Composition and siloxane-based thermoplastic resin using the same, and method for manufacturing the same

Abstract

A composition comprising a siloxane block-containing diol compound that is easy to manufacture industrially is provided. A composition comprising a siloxane block-containing diol compound, wherein the siloxane block-containing diol compound is represented by the following formula (I): [wherein R1 and R2 are each independently an alkyl group having 1 to 20 carbon atoms that may have a substituent, or an aryl group having 6 to 30 carbon atoms that may have a substituent, m is an integer from 1 to 25, n is an integer from 3 to 200, and X is each independently represented by the following formulas (I1) to (I6):].

Description

Technology Field

[0001] The present invention relates to a composition, a siloxane-based thermoplastic resin using the same, and a method for manufacturing the same. Background Technology

[0002] Conventionally, it is known that siloxane block-containing diol compounds are effective as raw materials for various resins containing silicon blocks in their structure, and are used for applications such as release layers in photocopying, photoresist materials, plasticizers for polycarbonates, and components of powder surface coating systems.

[0003] A siloxane block-containing diol compound having a hydroxyl group at the terminal end can impart functions such as chemical resistance, low-temperature impact resistance, weather resistance, and flame retardancy to the polycarbonate when copolymerized with, for example, polycarbonate.

[0004] As such, Patent Document 1 describes that a siloxane block-containing diol compound (hydroxyaryl-terminated polysiloxane) represented by the following formulas (a) to (c) is preferred as such a siloxane block-containing diol compound.

[0005] [Chemical Formula 1]

[0006]

[0007] Patent Document 1 describes that by adding a predetermined inorganic salt and / or organic salt to a siloxane block-containing diol compound as described above and preparing a polydiorganosiloxane-polyorganoblock copolymer by a solvent-free melting method, the melt stability, decomposition stability against solvent and water, and low-temperature impact resistance of the copolymer obtained are improved. Prior art literature

[0008] Japanese Patent Publication No. 2016-538362 The problem to be solved

[0009] However, it was found that the siloxane block-containing diol compound described in Patent Document 1 above has low reactivity between the siloxane compound and the diol compound used as raw materials, and that industrial manufacturing is difficult in some cases.

[0010] Therefore, the present invention provides a composition comprising a siloxane block-containing diol compound that is easy to manufacture industrially. means of solving the problem

[0011] The inventors conducted diligent research to solve the above problem. As a result, they discovered that the above problem could be solved by forming a siloxane block-containing diol compound with a predetermined structure, and thus completed the present invention. That is, the present invention is, for example, as follows.

[0012] [1] A composition comprising a siloxane block-containing diol compound,

[0013] The above siloxane block-containing diol compound is of the following formula (I):

[0014] [Chemical Formula 2]

[0015]

[0016] [During the meal,

[0017] R 1 and R 2 Each is independently an alkyl group having 1 to 20 carbon atoms that may have substituents, and an aryl group having 6 to 30 carbon atoms that may have substituents, and

[0018] m is an integer from 1 to 25, and

[0019] n is an integer from 3 to 200, and

[0020] X is, independently, the following equation (I 1 ) ~ (I 6 ) :

[0021] [Chemical Formula 3]

[0022]

[0023] is, and at this time,

[0024] A 1 and A 2 is, each independently, -(CR 6A R 6B ) q1 - or -( O-(CR 6A R 6B ) q2 ) q3 - and, here, R 6A and R 6B Each is independently H or an alkyl group having 1 to 6 carbon atoms, q1 is an integer from 0 to 10, q2 is an integer from 0 to 10, and q3 is an integer from 0 to 10, and

[0025] R 3 and R 4 Each is independently a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aromatic hydrocarbon oxy group having 6 to 20 carbon atoms, and a cycloalkoxyl group having 3 to 20 carbon atoms, and

[0026] p1 and p2 are each independently integers from 0 to 4, and

[0027] R 5 Each is independently H or an alkyl group having 1 to 6 carbon atoms, and

[0028] X 1 and X 2 is, each independently, a single combination or the gi represented below:

[0029] [Chemical Formula 4]

[0030]

[0031] and, here, R 7 and R 8Each is independently H, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms that may have substituents, an alkoxyl group having 1 to 20 carbon atoms that may have substituents, an aromatic hydrocarbon group having 6 to 20 carbon atoms that may have substituents, or R 7 and R 8 These may combine to form a carbon ring with 3 to 20 carbon atoms or a complex ring with 5 to 12 atoms; R 9 and R 10 Each is independently H, an alkyl group having 1 to 6 carbon atoms; R 11 ~ R 16 Each is independently a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms that may have substituents, an alkoxyl group having 1 to 20 carbon atoms that may have substituents, and an aromatic hydrocarbon group having 6 to 12 carbon atoms that may have substituents; r1 is an integer from 2 to 20, and

[0032] X 3 Each is independently a divalent aromatic hydrocarbon group having 15 to 32 carbon atoms, and

[0033] X 4 is, each independently, a divalent group comprising one or more hydrocarbon rings or heterocycles, wherein the divalent group comprising one or more hydrocarbon rings or heterocycles is R 5 , R 6A , and R 6B It may be formed by combining with at least one selected from the group consisting of, and

[0034] X 5 are, each independently, divalent saturated heterocyclic groups, where the divalent saturated heterocyclic group is R 5 , R 6A , and R 6B It may be formed by combining with at least one selected from the group consisting of, and

[0035] X 6Each is an alkylene group having 1 to 10 carbon atoms that may contain an oxygen atom, independently.

[0036] s1 and s2 are, independently, integers from 0 to 10.

[0037] A composition represented by

[0038] [2] A siloxane-based thermoplastic resin comprising a constituent unit derived from the siloxane block-containing diol compound described in [1] above.

[0039] [3] (A) The following formula (1):

[0040] [Chemical Formula 5]

[0041]

[0042] [During the meal,

[0043] R 1 and R 2 Each is independently an alkyl group that may have substituents, an alkenyl group that may have substituents, and an aryl group that may have substituents, and

[0044] n is an integer from 3 to 30.

[0045] Cyclic siloxane compounds represented by and / or the following formula (2):

[0046] [Chemical Formula 6]

[0047]

[0048] [During the meal,

[0049] R 3 and R 4 Each is independently an alkyl group that may have substituents, an alkenyl group that may have substituents, and an aryl group that may have substituents, and

[0050] X is, each independently, a hydrogen atom, a hydroxyl group, a C1-10 alkoxy group that may have substituents, a C1-10 siloxy group that may have substituents, a C1-10 hydrocarbon group that may have substituents, an C1-10 oxygen atom-containing group that may have substituents, a C1-10 nitrogen atom-containing group that may have substituents, and an amino group that may have substituents.

[0051] m is an integer from 2 to 10,000.

[0052] A straight-chain siloxane compound represented by, and

[0053] (B) The following equation (J 1 ) ∼ (J 6 ) :

[0054] [Chemical Formula 7]

[0055]

[0056] [During the meal, A 1 and A 2 , X 1 ~ X 6 , R 3 ~ R 5 , p1 ~ p2, and s1 ~ s2 are identical to the definitions in [1] above.

