Phenol-terminated siloxanes

Abstract

The invention relates to phenol-terminated siloxanes, to a method for the production thereof, and to the use of phenol-terminated siloxanes as modifiers (= siloxane-based modifiers) in organic resins.

Description

[0001] This invention relates to phenol-terminated siloxanes, their preparation methods, and the use of phenol-terminated siloxanes as modifiers (=siloxane modifiers) in organic resins.

[0002] Organically modified siloxanes have a wide range of applications. They are key additives for plastics, imparting important properties such as hydrophobicity and water-resistant protection. However, a crucial factor in determining whether siloxanes can be used in this way is their compatibility with the plastic to be modified. For example, siloxanes exhibit good compatibility when they form homogeneous composites with plastics, i.e., without exhibiting any phase separation. Any phase separation will become apparent as the modifier leaches out of the plastic.

[0003] Examples of plastics to be modified are epoxy (EP) resins or epoxy resin systems. They are used in a variety of applications and are now established as one of the most commonly used thermosetting types in composites, such as those combined with glass fibers, carbon fibers (CRP), or aromatic polyamide fibers. Furthermore, high-performance organic reactive resins, such as cyanate ester (CE) resins, bismaleimide (BMI) resins, polyimide (PI) resins, benzoxazine resins, or phthalonitrile resins, as well as reactive resin mixtures, such as bis(benzocyclobuteneimide) / bismaleimide, cyanate ester / epoxy resins, or bismaleimide / cyanate ester (BT resins), have become increasingly important as matrix resins in fiber composites for industrial, automotive, and aerospace applications in recent years. Compared to epoxy resins, CE, BMI, or PI-based polymer matrix resins combine, for example, high mechanical strength with high glass transition temperatures, high thermal stability, and high long-term stability, which greatly expands the possible applications of these thermosetting materials, especially in the high-temperature range.

[0004] However, thermosetting systems based on CE resins also have drawbacks. During thermosetting, reactive cyanate groups (=“N°CO-”) undergo a trimerization reaction to produce cyclic triazine rings, thereby forming a highly crosslinked polycyanurate network. Although the cured cyanate resins possess high mechanical stability due to their high crosslinking state, this network is therefore brittle, meaning they exhibit low fracture toughness and impact resistance. Another significant drawback of cyanate resin systems is the sensitivity of uncrosslinked resins and cured polycyanurate to hydrolysis: water penetrating the cured thermosetting network causes network degradation (hydrolytic degradation), which leads to impairment of material properties. Hydrolytic degradation also results in pore formation, which in turn impairs mechanical properties and thermal stability. In particular, highly crosslinked and relatively highly polar thermosetting materials based on phenolic varnish cyanate exhibit relatively high water absorption and hydrolysis rates in CE resins.

[0005] Therefore, for these CE reactive resins already on the market, it would be desirable to provide suitable modifiers that offer high-temperature stability, which can help reduce water absorption and improve fracture toughness in the cured thermosetting network, allowing them to be commercially used as matrix resins in composite applications requiring high temperatures, preferably in the aerospace industry. Crucially, the modifiers must be compatible with the cyanurate resins, meaning they can be processed into homogeneous mixtures, and the cured thermosetting mixtures should not show any signs of separation, such as siloxane components oozing from the polycyanurate network or surface stickiness. This is undesirable because separation leads to alterations in material properties on the one hand, and damage to matrix-fiber adhesion on the other.

[0006] The prior art provides a variety of methods for modifying polycyanurate networks with poly(diorganosiloxane) (“silicone”).

[0007] JP 2014012759 A2 and EP 4056371 A1 describe the production of a mixture of a cyanate resin having at least two cyanate groups and an incompatible, relatively high molecular weight poly(dimethyl)siloxane having terminal phenolic propyl groups in the working examples. However, complex measures are required to prevent phase separation of the incompatible components. Therefore, the mixture is thermally pre-crosslinked in solution (JP 2014012759 A2) or under solvent-free conditions (EP 4056371 A1) in the presence of a catalyst that accelerates the co-reaction of the cyanate groups and phenolic hydroxyl groups to obtain a prepolymer. In this context, "pre-crosslinked prepolymer" should be understood as an oligomer obtainable by partial trimerization of the cyanate groups and introduction of functional phenolic groups of the siloxane, i.e., both the reaction between cyanate groups and the co-reaction of phenolic groups with cyanate groups occur, while simultaneously forming a triazine ring.

[0008] The main drawbacks of these complex processes include: attaching phenolic groups to siloxanes via thermally unstable propyl groups; the use of organic solvents (JP 2014012759 A), which is problematic for economic, toxicological, and disposal reasons; the production of pre-crosslinked prepolymers, which, in the absence of solvents, are unsuitable for further processing in all process methods, such as impregnation, due to their high viscosity and in solvents, and have relatively low storage stability.

[0009] Neither of these two documents discloses how the modification of cyanate ester resins with phenol propyl-terminated poly(diorganosiloxane) affects the properties of the cured mixture, such as water absorption or fracture toughness. Nor do they disclose the compatibility of low molecular weight phenol-terminated siloxanes with relatively short chain lengths with cyanate ester resins without pre-crosslinking.

[0010] Therefore, the object of the present invention is to provide phenol-terminated siloxanes with different and short-chain lengths. These should be suitable for, for example, modifying organic resins, i.e., ensuring, in modified, cured resins, for example, a reduced water absorption rate and associated, improved hydrolysis resistance and higher fracture toughness (K). Ic Meanwhile, siloxane modifiers will retain the inherent beneficial properties of cyanate ester resins, such as thermal oxidation stability and high mechanical strength.

[0011] According to the present invention, this objective is achieved by linear poly(diorganosiloxanes) having at least one phenolic hydroxyl group and a Si-bonded aromatic group. This is because they are compatible with organic cyanurate resins, for example, in the presence of a catalyst, without pre-crosslinking, and can be processed into homogeneous single-phase mixtures. Cured thermosetting mixtures modified in this way do not show any signs of separation, such as leaching of the siloxane modifier from the polycyanurate network or surface stickiness.

