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    • 专利摘要:
    PROCESS FOR PRODUCING FUNCTIONAL SILOXANS OF CONTROLLED STRUCTURE The present invention relates to a process for preparing linear hydroxyaryloxy-functional polydiorganosiloxanes having controlled structures. The process includes the step of reacting an (Alpha), (Omega) -bisacyloxyprolidiorganosiloxane with at least one bisphenolic compound, or its hydroxy-functional oligomer, in such a way that the phenolic groups in the bisphenolic compound or the hydroxy-functional oligomer of that to the groups acyloxy in (Alpha), (Omega) -bisacyloxypolydiorganosiloxane is less than 2.0. Also described are hydroxyaryloxy-functional polydiorganosiloxanes produced from the process and polysiloxane / polyiorgan block copolymers made using the hydroxyaryloxy-functional siloxanes.
    公开号:BR112014025273B1
    申请号:R112014025273-4
    申请日:2013-04-09
    公开日:2020-12-22
    发明作者:John M. Huggins；Hubertus Eversheim
    申请人:Momentive Performance Materials Gmbh；
    IPC主号:
    专利说明:

    TECHNICAL FIELD
    [001] The present invention relates to hydroxyaryloxy-functional polydiorganosiloxanes having controlled structures and the processes of producing them. The present invention also relates to polydiorganosiloxanes / polyiorgan block copolymers made from hydroxyaryloxy-functional polydiorganosiloxanes and the processes for producing block copolymers. BACKGROUND OF THE INVENTION
    [002] Linear hydroxyaryloxy-functional siloxanes are useful starting materials for producing polydiorganosiloxane / polyiorgan block copolymers. There are three general ways to prepare hydroxyaryloxy-functional siloxanes.
    [003] The US Patent. No. 3,189,662 describes the reaction of chlorinated polysiloxanes with bisphenolic compounds, eliminating hydrochloric acid as the by-product. This process has the advantages of requiring the use of large amounts of a basic compound to neutralize the hydrochloric acid by-product and a tedious filtration of the resulting salt.
    [004] The US Patents. We. 4,584,360 and 4,732,949 describe the reaction of bisphenolic compounds with a, w-bisacyloxypolidimethylsiloxanes, which are represented by a structural formula of HO-Ar-O- (SiR2-O) o- (SiR2-O) p- (SiR12 - O) q-Ar-OH, where Ar are arylene radicals from diphenols, R and R1 are alkyl or aryl and the + p + q is from 5 to 100, in a molar ratio of 2: 1 to 20: 1 in an inert organic solvent using at least one inorganic base in at least stoichiometric amounts. According to the ‘360 and‘ 949 patents, the preferred inorganic bases are alkali metal and alkaline earth metal carbonates.
    [005] In order to dissolve the large excess of used bisphenolic compounds, the process described in the '360 and' 949 patents requires the use of large amounts of organic solvents, typically chlorinated organic solvents. The use of these chlorinated organic solvents in large quantities is not desirable for health, safety and environmental issues. Removing large amounts of solvents by distillation increases manufacturing costs. In addition, the base used in the reaction mixture forms salts, which are difficult to completely remove from the hydroxyaryloxy-terminated siloxane product by filtration. Thus, the isolation of hydroxyaryloxy-terminated siloxanes according to this process in a pure form that is free of undesirable impurities is tedious and expensive.
    [006] The US Patent. No. 6,258,968 describes the reaction of bisphenolic compounds with cyclodialkylsiloxanes in a solvent, in which an acid catalyst is used and the water by-product is removed from the reaction mixture by distillation. This process has a number of disadvantages. First, the process is limited to simple monocyclic bisphenols, such as hydroquinone, as bicyclic bisphenols such as bisphenol-A decompose under acid catalysis, forming unwanted by-product numbers. Second, it is difficult to control the structure of the functional hydroxyaryloxy polysiloxane products prepared by this process, given that the molecular weight of the product is determined by the exact amount of water removed and the reactivity of the bisphenol. Removing too little water leads to incomplete reaction and the formation of unwanted terminal Si-OH groups, in which removing too much water produces polymers of excessively high molecular weight and viscosity. It was concluded that it is extremely difficult to obtain polymers free of terminal Si-OH groups which are of sufficiently low viscosity for easy filtration. The filtration of high-viscosity polymers without applying heat is slow and tedious, adding significantly to the cost of such processes. Third, the salts formed after neutralization of the acid catalyst proved to be extremely difficult to remove by filtration, especially if there is unreacted bisphenol in the mixture.
    [007] Hydroxyaryloxy-terminated siloxanes can be used to prepare polydiorganosiloxane / polycarbonate block copolymers via a two-stage boundary process or a solvent-free, transesterification or fusion polycondensation process. As the solventless polycondensation process, transesterification or melting does not allow for a subsequent purification step, it is particularly sensitive to impurities. Residual by-products and impurities cannot be removed from hydroxyaryloxy-terminated siloxanes, such as neutralization salts, they can be detrimental to the properties of the resulting block copolymers. For example, such impurities can cause turbidity and surface defects in molded parts and reduce stability towards hydrolysis and chemicals.