[0057] Diol compounds represented by, and

[0058] (C) A method for preparing the composition described in [1] above, comprising a process of reacting a basic compound catalyst.

[0059] [4] A method for manufacturing a siloxane-based thermoplastic resin comprising the process of reacting the composition described in [1] above with a thermoplastic resin at 160 to 400°C in the presence of a catalyst. Effects of the invention

[0060] According to the present invention, a composition comprising a siloxane block-containing diol compound that is easy to manufacture industrially is provided. Specific details for implementing the invention

[0061] Hereinafter, embodiments for carrying out the present invention will be described in detail.

[0062] <Composition>

[0063] The composition of the present invention comprises a siloxane block-containing diol compound. The composition may also include, in addition, impurities derived from raw materials such as cyclic siloxane compounds, linear siloxane compounds, diol compounds, and basic compound catalysts, and decomposition products thereof.

[0064] [Siloxane block-containing diol compounds]

[0065] A diol compound containing a siloxane block is represented by the following formula (I).

[0066] In formula (I), the carbon atom bonded to the hydroxyl group in X (formula (I 1 ) ~ (I 6 -CHR in ) 5 -) is a primary carbon atom or a secondary carbon atom. This increases the reactivity of the diol compound that derives the constituent unit of X, and the cyclic siloxane compound and / or straight-chain siloxane compound that derives the siloxane block. As a result, the industrial production of the compound represented by formula (I), i.e., the siloxane block-containing diol compound, becomes easier.

[0067] [Chemical Formula 8]

[0068]

[0069] Among the above formulas, R 1 and R 2 Each is independently an alkyl group having 1 to 20 carbon atoms that may have substituents, and an aryl group having 6 to 30 carbon atoms that may have substituents.

[0070] The above alkyl group having 1 to 20 carbon atoms is not particularly limited, but examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, n-pentadecyl, n-icosyl, etc. Among these, the alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, even more preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably an alkyl group having 1 to 2 carbon atoms, and most preferably methyl.

[0071] The above aryl group having 6 to 30 carbon atoms is not particularly limited, but may include phenyl, indenyl, naphthyl, biphenyl, acenaphtenyl, fluorenyl, phenalenyl, phenanthrenyl, anthracenyl, triphenylenyl, pyrenyl, crisenyl, naphthacenyl, perylenyl, etc. Among these, the aryl group having 6 to 30 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms, and more preferably phenyl.

[0072] The above R 1 and R 2Examples of substituents include, but are not particularly limited, hydroxyl groups, halogen atoms, amino groups, vinyl groups, carboxyl groups, cyano groups, (meth)acryloxy groups, glycidyloxy groups, mercapto groups, etc. Additionally, in this specification, "amino group" includes, in addition to an unsubstituted amino group (-NH2), a monoalkylamino group substituted with one alkyl group having 1 to 6 carbon atoms, and a dialkylamino group substituted with two alkyl groups having 1 to 6 carbon atoms. Specific examples of said amino group are, but are not particularly limited, amino (-NH2); monoalkylamino groups such as methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, t-butylamino, n-pentylamino, n-hexylamino; Examples of dialkylamino groups include dimethylamino, diethylamino, di(n-propyl)amino, diisopropylamino, di(n-butyl)amino, diisobutylamino, di(n-pentyl)amino, di(n-hexyl)amino, ethylmethylamino, methyl(n-propyl)amino, n-butylmethylamino, ethyl(n-propyl)amino, n-butylethylamino, etc. Among these, the amino group is preferably an unsubstituted amino group (-NH2).

[0073] m is an integer from 1 to 25, preferably from 1 to 20, and more preferably from 3 to 15.

[0074] n is an integer from 3 to 200, preferably 3 to 100, more preferably 3 to 50, and even more preferably 3 to 10.

[0075] X is, independently, the following equation (I 1 ) ~ (I 6 It is represented as ).

[0076] [Chemical Formula 9]

[0077]

[0078] That is, in Equation (I), the -CHR to which the hydroxyl group is attached 5- is a primary carbon atom or a secondary carbon atom.

[0079] A 1 and A 2 is, each independently, -(CR 6A R 6B ) q1 - or -( O-(CR 6A R 6B ) q2 ) q3 - am.

[0080] At this time, R 6A and R 6B Each is independently H or an alkyl group having 1 to 6 carbon atoms.

[0081] Examples of the above alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, etc.

[0082] q1 is an integer from 0 to 10, preferably from 0 to 5, and more preferably from 0 to 3.

[0083] q2 is an integer from 0 to 10, preferably from 0 to 5, and more preferably from 0 to 3.

[0084] q3 is an integer from 0 to 10, preferably from 0 to 5, and more preferably from 0 to 3.

[0085] R 3 and R 4 Each is independently a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aromatic hydrocarbon oxy group having 6 to 20 carbon atoms, and a cycloalkoxyl group having 3 to 20 carbon atoms.

[0086] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0087] The aliphatic hydrocarbon group having 1 to 20 carbon atoms is a monovalent aliphatic hydrocarbon group and is not particularly limited, but may include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms.

[0088] The above alkyl group having 1 to 20 carbon atoms is not particularly limited, but examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, n-pentadecyl, n-icosyl, etc. Among these, the alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, even more preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably an alkyl group having 1 to 2 carbon atoms, and most preferably methyl.

[0089] The above alkenyl groups having 2 to 20 carbon atoms are not particularly limited, but examples include ethenyl (vinyl), 1-propenyl, 2-propenyl (allyl), isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, pentenyl, hexenyl, octenyl, decenyl, pentadecenyl, icocenyl, etc. Among these, the alkenyl groups having 2 to 20 carbon atoms are preferably alkenyl groups having 2 to 10 carbon atoms, more preferably alkenyl groups having 2 to 6 carbon atoms, and even more preferably ethenyl (vinyl) or 2-propenyl (allyl).

[0090] The above alkynyl groups having 2 to 20 carbon atoms are not particularly limited, but examples include ethinyl, 1-propynyl, 2-propynyl, 2-butynyl, 3-butynyl, pentynyl, hexinyl, octinyl, decinyl, pentadecinyl, icocinyl, etc. Among these, the alkynyl groups having 2 to 20 carbon atoms are preferably alkynyl groups having 2 to 10 carbon atoms, more preferably alkynyl groups having 2 to 6 carbon atoms, even more preferably alkynyl groups having 2 to 4 carbon atoms, and particularly preferably alkynyl groups having 2 to 3 carbon atoms.