[0012] It has been unexpectedly discovered that the poly(diorganosiloxane) of the present invention can modify organic cyanate resins, resulting in cured mixtures that more advantageously combine reduced water absorption (and associated reduced hydrolytic network degradation), higher fracture toughness, and high thermal oxidative stability, exceeding the levels known to date according to the prior art.

[0013] Therefore, the first aspect of the present invention relates to poly(diorganosiloxane) of general formula (I):

[0014] R a R 1 3-a Si-O-(R d R 1 2-d Si-O-) b -SiR c R 1 3-c (I)

[0015] in,

[0016] R is the same or different, and represents

[0017] -Aliphatic hydrocarbon group with a single valence and linked by a SiC bond, or

[0018] -Aromatic hydrocarbon groups without phenolic hydroxyl groups linked by SiC bonds, with a single valence.

[0019] R 1 Are they the same or different, and indicate

[0020] A monovalent aromatic hydrocarbon group having at least one phenolic hydroxyl group,

[0021] a can be 2 or 3, with 2 being the preferred choice.

[0022] b is an integer from 1 to 10, preferably from 1 to 7, and more preferably from 1 to 4.

[0023] c can be 2 or 3, with 2 being the preferred value.

[0024] d is 1 or 2, preferably 2.

[0025] The condition is that one or two R groups are present in each poly(diorganosiloxane) molecule of general formula (I). 1 Preferably, two groups R 1 .

[0026] In this invention, "phenolic hydroxyl group" refers to an aromatic hydroxyl compound in which a hydroxyl group is directly bonded to an aromatic carbon atom. Although not explicitly stated, it should be emphasized that an aromatic hydrocarbon group R having at least one phenolic hydroxyl group... 1 Direct bonding (i.e., bonding via aromatic carbon atoms) to silicon atoms.

[0027] Surprisingly, the short-chain poly(diorganosiloxane) according to the present invention exhibits excellent compatibility with the plastic to be modified. In contrast, long-chain poly(diorganosiloxane) known in the art exhibit a significant tendency to leach from plastic composites.

[0028] The aliphatic hydrocarbon group R, which is monovalent and linked by SiC bonds, preferably includes ether (≡COC≡), hydroxyl (-OH), and / or epoxy (=COC=) groups.

[0029] In a further embodiment, the monovalent, SiC-bonded aromatic hydrocarbon group R, which does not contain a phenolic hydroxyl group, can be interrupted by at least one heteroatom. This at least one heteroatom can be selected from the group consisting of O, S, N, and P, preferably O.

[0030] At 23°C and 1013 hPa, the poly(diorganosiloxane) according to the invention can be a solid or a liquid, preferably a liquid.

[0031] In a specific embodiment, the poly(diorganosiloxane) has a weight-average molar mass Mw of 300 to 2000 g / mol, preferably 300 g / mol to 1000 g / mol, and more preferably 300 g / mol to 700 g / mol.

[0032] In a specific embodiment, the number-average molar mass Mn of the poly(diorganosiloxane) is 300 to 1500 g / mol, preferably 300 g / mol to 1000 g / mol, and more preferably 300 g / mol to 700 g / mol.

[0033] In a preferred embodiment, R is selected from the group consisting of the following items:

[0034] -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl;

[0035] - Self-base, such as positive self-base;

[0036] -Henyl base, such as positive heptyl base;

[0037] -Octyl, such as n-octyl and isooctyl, such as 2,4,4-trimethylpentyl and 2,2,4-trimethylpentyl;

[0038] -Renji, such as Zheng Renji;

[0039] -decyl, such as n-decyl; dodecyl, such as n-dodecyl;

[0040] -Hexadecyl, such as n-hexadecyl;

[0041] -Octadecanyl, such as n-octadecyl;

[0042] -Cycloalkyl groups, such as cyclopentyl, cyclohexyl, cycloheptyl, and methylcyclohexyl;

[0043] -Alkenyl groups, such as vinyl, allyl, cyclopentenyl, and cyclohexenyl; and

[0044] -Epoxy groups, such as 3-glycidoxypropyl, ethylene-2-yl, and 2-(3,4-epoxycyclohexyl)ethyl.

[0045] In a preferred embodiment, R is selected from the group consisting of the following items:

[0046] -Aryl groups, such as phenyl, biphenyl, cumylphenyl, benzylphenyl, naphthyl, anthraceneyl, and phenanthrene;

[0047] -Alkyl groups, such as tolyl, xylyl, and ethylphenyl;

[0048] -Aryl groups, such as benzyl, cumyl, α-phenethyl and β-phenethyl;

[0049] -Alkoxyaryl, such as methoxyphenyl;

[0050] -Aryloxyaryl, such as phenoxyphenyl;

[0051] -Hydroaryl groups, such as fluorophenyl, chlorophenyl, bromophenyl, and trifluoromethylphenyl; and

[0052] - Heterocyclic aromatic groups, such as pyridyl, pyrazinyl, quinolinyl, furanyl and (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-10-yl)ethyl.

[0053] In a preferred embodiment, R is a monovalent alkyl or aryl group having 1 to 8 carbon atoms linked by SiC bonds. More preferably, R is methyl or phenyl, especially methyl.

[0054] In a preferred embodiment, R 1 Compounds selected from those described by the following chemical formula (II)

[0055] (II)

[0056] in,

[0057] R 4 R 5 R 6 R 7 and R 8 In their respective cases, each group independently represents a hydrogen atom, a hydroxyl group, or a hydrocarbon group that optionally has a hydroxyl group and is optionally interrupted by at least one heteroatom and has 1 to 18 carbon atoms.

[0058] The condition is that in formula (II), at least one group R 4 R 5 R 6 R 7 Or R 8 It is a phenolic hydroxyl group or contains a phenolic hydroxyl group.

[0059] Although not explicitly expressed in chemical formula (II), as another embodiment of the invention, two or more groups R 4 R 5 R 6 R 7 and R 8 It can represent a divalent hydrocarbon group that optionally has a hydroxyl group and is optionally interrupted by at least one heteroatom, and can together form one or more ring structures. For example, R 5 and R 6 They can form rings together, such as in 5,6,7,8-tetrahydro-1-naphthol or 1-naphthol.

[0060] R 4 R 5 R 6 R 7 and R 8 In each case, a hydrogen atom, a hydroxyl group, or optionally a hydroxyl group and optionally a hydrocarbon group having 1 to 8 carbon atoms can be represented independently.