    [008] So far, it has been believed that it is possible to prepare unwanted Si-OH-free hydroxyaryloxy-functional siloxanes and other by-products by the prior art processes discussed above in a reproducible and cost-effective manner. In addition, hydroxyaryloxy-functional siloxanes prepared by the prior art processes discussed above are typically contaminated by residual neutralizing salts and excess bisphenolic compounds. These hydroxyaryloxy-functional polydiorganosiloxanes, when used to prepare polydiorganosiloxane / polyiorgan block copolymers by solventless polycondensation, transesterification or fusion processes, can cause turbidity or impair the thermal and chemical stability of the copolymer product.
    [009] Consequently, there is a need for a cost-effective process for the preparation of hydroxyaryloxy-terminated polydialkylsiloxanes having controlled structure that are free of unwanted impurities. SUMMARY OF THE INVENTION
    [010] In one aspect, the present invention provides a hydroxyaryloxy-functional polydiorganosiloxane of General Formula (I)

    [011] Where Ar is a C6 to C30 aryl, alkylaryl or aryloxy divalent group, each occurrence of R is independently a C1 to C20 alkyl, alkylaryl or monovalent aryl, n has an average value of 10 to 400 and has an average value from 1.0 to 5.0.
    [012] In another aspect, the present invention relates to a process for preparing the hydroxyaryloxy-functional polydiorganosiloxane of general formula (I). The process includes the step of reacting a linear α, w-bisacyloxypoliorganosiloxane of General Formula (II) with at least one bisphenolic compound or a hydroxy-functional oligomer thereof, in such a molar ratio that the phenolic groups in the bisphenolic compound or its hydroxy-oligomer functional for the acyloxy groups in α, w-bisacyloxypolidiorganosiloxane is less than 2.0, where General Formula (II) is:

    [013] Where each occurrence of R and R1 is independently a C1 to C20 alkyl, alkylaryl or monovalent aryl group and n has an average value of 10 to 400.
    [014] In yet another aspect, the present invention relates to a polydiorganosiloxane / polyiorgan (AB) x block copolymer comprising (i) polydiorganosiloxane A blocks and (ii) polycarbonate, polysulfone, polyether ether ketone blocks, and / or polyester B with 2 to 500 bisoxiorgan groups, in which the polydiorganosiloxane A blocks are represented by the General Formula (III)

    [015] Where Ar is a divalent C6 to C30 aryl, alkylaryl or aryloxy group, each occurrence of R is independently a C1 to C20 alkyl, alkylaryl or monovalent aryl group, n has an average value of 10 to 400 and has a value average from 1.0 to 5.0 and where x is between 1 and 1000.
    [016] In yet another aspect, the present invention relates to a process for preparing the polydiorganosiloxane / polyiorgan (A-B) x block copolymers. The process includes the step of reacting a linear hydroxyaryloxy-functional polydialalkylsiloxane of General Formula (I) with a bisphenolic compound or its polycarbonate, polyester, polyether ether ketone or polysulfone oligomers under the conditions or a two-phase limit polycondensation process or one polycondensation process without solvent, transesterification or fusion.
    [017] These and other aspects will become clear by reading the detailed description of the invention. DESCRIPTION OF THE INVENTION
    [018] It was surprisingly concluded that using less than stoichiometric amounts of bisphenolic compounds and specific reaction conditions, hydroxyaryloxy-terminated polydiorganosiloxanes of controlled structures can be obtained. These siloxanes exhibit particularly advantageous properties for the preparation of polydiorganosiloxane / polyiorgan block copolymers because they have low impurity content, which can cause turbidity or impair the thermal or chemical stability of the copolymers. In particular, the process for preparing hydroxyaryloxy-terminated siloxanes according to the invention is highly cost-efficient and the product produced is particularly suitable for incorporation into polysiloxane / polyiorgan block copolymers via polycondensation, transesterification or fusion processes.
    [019] In one embodiment, the present invention provides hydroxyaryloxy-terminated polydiorganosiloxanes of General Formula (I)

    [020] Where Ar is a divalent C6 to C30 aryl, alkylaryl or aryloxy group, each occurrence of R is independently a C1 to C20 alkyl, alkylaryl or monovalent aryl, n has an average value of 10 to 400 and has an average value from 1.0 to 5.0.
    [021] In some embodiments, the hydroxyaryloxy-functional polydiorganosiloxanes of the General Formula (I) are those represented by the General Formulas (IV) and (V) below:


    [022] Where n has an average value of 10 to 400, specifically 10 to 100 and more specifically 15 to 50, m has an average value between 1.0 and 5.0, more specifically between 2.3 and 4.9 and the value of n times (m + 1) is between 20 and 200.
