Composition, silicone-based thermoplastic resin using the same, and method for producing the same

Abstract

The present invention provides a composition containing a diol compound containing a siloxane block which is easy to manufacture industrially. A composition containing a diol compound containing a siloxane block, wherein the diol compound containing a siloxane block is represented by the following formula (I), wherein R 1 and R 2 Each of them is independently an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent, m is an integer of 1 to 25, n is an integer of 3 to 200, and X is independently a group of the following formula (I 1 )~(I 6 ) group, *-CHR 5 ‑A 1 ‑X 3 ‑A 2 ‑CHR 5 ‑*(I 3 )*‑CHR 5 ‑A 1 ‑X 4 ‑A 2 ‑CHR 5 ‑*(I 4 ) * ‑CHR 5 ‑A 1 ‑X 5 ‑A 2 ‑CHR 5 ‑*(I 5 )

Description

Technical Field

[0001] The present invention relates to a composition, a silicone-based thermoplastic resin using the same, and a method for producing the same. Background Art

[0002] Currently, siloxane block-containing diol compounds are known to be effective as raw materials for various resins containing silicon blocks in their structures, and are used, for example, in release layers in photocopying, photoresist materials, plasticizers for polycarbonate, or components of powder surface coating systems.

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

[0004] As such a siloxane block-containing diol compound, Patent Document 1 describes that siloxane block-containing dihydroxy compounds (hydroxyaryl-terminated polysiloxanes) represented by the following formulae (a) to (c) are preferred.

[0005]

[0006] Patent Document 1 discloses that by adding a predetermined inorganic salt and / or organic salt to the above-mentioned siloxane block-containing dihydroxy compound and then producing a polydiorganosiloxane-polyorgano block copolymer by a solvent-free melt process, the melt stability, decomposition stability to solvents and water, and low-temperature impact resistance of the obtained copolymer can be improved.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application No. 2016-538362 Summary of the invention

[0010] Technical problem to be solved by the invention

[0011] However, in the siloxane block-containing diol compound described in Patent Document 1, the reactivity between the siloxane compound and the diol compound as raw materials is low, and industrial production may be difficult.

[0012] To this end, the present invention provides a composition containing a siloxane block-containing diol compound which can be easily produced industrially.

[0013] Technical solutions for solving technical problems

[0014] The present inventors have conducted intensive studies to solve the above technical problems. As a result, they have found that the above technical problems can be solved by making the diol compound containing a siloxane block into a predetermined structure, thereby completing the present invention. That is, the present invention is, for example, as follows.

[0015] [1] A composition containing a siloxane block-containing diol compound, wherein:

[0016] The above-mentioned siloxane block-containing diol compound is a compound represented by the following formula (I):

[0017]

[0018] In formula (I),

[0019] R 1 and R 2 are each independently an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent,

[0020] m is an integer from 1 to 25,

[0021] n is an integer from 3 to 200,

[0022] X is independently the following formula (I 1 )~(I 6 ) shown in:

[0023]

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

[0025] R 3 and R 4 are each independently a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkoxy 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 hydrocarbonoxy group having 6 to 20 carbon atoms, or a cycloalkoxy group having 3 to 20 carbon atoms,

[0026] p1 and p2 are each independently an integer of 0 to 4,

[0027] R 5 are each independently H or an alkyl group having 1 to 6 carbon atoms,

[0028] X 1 and X 2 are independently a single bond or the following groups:

[0029]

[0030] Among them, R 7 and R 8 are each independently H, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or R 7 and R 8 can combine to form a carbon ring with 3 to 20 carbon atoms or a heterocyclic ring with 5 to 12 members; R 9 and R 10 are independently H, an alkyl group having 1 to 6 carbon atoms; R 11 ~R 16 are independently a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent; r1 is an integer of 2 to 20,

[0031] X 3 are each independently a divalent aromatic hydrocarbon group having 15 to 32 carbon atoms,

[0032] X 4 are independently divalent groups containing one or more hydrocarbon rings or heterocyclic rings, wherein the divalent groups containing one or more hydrocarbon rings or heterocyclic rings may be selected from R 5 , R 6A and R 6B At least one of the

[0033] X 5 are independently a divalent saturated heterocyclic group, wherein the divalent saturated heterocyclic group may be selected from R 5 , R 6A and R 6B At least one of the

[0034] X 6 are each independently an alkylene group having 1 to 10 carbon atoms which may contain an oxygen atom,

[0035] s1 and s2 are each independently an integer of 0 to 10.

[0036] [2] A siloxane-based thermoplastic resin, wherein:

[0037] It contains a structural unit derived from the siloxane block-containing diol compound described in the above [1].

[0038] [3] A method for producing a composition, which is used to produce the composition described in [1] above, comprising:

[0039] (A) a cyclic siloxane compound represented by the following formula (1) and / or a linear siloxane compound represented by the following formula (2), and (B) a siloxane compound represented by the following formula (J 1 )~(J 6 ) and (C) a basic compound catalyst to react,

[0040]

[0041] In formula (1),

[0042] R 1 and R 2 are each independently an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent,

[0043] n is an integer from 3 to 30,

[0044]

[0045] In formula (2),

[0046] R 3 and R 4 are each independently an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent,

[0047] X is independently a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, a silyloxy group having 1 to 10 carbon atoms which may have a substituent, a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, an oxygen atom-containing group having 1 to 10 carbon atoms which may have a substituent, a nitrogen atom-containing group having 1 to 10 carbon atoms which may have a substituent, or an amino group which may have a substituent,

[0048] m is an integer from 2 to 10000,

[0049]

[0050] Formula (J 1 )~(J 6 ), A 1 and A2 , X 1 ~X 6 , R 3 ~R 5 , p1~p2 and s1~s2 are the same as those defined in [1] above.

[0051] [4] A method for producing a siloxane-based thermoplastic resin, comprising: reacting the composition according to [1] and a thermoplastic resin at a temperature of 160 to 400° C. in the presence of a catalyst.