[0091] The alkoxyl group having 1 to 20 carbon atoms is a straight-chain or branched-chain monovalent aliphatic hydrocarbon oxy group having 1 to 20 carbon atoms, and is not particularly limited, but may include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, t-butoxy, n-pentoxy, n-hexoxy, etc. Among these, the alkoxyl group having 1 to 20 carbon atoms is preferably an alkoxyl group having 1 to 10 carbon atoms, more preferably an alkoxyl group having 1 to 6 carbon atoms, even more preferably an alkoxyl group having 1 to 4 carbon atoms, particularly preferably an alkoxyl group having 1 to 2 carbon atoms, and most preferably a methoxy.

[0092] The cycloalkyl group having 3 to 20 carbon atoms is a monovalent cyclic saturated aliphatic hydrocarbon group having 3 to 20 carbon atoms, and is not particularly limited, but examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, etc. Among these, the cycloalkyl group having 3 to 20 carbon atoms is preferably a cycloalkyl group having 3 to 10 carbon atoms.

[0093] The aromatic hydrocarbon group having 6 to 20 carbon atoms is a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and is not particularly limited, but may include phenyl, indenyl, naphthyl, biphenyl, acenaphtenyl, fluorenyl, phenalenyl, phenanthrenyl, anthracenyl, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl, perylenyl, etc. Among these, the aromatic hydrocarbon group having 6 to 20 carbon atoms is preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, and more preferably phenyl.

[0094] The aralkyl group having 7 to 20 carbon atoms is an alkyl group substituted with one aromatic hydrocarbon group, and is not particularly limited, but examples include benzyl, phenethyl, phenylpropyl, naphthylmethyl, naphthylethyl, biphenylmethyl, etc. Among these, it is preferable that the aralkyl group having 7 to 20 carbon atoms be benzyl.

[0095] The aromatic hydrocarbon oxy group having 6 to 20 carbon atoms is a monovalent aromatic hydrocarbon oxy group having 6 to 20 carbon atoms, and is not particularly limited, but may include phenoxy, indenyloxy, naphthyloxy, biphenyloxy, acenaphtenyloxy, fluorenyloxy, phenalenyloxy, phenanthrenyloxy, anthracenyloxy, anthracenyloxy, triphenylenyloxy, pyrenyloxy, chrysenyloxy, naphthacenyloxy, perylenyloxy, etc. Among these, the aromatic hydrocarbon oxy group having 6 to 20 carbon atoms is preferably an aromatic hydrocarbon oxy group having 6 to 12 carbon atoms, and more preferably phenoxy.

[0096] Examples of cycloalkoxyl groups having 3 to 20 carbon atoms are not particularly limited, but include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, adamanthyloxy, cyclododecanyl, etc. Among these, it is preferable that the cycloalkoxyl group having 3 to 20 carbon atoms is a cycloalkyloxyl group having 3 to 12 carbon atoms.

[0097] p1 and p2 are each independently integers from 0 to 4, preferably from 0 to 2, and more preferably from 0 to 1.

[0098] R 5 Each is independently H or an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, etc.

[0099] X 1 and X 2 Each is independently a single bond or a group represented below.

[0100] [Chemical Formula 10]

[0101]

[0102] Among the above formulas, R 7 and R 8 Each is independently H, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms that may have substituents, an alkoxyl group having 1 to 20 carbon atoms that may have substituents, an aromatic hydrocarbon group having 6 to 20 carbon atoms that may have substituents, or R 7 and R 8 These may combine to form a carbon ring with 3 to 20 carbon atoms or a complex ring with 5 to 12 carbon atoms.

[0103] The aliphatic hydrocarbon group having 1 to 20 carbon atoms, the alkoxyl group having 1 to 20 carbon atoms, and the aromatic hydrocarbon group having 6 to 20 carbon atoms are as described above.

[0104] In addition, the substituents that the aliphatic hydrocarbon group having 1 to 20 carbon atoms and the alkoxyl group having 1 to 20 carbon atoms may have are not particularly limited, but may include an alkoxyl group having 1 to 6 carbon atoms, an acyl group having 1 to 7 carbon atoms, a halogen atom, an amino group, a nitro group, a cyano group, a carbamoyl group, etc.

[0105] Meanwhile, the substituents that the above-mentioned aromatic hydrocarbon group having 6 to 20 carbon atoms may have are not particularly limited, but include an alkyl group having 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, an acyl group having 1 to 7 carbon atoms, a halogen atom, an amino group, a nitro group, a cyano group, a carbamoyl group, etc.

[0106] R 7 and R 8 Examples of carbon rings having 3 to 20 carbon atoms formed by this bonding include condensation rings with 3 to 20 carbon atoms, cycloalkyl groups, and aromatic hydrocarbon groups that may have substituents, although they are not particularly limited. Examples of the above condensation rings include acenaphtenyl, fluorenyl, etc.

[0107] In addition, the substituents that the carbon ring having 3 to 20 carbon atoms may have are not particularly limited, but may include an alkyl group having 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, an acyl group having 1 to 7 carbon atoms, a halogen atom, an amino group, a nitro group, a cyano group, a carbamoyl group, etc.

[0108] Also, R 7 and R 8 Examples of 5 to 12-membered complex rings formed by this combination include, but are not particularly limited, oxiranil, aziridinil, tetrahydrofuranil, tetrahydrothiophenyl, pyrrolidinil, oxathioranil, piperidinil, 1(3H)-isobenzofuranonil, etc.

[0109] R 9 and R 10 Each is independently H, an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, etc.

[0110] r1 is an integer from 2 to 20, preferably from 2 to 10, and more preferably from 2 to 5.

[0111] R 11 ~ R 16 Each is independently a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms that may have substituents, an alkoxyl group having 1 to 20 carbon atoms that may have substituents, and an aromatic hydrocarbon group having 6 to 12 carbon atoms that may have substituents, and a specific example thereof is R 7 and R 8 It is identical to what is listed in.

[0112] Formula I 1 Diol compounds deriving X having are not particularly limited, but include α,ω-bis[3-(O-hydroxyphenyl)propyl]polydimethylsiloxane, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF), 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-t-butylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-isopropylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-cyclohexylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene, 2,2-bis(4-(2-hydroxyethoxy)phenyl)propane, Examples include 4,4-bis(2-hydroxyethoxy)biphenyl, 2,2'(9H-fluorene-9,9'-diyl)bis(ethanol-1-ol), 9H-fluorene-9,9-diyldimethanol, 2,2'-(1,4-phenylene)bis(ethanol-1-ol), 2,2'-(1,4-phenylene)bis(methanol-1-ol), 2,2'-(1,4-phenylenebis(oxy))bis(ethanol-1-ol), etc. Among these, Formula I 1 The diol compound that derives X having is preferably 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF).

[0113] In one embodiment, Formula I 1 The structure of a diol compound that induces X having is shown below.

[0114] [Chemical Formula 11]

[0115]

[0116] Formula I 2 Diol compounds that derive X having are not particularly limited, but include 9,9-bis[6-(1-hydroxymethoxy)naphthalene-2-yl]fluorene, 9,9-bis[6-(2-hydroxyethoxy)naphthalene-2-yl]fluorene, 9,9-bis[6-(3-hydroxypropoxy)naphthalene-2-yl]fluorene, 9,9-bis[6-(4-hydroxybutoxy)naphthalene-2-yl]fluorene, 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthalene, etc. Among these, Formula I 2 The diol compound that derives X having is preferably 9,9-bis[6-(2-hydroxyethoxy)naphthalene-2-yl]fluorene, 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthalene.