    [023] Hydroxyaryloxy-terminated polydiorganosiloxanes of General Formula (I) can be prepared by a process including the step of reacting a linear α, w-bisacyloxy-polydialalkylsiloxane of General Formula (II) with at least one bisphenolic compound or a hydroxy oligomer -functional of this, in such a molar ratio that the phenolic groups in the bisphenolic compound or the hydroxy-functional oligomer of that for the acyloxy groups in a, w-bisacyloxypolidialkylsiloxane is less than 2.0, where the General Formula (II) is:

    [024] Where each occurrence of R and R1 is independently a C1 to C20 alkyl, alkylaryl or monovalent aryl group and n has an average value of 10 to 400.
    [025] In conjunction with Formulas (I) and (II), n advantageously has an average value of 10 to 400, specifically 10 to 100 and more specifically 15 to 50; m has an average value greater than or equal to 1.0, specifically between 1.0 and 5.0, more specifically between 2.3 and 4.9; the value of n times (m + 1) is between 20 and 500, advantageously between 20 and 200; R and R1 are independently phenyl or C1 to C20 alkyl, specifically C1 to C10 alkyl, more specifically C1 to C5 alkyl, such as methyl, ethyl, propyl, butyl and pentyl, more specifically R and R1 are either methyl or phenyl; and Ar is at least one of the following structures:

    [026] This reaction is advantageously carried out in an inert solvent capable of dissolving at least part of the bisphenolic compound or its oligomer. Preferred solvents are aromatic hydrocarbons such as toluene, xylene, chlorobenzene and the like. Especially preferred inert solvents are polar organic acids, such as acetic acid and other C3 to C6 volatile organic carboxylic acids or the like. It is particularly advantageous to add the linear α-, w-bisacyloxydiorganosiloxane of Formula (II) to a solution of the bisphenolic compound in an organic carboxylic acid such as a C2 to C6 carboxylic acid, for example, acetic acid either alone or together with other inert solvents, at a temperature sufficient to dissolve a significant portion of the bisphenolic compound. Other methods of addition are also possible.
    [027] The reaction of a, w-bisacyloxypolidiorganosiloxane of the General Formula (II) with bisphenolic compounds or hydroxy-functional oligomers thereof, can be accelerated by the use of optional catalysts. Advantageously, the catalysts are the metal salts of organic acids, such as sodium or potassium acetate. Other catalysts known in the art to catalyze siloxane condensation reactions can also be used.
    [028] The linear hydroxyaryloxy-functional polydiorganosiloxanes of General Formula (I) can be used to produce polydiorganosiloxane / polyorganic block copolymers.
    [029] Consequently, in another embodiment, the present invention provides a process for the preparation of polydiorganosiloxane / polyiorgan (A-B) x block copolymers according to the two-stage limit polycondensation process. The two-stage limit polycondensation process is generally known and has been described in US Patents. We. 3,189,662, 4,584,360 and 4,732,949, all of which are incorporated herein by reference. According to the two-stage limit polycondensation process of the invention, a bisphenolic compound or the polycarbonate, polyester, polyether ether ketone or polysulfone oligomers and a linear hydroxyaryloxy-functional polyhydroorganosiloxane of General Formula (I) dissolved in such an organic solvent like a methylene chloride or chlorobenzene, they react with a carbonate donor in the presence of an aqueous solution of an inorganic base and an optional catalyst. In one embodiment, the carbonate donor is phosgene. Chain terminating agents, such as monophenols, can optionally be used in the reaction.
    [030] The linear hydroxyaryloxy-functional polydiorganosiloxanes of the General Formula (I) are particularly suitable for the preparation of polydiorganosiloxane / polyiorgan block copolymers according to solvent-free polycondensation, transesterification or fusion processes. In particular, the polysiloxanes of General Formula (I) exhibit very low levels of unwanted impurities.
    [031] Consequently, in another embodiment, the present invention provides a polycondensation process without solvent, transesterification or fusion to prepare the polydiorganosiloxane / polyorgangan block copolymers. The solventless polycondensation, transesterification or melting process is generally known and has been described in US Patents. We. 5,504,177, 5,340,905, 5,227,449, 5,783,651, 5,821,321 and 6,066,700, which are incorporated herein by reference. The solventless polycondensation, transesterification or fusion processes of the invention include the step of reacting hydroxyaryloxy-functional siloxanes of the General Formula (I) and bisphenolic compounds or their polycarbonate, polyester, polyether ether ketone or polysulfone oligomers in the absence of added solvents followed by removal of by-products by distillation, and the condensation of the terminal hydroxy aryl groups in the polysiloxane with the hydroxy, ester or carbonate groups of the bisphenolic compounds or their oligomers leads to the formation of new bonds between the block segments. Such a process may include the use of a carbonate donor such as diphenylcarbonate, chain terminating agents, such as phenol or C6 to C12-alkylphenols described in US 4,732,949, condensation linking groups, such as diarylcarbonate or oligocarbonates as described in US 5,504,177 and US 5,783,651 and catalysts known in the art.