[0052] Effects of the Invention

[0053] According to the present invention, a composition containing a siloxane block-containing diol compound which can be easily produced industrially can be provided. DETAILED DESCRIPTION

[0054] Hereinafter, specific embodiments of the present invention will be described in detail.

[0055] <Composition>

[0056] The composition of the present invention contains a siloxane block-containing diol compound. In addition, the composition may contain impurities derived from raw materials such as a cyclic siloxane compound, a linear siloxane compound, a diol compound, a basic compound catalyst, and their decomposition products.

[0057] [Siloxane block-containing diol compound]

[0058] The siloxane block-containing diol compound is represented by the following formula (I).

[0059] In formula (I), the carbon atom in X that is bonded to the hydroxyl group (formula (I) 1 )~(I 6 ) in -CHR 5 -) is a primary carbon atom or a secondary carbon atom. As a result, the reactivity of the diol compound from which the structural unit X is derived and the cyclic siloxane compound and / or the linear siloxane compound from which the siloxane block is derived becomes high. As a result, the compound represented by formula (I), i.e., the diol compound containing the siloxane block, becomes easy to manufacture industrially.

[0060]

[0061] In the above formula, R 1 and R 2 Each of them is independently an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent.

[0062] The alkyl group having 1 to 20 carbon atoms is not particularly limited, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, n-pentadecyl, n-eicosyl, 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, 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 a methyl group.

[0063] The aryl group having 6 to 30 carbon atoms is not particularly limited, and examples thereof include phenyl, indenyl, naphthyl, biphenyl, acenaphthenyl, fluorenyl, phenanthrenyl, phenanthrenyl, anthracenyl, triphenylenyl, pyrenyl, 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 a phenyl group.

[0064] As the above R 1 and R 2 The substituents are not particularly limited, and examples thereof include hydroxyl, halogen atoms, amino, vinyl, carboxyl, cyano, (meth)acryloyloxy, glycidoxy, mercapto, etc. It should be noted that in the present specification, "amino" includes, in addition to unsubstituted amino (-NH2), monoalkylamino substituted with one alkyl group having 1 to 6 carbon atoms, and dialkylamino substituted with two alkyl groups having 1 to 6 carbon atoms. Specific examples of the amino group include, but are not particularly limited to, amino (-NH2); monoalkylamino groups such as methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, tert-butylamino, n-pentylamino, and n-hexylamino; and dialkylamino groups such as 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, and n-butylethylamino. Among these, the amino group is preferably an unsubstituted amino group (-NH2).

[0065] m is an integer of 1-25, preferably 1-20, more preferably 3-15.

[0066] n is an integer of 3-200, preferably 3-100, more preferably 3-50, and even more preferably 3-10.

[0067] X is independently represented by the following formula (I 1 )~(I 6 )express.

[0068]

[0069] That is, in formula (I), the -CHR 5 - is a primary carbon atom or a secondary carbon atom.

[0070] A 1 and A 2 Each independently is -(CR 6A R 6B ) q1 -or-(O-(CR 6A R 6B ) q2 ) q3 -

[0071] At this time, R 6A and R 6B Each independently represents H or an alkyl group having 1 to 6 carbon atoms.

[0072] Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl.

[0073] q1 is an integer of 0-10, preferably 0-5, more preferably 0-3.

[0074] q2 is an integer of 0-10, preferably 0-5, more preferably 0-3.

[0075] q3 is an integer of 0-10, preferably 0-5, more preferably 0-3.

[0076] R 3 and R 4 Each of them is independently a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkoxy 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 hydrocarbonoxy group having 6 to 20 carbon atoms, or a cycloalkoxy group having 3 to 20 carbon atoms.

[0077] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0078] The aliphatic hydrocarbon group having 1 to 20 carbon atoms is a monovalent aliphatic hydrocarbon group, and is not particularly limited, and examples thereof include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an alkynyl group having 2 to 20 carbon atoms.

[0079] The alkyl group having 1 to 20 carbon atoms is not particularly limited, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, n-pentadecyl, n-eicosyl, 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, 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 a methyl group.

[0080] As the alkenyl group having 2 to 20 carbon atoms, there are no particular restrictions, and examples thereof include vinyl (vinyl), 1-propenyl, 2-propenyl (allyl), isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, pentenyl, hexenyl, octenyl, decenyl, pentadecenyl, eicosenyl, etc. Among these, as the alkenyl group having 2 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms is preferred, an alkenyl group having 2 to 6 carbon atoms is more preferred, and vinyl (vinyl) and 2-propenyl (allyl) are more preferred.

[0081] The alkynyl group having 2 to 20 carbon atoms is not particularly limited, and examples thereof include ethynyl, 1-propynyl, 2-propynyl, 2-butynyl, 3-butynyl, pentynyl, hexynyl, octynyl, decynyl, pentadecynyl, eicosynyl, etc. Among these, the alkynyl group having 2 to 20 carbon atoms is preferably an alkynyl group having 2 to 10 carbon atoms, more preferably an alkynyl group having 2 to 6 carbon atoms, more preferably an alkynyl group having 2 to 4 carbon atoms, and particularly preferably an alkynyl group having 2 to 3 carbon atoms.

[0082] The alkoxy group having 1 to 20 carbon atoms is a linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and is not particularly limited, and examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, n-hexoxy, etc. Among these, the alkoxy group having 1 to 20 carbon atoms is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, particularly preferably an alkoxy group having 1 to 2 carbon atoms, and most preferably a methoxy group.

[0083] 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, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl. Among these, the cycloalkyl group having 3 to 20 carbon atoms is preferably a cycloalkyl group having 3 to 10 carbon atoms.

[0084] 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, and examples thereof include phenyl, indenyl, naphthyl, biphenyl, acenaphthenyl, fluorenyl, phenanthrenyl, phenanthrenyl, anthracenyl, triphenylenyl, pyrenyl, 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 a phenyl group.