[0117] X 3 Each is independently a divalent aromatic hydrocarbon group having 15 to 32 carbon atoms.

[0118] Examples of the above divalent aromatic hydrocarbon groups having 15 to 32 carbon atoms include, but are not particularly limited, divalent condensed polycyclic aromatic hydrocarbon groups such as fluorantenylene, acephenantrilenylene, aceantrilenylene, triphenylene, pyrenylene, chrysenylene, naphthacenylene, pyradenylene, picenylene, perirenylene, biphenylene, pentaphenylene, pentacenylene, tetraphenylenylene, hexaphenylene, hexacenylene, rubisenylene, coronenylene, trinaphthylenylene, heptaphenylene, heptacenylene, pyrantrilenylene, ovalenylene; terphenylene, quaternylene, etc.

[0119] Formula I 3Examples of diol compounds that derive X having are not particularly limited, but include binaphthalenediol compounds. Specifically, examples include 2,2'-bis(1-hydroxymethoxy)-1,1'-binaphthalene, 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene, 2,2'-bis(3-hydroxypropyloxy)-1,1'-binaphthalene, 2,2'-bis(4-hydroxybutoxy)-1,1'-binaphthalene, etc. Among these, Formula I 3 The diol compound that induces X having is preferably 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene.

[0120] X 4 Each is a divalent group containing one or more hydrocarbon rings or heterorings, independently.

[0121] The above hydrocarbon ring or heteroring may include, although not particularly limited, a divalent aromatic hydrocarbon group having 6 to 32 carbon atoms that may have a substituent, a divalent cycloalkyl group having 3 to 20 carbon atoms that may have a substituent, and a divalent group having at least one each of a divalent aromatic hydrocarbon group having 6 to 32 carbon atoms that may have a substituent and a divalent cycloalkyl group having 3 to 20 carbon atoms.

[0122] The above divalent aromatic hydrocarbon group having 6 to 32 carbon atoms may include a heteroatom selected from oxygen, sulfur, and nitrogen atoms, provided that it exhibits aromaticity as a whole. The divalent aromatic hydrocarbon group having 6 to 32 carbon atoms is not particularly limited, but the following may be examples.

[0123] [Chemical Formula 12]

[0124]

[0125] The above divalent cycloalkyl group having 3 to 20 carbon atoms may include a heteroatom selected from an oxygen atom, a sulfur atom, and a nitrogen atom. The divalent cycloalkyl group having 3 to 20 carbon atoms is not particularly limited, but the following may be examples.

[0126] [Chemical Formula 13]

[0127]

[0128] The divalent groups having at least one each of the divalent aromatic hydrocarbon group having 6 to 32 carbon atoms and the divalent cycloalkyl group having 3 to 20 carbon atoms are not particularly limited, but the following may be examples.

[0129] [Chemical Formula 14]

[0130]

[0131] Substituents that may be present in a divalent group having one or more of each of a divalent aromatic hydrocarbon group having 6 to 32 carbon atoms, a divalent cycloalkyl group having 3 to 20 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 32 carbon atoms, and a divalent cycloalkyl group having 3 to 20 carbon atoms are not particularly limited, but include an alkyl group having 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, an acyl group having 1 to 7 carbon atoms, a halogen atom, an amino group, a nitro group, a cyano group, a carbamoyl group, etc.

[0132] In addition, the 2-valent saturated heterocyclic group, R 5 , R 6A , and R 6B It may be formed by combining with at least one selected from the group consisting of. For example, Formula I 4 1,4-cyclohexanedimethanol (CHDM), a diol compound that derives X having R 5 , R 6A , and R 6B By combining with, X in formula (I) has a cyclohexane ring.

[0133] X 5 Each is independently a 2-valent saturated heterocyclic group.

[0134] The above 2 saturated heterocyclic groups are not particularly limited, but the following may be examples.

[0135] [Chemical Formula 15]

[0136]

[0137] In addition, the 2-valent saturated heterocyclic group, R 5 , R 6A , and R 6B It may be formed by combining with at least one selected from the group consisting of. For example, Formula I 4 2,4-dihydroxy-1,4-dioxane, a diol compound that induces X having, is, R 5 , R 6A , and R 6B By combining with, X in formula (I) has a cyclohexane ring.

[0138] X 6 Each is an alkylene group having 1 to 10 carbon atoms that may contain an oxygen atom, independently.

[0139] Examples of alkylene groups having 1 to 10 carbon atoms that may include the above oxygen atom include, but are not particularly limited, alkylenes such as methylene, ethylene, propylene, isopropylene, butylene; and oxygen-containing alkylenes such as oxymethylene (-CH2-O-), oxyethylene (-CH2CH2-O-), deoxyethylene (-CH2CH2-O-CH2CH2-O-), and trioxyethylene (-CH2CH2-O-CH2CH2-O-).

[0140] Also, s1 and s2 are each independently integers from 0 to 10, preferably from 0 to 5, and more preferably from 0 to 3.

[0141] Formula I 6Examples of diol compounds that induce X having ethylene glycol (EG), 1,3-propanediol (PG), 1,4-butanediol (BD), 2-butyl-2-ethyl-1,3-propanediol (BEPG), neopentyl glycol (NPG), etc.

[0142] The siloxane block-containing diol compound described above may be included alone in the composition, or two or more types may be included in combination.

[0143] The weight average molecular weight (Mw) of the siloxane block-containing diol compound is preferably 10,000 to 1,000,000, more preferably 30,000 to 800,000, and even more preferably 40,000 to 250,000. Additionally, in this specification, the value of "weight average molecular weight (Mw)" shall be adopted as the value measured by the method of the example.

[0144] The number average molecular weight (Mn) of the siloxane block-containing diol compound is preferably 10,000 to 500,000, more preferably 20,000 to 300,000, and even more preferably 30,000 to 200,000. In addition, in this specification, the value of "number average molecular weight (Mn)" shall be adopted as the value measured by the method of the example.

[0145] The weight average molecular weight (Mw) (Mw / Mn) relative to the number average molecular weight (Mn) of the siloxane block-containing diol compound is preferably 1 to 4, more preferably 1.05 to 3, and even more preferably 1.1 to 2.

[0146] <Method for preparing a siloxane block-containing diol compound>

[0147] According to one embodiment of the present invention, a method for preparing the siloxane block-containing diol compound described above is provided.

[0148] A method for preparing a siloxane block-containing diol compound comprises a process of reacting (A) a cyclic siloxane compound and / or a linear siloxane compound, (B) a diol compound, and (C) a basic compound catalyst.

[0149] [(A) Cyclic siloxane compounds and / or linear siloxane compounds]

[0150] Cyclic siloxane compounds are represented by the following formula (1).