[0061] Preferred poly(diorganosiloxanes) are characterized by the following fact: R 6 It represents a hydroxyl group, and the group R 4R 5 R 7 and R 8 In each case, a hydrogen atom is represented independently or optionally, a hydrocarbon group having 1 to 12 carbon atoms is bonded together via an oxygen (-O-) unit.

[0062] In a preferred embodiment, R 6 Represents hydroxyl group, group R 4 R 5 R 7 and R 8 In each case, it independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

[0063] In preferred poly(diorganosiloxanes), R 6 Represents hydroxyl group, group R 4 R 5 R 7 and R 8 It represents a hydrogen atom.

[0064] In a preferred embodiment, R 1 Selected from the following group, which consists of the following items: hydroxyphenyl [-C6H4(OH)], hydroxy(methyl)phenyl [-C6H3(OH)(CH3)], hydroxy(dimethyl)phenyl [-C6H2(OH)(CH3)2], hydroxy(ethyl)phenyl [-C6H3(OH)(CH2CH3)], hydroxy(methyl)(isopropyl)phenyl [-C6H3(OH)(CH3)(CH(CH3)2)], hydroxy(methoxy)phenyl [-C6H3(OH)(OCH3)], hydroxy(phenoxy)phenyl [-C6H3(OH)(OC6H5)], (hydroxyphenyl)phenyl [-C6H4(C6H4(OH))], hydroxynaphthyl [-C 10 The groups are preferably selected from the group consisting of hydroxyphenyl, hydroxy(methyl)phenyl, hydroxy(dimethyl)phenyl, hydroxy(ethyl)phenyl and hydroxy(methyl)(isopropyl)phenyl, particularly hydroxyphenyl.

[0065] Examples of poly(diorganosiloxanes) according to the present invention may correspond to one of the following formulas (IIIa), (IIIb), (IIIc), (IV) to (XII), preferably formulas (IIIa), (IIIb), (IIIc), (VI), (X) and (XI), and more preferably formulas (IIIa), (X) and (XI):

[0066] (IIIa)

[0067] (IIIb)

[0068] (IIIc)

[0069] (IV)

[0070] (V),

[0071] (VI)

[0072] (VII)

[0073] (VIII)

[0074] (IX),

[0075] (X),

[0076] (XI),

[0077] Where R 9 Selected from the following group, which consists of the following items: Me, Ph, VI (corresponding to -CH=CH2), H, especially Me,

[0078] (XII)

[0079] Where Me is methyl and Ph is phenyl.

[0080] m is an integer from 2 to 11, preferably from 2 to 8, and more preferably from 2 to 5;

[0081] n is an integer from 1 to 10, preferably from 1 to 7, more preferably from 1 to 4, and o is an integer from 1 to 10, preferably from 1 to 7, more preferably from 1 to 4, provided that the sum of n + o is 2 to 11, preferably from 2 to 8, more preferably from 2 to 5.

[0082] More preferably, the poly(diorganosiloxane) according to the invention is one having the chemical formula (IIIa), (X) or (XI), wherein m is 2 to 5.

[0083] In particular, the poly(diorganosiloxane) according to the invention is a poly(diorganosiloxane) of formula (IIIa) and (X) wherein m is 2 to 5.

[0084] In particular, the poly(diorganosiloxane) according to the present invention is a poly(diorganosiloxane) of formula (XI) wherein m is 3.

[0085] A further aspect of the invention relates to a method for preparing poly(diorganosiloxane) according to the invention, comprising the following steps in a specified order:

[0086] (A) Provides an aromatic hydrocarbon compound having the chemical formula (XIII).

[0087] R 1 -X (XIII),

[0088] in,

[0089] R 1 This indicates a monovalent aromatic hydrocarbon group having at least one phenolic hydroxyl group, and

[0090] X represents F, Cl, Br or I, preferably Cl, Br or I, more preferably Br or Cl, especially Cl;

[0091] (B) Protecting R with suitable protecting groups 1 The at least one phenolic hydroxyl group in -X;

[0092] (C) The protected compound R obtained after step (B) 1 -X reaction to form organometallic compound R 1 -M, wherein M preferably represents Li, Mg-X or Zn-X, especially Li and Mg-X;

[0093] (D) React the organometallic compound obtained after step (C) with a siloxane having the chemical formula (XIV).

[0094] R a Y 3-a Si-O-(R d Y 2-d Si-O-) b -SiR c Y 3-c (XIV)

[0095] in,

[0096] R is the same or different, and represents

[0097] -Aliphatic hydrocarbon group with a single valence and linked by a SiC bond, or

[0098] -Aromatic hydrocarbon groups without phenolic hydroxyl groups linked by SiC bonds, with a single valence.

[0099] Y is the same or different, and

[0100] Represents Cl, MeO, EtO, or O i Pr, especially Cl,

[0101] a can be 2 or 3, with 2 being the preferred choice.

[0102] b is an integer from 1 to 10, preferably from 1 to 7, and more preferably from 1 to 4.

[0103] c can be 2 or 3, with 2 being the preferred value.

[0104] d is 1 or 2, preferably 2; and

[0105] (E) Deprotect the protected poly(diorganosiloxane) obtained after step (D);

[0106] To obtain the poly(diorganosiloxane) according to the present invention as described above.

[0107] The protected compound R obtained after step (B) 1 -X forms an organometallic compound R 1 The reaction of -M (where M represents Mg-X) is a Grignard reaction and follows a reaction mechanism suitable for this type of reaction under suitable reaction conditions.

[0108] It should be noted that in the conversion reaction of step (D), unit Y is converted by unit R. 1 The poly(diorganosiloxane) according to the present invention is produced by substitution.

[0109] In the context of this invention, protection should be understood as a reaction in which an ether bond is formed between the phenolic hydroxyl group to be protected and a suitable protecting group.

[0110] In the context of this invention, deprotection should be understood as the removal of the protecting group to reform the phenolic hydroxyl group that was present prior to protection.

[0111] The aliphatic hydrocarbon group R, which is monovalent and linked by SiC bonds, preferably includes ether (≡COC≡), hydroxyl (-OH), and / or epoxy (=COC=) groups.