[0085] The aralkyl group having 7 to 20 carbon atoms is an alkyl group substituted with one aromatic hydrocarbon group, and is not particularly limited, and examples thereof include benzyl, phenethyl, phenylpropyl, naphthylmethyl, naphthylethyl, biphenylmethyl, etc. Among these, the aralkyl group having 7 to 20 carbon atoms is preferably benzyl.

[0086] The aromatic hydrocarbonoxy group having 6 to 20 carbon atoms is a monovalent aromatic hydrocarbonoxy group having 6 to 20 carbon atoms, and is not particularly limited, and examples thereof include phenoxy, indenyloxy, naphthyloxy, biphenyloxy, acenaphthyloxy, fluorenyloxy, phenanthrenyloxy, phenanthrenyloxy, anthracenyloxy, anthracenyloxy, triphenyleneoxy, pyreneoxy, Oxy, naphthyleneoxy, peryleneoxy, 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 a phenoxy group.

[0087] The cycloalkyloxy group having 3 to 20 carbon atoms is not particularly limited, and examples thereof include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, adamantyloxy, cyclododecyl, etc. Among these, the cycloalkyloxy group having 3 to 20 carbon atoms is preferably a cycloalkyloxy group having 3 to 12 carbon atoms.

[0088] p1 and p2 are each independently an integer of 0-4, preferably 0-2, and more preferably 0-1.

[0089] R 5 Each independently represents H or an alkyl group having 1 to 6 carbon atoms. In this case, examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl.

[0090] X 1 and X 2 Each independently represents a single bond or a group shown below.

[0091]

[0092] In the above formula, R 7 and R 8Each independently may be H, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or R 7 and R 8 They may be combined to form a carbocyclic ring having 3 to 20 carbon atoms or a heterocyclic ring having 5 to 12 members.

[0093] The aliphatic hydrocarbon group having 1 to 20 carbon atoms, the alkoxy group having 1 to 20 carbon atoms, and the aromatic hydrocarbon group having 6 to 20 carbon atoms are as described above.

[0094] In addition, there are no particular restrictions on the substituents that the aliphatic hydrocarbon group having 1 to 20 carbon atoms and the alkoxy group having 1 to 20 carbon atoms may have, and examples thereof include an alkoxy 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, and a carbamoyl group.

[0095] On the other hand, there are no particular restrictions on the substituents that the aromatic hydrocarbon having 6 to 20 carbon atoms may have, and examples thereof include alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, acyl groups having 1 to 7 carbon atoms, halogen atoms, amino groups, nitro groups, cyano groups, carbamoyl groups, and the like.

[0096] As R 7 and R 8 The carbon ring having 3 to 20 carbon atoms formed by the combination is not particularly limited, and examples thereof include a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent, and a condensed ring of a cycloalkyl group and an aromatic hydrocarbon group. Examples of the condensed ring include acenaphthenyl and fluorenyl groups.

[0097] It should be noted that there are no particular restrictions on the substituents that the above-mentioned carbon ring having 3 to 20 carbon atoms may have, and examples thereof include alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, acyl groups having 1 to 7 carbon atoms, halogen atoms, amino groups, nitro groups, cyano groups, carbamoyl groups, and the like.

[0098] In addition, as R 7 and R 8 The 5- to 12-membered heterocyclic ring formed by the combination is not particularly limited, and examples thereof include oxiranyl, aziridinyl, tetrahydrofuranyl, tetrahydrophenylthio, pyrrolidinyl, oxathiolanyl, piperidinyl, and 1(3H)-isobenzofuranonyl.

[0099] R 9 and R 10 Each independently represents H or an alkyl group having 1 to 6 carbon atoms. In this case, examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl.

[0100] r1 is an integer of 2-20, preferably 2-10, more preferably 2-5.

[0101] R 11 ~R 16 are independently a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent. Specific examples thereof are the same as those of R 7 and R 8 The same as the examples recorded in.

[0102] As a derivative having formula I 1 The diol compound of X is not particularly limited, and examples thereof 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-tert-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-isopropyl ... 9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene, 2,2-bis(4-(2-hydroxyethoxy)phenyl)propane, 4,4-bis(2-hydroxyethoxy)biphenyl, 2,2'(9H-fluorene-9,9'-diyl)bis(ethane-1-ol), 9H-fluorene-9,9-diyldimethanol, 2,2'-(1,4-phenylene)bis(ethane-1-ol), 2,2'-(1,4-phenylene)bis(methane-1-ol), 2,2'-(1,4-phenylenebis(oxy))bis(ethane-1-ol), etc. Among these, as a derivative having the formula I 1 The diol compound of X is preferably 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF).

[0103] In one embodiment, a derivative having formula I 1 The structure of the diol compound of X is shown below.

[0104]

[0105] As a derivative having formula I 2The diol compound of X is not particularly limited, and examples thereof include 9,9-bis[6-(1-hydroxymethoxy)naphth-2-yl]fluorene, 9,9-bis[6-(2-hydroxyethoxy)naphth-2-yl]fluorene, 9,9-bis[6-(3-hydroxypropoxy)naphth-2-yl]fluorene, 9,9-bis[6-(4-hydroxybutoxy)naphth-2-yl]fluorene, 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl, and the like. Among these, derivatives having the formula I 2 The diol compound of X is preferably 9,9-bis[6-(2-hydroxyethoxy)naphth-2-yl]fluorene or 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl.

[0106] X 3 Each independently is a divalent aromatic hydrocarbon group having 15 to 32 carbon atoms.