[0151] [Chemical Formula 16]

[0152]

[0153] During the meal, R 1 and R 2 is, respectively, an alkyl group that may have substituents, an alkenyl group that may have substituents, and an aryl group that may have substituents. In this case, R 1 and R 2 It is preferable that the group be an alkyl group having a total of 1 to 20 carbon atoms that may have substituents, or an aryl group having a total of 6 to 30 carbon atoms.

[0154] The alkyl group having a total of 1 to 20 carbon atoms that may have the above substituent is preferably an alkyl group having a total of 1 to 10 carbon atoms, more preferably an alkyl group having a total of 1 to 6 carbon atoms, and even more preferably an alkyl group having a total of 1 or 2 carbon atoms.

[0155] The above aryl group having a total of 6 to 30 carbon atoms is preferably an aryl group having a total of 6 to 20 carbon atoms, more preferably an aryl group having a total of 6 to 12 carbon atoms, and even more preferably an aryl group having a total of 6 to 8 carbon atoms.

[0156] Examples of the above substituents include hydroxyl groups, halogens, amino groups, vinyl groups, carboxyl groups, cyano groups, (meth)acryloxy groups, glycidyloxy groups, mercapto groups, etc.

[0157] R 1 and R 2Preferred specific examples include methyl groups, phenyl groups, vinyl groups, and propyl groups.

[0158] n is an integer from 3 to 30, preferably 3 to 15, more preferably 3 to 10, even more preferably 3 to 8, and particularly preferably 3 to 5.

[0159] The molecular weight of the cyclic siloxane compound represented by formula (1) is preferably 2000 or less, more preferably 1600 or less, even more preferably 1200 or less, and particularly preferably 1000 or less. In addition, the molecular weight of the cyclic siloxane compound represented by formula (1) is preferably 100 or more, more preferably 150 or more, and even more preferably 200 or more.

[0160] Preferred specific examples of the cyclic siloxane compound represented by formula (1) include decamethylcyclopentasiloxane (D5), octamethylcyclotetrasiloxane (D4), and octaphenylcyclotetrasiloxane (OPTS).

[0161] Straight-chain siloxane compounds are represented by the following formula (2).

[0162] [Chemical Formula 17]

[0163]

[0164] During the meal, R 3 and R 4 Each is independently a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aromatic hydrocarbon oxy group having 6 to 20 carbon atoms, and a cycloalkoxyl group having 3 to 20 carbon atoms. In this case, R 3 and R 4It is preferable that the group be an alkyl group having a total of 1 to 20 carbon atoms that may have substituents, or an aryl group having a total of 6 to 30 carbon atoms.

[0165] Among the alkyl groups having a total of 1 to 20 carbon atoms that may have the above substituents, it is preferable that they be alkyl groups having a total of 1 to 10 carbon atoms, more preferable that they be alkyl groups having a total of 1 to 8 carbon atoms, and even more preferable that they be alkyl groups having a total of 1 or 2 carbon atoms.

[0166] The above aryl group having a total of 6 to 30 carbon atoms is preferably an aryl group having a total of 6 to 20 carbon atoms, more preferably an aryl group having a total of 6 to 12 carbon atoms, and even more preferably an aryl group having a total of 6 to 8 carbon atoms.

[0167] Examples of the above substituents include hydroxyl groups, halogens, amino groups, vinyl groups, carboxyl groups, cyano groups, (meth)acryloxy groups, glycidyloxy groups, mercapto groups, etc.

[0168] R 3 and R 4 Preferred specific examples include methyl groups, phenyl groups, vinyl groups, and propyl groups.

[0169] X is, each independently, a hydrogen atom, a hydroxyl group, a C1-10 alkoxy group that may have a substituent, a C1-10 siloxy group that may have a substituent, a C1-10 hydrocarbon group that may have a substituent, an C1-10 oxygen atom-containing group that may have a substituent, a C1-10 nitrogen atom-containing group that may have a substituent, and an amino group that may have a substituent. Among these, X is preferably a hydroxyl group, a siloxy group having 1 to 10 carbon atoms that may have a substituent, or a hydrocarbon group having 1 to 10 carbon atoms that may have a substituent; more preferably a hydroxyl group, a siloxy group having 1 to 5 carbon atoms that may have a substituent, or a hydrocarbon group having 1 to 5 carbon atoms that may have a substituent; and even more preferably a hydroxyl group, a trimethylsilyloxy group, a triethylsilyloxy group, a t-butyldimethylsilyloxy group, methyl, ethyl, propyl, isopropyl, butyl, n-butyl, s-butyl, or t-butyl.

[0170] m is an integer from 2 to 10000, preferably 10 to 7000, more preferably 100 to 2000, and even more preferably 200 to 500.

[0171] The molecular weight of the straight-chain siloxane compound represented by Formula (2) is preferably 60,000 or less, more preferably 56,000 or less, even more preferably 50,000 or less, and particularly preferably 45,000 or less. In addition, the molecular weight of the straight-chain siloxane compound represented by Formula (2) is preferably 1,000 or more, more preferably 5,000 or more, and even more preferably 10,000 or more.

[0172] A preferred specific example of the straight-chain siloxane compound represented by formula (2) is straight-chain polydimethylsiloxane (straight-chain PDSM).

[0173] Cyclic siloxane compounds and linear siloxane compounds may be used alone or in combination of two or more types.

[0174] [(B) Diol Compounds]

[0175] As for diol compounds, they are not particularly limited, but are of the following formula (J 1 ) ∼ (J 6 Examples of diol compounds represented as ) can be found.

[0176] [Chemical Formula 18]

[0177]

[0178] Among the above formulas, A 1 and A 2 , X 1 ~ X 6 , R 3 ~ R 5 , p1 ~ p2, and s1 ~ s2 are identical to those described above.

[0179] Among these, the diol compound is preferably 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF), 1,4-cyclohexanedimethanol (CHDM), ethylene glycol (EG), 1,3-propanediol (PG), 1,4-butanediol (BD), 2-butyl-2-ethyl-1,3-propanediol (BEPG), and neopentyl glycol (NPG).

[0180] The diol compounds described above may be used alone or in combination of two or more.

[0181] [(C) Basic compound catalyst]

[0182] A basic compound catalyst has the function of promoting the reaction of (A) a cyclic siloxane compound and / or a straight-chain siloxane compound and (B) a diol compound.

[0183] Examples of the above basic compound catalysts include alkali metal compounds and alkaline earth metal compounds.

[0184] Examples of the above alkali metal compounds include, but are not particularly limited, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; and alkali metal bicarbonates such as sodium bicarbonate, potassium bicarbonate, and cesium bicarbonate.

[0185] Examples of the above alkaline earth metal compounds include, but are not particularly limited, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; alkaline earth metal carbonates such as magnesium carbonate and calcium carbonate; and the like.

