkoxy group are linear or branched, and z is an integer of 3 to 10)
And a step 1-2 of reacting the intermediate product (1) with an alkoxy silane of the formula (M3) in the presence of a metal catalyst and any solvent to obtain an end product of any one of the following formulas AI to II: Way.
[Starting material]
(A substituent and k and l in the formula AS to DS is hydrogen, m to p are hydrogen, an alkyl group, an alkenyl (alkenyl) group, or an aryl (aryl) AS Y in the formula is -CH 2 -., -C ( CH 3) 2 -, -C ( CF 3) 2 -, -S- or -SO 2 -, and
Formula ES to a more than one of the substituents of q to t IS is hydrogen and the other is alkyl, can be an alkenyl (alkenyl) group, or an aryl (aryl), in the formula HS M is -CH 2 -, -C ( CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -, and the formula IS may be substituted with a linear or branched C 1 -C 10 alkyl group at the meta position of oxygen.
(M2)
X- (CH 2) z-2 -CH = CH 2
(Wherein, X is Cl, Br or halides of I, -O-SO 2 -CH 3 , -O-SO 2 -CF 3, -O-SO 2 -C 6 H 4 -CF 3, -O-SO 2 -C 6 H 4 -NO 2 Or -O-SO 2 -C 6 H 4 -CH 3 , and z is an integer from 3 to 10.)
[Intermediate (1)]
Substituents k1 and l1 in the above formulas A1 to D1 are - (CH 2 ) Z-2 CH═CH 2 (Z is an integer of 3 to 10) and substituents m 1 to p 1 are hydrogen, an alkyl group, an alkenyl group, ) can group, in the formula A1 Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3) 2 -, -S- or -SO 2 -, and
Formula E1 to a substituent two or more of q1 to t1 of I1 is - (CH 2) Z-2 CH = CH 2 (Z 3 to 10 of an integer), and the other is hydrogen, an alkyl group, an alkenyl (alkenyl) group, or An aryl group,
In Formula H1 M is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3) 2 -, -S- or -SO 2 -, and wherein the formula I1 is a straight-chain or at the meta position of the oxygen And may be substituted with a branched C1-C10 alkyl group.
[Formula M3]
HSiR 1 R 2 R 3
Wherein at least one of R 1 to R 3 is a C 1 -C 10 alkoxy group and the remainder is a straight or branched C 1 -C 10 alkyl group, and the alkoxy group and the alkyl group are linear or branched.
[Final product]
Substituents a and b of the above formulas AI to DI have the following formula S1 and substituents c to f may be the formula S1, hydrogen, an alkyl group, an alkenyl group, or an aryl group,
In the formula (AI), Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -
At least two of the substituents g to j in the above formulas (EI) to (II) are represented by the following formula (S1), and the remainder may be hydrogen, an alkyl group, an alkenyl group, or an aryl group,
Wherein M is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 - in the formula HI, May be substituted with a branched C1-C10 alkyl group.
[Formula (S1)
- (CH 2 ) z -SiR 1 R 2 R 3
(In the formula (S1), R 1 to R 3 Is an alkoxy group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group are branched or branched, and z is an integer of 3 to 10.)
(CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) substituted in the step 1-3 is reacted with an alkoxy silane of the formula M 3 in the presence of a metal catalyst and any solvent to obtain a compound of the formula S1. ≪ / RTI >
(M2)
X- (CH 2) z-2 -CH = CH 2
(Wherein, X is Cl, Br or halides of I, -O-SO 2 -CH 3 , -O-SO 2 -CF 3, -O-SO 2 -C 6 H 4 -CF 3, -O-SO 2 -C 6 H 4 -NO 2 Or -O-SO 2 -C 6 H 4 -CH 3 , and z is an integer from 3 to 10.)
[Formula M3]
HSiR 1 R 2 R 3
Wherein at least one of R 1 to R 3 is a C 1 -C 10 alkoxy group and the remainder is a straight or branched C 1 -C 10 alkyl group, and the alkoxy group and the alkyl group are linear or branched.