    [032] Particularly preferred is the preparation of block copolymers from linear hydroxyaryloxy-functional polydiorganosiloxanes of the General Formula (I) and polycarbonate oligomers of bisphenolic compounds in the solventless polycondensation, transesterification or fusion process, using chain termination groups and optional diarylcarbonates or oligocarbonates, to control the molecular weight of the resulting copolymer and catalysts to promote the reaction. In one embodiment, suitable catalysts are quaternary ammonium or quaternary phosphonium based catalysts, as known in the art. Advantageously, the polycondensation process without solvent, transesterification or fusion is carried out at temperatures between 160 and 320 ° C using a vacuum to assist in the removal of by-products.
    [033] In a further aspect of the present invention, condensation of polydiorganosiloxanes of General Formula (I) with polycarbonate oligomers can also include co-condensation with mono- or diester compounds or polyester oligomers to form triblock polydialalkylsiloxane / polyester / polycarbonate copolymers .
    [034] Bisphenolic compounds or their oligomers suitable for use in the processes for preparing the hydroxyaryloxy-functional polydiorganosiloxane in General Formula (I) and the copolymer (AB) x are bisphenolic compounds described in US Patents. We. 4,732,949 and 5,109,076 or their oligomers, in which the contents of the '949 and' 076 patents are incorporated herein by reference. In one embodiment, the appropriate bisphenolic compounds or their oligomers are those of the following structures:

    and its polycarbonate, polysulfone and polyester oligomers. Advantageously, at least 90% of the bisoxyaryl groups in the polycarbonate oligomers are derived from the preferred bisphenolic compounds described above and at least 50% of the terminal groups are phenolic.
    [035] Advantageously, the oligomers are the polycarbonate oligomers of the bisphenolic compounds described above. They are represented by the General Formula (VI)
    where Z is a C6 to C30 aryl, bisarylalkyl or bisalyloxy divalent group, p is a number between 2 and 500, preferably between 2 and 150. In the preparation of the hydroxyaryloxy-functional polydiorganosiloxane of General Formula (I), the oligomer (VI) it is advantageously hydroxy-functional in which Q1 and Q2 are hydrogen. In the preparation of polydialkylsiloxane / polyiorgan (AB) x block copolymers under the conditions of a two-phase limit polycondensation process together with phosgene, advantageously, Q1 and Q2 are independently of each other or hydrogen or a -C group (= O) -X and X is a halogen, a hydroxy group, C1-C20 alkyloxy, alkylaryloxy or aryloxy. In the preparation of polydialkylsiloxane / polyiorgan (AB) x block copolymers according to solventless polycondensation, transesterification or fusion processes, advantageously, Q1 and Q2 are independently of each other or hydrogen or a -C (= O) -X group and X is a hydroxy, C1-C20 alkyloxy, alkylaryloxy or aryloxy group.
    [036] Advantageously, the oligomers are the polyester oligomers represented by the General Formula (VII): wherein Z1, Z2 and Z3 are independently a group C6 to C30 aryl, bisarylalkyl or bisalyloxy divalent and Q1, Q2 and p are as defined here above in context of Formula (VI).

    [037] Advantageously, the oligomers are the polysulfone oligomers represented by the General Formula (VIII):
    wherein Z1, Z2 and Z3 are independently a C6 to C30 aryl, bisarylalkyl or bisalyloxy divalent group and Q1, Q2 and p are as defined herein above in the context of Formula (VI).
    [038] Advantageously, the oligomers are the polyether ether ketone oligomers represented by the General Formula (IX)
    wherein Z1, Z2 and Z3 are independently a C6 to C30 aryl, bisarylalkyl or bisalyloxy divalent group and Q1, Q2 and p are as defined herein above in the context of Formula (VI).
    [039] The polydialkylsiloxane / polyiorgan block copolymers produced by the above processes are block copolymers (AB) x. Advantageously, the block copolymers comprise blocks of polydiorganosiloxane (A) represented by the General Formula (III):
    and polycarbonate blocks (B) of general structure (X)
    or polyester blocks (B) of general structure (XI)
    or polysulfone blocks (B) of general structure (XII)
    or blocks of polyether ether ketone (B) of the general structure (XIII)
    where Ar is a divalent C6 to C30 aryl, alkylaryl or aryloxy group, each occurrence of R is independently a Covalent C1 to C20 alkyl, alkylaryl or monovalent group, n is between 10 and 400, advantageously between 10 and 100 and most advantageously between 15 and 50, m is between 1.0 and 5.0, advantageously between 2.3 and 4.9, the value of n times (m + 1) is between 20 and 500, advantageously between 20 and 200, each one among Z, Z1, Z2 and Z3 is independently a C6 to C30 aryl, bisarylalkyl or bisaryloxy group, p is a number between 2 and 500, Y1 and Y2 are either a direct bond or carbonate or ester bond groups and ex is between 1 and 1000 .