[0112] In a further embodiment, the monovalent, SiC-bonded aromatic hydrocarbon group R, which does not contain a phenolic hydroxyl group, can be interrupted by at least one heteroatom. This at least one heteroatom can be selected from the group consisting of O, S, N, and P, preferably O.

[0113] In a preferred embodiment, R is selected from the group consisting of the following items:

[0114] -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl;

[0115] - Self-base, such as positive self-base;

[0116] -Henyl base, such as positive heptyl base;

[0117] -Octyl, such as n-octyl and isooctyl, such as 2,4,4-trimethylpentyl and 2,2,4-trimethylpentyl;

[0118] -Renji, such as Zheng Renji;

[0119] -decyl, such as n-decyl; dodecyl, such as n-dodecyl;

[0120] -Hexadecyl, such as n-hexadecyl;

[0121] -Octadecanyl, such as n-octadecyl;

[0122] -Cycloalkyl groups, such as cyclopentyl, cyclohexyl, cycloheptyl, and methylcyclohexyl;

[0123] -Alkenyl groups, such as vinyl, allyl, cyclopentenyl, and cyclohexenyl; and

[0124] -Epoxy groups, such as 3-glycidoxypropyl, ethylene-2-yl, and 2-(3,4-epoxycyclohexyl)ethyl.

[0125] In a preferred embodiment, R is selected from the group consisting of the following items:

[0126] -Aryl groups, such as phenyl, biphenyl, cumylphenyl, benzylphenyl, naphthyl, anthraceneyl, and phenanthrene;

[0127] -Alkyl groups, such as tolyl, xylyl, and ethylphenyl;

[0128] -Aryl groups, such as benzyl, cumyl, α-phenethyl and β-phenethyl;

[0129] -Alkoxyaryl, such as methoxyphenyl;

[0130] -Aryloxyaryl, such as phenoxyphenyl;

[0131] -Hydroaryl groups, such as fluorophenyl, chlorophenyl, bromophenyl, and trifluoromethylphenyl; and

[0132] - Heterocyclic aromatic groups, such as pyridyl, pyrazinyl, quinolinyl, furanyl and (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-10-yl)ethyl.

[0133] In a preferred embodiment, R is a monovalent alkyl or aryl group having 1 to 8 carbon atoms linked by SiC bonds. More preferably, R is methyl or phenyl, especially methyl.

[0134] In a preferred embodiment, R1 Compounds selected from those described by the following chemical formula (II)

[0135] (II)

[0136] in,

[0137] R 4 R 5 R 6 R 7 and R 8 In their respective cases, each group independently represents a hydrogen atom, a hydroxyl group, or a hydrocarbon group that optionally has a hydroxyl group and is optionally interrupted by at least one heteroatom and has 1 to 18 carbon atoms.

[0138] The condition is that in formula (II), at least one group R 4 R 5 R 6 R 7 Or R 8 It is a phenolic hydroxyl group or contains a phenolic hydroxyl group.

[0139] Although not explicitly expressed in chemical formula (II), as another embodiment of the invention, two or more groups R 4 R 5 R 6 R 7 and R 8 It can represent a divalent hydrocarbon group that optionally has a hydroxyl group and is optionally interrupted by at least one heteroatom, and can together form one or more ring structures. For example, R 5 and R 6 They can form rings together, such as in 5,6,7,8-tetrahydro-1-naphthol or 1-naphthol.

[0140] R 4 R 5 R 6 R 7 and R 8 In each case, a hydrogen atom, a hydroxyl group, or optionally a hydroxyl group and optionally a hydrocarbon group having 1 to 8 carbon atoms can be represented independently.

[0141] Preferred poly(diorganosiloxanes) are characterized by the following fact: R 6 It represents a hydroxyl group, and the group R 4 R 5 R 7 and R 8 In each case, a hydrogen atom is represented independently or optionally, a hydrocarbon group having 1 to 12 carbon atoms is bonded together via an oxygen (-O-) unit.

[0142] In a preferred embodiment, R 6 Represents hydroxyl group, group R 4 R 5 R 7 and R 8 In each case, it independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

[0143] In preferred poly(diorganosiloxanes), R 6 Represents hydroxyl group, group R 4 R 5 R 7 and R 8 It represents a hydrogen atom.

[0144] In a preferred embodiment, R 1 Selected from the following group, which consists of the following items: hydroxyphenyl [-C6H4(OH)], hydroxy(methyl)phenyl [-C6H3(OH)(CH3)], hydroxy(dimethyl)phenyl [-C6H2(OH)(CH3)2], hydroxy(ethyl)phenyl [-C6H3(OH)(CH2CH3)], hydroxy(methyl)(isopropyl)phenyl [-C6H3(OH)(CH3)(CH(CH3)2)], hydroxy(methoxy)phenyl [-C6H3(OH)(OCH3)], hydroxy(phenoxy)phenyl [-C6H3(OH)(OC6H5)], (hydroxyphenyl)phenyl [-C6H4(C6H4(OH))], hydroxynaphthyl [-C 10 The groups are preferably selected from the group consisting of hydroxyphenyl, hydroxy(methyl)phenyl, hydroxy(dimethyl)phenyl, hydroxy(ethyl)phenyl and hydroxy(methyl)(isopropyl)phenyl, particularly hydroxyphenyl.

[0145] In a preferred embodiment, the suitable protecting group in step (B) is selected from benzyl, benzyl derivatives, allyl, tetrahydropyran (THP), methoxymethyl (MOM), silyl ethers, such as trimethylsilyl, p-methoxybenzyl, benzyloxymethyl, preferably benzyl and allyl, more preferably benzyl.

[0146] If a benzyl protecting group is introduced, the protection in step (B) is preferably achieved by making R 1-X is achieved by reacting with benzyl bromide or benzyl chloride, particularly 1.0 equivalent of benzyl bromide or benzyl chloride. This protection may also include the addition of 1.1 to 1.4 equivalents of K₂CO₃. The reaction is preferably carried out in a suitable solvent (e.g., selected from acetonitrile and acetone). The reaction is preferably carried out at room temperature of 23°C or at the boiling point of the solvent used. The protecting reaction in step (B) typically takes place for 2 to 18 hours, preferably 2 to 12 hours.