[0107] The divalent aromatic hydrocarbon group having 15 to 32 carbon atoms is not particularly limited, and examples thereof include fluoranthenylene, acetophenanthrenylene, acetoanthrylene, triphenylene, pyrene, divalent condensed polycyclic aromatic hydrocarbon groups such as terphenylene, tetraphenylene, heptahedralene, perylene, biphenylene, pentaphenylene, pentaphenylene, tetra-o-phenylene, hexaphenylene, hexaphenylene, rubidinyl, coronenylidene, trinaphthylene, heptaphenylene, heptahedralene, pyranthrylene and ovarenylene; terphenylene and quaterphenylene;

[0108] As a derivative having formula I 3 The diol compound of X is not particularly limited, and examples thereof include binaphthyl diol compounds. Specifically, examples thereof include 2,2'-bis(1-hydroxymethoxy)-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl, 2,2'-bis(3-hydroxypropyloxy)-1,1'-binaphthyl, and 2,2'-bis(4-hydroxybutoxy)-1,1'-binaphthyl. Among these, derivatives having formula I 3 The diol compound of X is preferably 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl.

[0109] X 4 Each independently is a divalent group containing one or more hydrocarbon rings or heterocyclic rings.

[0110] The hydrocarbon ring or heterocyclic ring is not particularly limited, and examples thereof include divalent groups each having one or more of a divalent aromatic hydrocarbon group having 6 to 32 carbon atoms which may have a substituent, a divalent cycloalkyl group having 3 to 20 carbon atoms which may have a substituent, a divalent aromatic hydrocarbon group having 6 to 32 carbon atoms which may have a substituent, and a divalent cycloalkyl group having 3 to 20 carbon atoms which may have a substituent.

[0111] The divalent aromatic hydrocarbon group having 6 to 32 carbon atoms may be a group containing a heteroatom selected from an oxygen atom, a sulfur atom, and a nitrogen atom as long as it exhibits aromaticity as a whole. The divalent aromatic hydrocarbon group having 6 to 32 carbon atoms is not particularly limited, and the following groups may be mentioned.

[0112]

[0113] The divalent cycloalkyl group having 3 to 20 carbon atoms may be a group containing 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, and the following groups may be mentioned.

[0114]

[0115] The divalent group having one or more of each of the divalent aromatic hydrocarbon group having 6 to 32 carbon atoms and the divalent cycloalkyl group having 3 to 20 carbon atoms is not particularly limited, and the following groups may be mentioned.

[0116]

[0117] There are no particular restrictions on the substituents that the divalent group having one or more divalent aromatic hydrocarbon groups having 6 to 32 carbon atoms, divalent cycloalkyl groups having 3 to 20 carbon atoms, divalent aromatic hydrocarbon groups having 6 to 32 carbon atoms, and divalent cycloalkyl groups having 3 to 20 carbon atoms may have, and examples thereof include alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, acyl groups having 1 to 7 carbon atoms, halogen atoms, amino groups, nitro groups, cyano groups, carbamoyl groups, and the like.

[0118] It should be noted that the divalent saturated heterocyclic group may be selected from R 5 , R 6A and R 6B For example, as a derivative having formula I 4 The diol compound X, 1,4-cyclohexanedimethanol (CHDM), is reacted with R 5 , R 6A and R 6B Together, X in the formula (I) has a cyclohexane ring.

[0119] X 5Each independently is a divalent saturated heterocyclic group.

[0120] The divalent saturated heterocyclic group is not particularly limited, and the following groups may be mentioned.

[0121]

[0122] It should be noted that the divalent saturated heterocyclic group may be selected from R 5 , R 6A and R 6B For example, a derivative having formula I 4 The diol compound X of 2,4-dihydroxy-1,4-dioxane is reacted with R 5 , R 6A and R 6B Together, X in the formula (I) has a cyclohexane ring.

[0123] X 6 Each independently represents an alkylene group having 1 to 10 carbon atoms which may contain an oxygen atom.

[0124] There are no particular restrictions on the alkylene groups having 1 to 10 carbon atoms that may contain the above-mentioned oxygen atom, and examples thereof include alkylene groups such as methylene, ethylene, propylene, isopropylene, and butylene; and alkylene groups containing oxygen atoms such as oxymethylene (-CH2-O-), oxyethylene (-CH2CH2-O-), dioxyethylene (-CH2CH2-O-CH2CH2-O-), and trioxyethylene (-CH2CH2-O-CH2CH2-O-CH2CH2-O-).

[0125] In addition, s1 and s2 are each independently an integer of 0-10, preferably 0-5, and more preferably 0-3.

[0126] As a derivative having formula I 6 Examples of the diol compound represented by X include ethylene glycol (EG), 1,3-propylene glycol (PG), 1,4-butylene glycol (BD), 2-butyl-2-ethyl-1,3-propanediol (BEPG), and neopentyl glycol (NPG).

[0127] The above-mentioned siloxane block-containing diol compound may be contained in the composition alone or in combination of two or more.

[0128] 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. In this specification, the value of "weight average molecular weight (Mw)" is the value measured by the method of Examples.

[0129] 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 this specification, the value of "number average molecular weight (Mn)" is the value measured by the method of Examples.

[0130] The weight average molecular weight (Mw) 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 relative to the number average molecular weight (Mn) (Mw / Mn).

[0131] <Method for producing siloxane block-containing diol compound>

[0132] In one embodiment of the present invention, a method for producing the above-mentioned siloxane block-containing diol compound can be provided.

[0133] The method for producing a siloxane block-containing diol compound includes a step of reacting (A) a cyclic siloxane compound and / or a linear siloxane compound, (B) a diol compound, and (C) a basic compound catalyst.

[0134] [(A) Cyclic siloxane compound and / or linear siloxane compound]

[0135] The cyclic siloxane compound is represented by the following formula (1).

[0136]

[0137] In the formula, R 1 and R 2 are independently an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent. 1 and R 2 An alkyl group having a total of 1 to 20 carbon atoms and an aryl group having a total of 6 to 30 carbon atoms which may have a substituent are preferred.

[0138] The alkyl group having a total of 1 to 20 carbon atoms which may have a 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 still more preferably an alkyl group having a total of 1 or 2 carbon atoms.

[0139] The aryl group having 6 to 30 carbon atoms in total is preferably an aryl group having 6 to 20 carbon atoms in total, more preferably an aryl group having 6 to 12 carbon atoms in total, and still more preferably an aryl group having 6 to 8 carbon atoms in total.