    [040] Advantageously, in the polydiorganosiloxane / polyiorgan (AB) x block copolymer of the present invention at least 90% of the diorganosiloxane blocks (A) are polydimethylsiloxanes and the copolymer blocks (B) are at least 90% polycarbonate blocks prepared from the preferred bisphenolic compounds described above.
    [041] The polydiorganosiloxane / polyiorgan block copolymers of the present invention can be prepared at low cost and in good yields with very low levels of interfering impurities, in particular inorganic salts. In addition, the polydiorganosiloxane / polyiorgan block copolymers of the present invention exhibit enhanced control of the block domain structure in molded articles. This leads to reproducible and enhanced physical properties such as low temperature impact resistance, as well as hydrolysis and chemical resistance. The polydiorganosiloxane / polyiorgan block copolymers of the invention also exhibit better surface tension properties that can lead to improved mold flow and chemical resistance properties compared to block copolymers prepared by prior art processes.
    [042] The following examples are intended to illustrate, but in no way limit the scope of the present invention. All percentages are by weight based on the total weight of the composition and all temperatures are in degrees Celsius, unless explicitly stated otherwise. Examples Example 1
    [043] In a reaction flask equipped with a thermostat heater, stirrer, thermometer and reflux condenser, 250 g of a a, w-bisacyloxypolidimethylsiloxane, with an average chain length of 31.8 dimethylsiloxide units as determined by 29Si NMR and 230 mmols of terminal acyloxy groups, were added by dripping over 4 hours to a solution of 35.1 g (150 mmols) of bisphenol-A in 50 g of xylenes, 25 g of acetic acid and 0.5 g of sodium acetate, while heating to a moderate reflux to 105 ° C. After complete addition, the clear solution was stirred for an additional hour. Then, the solvents and volatiles were removed by vacuum distillation at 160 ° C and 0.3 kPa (3 mbar) pressure. After cooling, the crude product was easily filtered over a 3 micron filter (Seitz K300) to obtain 236 g (83% theory) of a clear, colorless liquid, which had the following structure and characteristics: Structure:
    NMR (found): n = 33.5; m = 2.3; Viscosity (23 ° C): 611 mPa.s; % solids (160 ° C, 30 min): 99.4%; nD23 = 1.4274; and Hydroxy content: 13.3 mg KOH / g. Example 2
    [044] In a reaction flask as in Example 1, 180 g of an α, w- bisacyloxydimethylsiloxane, with an average chain length of 20.5 dimethylsiloxy units as determined by 29Si NMR and 221 mmols of terminal acyloxy groups, added by dripping over 3 hours to a solution of 15.8 g (144 mmols) of hydroquinone in 72 g of xylenes, 36 g of acetic acid and 0.36 g of sodium acetate, while heating to a moderate reflux at 110 ° C. After complete addition, the clear solution was stirred for an additional hour. Then, the solvents and volatiles were removed by vacuum distillation at 150 ° C and 0.3 kPa (3 mbar) pressure. After cooling, the crude product was easily filtered over a 3 micron filter (Seitz K300) to obtain 165 g (84% theory) of a clear, colorless liquid, which had the following structure and characteristics: Structure:
    NMR (found): n = 20.8; m = 4.88; Viscosity (23 ° C): 440 mPa.s; % solids (160 ° C, 30 min): 99.45%; nD23 = 1.4200; and Hydroxy content: 12.0 mg KOH / g. Comparative Example A according to US 4,584,360
    [045] In a reaction flask as in Example 1, a 109 g solution of a a, w-bisacyloxypolidimethylsiloxane, with an average chain length of 31.8 dimethylsiloxy units as determined by 29Si NMR and 88 moles of acyloxy groups terminal, in 60 g of chlorobenzene was added dropwise over 4 hours to a solution of 50 g (214 mmols) of bisphenol-A in 352 g of chlorobenzene and 12.2 g (88 mmol) of K2CO3, while heating the a moderate reflux. After complete addition, the solution was stirred for an additional hour and then filtered while still hot. Upon cooling, a significant amount of precipitate formed. Then, the solvents and volatiles were removed by vacuum distillation at 160 ° C and 0.3 kPa (3 mbar) pressure. The raw product was cold filtered over a 3 micron filter (Seitz K300) to obtain 82 g of a low yield product (66% theory). After standing, the liquid product became cloudy, precipitating more unreacted bisphenol-A. The product had the following structure and characteristics: Structure:
    NMR (found): n = 33.0; m = 0.95; Viscosity (23 ° C): 326 mPa.s; % solids (160 ° C, 30 min): 99.37%; nD23 = 1.4312; and Hydroxy content: 22.8 mg KOH / g. Comparative Example B according to US 6,258,968