[0147] If an allyl protecting group is introduced, the protection in step (B) is preferably achieved by making R 1 -X is achieved by reacting with allyl bromide or allyl chloride, preferably allyl bromide, particularly in amounts of 1.1 equivalents of allyl bromide or allyl chloride. This protection may also include the addition of 1.1 to 1.5 equivalents of K₂CO₃. The reaction is preferably carried out in a suitable solvent, such as DMF and acetone. The reaction is preferably carried out at room temperature (23°C) or at 60°C. Particularly when DMF or acetone is used as the solvent, the reaction is carried out at 60°C in the former case and at room temperature in the latter case. The protecting reaction in step (B) is typically carried out for 6 to 18 hours in the presence of DMF as the solvent, or for 4 to 8 hours in the presence of acetone as the solvent.

[0148] If a THP protecting group is introduced, the protection in step (B) is preferably achieved through R. 1 -X is achieved by reacting with dihydropyran, particularly with 1.10 equivalents of dihydropyran. This protection may also include the addition of 4-bromophenol and / or hydrochloric acid. The protecting reaction in step (B) typically takes place over a time period of 30 to 120 minutes and / or at room temperature.

[0149] If a MOM protecting base is introduced, the protection in step (B) is preferably achieved by making R 1 -X is achieved by reacting with (chloromethyl)methyl ether, particularly with 1.0 to 1.5 equivalents of (chloromethyl)methyl ether. Protection may also include the addition of K₂CO₃. The reaction is preferably carried out in a suitable solvent, such as acetone.

[0150] In step (C) R 1 -X forms organometallic compounds R 1 The reaction of -M is preferably achieved through the following methods:

[0151] When M represents Li, let R 1 -X and organolithium compounds, especially n -BuLi reaction; or

[0152] When M represents Mg-X, make R 1 -X reacts with Mg to form Grignard compounds; or

[0153] When M represents Zn-X, make R 1 -X reacts with Zn to form organozinc compounds.

[0154] In a preferred embodiment, deprotection in step (E) is achieved by a suitable reaction scheme known in the art. For example, deprotection can be achieved by hydrogenolysis or under acidic conditions, particularly by hydrogenolysis. The protecting group used specifically determines whether the deprotection is achieved by hydrogenolysis or under acidic conditions. For example, deprotection can be achieved by hydrogenolysis with protecting groups selected from benzyl, benzyl derivatives, and allyl. With protecting groups selected from tetrahydropyran (THP), methoxymethyl (MOM), silyl ethers (such as trimethylsilyl), p-methoxybenzyloxy, and benzyloxymethyl, deprotection is achieved under acidic conditions.

[0155] Hydrogen deprotection is based on the cleavage of covalent bonds using hydrogen and a suitable catalyst. Suitable catalysts are, for example, heterogeneous catalysts, such as those utilizing iron-platinum group elements. Examples of such catalysts are carbon-supported palladium (Pd / C) or Raney nickel. The amount of catalyst is preferably from 0.1% to 2% by weight, based on the total mass of the reaction mixture.

[0156] Deprotection via hydrogenolysis can be achieved in a pressure autoclave or glass flask. Hydrogen can be added directly (e.g., 1 atm of H2) or generated in situ from a suitable starting material (e.g., ammonium formate). If the starting material is used for in-situ hydrogen generation, it is preferable to use 1.5 to 3 equivalents of starting material per OH group to be deprotected.

[0157] Hydrogen deprotection is preferably carried out at a temperature ranging from 23°C to 80°C and / or for 1 to 18 hours and / or at a pressure ranging from 1 to 20 bar.

[0158] The poly(diorganosiloxane) prepared according to the invention is characterized by being a specific poly(diorganosiloxane). In the context of this invention, "specific siloxane" refers to a siloxane having a substantially uniform chain length (i.e., the number of repeating units) and / or a particularly narrow molar mass distribution. A suitable measure for describing such a narrow molar mass distribution is, for example, the polydispersity index (PDI), expressed as the ratio of Mw / Mn. The poly(diorganosiloxane) according to the invention preferably has a PDI in the range of 0.8 to 1.5, preferably from 1.0 to 1.5, and particularly from 1.1 to 1.3.

[0159] PDI can be determined using various methods known to those skilled in the art, such as gel permeation chromatography.

[0160] In contrast, it should be noted that poly(diorganosiloxanes) prepared by methods known in the prior art (usually equilibration) have a wide molar mass distribution. The PDI of such siloxanes is typically in the range of at least 2.0.

[0161] In the context of this invention, "equilibrium" should be understood as a rearrangement based on the equilibrium of siloxane bond formation and breaking and rearranging. Equilibrium can be considered a special case of polymerization in which a mixture of siloxanes with different molecular sizes is brought into molecular equilibrium and equilibrated. The effect of this method is to transform a mixture of siloxanes with multiple maxima in its molecular weight distribution curve into a polymer molecular structure with a molecular size characterized by only one broad maxima. A random mixture of siloxanes with a broad molar mass distribution is obtained.

[0162] Another aspect of the invention relates to the use of poly(diorganosiloxane) according to the invention as a modifier in organic resins, preferably as a toughening modifier, a hydrophobic agent, or a modifier for improving flame retardancy, thermal oxidation properties, dielectric properties, moisture resistance, chemical resistance, and / or processing properties.

[0163] Examples of organic resins are epoxy resins, cyanate ester resins, phenolic varnish resins, phenolic resins, UP resins, vinyl ester resins, and BT resins, especially cyanate ester resins.

[0164] Working Example

[0165] The following examples were carried out at ambient atmospheric pressure (i.e., at about 10¹³ hPa) and room temperature (i.e., about 23°C), or at a temperature established when the reactants were mixed at room temperature, without the need for additional heating or cooling, and describe in principle how the invention can be implemented, but do not limit the invention to what is disclosed herein.

[0166] Synthesis of poly(diorganosiloxanes)

[0167] Example 1 (Tetrasiloxane = (C6H4OBn)SiMe2-[OSiMe2]2-OSiMe2(C6H4OBn))

[0168] 125 g of 1-(benzyloxy)-4-bromobenzene was dissolved in 1 L of THF, and 200 mL of a 2.5 M n-butyllithium solution in hexane was added dropwise at -78°C. The mixture was stirred and 83 mL of 1,7-dichlorooctamethyltetrasiloxane was added. The cooling bath was removed, and the mixture was then heated to room temperature. 20 mL of triethylamine was added, followed by 300 mL of a saturated aqueous solution of ammonium chloride, and the phase was separated. After extraction with diethyl ether, the combined organic phases were dried over sodium sulfate and filtered. The solvent was removed, yielding 153 g of a colorless solid.