≪ RTI ID =
OCN- (CH 2 ) z -SiR 1 R 2 R 3
Wherein at least one of R 1 to R 3 is a C 1 -C 10 alkoxy group and the remainder is a straight or branched C 1 -C 10 alkyl group, the alkoxy group and the alkyl group are linear or branched, and z is 3 to 10 .
A second step (2-2) of obtaining an intermediate product (22) having a hydroxy group by carrying out a rearrangement reaction with respect to the intermediate product (21);
Reacting the intermediate product (22) with an alkenyl compound of the following formula (M2) in the presence of an optional base and any solvent to obtain a compound wherein the hydroxy group is - (CH 2 ) Z-2 CH = CH 2 To obtain an intermediate product (23) which is substituted with a halogen atom; And
And a step (2-4) of reacting the intermediate product (23) with an alkoxy silane of the formula (M3) in the presence of a metal catalyst and any solvent to obtain an end product of any one of the following formulas AI to DI: Way.
[Starting material]
(A substituent k to p of the above formula to AS DS is hydrogen, in formula AS Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3) 2 -, -S- or -SO 2 -.)
(M2)
X- (CH 2) z-2 -CH = CH 2
(Wherein, X is Cl, Br or halides of I, -O-SO 2 -CH 3 , -O-SO 2 -CF 3, -O-SO 2 -C 6 H 4 -CF 3, -O-SO 2 -C 6 H 4 -NO 2 or -O-SO 2 -C 6 H 4 -CH 3 , and z is an integer from 3 to 10.)
[Intermediate (21)]
(Substituent k1 and l1 of Formula A21 to D21 is - and (CH 2) Z-2 CH = CH 2 (Z is an integer of 3 to 10), m1 to p1 is hydrogen, in formula A21 Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -.
[Intermediate (22)]
(In the substituents k2 to p2 of the above formulas A22 to D22, any one of m2 and n2 and any of o2 and p2 is - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) and the other is hydrogen, in formula A22 Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3) 2 -, -S- or -SO 2 - a).
[Intermediate (23)]
(In the substituent k3 to p3 of Formula A23 to D23, k3; l3; m3 or any one of n3; any one, and o3 or p3 is - (CH 2) Z-2 CH = CH 2 (Z 3 to 10 is an integer), and the other is hydrogen, in formula A23 Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3) 2 -, -S- or -SO 2 - a. )
[Formula M3]
HSiR 1 R 2 R 3
Wherein at least one of R 1 to R 3 is a C 1 -C 10 alkoxy group and the remainder is a straight or branched C 1 -C 10 alkyl group, and the alkoxy group and the alkyl group are linear or branched.
[Final product]
(Wherein at least two of the substituents a to f of the formulas AI to DI have the following formula S1 and the remainder are hydrogen or - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -.
[Formula (S1)
- (CH 2 ) z -SiR 1 R 2 R 3
(In the formula (S1), R 1 to R 3 Is an alkoxy group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group are branched or branched and z is an integer of 3 to 10.)
≪ / RTI > further comprising an alkoxysilyl compound.
[Intermediate (22)]
(In the substituents k2 to p2 of the above formulas A22 to D22, any one of m2 and n2 and any of o2 and p2 is - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) and the other is hydrogen, in formula A22 Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3) 2 -, -S- or -SO 2 - a).
≪ RTI ID =
OCN- (CH 2 ) z -SiR 1 R 2 R 3
Wherein at least one of R 1 to R 3 is a C 1 -C 10 alkoxy group and the remainder is a straight or branched C 1 -C 10 alkyl group, the alkoxy group and the alkyl group are linear or branched, and z is 3 to 10 .
[Final product]
Substituents a and b of the above formulas AI to DI are represented by the following formula (S2), and either one of c and d and either e or f is - (CH 2 ) Z-2 CH = CH 2 (Z is 3-10 And Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -.