[0140] Examples of the substituent include a hydroxyl group, a halogen group, an amino group, a vinyl group, a carboxyl group, a cyano group, a (meth)acryloyloxy group, a glycidoxy group, and a mercapto group.

[0141] As R 1 and R 2 Preferred specific examples include methyl, phenyl, vinyl and propyl.

[0142] n is an integer of 3-30, preferably 3-15, more preferably 3-10, further preferably 3-8, particularly preferably 3-5.

[0143] The molecular weight of the cyclic siloxane compound represented by formula (1) is preferably 2000 or less, more preferably 1600 or less, more preferably 1200 or less, and particularly preferably 1000 or less. 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.

[0144] Preferred specific examples of the cyclic siloxane compound represented by the formula (1) include decamethylcyclopentasiloxane (D5), octamethylcyclotetrasiloxane (D4), and octaphenylcyclotetrasiloxane (OPTS).

[0145] The linear siloxane compound is represented by the following formula (2).

[0146]

[0147] In the formula, R 3 and R 4 are independently a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkoxy 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 hydrocarbonoxy group having 6 to 20 carbon atoms, or a cycloalkoxy group having 3 to 20 carbon atoms. 3 and R 4 An alkyl group having a total of 1 to 20 carbon atoms and an aryl group having a total of 6 to 30 carbon atoms which may have a substituent are preferred.

[0148] The alkyl group having a total of 1 to 20 carbon atoms which may have a 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 8 carbon atoms, and still more preferably an alkyl group having a total of 1 or 2 carbon atoms.

[0149] The aryl group having 6 to 30 carbon atoms in total is preferably an aryl group having 6 to 20 carbon atoms in total, more preferably an aryl group having 6 to 12 carbon atoms in total, and still more preferably an aryl group having 6 to 8 carbon atoms in total.

[0150] Examples of the substituent include a hydroxyl group, a halogen group, an amino group, a vinyl group, a carboxyl group, a cyano group, a (meth)acryloyloxy group, a glycidoxy group, and a mercapto group.

[0151] As R 3 and R 4 Preferred specific examples include methyl, phenyl, vinyl and propyl.

[0152] X is independently a hydrogen atom, a hydroxyl group, an alkoxyl group having 1 to 10 carbon atoms which may have a substituent, a silyloxy group having 1 to 10 carbon atoms which may have a substituent, a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, an oxygen atom-containing group having 1 to 10 carbon atoms which may have a substituent, a nitrogen atom-containing group having 1 to 10 carbon atoms which may have a substituent, or an amino group which may have a substituent. Among these, X is preferably a hydroxyl group, a silyloxy group having 1 to 10 carbon atoms which may have a substituent, or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, more preferably a hydroxyl group, a silyloxy group having 1 to 5 carbon atoms which may have a substituent, or a hydrocarbon group having 1 to 5 carbon atoms which may have a substituent, and more preferably a hydroxyl group, a trimethylsilyloxy group, a triethylsilyloxy group, a tert-butyldimethylsilyloxy group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group.

[0153] m is an integer of 2 to 10,000, preferably 10 to 7,000, more preferably 100 to 2,000, and even more preferably 200 to 500.

[0154] The molecular weight of the linear siloxane compound represented by formula (2) is preferably 60,000 or less, more preferably 56,000 or less, more preferably 50,000 or less, and particularly preferably 45,000 or less. In addition, the molecular weight of the linear 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.

[0155] Preferred specific examples of the linear siloxane compound represented by formula (2) include linear polydimethylsiloxane (linear PDSM).

[0156] The cyclic siloxane compound and the linear siloxane compound may be used alone or in combination of two or more.

[0157] [(B) Diol compound]

[0158] The diol compound is not particularly limited, and examples thereof include the following: 1 )~(J 6 ) is a diol compound shown in FIG.

[0159]

[0160] In the above formula, A 1 and A 2 , X 1 ~X 6 , R 3 ~R 5 , p1~p2 and s1~s2 have the same meanings as above.

[0161] 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-propylene glycol (PG), 1,4-butanediol (BD), 2-butyl-2-ethyl-1,3-propanediol (BEPG), or neopentyl glycol (NPG).

[0162] The above-mentioned diol compounds may be used alone or in combination of two or more.

[0163] [(C) Basic compound catalyst]

[0164] The basic compound catalyst has a function of accelerating the reaction between the (A) cyclic siloxane compound and / or the linear siloxane compound and the (B) diol compound.

[0165] Examples of the basic compound catalyst include alkali metal compounds and alkaline earth metal compounds.

[0166] The alkali metal compound is not particularly limited, and examples thereof include 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 hydrogen carbonates such as sodium hydrogen carbonate, potassium hydrogen carbonate, and cesium hydrogen carbonate.

[0167] The alkaline earth metal compound is not particularly limited, and examples thereof include alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; and alkaline earth metal carbonates such as magnesium carbonate and calcium carbonate.

[0168] Among the above, the basic compound catalyst is preferably an alkali metal carbonate, an alkali metal bicarbonate, more preferably sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate, more preferably potassium carbonate, cesium carbonate, particularly preferably cesium carbonate. It should be noted that the above-mentioned basic compound catalyst can be used alone or in combination of two or more.

[0169] The amount of the basic compound catalyst added is not particularly limited, but is preferably 1.5 to 100 times the mole of the diol compound, more preferably 2.0 to 50 times the mole, further preferably 3.0 to 30 times the mole, and particularly preferably 4.0 to 20 times the mole.

[0170] [reaction]

[0171] The reaction is not particularly limited, but it is preferred that the (A) cyclic siloxane compound and / or linear siloxane compound and the (B) diol compound be reacted by heating in the presence of the (C) basic compound catalyst.

[0172] 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.

[0173] The reaction atmosphere is not particularly limited, but is preferably carried out in an inert gas atmosphere. Examples of the inert gas include nitrogen and argon.