    [046] In a three-necked reaction flask with a heater, stirrer, thermometer, water separator and reflux condenser, 3210 g of octamethylcyclotetrasiloxane, 1200 g of xylenes, 318 g of hydroquinone and 1000 ppm of concentrated sulfuric acid were added and 500 ppm of perfluoro alkylsulfonic acid. The mixture was heated to reflux for 3 hours, removing 28 g of water. The reaction mixture was cooled to 60 ° C and 10.5 g of ammonium carbonate was added and stirred for 1 hour at 60 ° C. Then, the solvents and volatiles were removed by vacuum distillation at 150 ° C and 0.5 kPa (5 mbar) pressure. After cooling, the crude product could only be filtered over a 3 micron filter (Seitz K300) with difficulty producing significant quantities of filter cake and a clear liquid product in low yield, which, upon rest, precipitated additional unreacted hydroquinone and salts . A second filtration over a 3 micron filter (Seitz K300) provides a colorless liquid, which had the following structure and characteristics: Structure:
    NMR (found): n = 29.2; m = 9.0; Viscosity (23 ° C): 2320 mPa.s; % solids (160 ° C, 30 min): 96.9%; nD23 = 1.416; and Hydroxy content: 6.5 mg KOH / g. Comparative Example C according to US 6,258,968
    [047] In a reaction flask as in Comparative Example B, 350 g of octamethylcyclotetrasiloxane, 300 g of toluene, 74.5 g of bisphenol-A and 1000 ppm of concentrated sulfuric acid and 500 ppm of a perfluoro alkyl sulfonic acid were added. The mixture was heated to reflux for 5 hours while removing 3.8 g of water. The reaction mixture was cooled to 60 ° C and 12 g of sodium carbonate was added and stirred for 1 hour at 60 ° C. Then, the solvents and volatiles were removed by vacuum distillation at 155 ° C and 0.1 kPa (1 mbar) pressure. After cooling, the raw product could only be filtered over a 3 micron filter (Seitz K300) with difficulty producing significant quantities of filter cake and a yellowish cloudy product in low yield, which, upon rest, precipitated additional by-products and salts. NMR analysis of the product confirmed the confirmed formation of large amounts of undesirable by-products from the decomposition of bisphenol-A.
    [048] While the invention has been described above with respect to its specific modalities, it is clear that many changes, modifications and variations can be made without abandoning the concept of the invention described here. Consequently, it is intended to cover such changes, modifications and variations that are within the spirit and broad scope of the attached claims.
    权利要求:
    Claims (16)
    [0001]
    1. Process for preparing a linear hydroxyaryloxy-functional polydialkylsiloxane of General Formula (I)
    [0002]
    2. Process, according to claim 1, CHARACTERIZED by the fact that n has an average value of 15 to 50 and the value of n times (m + 1) is between 20 and 200.
    [0003]
    3. Process, according to claim 1, CHARACTERIZED by the fact that each occurrence of R is methyl or phenyl.
    [0004]
    4. Process, according to claim 1, CHARACTERIZED by the fact that Ar is represented by one of the following structures:
    [0005]
    5. Process according to claim 1, CHARACTERIZED by the fact that the inert solvent comprises acetic acid.
    [0006]
    6. Process according to claim 1, CHARACTERIZED by the fact that the catalyst is a metallic salt of an organic acid.
    [0007]
    7. Process according to claim 1, CHARACTERIZED by the fact that the metallic salt of an organic acid is sodium acetate or potassium acetate.
    [0008]
    8. Process, according to claim 1, CHARACTERIZED by the fact that the bisphenolic compound or the hydroxy-functional oligomer thereof is selected from the group consisting of:
    [0009]
    9. Process for preparing a polydiorganosiloxane / polyiorgan (AB) x block copolymer comprising (i) polydiorganosiloxane A blocks and (ii) B blocks of polycarbonate, polyester, polysulfone and / or polyether ether ketone oligomers with 2 to 500 groups bisoxiorgan, where blocks A of polydialkylsiloxane are represented by the General Formula (III)
    [0010]
    10. Process according to claim 9, CHARACTERIZED by the fact that each occurrence of R is independently a methyl or phenyl group.
    [0011]
    11. Process, according to claim 9, CHARACTERIZED by the fact that Ar is represented by one of the following structures:
    [0012]
    12. Process, according to claim 9, CHARACTERIZED by the fact that blocks B are represented by the General Formulas (X), (XI), (XII) or (XIII):
    [0013]
    13. Process, according to claim 9, CHARACTERIZED by the fact that the bisphenolic compound is selected from the group consisting of:
    [0014]
    14. Process, according to claim 9, CHARACTERIZED by the fact that the blocks of polycarbonate, polyester, polysulfone and polyether ether ketone oligomers have the General Formulas (VI), (VII), (VIII) and (IX), respectively:
    [0015]
    15. Process according to claim 9, CHARACTERIZED by the fact that the chain terminating groups or condensation linking groups are used to control the molecular weight of the block copolymer (A-B) x.