[0169] Example 1 (Adapted)

[0170] 125 g of 1-(benzyloxy)-4-bromobenzene was dissolved in 0.5 L of THF, and 200 mL of a 2.5 M n-butyllithium solution in hexane was added dropwise at -78°C. The mixture was stirred and 80 mL of 1,7-dichlorooctamethyltetrasiloxane was added. The cooling bath was removed, and the mixture was then heated to room temperature. After adding 20 mL of triethylamine, 300 mL of a saturated aqueous solution of ammonium chloride was added, and the phase was separated. After extraction with diethyl ether, the combined organic phases were dried over sodium sulfate and filtered. The solvent was removed, and 151 g of a colorless solid was obtained.

[0171] Example 2 (monosilanes = Me2Si(C6H4OBn)2)

[0172] 20 g of 1-(benzyloxy)-4-bromobenzene was dissolved in 200 mL of THF, and 200 mL of a 2.5 M n-butyllithium solution in hexane was added dropwise over 30 minutes at -78°C, followed by the addition of 50 mL of THF. The mixture was stirred and 4.7 mL of 1,1-dichlorodimethylsilane was added. The cooling bath was removed, and the mixture was then heated to room temperature and stirred for one hour. Water was then added and the mixture was extracted with diethyl ether. The combined organic phases were dried over sodium sulfate and filtered. The solvent was removed, and 15 g of a colorless solid was obtained. The obtained material remained stable in air for 2 months.

[0173] Example 3 (Trisiloxane = (C6H4OBn)SiMe2-OSiMe2-OSiMe2(C6H4OBn))

[0174] 63 g of 1-(benzyloxy)-4-bromobenzene was dissolved in 700 mL of THF, and 100 mL of a 2.5 M n-butyllithium solution in hexane was added dropwise at -78°C. The mixture was stirred, and 32 g of 1,5-dichlorohexamethyltrisiloxane was added. The cooling bath was removed, and the mixture was then heated to room temperature. After adding 20 mL of triethylamine, 300 mL of a saturated aqueous solution of ammonium chloride was added, and the phase was separated. After extraction with diethyl ether, the combined organic phases were dried over sodium sulfate and filtered. The solvent was removed, and 54 g of a colorless solid was obtained.

[0175] Example 4 (disiloxane = (C6H4OBn)SiMe2-O-SiMe2(C6H4OBn))

[0176] 63 g of 1-(benzyloxy)-4-bromobenzene was dissolved in 650 mL of THF, and 100 mL of a 2.5 M n-butyllithium solution in hexane was added dropwise at -78°C. The mixture was stirred and 23.7 g of 1,3-dichlorotetramethyldisiloxane was added. The cooling bath was removed, and the mixture was then heated to room temperature. After adding 20 mL of triethylamine, 300 mL of a saturated aqueous solution of ammonium chloride was added, and the phase was separated. After extraction with diethyl ether, the combined organic phases were dried over sodium sulfate and filtered. The solvent was removed, and 57 g of a colorless solid was obtained.

[0177] Example 5 (disiloxane = (C6H4OBn)SiMe2-O-SiMe2(C6H4OBn); Grignard batch)

[0178] 2.9 g of magnesium shavings were suspended in 30 mL of THF, and 0.1 g of iodine was added. A solution of 26 g of 1-(benzyloxy)-4-bromobenzene in 30 mL of THF was added dropwise, and after a 1 h reaction time, a Grignard reagent was added dropwise to a THF solution of 9.2 g of 1,3-dichloro-1,1,3,3-tetramethyldisiloxane. The batch was stirred for 16 h, and the reaction was terminated by adding water. The aqueous phase was extracted with diethyl ether, and the combined organic extracts were dried over magnesium sulfate and filtered. 22 g of a yellow solid was obtained.

[0179] Example 6 (Pentasiloxane = (C6H4OBn)SiMe2-[OSiMe2]3-OSiMe2(C6H4OBn))

[0180] 125 g of 1-(benzyloxy)-4-bromobenzene was dissolved in 800 mL of THF, and 200 mL of a 2.5 M n-butyllithium solution in hexane was added dropwise at -78°C. The mixture was stirred and 100 g of 1,9-dichlorodecamethylpentanesiloxane was added. The cooling bath was removed, and the mixture was then heated to room temperature. 20 mL of triethylamine was added, followed by 300 mL of saturated ammonium chloride aqueous solution, and the phase was separated. After extraction with diethyl ether, the combined organic phases were dried over sodium sulfate and filtered. The solvent was removed, yielding 168 g of a colorless solid.

[0181] Example 7 (disiloxane = (C6H4OAll)SiMe2-O-SiMe2(C6H4OAll))

[0182] 48 g of 1-allyloxy-4-bromobenzene was dissolved in 400 mL of THF, and 100 mL of a 2.5 M n-butyllithium solution in hexane was added dropwise at -78°C. After 60 minutes, 1,3-dichlorotetramethyldisiloxane was added dropwise and the mixture was stirred for another 1 h. The batch was brought to room temperature and 15 mL of triethylamine was added. After extraction with diethyl ether and ammonium formate, the organic phase was dried over magnesium sulfate and filtered off. The solvent was removed, yielding 29 g of a pale yellow oil.

[0183] Example 8 (Tetrasiloxane = (C6H4OBn)SiMe2-[OSiMe2]2-OSiMe2(C6H4OBn); Grignard batch)

[0184] 5.6 g of magnesium shavings were suspended in 60 mL of THF, and 0.1 g of iodine was added. A solution of 52 g of 1-(benzyloxy)-4-bromobenzene in 60 mL of THF was added dropwise, and after a 1 h reaction time, Grignard reagent was added dropwise to a THF solution of 27.7 g of 1,5-dichloro-1,1,3,3,5,5-hexamethyltrisiloxane. The batch was stirred for 2 h, and then the reaction was terminated by adding water. The aqueous phase was extracted with diethyl ether, and the combined organic extracts were dried over magnesium sulfate and filtered. 54 g of a yellow solid was obtained.