[0174] By carrying out the above reaction, a composition containing a siloxane block-containing diol compound can be produced.

[0175] It should be noted that impurities having a relatively low boiling point (such as cyclic siloxane compounds) among the side reaction products and unreacted raw materials contained in the product obtained by the reaction can be appropriately removed by distillation under reduced pressure.

[0176] <Siloxane-based thermoplastic resin>

[0177] In one embodiment of the present invention, there is provided a siloxane-based thermoplastic resin containing a structural unit derived from the above-mentioned siloxane block-containing diol compound.

[0178] The above-mentioned siloxane-based thermoplastic resin is not particularly limited, and examples thereof include polycarbonate resins, polyester carbonate resins, acrylic resins such as polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethylene naphthalate (PEN), polyimide (PI), cycloolefin copolymer (COC), norbornene-containing resins, polyether sulfone, cellophane, aromatic polyamide, and the like.

[0179] In one embodiment, the siloxane-based thermoplastic resin is a copolymer obtained by reacting a siloxane block-containing diol compound with the above-mentioned thermoplastic resin or a monomer thereof.

[0180] Hereinafter, the case where the siloxane-based thermoplastic resin is a siloxane-based polycarbonate resin will be described in detail.

[0181] The siloxane-based polycarbonate resin contains a structural unit derived from a siloxane block-containing diol compound and a structural unit derived from a carbonate compound.

[0182] The carbonate compound is not particularly limited as long as it is a substance that can introduce the carbonyl group (-CO- group) of the polycarbonate structural unit into the siloxane-based polycarbonate resin. For example, diaryl carbonates such as diphenyl carbonate, dibenzyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, and m-tolyl carbonate; dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate; and monoaryl monoalkyl carbonates.

[0183] These carbonate compounds may be used alone or in combination of two or more.

[0184] The siloxane-based polycarbonate resin may further contain other structural units. Such other structural units are not particularly limited, and examples thereof include structural units derived from aromatic diol compounds and structural units derived from diaryloxysilane compounds.

[0185] The weight average molecular weight of the siloxane 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.

[0186] The molar ratio of the structural unit derived from the siloxane block-containing diol compound to the structural unit derived from the carbonate compound in the siloxane-based polycarbonate resin is preferably 0.01:99.99 to 99.99:0.01, more preferably 1:99 to 99:1, further preferably 10:90 to 90:10, particularly preferably 30:70 to 70:30.

[0187] Since the above-mentioned siloxane-based thermoplastic resin contains a structural unit derived from a diol compound containing a siloxane block, it is excellent in chemical resistance, low-temperature impact resistance, weather resistance, flame retardancy, and the like.

[0188] <Method for producing siloxane-based thermoplastic resin>

[0189] According to one embodiment of the present invention, there is provided a method for producing a siloxane-based thermoplastic resin, wherein the method comprises reacting a composition and a thermoplastic resin at a temperature of 160 to 400° C. in the presence of a catalyst.

[0190] [Composition]

[0191] As the composition, a composition containing the above-mentioned siloxane block-containing diol compound can be used.

[0192] [Thermoplastic resin]

[0193] Thermoplastic resins are not particularly limited, and examples thereof include polycarbonate resins, polyester carbonate resins, acrylic resins such as polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethylene naphthalate (PEN), polyimide (PI), cycloolefin copolymers (COC), norbornene-containing resins, polyether sulfone, cellophane, aromatic polyamide, and monomers thereof.

[0194] [catalyst]

[0195] The catalyst is not particularly limited, and examples thereof include alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, and metal salts.

[0196] The alkali metal compound is not particularly limited, and examples thereof include 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 phenylborate, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenylphosphate, sodium gluconate, disodium salt, dipotassium salt, dicesium salt, dilithium salt of bisphenol A, sodium salt, potassium salt, cesium salt, lithium salt of phenol, and the like.

[0197] The alkaline earth metal compound is not particularly limited, and examples thereof include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydrogen carbonate, calcium hydrogen carbonate, strontium hydrogen carbonate, barium hydrogen carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, and magnesium phenylphosphate.

[0198] The nitrogen-containing compound is not particularly limited, and examples thereof include quaternary ammonium hydroxides having alkyl 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; bases or basic salts, such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylammonium borohydride, and tetraphenylammonium tetraphenylammonium borohydride, and the like.

[0199] The above-mentioned metal salt is not particularly limited, and examples thereof include zinc salts such as zinc acetate, zinc benzoate, and zinc 2-ethylhexanoate; tin salts such as tin (II) chloride, tin (IV) chloride, tin (II) acetate, tin (IV) acetate, dibutyltin dilaurate, dibutyltin oxide, and dibutyldimethoxytin; zirconium salts such as zirconium acetylacetonate, zirconium oxyacetate, and tetrabutoxyzirconium; lead salts such as lead (II) acetate and lead (IV) acetate, etc.

[0200] The above-mentioned catalysts may be used alone or in combination of two or more.

[0201] [reaction]

[0202] The reaction is not particularly limited, but it is preferred that the composition and the thermoplastic resin be reacted in the presence of a catalyst.

[0203] At this time, the reaction temperature is 160 to 400°C, preferably 200 to 350°C, more preferably 220 to 320°C, and even more preferably 240 to 310°C.

[0204] By carrying out the above reaction, a siloxane-based thermoplastic resin can be produced.

[0205] Example

[0206] Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto. It should be noted that "%" is based on mass unless otherwise specified.

[0207] [Measurement conditions]

[0208] <Polysiloxane and Cyclic Siloxane Content>

[0209] Calculated using NMR. 1 The chemical shift in H-NMR analysis was based on 0 ppm of the peak of TMS (tetramethylsilane).