    [0016]
    16. Process, according to claim 9, CHARACTERIZED by the fact that the reaction is conducted under the conditions of a polycondensation process without solvent, transesterification or fusion.
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    同族专利:
    公开号 | 公开日
    US8912290B2|2014-12-16|
    JP2015512999A|2015-04-30|
    KR20150010725A|2015-01-28|
    BR112014025273A2|2017-07-11|
    EP2836538B1|2018-08-29|
    CA2869906A1|2013-10-17|
    CN104350088B|2017-03-15|
    RU2014145007A|2016-05-27|
    KR102080335B1|2020-04-08|
    EP2836538A1|2015-02-18|
    CN104350088A|2015-02-11|
    IN2014MN01994A|2015-07-10|
    US20130267665A1|2013-10-10|
    JP6250632B2|2017-12-20|
    WO2013155046A1|2013-10-17|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2885384A|1954-05-25|1959-05-05|Union Carbide Corp|Bisalkane reacted with polyorgano-siloxane resins|
    US3189662A|1961-01-23|1965-06-15|Gen Electric|Organopolysiloxane-polycarbonate block copolymers|
    US3539657A|1968-03-21|1970-11-10|Union Carbide Corp|Two-phase siloxane-polyarylene polyether block copolymers|
    CH591535A5|1974-03-25|1977-09-30|Ciba Geigy Ag|
    US4022753A|1974-03-25|1977-05-10|Ciba-Geigy Corporation|Reaction products of polysiloxanes and polyphenols|
    CH588517A5|1974-03-25|1977-06-15|Ciba Geigy Ag|
    US4501872A|1983-01-31|1985-02-26|Ppg Industries, Inc.|Moisture curable compositions containing reaction products of hydrophobic polyols and organosilicon-containing materials|
    DE3334782C2|1983-04-19|1987-11-26|Bayer Ag, 5090 Leverkusen, De|
    DE3506472A1|1985-02-23|1986-08-28|Bayer Ag, 5090 Leverkusen|NEW POLYDIORGANOSILOXANE POLYCARBONATE BLOCK COPOLYMERS|
    US4814392A|1987-11-25|1989-03-21|General Electric Company|Silicone-polyarylene ether block copolymers, and method for making|
    EP0374635A3|1988-12-21|1991-07-24|Bayer Ag|Polycarbonate-polysiloxane block copolymers based on dihydroxydiphenyl cycloalkanes|
    DE3924992A1|1989-07-28|1991-01-31|Bayer Ag|SPECIAL POLYDIORGANOSILOXANE BLOCK COPOLY CARBONATES|
    US5227449A|1990-07-02|1993-07-13|Xerox Corporation|Photoconductive imaging members with polycarbonate binders|
    DE4238123C2|1992-11-12|2000-03-09|Bayer Ag|Process for the production of thermoplastic polycarbonates|
    US5723541A|1993-06-16|1998-03-03|Rasor Associates, Inc.|Ocular lens composition and method of formation|
    US5385984A|1993-10-21|1995-01-31|General Electric Company|Polyarylene ether-organopolysiloxane copolymers|
    US5504177A|1995-03-02|1996-04-02|General Electric Company|Method for preparation of block copolysiloxanecarbonates|
    DE19539290A1|1995-10-23|1997-04-24|Bayer Ag|Process for the preparation of poly -polycarbonate block copolymers|
    WO1998037126A1|1997-02-20|1998-08-27|Ge Bayer Silicones Gmbh & Co. Kg|Method for producing organofunctional siloxanes and use of same|
    US6066700A|1997-03-12|2000-05-23|Bayer Aktiengesellschaft|Process for the production of polysiloxane/polycarbonate block co-condensation products|
    US5821321A|1997-09-16|1998-10-13|Bayer Corporation|Molding composition having improved impact strength|
    US7695815B2|2005-08-26|2010-04-13|Sabic Innovative Plastics Ip B.V.|Low smoke polycarbonate composition and laminates, method of manufacture and product made therefrom|
    US20070060716A1|2005-09-13|2007-03-15|Bala Ambravaneswaran|Fatigue resistant thermoplastic composition, method of making, and articles formed therefrom|
    US7524919B2|2006-09-29|2009-04-28|Sabic Innovative Plastics Ip B.V.|Polycarbonate-polysiloxane copolymers, method of making, and articles formed therefrom|
    US7858680B2|2008-12-29|2010-12-28|Sabic Innovative Plastics Ip B.V.|Thermoplastic polycarbonate compositions|JP5876450B2|2013-08-26|2016-03-02|信越化学工業株式会社|Polymer compound, chemically amplified negative resist material, photocurable dry film and method for producing the same, laminate, and pattern forming method|
    ES2638216T3|2013-10-08|2017-10-19|Covestro Deutschland Ag|Preparation process of co-condensates of polysiloxane-polycarbonate blocks|