≪ RTI ID = 0.0 &
-CONH (CH 2 ) z -SiR 1 R 2 R 3
(In the above formula (S2), R 1 to R 3 Is an alkoxy group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group are branched or branched and z is an integer of 3 to 10.)
[Formula M3]
HSiR 1 R 2 R 3
(Wherein at least one of R 1 to R 3 is a C 1 -C 10 alkoxy group and the remainder is a straight or branched C 1 -C 10 alkyl group, and the alkoxy group and the alkyl group are linear or branched.)
[Final product]
(Wherein the substituents of formula AI to DI a and b the following formula S2, any one of c and d, and one of e and f is the formula for S1, and the others are hydrogen, in formula Y is -CH 2 AI -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -.
[Formula (S1)
- (CH 2 ) z -SiR 1 R 2 R 3
≪ RTI ID = 0.0 &
-CONH (CH 2 ) z -SiR 1 R 2 R 3
(In the formulas (S1) and (S2), R 1 to R 3 Is an alkoxy group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group are branched or branched and z is an integer of 3 to 10.)
Further comprising a step 3-2 of reacting the intermediate product (31) with an alkoxy silane of the formula (M3) in the presence of a metal catalyst and any solvent to obtain an end product of any one of the following formulas AI to DI: ≪ / RTI >
[Intermediate (31)]
(Substituent k1 and l1 of Formula A31 to D31 is hydrogen, m1 to p1 is - (CH 2) Z-2 CH = CH 2 (Z is an integer of 3 to 10), Y in the above formula A31 is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -.
[Formula M3]
HSiR 1 R 2 R 3
(Wherein at least one of R 1 to R 3 is a C 1 -C 10 alkoxy group and the remainder is a straight or branched C 1 -C 10 alkyl group, and the alkoxy group and the alkyl group are linear or branched.)
[Final product]
(Wherein the substituents a and b in the above formulas AI to DI are hydrogen, at least two of c to f are represented by the following formula S1, and the remainder are - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -.
[Formula (S1)
- (CH 2 ) z -SiR 1 R 2 R 3
(In the formula (S1), R 1 to R 3 Is an alkoxy group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group are branched or branched, and z is an integer of 3 to 10.)
Step 3-4 in which the intermediate product (32) is reacted with an alkoxy silane of the formula (M3) in the presence of a metal catalyst and any solvent to obtain an end product of any one of the following formulas AI to DI
≪ / RTI > further comprising an alkoxysilyl compound.
(M2)
X- (CH 2) z-2 -CH = CH 2
(Wherein, X is Cl, Br or halides of I, -O-SO 2 -CH 3 , -O-SO 2 -CF 3, -O-SO 2 -C 6 H 4 -CF 3, -O-SO 2 -C 6 H 4 -NO 2 or -O-SO 2 -C 6 H 4 -CH 3 , and z is an integer from 3 to 10.)
[Intermediate (32)]
(The above formula A32 to D32 substituent of k2 to p2 is - (CH 2) Z-2 CH = CH 2 (Z is an integer of 3 to 10), and, Y in the above formula A31 is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -.
[Formula M3]
HSiR 1 R 2 R 3
(Wherein at least one of R 1 to R 3 is a C 1 -C 10 alkoxy group and the remainder is a straight or branched C 1 -C 10 alkyl group, and the alkoxy group and the alkyl group are linear or branched.)
[Final product]
(Wherein at least two of the substituents a to f of the formulas AI to DI have the following formula S1 and the remainder are - (CH 2 ) Z-2 CH = CH 2 (Z is an integer of 3 to 10) Is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -.
[Formula (S1)
- (CH 2 ) z -SiR 1 R 2 R 3
(In the formula (S1), R 1 to R 3 Is an alkoxy group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group are branched or branched and z is an integer of 3 to 10.)