[0210] pass 1 H-NMR observed peaks from methyl groups on Si of decamethylpentacyclosiloxane (D5) and octamethyltetracyclosiloxane (D4), which are cyclic siloxanes corresponding to polysiloxane, at 0.1-1.0 ppm, 0.079 ppm, and 0.094 ppm, respectively. The sum of the peak areas of 0.079 ppm and 0.094 ppm was taken as the cyclic siloxane content, and the value of the peak areas of 0.079 ppm and 0.094 ppm was subtracted from the peak area of ​​0.1-1.0 ppm as the polysiloxane content, and the polysiloxane generation rate and cyclic siloxane generation rate were calculated based on this value.

[0211] <Polystyrene equivalent weight average molecular weight (Mw, Mn, Mw / Mn)>

[0212] GPC (gel permeation chromatography) was used, chloroform was used as the developing solvent, and a standard polystyrene (Shodex STANDARD, SM-105) with a known molecular weight (molecular weight distribution = 1) was used to prepare a calibration curve. The elution time and molecular weight value of each peak were marked with the measured standard polystyrene, and approximated by a cubic equation to prepare a calibration curve.

[0213] Thereafter, based on the obtained calibration curve, the weight average molecular weight (Mw) was determined as a polystyrene-equivalent value from the following formula.

[0214] [Calculation formula]

[0215] Mw=Σ(Wi×Mi) / Σ(Wi)

[0216] Mn=Σ(Ni×Mi) / Σ(Ni)

[0217] In the above formula, i represents the i-th split point when splitting the molecular weight M, Wi represents the i-th weight, Mi represents the i-th molecular weight, and Ni represents the number of molecules of the i-th. In addition, the molecular weight M represents the molecular weight value converted to polystyrene at the same dissolution time in the normalized curve.

[0218] It should be noted that Mw / Mn represents molecular weight dispersion and is a parameter for determining whether the molecular weight distribution is broad or narrow. A value closer to 1.0 indicates a narrower molecular weight distribution, and a larger value indicates a wider molecular weight distribution.

[0219] [Measurement conditions]

[0220] ·Device: Labsolutions manufactured by Shimadzu Corporation

[0221] Chromatographic columns: guard column (Shodex GPC K-G 4A) × 1, analytical column (Shodex GPC K-805L) × 2

[0222] Solvent: Chloroform (HPLC grade)

[0223] Injection volume: 10μL

[0224] Sample concentration: 2000ppm

[0225] Solvent flow rate: 1mL / min

[0226] ·Measurement temperature: 40℃

[0227] Detector: RI

[0228] <Measurement of glass transition temperature (Tg)>

[0229] As a measurement sample, 5 to 12 mg of a test piece was accurately weighed in a sample container for an AI automatic sampler (RDC aluminum container, a cylindrical container with a diameter of 6.8 mm and a height of 2.5 mm), and the upper part of the sample container was sealed with a lid for an AI automatic sampler.

[0230] The measurement was performed using a differential scanning calorimeter (DSC) in a nitrogen atmosphere (nitrogen flow rate: 50 ml / min), and 10.0 mg of sapphire was used as a standard substance in a control dish. After that, the measurement sample adjusted to 30°C was heated to 280°C at 20°C / min, and then cooled to 30°C at 20°C / min. Thereafter, the temperature was raised to 280°C at 10°C / min for measurement.

[0231] Measuring device: Differential scanning calorimeter (DSC) (product name "DSC-7020", manufactured by Hitachi High-Technologies Corporation)

[0232] [Example 1]

[0233] 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 heated to 150° C. under a nitrogen atmosphere. The mixture was stirred at 150° C. for 2 hours to obtain a colorless oily composition containing a diol compound (polysiloxane compound) containing a siloxane block.

[0234] [Example 2]

[0235] 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, 17.5 mg (0.29 mmol) of acetic acid was added after cooling to room temperature. By heating at 80°C for 2 hours under reduced pressure (2 hPa), most of the cyclic siloxane was distilled off, and a composition containing a diol compound (polysiloxane compound) containing a siloxane block was produced.

[0236] [Examples 3 to 17, Comparative Examples 1 to 4]

[0237] The same procedure as in Example 1 was carried out except that the raw materials, reaction temperature and reaction time were changed as shown in Table 1.

[0238] [Table 1]

[0239]

[0240] It should be noted that the meanings of the abbreviations in Table 1 are as follows.

[0241] (A) Siloxane compounds

[0242] D5: Decamethylcyclopentasiloxane

[0243] D4: Octamethylcyclotetrasiloxane

[0244] OPTS: Octaphenylcyclotetrasiloxane

[0245] Linear PDSM: Linear polydimethylsiloxane

[0246] (B) Diol Compound

[0247] NPG: Neopentyl Glycol

[0248] BEPG: 2-butyl-2-ethyl-1,3-propanediol

[0249] EG: Ethylene glycol

[0250] PG: 1,3-propylene glycol

[0251] BD: 1,4-Butanediol

[0252] CHDM: 1,4-cyclohexanedimethanol

[0253] BPEF: 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene

[0254] BPA: Bisphenol A

[0255] HQ: Hydroquinone

[0256] AD: 1.3-adamantanediol

[0257] PHEP: 2-(4-hydroxyphenyl)ethanol

[0258] (C) Basic compound catalyst

[0259] Cs2CO3: Cesium carbonate

[0260] K2CO3: Potassium carbonate

[0261] The compositions obtained in Examples 1 to 17 and Comparative Examples 1 to 4 were used 1 H-NMR and GPC were performed for analysis. The obtained results are shown in Table 2 below.

[0262] [Table 2]

[0263]

[0264] As can be seen from the results in Table 2, in Examples 1 to 17, the siloxane block-containing diol compound can be produced satisfactorily.

[0265] Comparison of Examples 1 and 10 to 15 using a primary alcohol as the (B) diol compound with Example 17 using a secondary alcohol as the (B) diol compound shows that Examples 1 and 10 to 15 can produce siloxane block-containing diol compounds at high yields.

[0266] [Example a]

[0267] A polycarbonate copolymer was produced using the composition produced in Example 2 (most of the cyclic siloxane was removed by distillation) and a polycarbonate compound.