    US9828463B2|2013-10-08|2017-11-28|Covestro Deutschland Ag|Process for preparing polysiloxane-polycarbonate block cocondensates using a salt of a weak acid|
    JP6605456B2|2013-10-08|2019-11-13|コベストロ、ドイチュラント、アクチエンゲゼルシャフト|Polysiloxane-polycarbonate block cocondensate|
    JP6457384B2|2013-12-10|2019-01-23|出光興産株式会社|Polycarbonate-polyorganosiloxane copolymer and method for producing the same|
    KR101687683B1|2014-09-05|2016-12-19|주식회사 엘지화학|Copolycarbonate and composition comprising the same|
    KR20160067714A|2014-12-04|2016-06-14|주식회사 엘지화학|Copolycarbonate and article containing the same|
    KR101685665B1|2014-12-04|2016-12-12|주식회사 엘지화학|Copolycarbonate and composition comprising the same|
    KR20170106402A|2015-01-20|2017-09-20|코베스트로 도이칠란트 아게|A flame retardant molding compound containing a siloxane-containing polycarbonate block co-condensate and containing glass fibers|
    TWI691552B|2015-01-20|2020-04-21|德商科思創德意志股份有限公司|Flame-retardant moulding compositions comprising siloxane-containing polycarbonate block cocondensate|
    CN104672450B|2015-03-06|2018-05-18|湖州睿高新材料有限公司|Poly dimethyl silicic acid bromo hydroquinone ester polymer and preparation method thereof|
    EP3280759A1|2015-04-07|2018-02-14|Covestro Deutschland AG|Block co-condensates of polysiloxanes and dihydroxydiphenylcycloalkane-based n polycarbonates|
    KR101859160B1|2015-09-01|2018-06-28|주식회사 엘지화학|Copolycarbonate and method for preparing the same|
    US11130321B2|2016-06-03|2021-09-28|Covestro Deutschland Ag|Multi-layer composite material containing special copolycarbonates as a matrix material|
    JP2019524970A|2016-08-24|2019-09-05|コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ|Polycarbonate composition containing talc|
    KR20190094429A|2016-12-19|2019-08-13|코베스트로 도이칠란트 아게|Preparation of siloxane-containing block copolycarbonates using compatibilizers|
    CN107033356A|2017-05-12|2017-08-11|惠州市佳的利实业有限公司|A kind of silicon systems polymer of silicon phenolic group block and preparation method thereof and composition|
    EP3502306B1|2017-12-19|2022-03-02|Covestro Deutschland AG|Multilayer body, comprising a substrate layer containing polycarbonate, talc and wax|
    EP3794073A1|2018-05-17|2021-03-24|Covestro Intellectual Property GmbH & Co. KG|Filled polycarbonate compositions having good scratch resistance and reduced yellowing behavior|
    CA3099861A1|2018-05-17|2019-11-21|Evonik Operations Gmbh|Linear polydimethylsiloxane-polyoxyalkylene block copolymers of the structural type aba|
    EP3611216A1|2018-08-15|2020-02-19|Evonik Operations GmbH|Linear polydimethylsiloxane polyoxyalkylene block copolymers of structure type aba|
    US20210403707A1|2018-11-29|2021-12-30|Covestro Intellectual Property Gmbh & Co. Kg|SiCoPC BLEND CONTAINING PHOSPHAZENE AND SILICONE/ACRYLATE IMPACT MODIFIER|
    CN113614144A|2019-03-22|2021-11-05|三菱瓦斯化学株式会社|Method for producing polycarbonate copolymer and polysiloxane compound, polycarbonate copolymer, polysiloxane compound, composition, and molded article|
    EP3719077A1|2019-04-02|2020-10-07|Covestro Deutschland AG|Siloxane-containing block copolycarbonates with small domain sizes|
    WO2021233773A1|2020-05-22|2021-11-25|Covestro Deutschland Ag|Flame-retardant polycarbonate composition|
    WO2021233774A1|2020-05-22|2021-11-25|Covestro Deutschland Ag|Flame-retardant polycarbonate composition|
    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2020-02-04| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-10-13| B09A| Decision: intention to grant|
    2020-12-22| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 09/04/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201261622144P| true| 2012-04-10|2012-04-10|
    US61/622.144|2012-04-10|
    US201261739935P| true| 2012-12-20|2012-12-20|
    US61/739.935|2012-12-20|
    PCT/US2013/035734|WO2013155046A1|2012-04-10|2013-04-09|Process for producing functional siloxanes of controlled structure|
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