[0186] Among those described above, the basic compound catalyst is preferably an alkali metal carbonate or an alkali metal bicarbonate, more preferably a sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, or potassium bicarbonate, even more preferably a potassium carbonate or cesium carbonate, and particularly preferably a cesium carbonate. In addition, the basic compound catalyst described above may be used alone or in combination of two or more types.

[0187] The amount of basic compound catalyst added is not particularly limited, but it is preferable to have 1.5 to 100 times the mole relative to the diol compound, more preferable to have 2.0 to 50 times the mole, even more preferable to have 3.0 to 30 times the mole, and particularly preferable to have 4.0 to 20 times the mole.

[0188] [reaction]

[0189] The reaction is not particularly limited, but it is preferable to heat and react (A) a cyclic siloxane compound and / or a straight-chain siloxane compound and (B) a diol compound in the presence of (C) a basic compound catalyst.

[0190] The reaction temperature is not particularly limited, but is preferably 30 to 300°C, more preferably 80 to 250°C, and even more preferably 100 to 230°C.

[0191] The reaction atmosphere is not particularly limited, but it is preferable to carry out the reaction in an inert gas atmosphere. Examples of the inert gas include nitrogen gas and argon gas.

[0192] By carrying out the above reaction, a composition containing a siloxane block-containing diol compound can be prepared.

[0193] In addition, among the by-products and unreacted raw materials that may be included in the product obtained by the reaction, relatively low-boiling point impurities (such as cyclic siloxane compounds) may be appropriately removed by vacuum distillation.

[0194] Siloxane-based thermoplastic resins

[0195] According to one embodiment of the present invention, a siloxane-based thermoplastic resin is provided, comprising a constituent unit derived from the siloxane block-containing diol compound described above.

[0196] The above siloxane-based thermoplastic resins are not particularly limited, but may include polycarbonate resin, polyester carbonate resin, acrylic resin such as polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), triacetylcellulose (TAC), polyethylene naphthalate (PEN), polyimide (PI), cycloolefin copolymer (COC), norbornene-containing resin, polyethersulfone, cellophane, aromatic polyamide, etc.

[0197] In one embodiment, the siloxane-based thermoplastic resin is a copolymer formed by reacting a siloxane block-containing diol compound with the thermoplastic resin or its monomer.

[0198] Below, the case where the siloxane-based thermoplastic resin is a siloxane-based polycarbonate resin is described in detail.

[0199] The siloxane-based polycarbonate resin comprises a constituent unit derived from a siloxane block-containing diol compound and a constituent unit derived from a carbonate compound.

[0200] The above carbonate compound is not particularly limited as long as it is capable of introducing a carbonyl group (-CO- group) of the polycarbonate constituent unit into the siloxane-based polycarbonate resin. Examples include diaryl carbonates such as diphenyl carbonate, dibenzyl carbonate, ditolyl carbonate, bis(chlorophenyl)carbonate, and m-crezyl carbonate; dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate; and monoaryl monoalkyl carbonates.

[0201] These carbonate compounds may be used alone or in combination of two or more.

[0202] Siloxane-based polycarbonate resins may additionally include other constituent units. Such other constituent units are not particularly limited, but may include constituent units derived from aromatic diol compounds, constituent units derived from diaryloxysilane compounds, etc.

[0203] The weight average molecular weight of the siloxane-based polycarbonate resin is preferably 10,000 to 1,000,000, more preferably 20,000 to 800,000, and even more preferably 30,000 to 700,000.

[0204] The molar ratio of the constituent unit derived from the siloxane block-containing diol compound and the constituent unit derived from the carbonate compound of the siloxane-based polycarbonate resin is preferably 0.01 : 99.99 to 99.99 : 0.01, more preferably 1 : 99 to 99 : 1, even more preferably 10 : 90 to 90 : 10, and particularly preferably 30 : 70 to 70 : 30.

[0205] The siloxane-based thermoplastic resin described above can have excellent chemical resistance, low-temperature impact resistance, weather resistance, flame retardancy, etc. because it contains constituent units derived from siloxane block-containing diol compounds.

[0206] <Method for Manufacturing Siloxane-Based Thermoplastic Resin>

[0207] According to one embodiment of the present invention, a method for manufacturing a siloxane-based thermoplastic resin is provided. The method for manufacturing the siloxane-based thermoplastic resin comprises a process of reacting a composition and a thermoplastic resin at 160 to 400°C in the presence of a catalyst.

[0208] [Composition]

[0209] As a composition, a composition comprising the siloxane block-containing diol compound described above may be used.

[0210] [Thermoplastic Resin]

[0211] Examples of thermoplastic resins include, but are not particularly limited, polycarbonate resin, polyester carbonate resin, acrylic resin such as polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), triacetylcellulose (TAC), polyethylene naphthalate (PEN), polyimide (PI), cycloolefin copolymer (COC), norbornene-containing resin, polyethersulfone, cellophane, aromatic polyamide, and monomers thereof.

[0212] [catalyst]

[0213] Examples of catalysts include alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, and metal salts, although they are not particularly limited.

[0214] Examples of the above alkali metal compounds include, but are not particularly limited, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium phenylborohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, disodium hydrogen phosphate, disodium hydrogen phosphate, disodium phenylphosphate, sodium gluconate, disodium salt, disodium salt, disodium salt, disodium salt of bisphenol A, sodium salt, potassium salt, cesium salt, lithium salt of phenol, etc.

[0215] Examples of the above alkaline earth metal compounds include, but are not particularly limited, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, magnesium phenylphosphate, etc.

[0216] The above nitrogen-containing compounds are not particularly limited, but may include quaternary ammonium hydroxides having alkyl groups and / or aryl groups such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide; tertiary amines such as triethylamine, dimethylbenzylamine, and triphenylamine; secondary amines such as diethylamine and dibutylamine; primary amines such as propylamine and butylamine; imidazoles such as 2-methylimidazole, 2-phenylimidazole, and benzimidazole; and bases or basic salts such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetraphenylammonium tetraphenylborate.

[0217] The above metal salts are not particularly limited but may include zinc salts such as zinc acetate, zinc benzoate, and zinc 2-ethylhexanoate; tin salts such as tin chloride (II), tin chloride (IV), tin acetate (II), tin acetate (IV), dibutyltin dilaurate, dibutyltin oxide, and dibutyltin dimethoxide; zirconium salts such as zirconium acetylacetonate, zirconium oxyacetate, and zirconium tetrabutoxide; and lead salts such as lead acetate (II) and lead acetate (IV).

[0218] The catalyst described above may be used alone or in combination of two or more types.

[0219] [reaction]

[0220] The reaction is not particularly limited, but it is preferable to react the composition and the thermoplastic resin in the presence of a catalyst.

[0221] At this time, the reaction temperature is 160 to 400 ℃, preferably 200 to 350 ℃, more preferably 220 to 320 ℃, and even more preferably 240 to 310 ℃.

[0222] By carrying out the above reaction, a siloxane-based thermoplastic resin can be manufactured.

[0223] Examples

[0224] The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. Also, unless otherwise noted, "%" is based on mass.