[0185] Deprotection

[0186] MuM408–Ammonium formate method Si4 (tetrasiloxane=(HOC6H4)SiMe2-[OSiMe2]2-OSiMe2(C6H4OH))

[0187]

[0188] 35 g of benzyl-protected α,ω-phenol-substituted octamethyltetrasiloxane was dissolved in a 1:3 mixture of MeOH and THF. 15.1 g of ammonium formate and 2.0 g of Pd / C (10 wt%) were added, and the mixture was stirred in an autoclave at 60°C for 24 h. After pressure release, the batch was filtered, diluted with ethyl acetate, and washed until neutral. The solvent was removed after drying with magnesium sulfate and filtration, yielding 18.4 g of a yellow solid.

[0189] MuM408-Adaptor 1 (Tetrasiloxane = (HOC6H4)SiMe2-[OSiMe2]2-OSiMe2(C6H4OH))

[0190]

[0191] 35 g of benzyl-protected α,ω-phenol-substituted octamethyltetrasiloxane was dissolved in a 1:5 mixture of MeOH and THF. 15.1 g of ammonium formate and 2.0 g of Pd / C (10 wt%) were added, and the mixture was stirred in an autoclave at 60°C for 12 h. After pressure release, the batch was filtered, diluted with ethyl acetate, and washed until neutral. After drying with magnesium sulfate and filtering, the solvent was removed, and 20.1 g of a yellow solid was obtained.

[0192] MuM408-Adaptor 2 (Tetrasiloxane = (HOC6H4)SiMe2-[OSiMe2]2-OSiMe2(C6H4OH))

[0193]

[0194] 35 g of benzyl-protected α,ω-phenol-substituted octamethyltetrasiloxane was dissolved in a 1:4 mixture of MeOH and THF. 27.2 g of ammonium formate and 2.0 g of Pd / C (10 wt%) were added, and the mixture was stirred in an autoclave at 60°C for 4 h. After pressure release, the batch was filtered, diluted with ethyl acetate, and washed until neutral. The solvent was removed after drying with magnesium sulfate and filtration, yielding 19.4 g of a yellow oil.

[0195] MuM408-Adaptor 3 (Tetrasiloxane=(HOC6H4)SiMe2-[OSiMe2]2-OSiMe2(C6H4OH))

[0196]

[0197] 35 g of benzyl-protected α,ω-phenol-substituted octamethyltetrasiloxane was dissolved in a 1:3 mixture of MeOH and THF. 27.2 g of ammonium formate and 2.0 g of Pd / C (10 wt%) were added, and the mixture was stirred at 60°C for 8 h. After removing the catalyst, the batch was diluted with ethyl acetate and washed until neutral. The organic phase was dried over magnesium sulfate and filtered. The solvent was removed, yielding 21.9 g of a yellow oil.

[0198] MuM417 – Hydrogen method (Tetrasiloxane = (HOC6H4)SiMe2-[OSiMe2]2-OSiMe2(C6H4OH))

[0199]

[0200] 15 g of benzyl-protected α,ω-phenol-substituted octamethyltetrasiloxane was dissolved in a 1:2 mixture of MeOH and THF. 1.6 g of Pd / C (10 wt%) was added, and the mixture was stirred under hydrogen (15 bar) for 16 h. After removing the catalyst, the batch was diluted with ethyl acetate and washed until neutral. The organic phase was dried over magnesium sulfate and filtered. The solvent was removed, yielding 7.8 g of a yellow oil.

[0201] KnA2768 Si2 (disiloxane = (HOC6H4)SiMe2-O-SiMe2(C6H4OH))

[0202]

[0203] 30 g of benzyl-protected α,ω-phenol-substituted tetramethyldisiloxane was dissolved in 120 mL of a 1:3 mixture of MeOH and THF. 22.5 g of ammonium formate and 1.5 g of Pd / C (10 wt%) were added, and the mixture was stirred in an autoclave at 50°C for 10 h. After pressure release, the batch was filtered, diluted with ethyl acetate, and washed until neutral. The solvent was removed after drying with magnesium sulfate and filtration, yielding 17.2 g of a brown oil. Recrystallization from toluene and n-hexane gave a yellow solid.

[0204] KnA2795 Si3 (Trisiloxane = (HOC6H4)SiMe2-OSiMe2-OSiMe2(C6H4OH))

[0205]

[0206] 31 g of benzyl-protected α,ω-phenol-substituted hexamethyltrisiloxane was dissolved in 110 mL of a 1:3 mixture of MeOH and THF. 20.5 g of ammonium formate and 1.6 g of Pd / C (10 wt%) were added, and the mixture was stirred in an autoclave at 60°C for 8 h. After pressure release, the batch was filtered, diluted with ethyl acetate, and washed until neutral. After drying with magnesium sulfate and filtering, the solvent was removed, yielding 18.5 g of a yellow oil.

[0207] MuM245 Si4 (Tetrasiloxane = (HOC6H4)SiMe2-[OSiMe2]2-OSiMe2(C6H4OH))

[0208]

[0209] Eight g of allyl-protected α,ω-phenol-substituted tetramethyldisiloxane was dissolved in 40 mL of a 1:3 mixture of MeOH and THF. Six 6.3 g of ammonium formate and 0.4 g of Pd / C (10% by weight) were added, and the mixture was stirred in an autoclave at 60°C for 6 h. After pressure release, the batch was filtered, diluted with ethyl acetate, and washed until neutral. After drying with magnesium sulfate and filtering, the solvent was removed, yielding 5.3 g of a yellow oil.

[0210] molar mass

[0211] In the context of this invention, the weight-average molar mass Mw and the number-average molar mass Mn (in g / mol in each case, rounded to the nearest 10 according to DIN 1333:1992-02, Section 4) were determined by size exclusion chromatography (SEC / GPC) according to DIN 55672-1 / ISO 160414-1 and ISO 160414-3, using tetrahydrofuran (THF) as the eluent, and employing a column array based on polystyrene-co-divinylbenzene as the stationary phase (consisting of three columns with different pore sizes in sequence of 10,000 Å, 500 Å, and 100 Å, with a cutoff size greater than 450,000 g / mol), calibrated with polystyrene standards. The analysis was performed at a column temperature of 45 ± 1°C using a refractive index detector.