[0268] 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 was added as a catalyst, containing 0.167 μmol relative to the molar number of bisphenol A, Tg = 122° C.) were heated to 230° C. under reduced pressure (2 hPa). By stirring at 230° C. for 2 hours, a white siloxane block copolymer polycarbonate was obtained.

[0269] The Mw and Mn of the siloxane block copolymer polycarbonate were measured by GPC and were found to be Mw 44,619 and Mn 25,003.

[0270] [Example b]

[0271] A polycarbonate copolymer was produced using the composition produced in Example 2 and a polycarbonate compound.

[0272] 20.00 g of polycarbonate (molecular weight = Mw 18,783, Mn 10,227, cesium carbonate was added as a catalyst, 0.167 μmol relative to the molar number of bisphenol A, Tg = 122°C) was heated to 240°C in a nitrogen atmosphere to melt. After the polycarbonate was melted, 10.00 g of the composition prepared in Example 2 was dropped using a dropping funnel. The pressure was gradually reduced at 240°C, and the temperature was raised to 260°C after reaching 2 hPa, and stirred for 1 hour, thereby obtaining a white siloxane block copolymer polycarbonate.

[0273] The Mw and Mn of the siloxane block copolymer polycarbonate were measured by GPC and were found to be Mw 101,401 and Mn 57,702.

[0274] [Example c]

[0275] A polycarbonate copolymer was produced using the composition produced in Example 2 and a polycarbonate compound.

[0276] 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 was added as a catalyst, containing 0.167 μmol relative to the molar number of bisphenol A, Tg = 122° C.) were heated to 260° C. under reduced pressure (2 hPa). Stirring was carried out at 260° C. for 1 hour and 20 minutes, thereby obtaining a white powdery siloxane block copolymer polycarbonate.

[0277] The Mw and Mn of the siloxane block copolymer polycarbonate were measured by GPC and were found to be Mw 356,597 and Mn 79,718. The Tg was 140°C.

Claims

1. A composition containing a diol compound containing a siloxane block, characterized in that: The diol compound containing a siloxane block is a compound represented by the following formula (I): In formula (I), R 1 and R 2 are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, m is an integer from 1 to 25, n is an integer from 3 to 200, X is independently the following formula (I 1 )~(I 6 ) shown in: *-CHR 5 -A 1 -X 3 -A 2 -CHR 5 -* (I 3 ) *-CHR 5 -A 1 -X 4 -A 2 -CHR 5 -*(I 4 ) *-CHR 5 -A 1 -X 5 -A 2 -CHR 5 -* (I 5 ) Among them, A 1 and A 2 Each independently is -(CR 6A R 6B ) q1 -or-(O-(CR 6A R 6B ) q2 ) q3 -, where R 6A and R 6B are independently H or an alkyl group having 1 to 6 carbon atoms, q1 is an integer of 0 to 10, q2 is an integer of 0 to 10, and q3 is an integer of 0 to 10, R 3 and R 4 are each independently a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkoxy 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 hydrocarbonoxy group having 6 to 20 carbon atoms, or a cycloalkoxy group having 3 to 20 carbon atoms, p1 and p2 are each independently an integer of 0 to 4, R 5 are each independently H or an alkyl group having 1 to 6 carbon atoms, X 1 and X 2 are independently a single bond or the following groups: Among them, R 7 and R 8 are each independently H, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or R 7 and R 8 Combined to form a carbon ring with 3 to 20 carbon atoms or a heterocyclic ring with 5 to 12 members; R 9 and R 10 are independently H, an alkyl group having 1 to 6 carbon atoms; R 11 ~R 16 are independently a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms; r1 is an integer of 2 to 20, X 3 are each independently a divalent aromatic hydrocarbon group having 15 to 32 carbon atoms, X 4 are independently a divalent group containing one or more hydrocarbon rings or heterocyclic rings, or are selected from R 5 , R 6A and R 6B At least one of the above is combined to form a divalent group containing one or more hydrocarbon rings or heterocyclic rings, X 5 are independently a divalent saturated heterocyclic group, or are selected from R 5 , R 6A and R 6B At least one of them is combined together to form a divalent saturated heterocyclic group, X 6 are each independently an alkylene group having 1 to 10 carbon atoms, s1 and s2 are each independently an integer of 0 to 10.

2. A siloxane-based thermoplastic resin, characterized in that: It contains a structural unit derived from the siloxane block-containing diol compound of claim 1.

3. A method for producing a composition, which is used to produce the composition according to claim 1, wherein the method comprises: (A) a cyclic siloxane compound represented by the following formula (1) and / or a linear siloxane compound represented by the following formula (2), and (B) a siloxane compound represented by the following formula (J 1 )~(J 6 ) and (C) a basic compound catalyst to react, In formula (1), R 1 and R 2 are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, n is an integer from 3 to 30; In formula (2), R 3’ and R 4’ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, X' is independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted oxygen atom-containing group having 1 to 10 carbon atoms, a substituted or unsubstituted nitrogen atom-containing group having 1 to 10 carbon atoms, or a substituted or unsubstituted amino group, m is an integer from 2 to 10000; HO—CHR 5 -A 1 -X 3 -A 2 -CHR 5 -OH (J 3 ) HO—CHR 5 —A 1 -X 4 -A 2 -CHR 5 —OH (J 4 ) HO—CHR 5 -A 1 -X 5 -A 2 -CHR 5 -OH (J 5 ) Formula (J 1 )~(J 6 ), A 1 and A 2 , X 1 ~X 6 , R 3 ~R 5 , p1~p2 and s1~s2 are the same as defined in claim 1.

4. The manufacturing method according to claim 3, characterized in that: The oxygen-atom-containing group having 1 to 10 carbon atoms represented by X' is a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms or a substituted or unsubstituted siloxy group having 1 to 10 carbon atoms.

5. A method for producing a silicone-based thermoplastic resin, characterized in that: include: A step of reacting the composition according to claim 1 and a thermoplastic resin at a temperature of 160 to 400° C. in the presence of a catalyst.

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