[0225] [Measurement Conditions]

[0226] <Content of Polysiloxane and Cyclic Siloxane>

[0227] It was calculated using NMR. In addition, the following 1 The chemical shift in H-NMR analysis was based on the 0 ppm peak of TMS (tetramethylsilane).

[0228] 1 By H-NMR, peaks of methyl groups on Si corresponding to polysiloxane, cyclic siloxane decamethylpentacyclosiloxane (D5), and octamethyltetracyclosiloxane (D4) are observed at 0.1 to 1.0 ppm, 0.079 ppm, and 0.094 ppm, respectively. The sum of the peak areas at 0.079 ppm and 0.094 ppm is the cyclic siloxane content, and the value obtained by subtracting the peak areas at 0.079 ppm and 0.094 ppm from the peak area at 0.1 to 1.0 ppm is the polysiloxane content. Based on these values, the polysiloxane production rate and cyclic siloxane production rate were calculated.

[0229] <Polystyrene Weight Average Molecular Weight (Mw, Mn, Mw / Mn)>

[0230] A calibration curve was constructed using GPC (gel penetration chromatography) with chloroform as the developing solvent and standard polystyrene (Shodex STANDARD, SM-105) of a known molecular weight (molecular weight distribution = 1). The elution time and molecular weight value of each peak were plotted from the measured standard polystyrene, and a calibration curve was obtained by approximating using a cubic equation.

[0231] Then, based on the obtained calibration curve, the weight-average molecular weight (Mw) was calculated as a polystyrene equivalent value from the following formula.

[0232] [Calculation Formula]

[0233] Mw = Σ (Wi × Mi) / Σ (Wi)

[0234] Mn = Σ (Ni × Mi) / Σ (Ni)

[0235] In the above formula, i represents the i-th splitting point when the molecular weight M is split, Wi represents the i-th weight, Mi represents the i-th molecular weight, and Ni represents the i-th number of molecules. Also, the molecular weight m represents the molecular weight value in polystyrene equivalent at the same dissolution time of the calibration curve.

[0236] In addition, Mw / Mn represents the molecular weight dispersion. It is a parameter used to determine whether the molecular weight distribution is wide or narrow; a value closer to 1.0 indicates a narrow molecular weight distribution, while a larger value indicates a wide molecular weight distribution.

[0237] [Measurement Conditions]

[0238] · Device: Manufactured by Shimadzu Corporation, Labsolutions

[0239] · Columns: Guard column (Shodex GPC KG 4A) × 1, Analysis column (Shodex GPC K-805L) × 2

[0240] · Solvent: Chloroform (HPLC grade)

[0241] · Injection volume: 10 μL

[0242] · Sample concentration: 2000 ppm

[0243] · Solvent flow rate: 1 mL / min

[0244] · Measured temperature: 40 ℃

[0245] · Detector: RI

[0246] <Measurement of Glass Transition Temperature (Tg)>

[0247] As a measurement sample, a test specimen of 5 to 12 mg was weighed into a sample container for an AI autosampler (RDC aluminum pan, cylindrical container with a diameter of 6.8 mm and a height of 2.5 mm), and the top of the sample container was sealed with an AI autosampler cover.

[0248] Measurements were performed using a differential scanning calorimeter (DSC) under a nitrogen atmosphere (nitrogen flow rate: 50 ml / min), and 10.0 mg of sapphire was used as a standard in the reference cell. Then, the measurement sample, adjusted to 30 ℃, was heated to 280 ℃ at a rate of 20 ℃ / min, and then cooled down to 30 ℃ at a rate of 20 ℃ / min. Afterward, the temperature was raised to 280 ℃ at a rate of 10 ℃ / min for measurement.

[0249] Measuring device: Differential Scanning Calorimeter (DSC) (Product name "DSC-7020", manufactured by Hitachi High-Tech Science Corp.)

[0250] [Example 1]

[0251] 3.708 g (10 mmol, Si molar amount: 50 mmol) of decamethylcyclopentasiloxane (D5), 0.052 g (0.5 mmol) of neopentyl glycol (NPG), and 3.2582 mg (10 μmol) of cesium carbonate (Ca2CeO3) as a catalyst were substituted under a nitrogen atmosphere and heated to 150 °C. By stirring at 150 °C for 2 hours, a composition containing a colorless oily siloxane block-containing diol compound (polysiloxane compound) was obtained.

[0252] [Example 2]

[0253] 37.05 g (100 mmol, Si molar amount: 500 mmol) of decamethylcyclopentasiloxane (D5), 3.205 g (20 mmol) of 2-butyl-2-ethyl-1,3-propanediol (BEPG), and 1.3 mg (4 μmol) of cesium carbonate (Ca2CeO3) as a catalyst were heated to 200 °C under a nitrogen atmosphere. After stirring at 200 °C for 1 hour, the mixture was cooled to room temperature and 17.5 mg (0.29 mmol) of acetic acid was added. By heating at 80 °C for 2 hours under reduced pressure (2 hPa), a composition containing a siloxane block-containing diol compound (polysiloxane compound) was prepared while most of the cyclic siloxanes were removed by distillation.

[0254] [Examples 3–17, Comparative Examples 1–4]

[0255] The procedure was carried out in the same manner as Example 1, except that the raw materials, reaction temperature, and reaction time were changed to those listed in Table 1.

[0256]

[0257] In addition, the abbreviations in Table 1 are as follows.

[0258] (A) Siloxane compound

[0259] D5: Decamethylcyclopentasiloxane

[0260] D4: Octamethylcyclotetrasiloxane

[0261] OPTS: Octaphenylcyclotetrasiloxane

[0262] Straight-chain PDSM: Straight-chain polydimethylsiloxane

[0263] (B) Diol compound

[0264] NPG: Neopentyl glycol

[0265] BEPG: 2-butyl-2-ethyl-1,3-propanediol

[0266] EG: Ethylene glycol

[0267] PG: 1,3-propanediol

[0268] BD: 1,4-butanediol

[0269] CHDM : 1,4-cyclohexanedimethanol

[0270] BPEF : 9,9-Bis[4-(2-hydroxyethoxy)phenyl]fluorene

[0271] BPA: Bisphenol A

[0272] HQ: Hydroquinone

[0273] AD : 1,3-Adamantanediol

[0274] PHEP : 2-(4-hydroxyphenyl)ethanol

[0275] (C) Basic compound catalyst

[0276] Cs2CO3: Cesium carbonate

[0277] K2CO3: Potassium carbonate

[0278] The compositions obtained in Examples 1 to 17 and Comparative Examples 1 to 4 1 Analysis was performed using H-NMR and GPC. The results obtained are shown in Table 2 below.

[0279]

[0280] From the results of Table 2, it can be seen that siloxane block-containing diol compounds could be preferably prepared in Examples 1 to 17.