≪ / RTI >
≪ RTI ID =
OCN- (CH 2 ) z -SiR 1 R 2 R 3
Wherein at least one of R 1 to R 3 is a C 1 -C 10 alkoxy group and the remainder is a straight or branched C 1 -C 10 alkyl group, the alkoxy group and the alkyl group are linear or branched, and z is 3 to 10 .
[Final product]
(Note that the formula AI to substituents of DI a and b have the following formula S2, c to f is - (CH 2) Z-2 CH = CH 2 (Z 3 to 10 of an integer), and, Y in the formula AI is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -.
≪ RTI ID = 0.0 &
-CONH (CH 2 ) z -SiR 1 R 2 R 3
(In the above formula (S2), R 1 to R 3 Is an alkoxy group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group are branched or branched and z is an integer of 3 to 10.)
[Formula M3]
HSiR 1 R 2 R 3
(Wherein at least one of R 1 to R 3 is a C 1 -C 10 alkoxy group and the remainder is a straight or branched C 1 -C 10 alkyl group, and the alkoxy group and the alkyl group are linear or branched.)
[Final product]
(Wherein the substituents a and b in the formulas AI to DI are represented by the following formula (S2), at least two of c to f are represented by the following formula (S1), and the remainder are - (CH 2 ) Z-2 CH = CH 2 Wherein Y is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -S- or -SO 2 -.
[Formula (S1)
- (CH 2 ) z -SiR 1 R 2 R 3
≪ RTI ID = 0.0 &
-CONH (CH 2 ) z -SiR 1 R 2 R 3
(In the formulas (S1) and (S2), R 1 to R 3 Is an alkoxy group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group are branched or branched and z is an integer of 3 to 10.)
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Cited By (4)
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| WO2016093383A1 (en) * | 2014-12-09 | 2016-06-16 | 한국생산기술연구원 | Thermosetting alkoxysilyl compound having two or more alkoxysilyl groups, composition and cured product comprising same, use thereof, and method for preparing alkoxysilyl compound |
| KR20170092468A (en) * | 2016-02-03 | 2017-08-11 | 한국생산기술연구원 | Compound having alkoxysilyl group and active ester group, preparing method thereof, composition comprising the same, and use thereof |
| JP2017197455A (en) * | 2016-04-26 | 2017-11-02 | 信越化学工業株式会社 | Nitrogen-containing organoxysilane compound and method for producing the same |
| CN108043235A (en) * | 2017-12-20 | 2018-05-18 | 河北工业大学 | A kind of method for enhancing interfacial adhesion between organic separation membrane and backing material |
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| KR102637326B1 (en) * | 2019-12-06 | 2024-02-15 | 주식회사 엘지화학 | Positive-type photosensitive resin comopsition and display device comprising black bank formed by using same |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016093383A1 (en) * | 2014-12-09 | 2016-06-16 | 한국생산기술연구원 | Thermosetting alkoxysilyl compound having two or more alkoxysilyl groups, composition and cured product comprising same, use thereof, and method for preparing alkoxysilyl compound |
| US10428176B2 (en) | 2014-12-09 | 2019-10-01 | Korea Institute Of Industrial Technology | Thermosetting alkoxysilyl compound having two or more alkoxysilyl groups, composition and cured product comprising same, use thereof, and method for preparing alkoxysilyl compound |
| KR20170092468A (en) * | 2016-02-03 | 2017-08-11 | 한국생산기술연구원 | Compound having alkoxysilyl group and active ester group, preparing method thereof, composition comprising the same, and use thereof |
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| CN108043235A (en) * | 2017-12-20 | 2018-05-18 | 河北工业大学 | A kind of method for enhancing interfacial adhesion between organic separation membrane and backing material |
| CN108043235B (en) * | 2017-12-20 | 2021-04-27 | 河北工业大学 | Method for enhancing interfacial adhesion between organic separation membrane and support material |
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