[0281] In addition, when comparing Examples 1, 10 to 15, in which a primary alcohol is used as (B) the diol compound, with Example 17, in which a secondary alcohol is used as (B) the diol compound, it can be seen that Examples 1, 10 to 15 can produce a siloxane block-containing diol compound with a high yield.

[0282] [Example a]

[0283] A polycarbonate copolymer was prepared using the composition prepared in Example 2 (most cyclic siloxanes were removed by distillation) and a polycarbonate compound.

[0284] Specifically, 2.00 g of the composition prepared in Example 2 and 20.01 g of polycarbonate (molecular weight = Mw 18,783, Mn 10,227, cesium carbonate injected as a catalyst, containing 0.167 μmol relative to the molar amount of bisphenol A, Tg = 122 ℃) were heated to 230 ℃ under reduced pressure (2 hPa). By stirring at 230 ℃ for 2 hours, a white siloxane block copolymer polycarbonate was obtained.

[0285] The Mw and Mn of the siloxane block copolymer polycarbonate were measured using GPC, and the results were Mw 44,619 and Mn 25,003.

[0286] [Example b]

[0287] A polycarbonate copolymer was prepared using the composition prepared in Example 2 and a polycarbonate compound.

[0288] 20.00 g of polycarbonate (molecular weight = Mw 18,783, Mn 10,227, cesium carbonate injected as a catalyst, containing 0.167 μmol relative to the molar amount of bisphenol A, Tg = 122 ℃) was heated to 240 ℃ under a nitrogen atmosphere and melted. After the polycarbonate was melted, 10.00 g of the composition prepared in Example 2 was added dropwise using a dropping funnel. The pressure was gradually reduced from 240 ℃, and after reaching 2 hPa, the temperature was raised to 260 ℃ and stirred for 1 hour to obtain a white siloxane block copolymer polycarbonate.

[0289] The Mw and Mn of the siloxane block copolymer polycarbonate were measured using GPC, and the results were Mw 101,401 and Mn 57,702.

[0290] [Example c]

[0291] A polycarbonate copolymer was prepared using the composition prepared in Example 2 and a polycarbonate compound.

[0292] Specifically, 2.50 g of the composition prepared in Example 2 and 10.00 g of polycarbonate (molecular weight = Mw 18,783, Mn 10,227, cesium carbonate injected as a catalyst, containing 0.167 μmol relative to the molar amount of bisphenol A, Tg = 122 ℃) were heated to 260 ℃ under reduced pressure (2 hPa). By stirring at 260 ℃ for 1 hour and 20 minutes, a white, powder-like siloxane block copolymer polycarbonate was obtained.

[0293] As a result of measuring the Mw and Mn of the siloxane block copolymer polycarbonate using GPC, Mw was 356,597 and Mn was 79,718. Also, Tg was 140 °C.

Claims

Claim 1 A composition comprising a siloxane block-containing diol compound, wherein the siloxane block-containing diol compound is of the following formula (I): [In the middle of the meal, R 1 and R 2 is, each independently, an alkyl group having 1 to 20 carbon atoms that may have substituents, or an aryl group having 6 to 30 carbon atoms that may have substituents; m is an integer from 1 to 25; n is an integer from 3 to 200; and X is, each independently, of the following formula (I 1 ) ~ (I 6 ) : and, at this time, A 1 and A 2 is, each independently, -(CR 6A R 6B ) q1 - or -( O-(CR 6A R 6B ) q2 ) q3 - and, here, R 6A and R 6B are each independently H or an alkyl group having 1 to 6 carbon atoms, q1 is an integer from 0 to 10, q2 is an integer from 0 to 10, q3 is an integer from 0 to 10, and R 3 and R 4 are, each independently, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aromatic hydrocarbon oxy group having 6 to 20 carbon atoms, and a cycloalkoxyl group having 3 to 20 carbon atoms; p1 and p2 are, each independently, integers from 0 to 4, and R 5 is, each independently, H or an alkyl group having 1 to 6 carbon atoms, and X 1 and X 2 is, each independently, a single combination or the gi represented below: and, here, R 7 and R 8 Each is independently H, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms that may have substituents, an alkoxyl group having 1 to 20 carbon atoms that may have substituents, an aromatic hydrocarbon group having 6 to 20 carbon atoms that may have substituents, or R 7 and R 8 These may combine to form a carbon ring with 3 to 20 carbon atoms or a complex ring with 5 to 12 atoms; R 9 and R 10 Each is independently H, an alkyl group having 1 to 6 carbon atoms; R 11 ~ R 16 Each is independently a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms that may have substituents, an alkoxyl group having 1 to 20 carbon atoms that may have substituents, and an aromatic hydrocarbon group having 6 to 12 carbon atoms that may have substituents; r1 is an integer from 2 to 20, and X 3 Each is independently a divalent aromatic hydrocarbon group having 15 to 32 carbon atoms, and X 4 is, each independently, a divalent group comprising one or more hydrocarbon rings or heterocycles, wherein the divalent group comprising one or more hydrocarbon rings or heterocycles is R 5 , R 6A , and R 6B It may be formed by combining with at least one selected from the group consisting of, and X 5 are, each independently, divalent saturated heterocyclic groups, where the divalent saturated heterocyclic group is R 5 , R 6A , and R 6B It may be formed by combining with at least one selected from the group consisting of, and X 6 A composition represented as follows: s1 and s2 are each independently an alkylene group having 1 to 10 carbon atoms that may contain an oxygen atom, and s1 and s2 are each independently integers from 0 to 10. Claim 2 A siloxane-based thermoplastic resin comprising a constituent unit derived from a siloxane block-containing diol compound described in claim 1. Claim 3 (A) The following formula (1): [In the middle of the meal, R 1 and R 2 [A, each independently, is an alkyl group that may have a substituent, an alkenyl group that may have a substituent, and an aryl group that may have a substituent, and n is an integer from 3 to 30.] Cyclic siloxane compounds represented by the following formula (2) : [In the middle of the meal, R 3 and R 4 [A, each independently an alkyl group that may have substituents, an alkenyl group that may have substituents, and an aryl group that may have substituents; X, each independently a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms that may have substituents, a siloxy group having 1 to 10 carbon atoms that may have substituents, a hydrocarbon group having 1 to 10 carbon atoms that may have substituents, an oxygen atom-containing group having 1 to 10 carbon atoms that may have substituents, a nitrogen atom-containing group having 1 to 10 carbon atoms that may have substituents, and an amino group having substituents; and m is an integer from 2 to 10000.] and a straight-chain siloxane compound represented by the following formula (J 1 ) ∼ (J 6 ) : [During the meal, A 1 and A 2 , X 1 ~ X 6 , R 3 ~ R 5 A method for preparing the composition described in claim 1, comprising a process of reacting a diol compound represented as [p1 to p2 and s1 to s2 are identical to the definition of claim 1] with a basic compound catalyst (C). Claim 4 A method for manufacturing a siloxane-based thermoplastic resin, comprising a process of reacting the composition described in claim 1 with a thermoplastic resin at 160 to 400°C in the presence of a catalyst.

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