[0212] Sample preparation

[0213] For better processability, the cyanate ester resin (A) was first heated to 80°C and thoroughly mixed. Then, poly(diorganosiloxane) (B) was added, and the mixture was homogenized at 110°C for 1 hour. Afterward, it was degassed at 110°C and 10 mbar for 1 hour, and immediately poured into a two-part spiral-closed aluminum mold preheated to 160°C after releasing the vacuum with nitrogen. The mold cavity dimensions were 200 mm x 100 mm x 6.5 mm (length x width x height), used to produce specimens for determining fracture toughness, water absorption, and thermal oxidation stability, as well as for dynamic mechanical analysis (DMA). To prevent adhesion and leakage, the inner surface of the mold cavity was treated with a release agent (LOCTITE FREKOTE HMT-2; purchased from Henkel AG & Co. KGaA in Düsseldorf, Germany), and a 2 mm thick, 75 Shore A fluororubber circular sealing strip was placed around the mold cavity. To achieve curing, the filled mold is stored in a convection oven according to the following temperature program:

[0214] 1) Curing at 180°C for 18 hours

[0215] 2) The temperature rises to 200°C within 30 minutes.

[0216] 3) Curing at 200°C for 3 hours

[0217] 4) The temperature rises to 240°C within 30 minutes.

[0218] 5) Curing at 240°C for 2 hours.

[0219] The specimens were then allowed to cool to ambient temperature in the mold before demolding. For further use, the top 10 mm of the cured side of the specimen, which had been opened and exposed to air during curing in the mold, was removed and discarded. Specimens for measuring fracture toughness, water absorption, and DMA were then cut from a large cured sample plate with a height of 6.5 mm using a diamond saw to appropriate dimensions of length x width; specimens with a thickness of 2.00 mm for measuring water absorption were cut from the inside of the pre-cut section using a diamond hole saw, ensuring that all six surfaces of these specimens were sawn.

[0220] fracture toughness K Ic

[0221] Fracture toughness or critical stress intensity factor K was determined at 23°C and 50% relative humidity, as described in publication "Reactive and Functional Polymers" 142 (2019) 159-182. IcThe measurement was performed; the thickness of the sample used was 6.5 mm. According to DIN 1333:1992-02, Section 4, the values ​​reported in Table 1 are expressed in MN×m. -3 / 2 Fracture toughness in units of K Ic The value is rounded to two decimal places.

[0222] Dynamic mechanical analysis (DMA)

[0223] Measurement conditions:

[0224] Measuring instrument: ARES rheometer (TA Instruments)

[0225] Temperature range: -100°C to 300°C

[0226] Heating rate: 4 K / min under nitrogen purging

[0227] Frequency: 1 Hz

[0228] Strain: Initially 0.03%, automatically increases when the measured signal falls below the threshold.

[0229] The test was conducted using a cubic specimen with dimensions of length x width x height = 40 mm x 6 mm x 3 mm; the resulting clamping length was 25 mm.

[0230] In this invention, the glass transition temperature T G The maximum value corresponding to the tangent delta curve (= tandelta) max That is, the temperature at which the ratio of loss modulus G'' to storage modulus G' is greatest.

[0231] The glass transition temperature T reported in Table 1 G The value is rounded to the nearest integer according to DIN 1333:1992-02, Section 4.

[0232] Water absorption rate

[0233] In this invention, the water absorption rate is determined by gravimetric analysis after the sample is stored in temperature-controlled water. A cubic sample with dimensions of length x width x thickness = 30.00 mm x 17.00 mm x 2.00 mm is used; the accuracy of the weight measurement is +0.01 mg. The sample is first dried to constant weight in a vacuum oven at 70°C and 30 mbar, and the weight is measured at 24-hour intervals. The test sample is considered "dry" when no further weight loss is measured within 48 hours. In each case, the dried sample is then immersed in 45 ml of deionized water in a suitable sealable container; this sealed container is then placed in a convection oven preheated to 70°C and maintained at this temperature throughout the test. After 1600 hours, the sample is removed, cooled to ambient temperature, and the surface is wiped with a cloth; the weight of the sample is then recalculated. The water absorption rate (or weight gain) is calculated based on the following: Table 1 reports the water absorption values, in % and rounded to two decimal places according to DIN 1333:1992-02, Section 4.

[0234] Compatibility

[0235] The compatibility of compound (B) with cyanate ester resin (A) was visually evaluated according to the standards shown in Table 1:

[0236] - After storing the mixture at 100°C for 15 minutes before curing:

[0237] "+" indicates that the mixture is single-phase, while "-" indicates that the mixture is two-phase.

[0238] -After curing:

[0239] "+" indicates good compatibility, meaning compound (B) shows no leaching or precipitation from the visibly cured mixture, while "-" indicates poor compatibility, meaning component (B) shows visible leaching or precipitation from the cured mixture. Furthermore, LDPE membranes (CAS: 9002-88-4) and filter paper (Whatman) are used. TM (Filter paper type 589 / 2) The stickiness or oiliness of the air-side surface is determined by pressing a membrane or filter paper onto the surface and then peeling it off. As reported in Table 1, surface stickiness / oiliness is distinguished as “+” (dry sample surface, non-sticky and non-oily (dry filter paper)) and “-” (soft sample surface, sticky and / or oily (wet filter paper)).

[0240] Example E1

[0241] As described in the “Sample Preparation” section, 85 g of polyphenol cyanate resin (CAS 87397-54-4; purchased from Arxada Ltd., CH-4002 Basel under the trade name Primaset® PT-15) was mixed as component (A) with 15 g of pre-prepared modifier “MuM408–Si4” as component (B), and then processed.

[0242] The results are shown in Table 1.

[0243] Example E2

[0244] Repeat Example E1, but replace the polyphenol cyanate resin used therein with polyphenol cyanate resin PRIMASET® PT-30 (CAS 87397-54-4; purchased from Arxada Ltd., CH-4002 Basel) instead of PRIMASET® PT-15, and replace the modifier "MuM408–Si4" with "KnA2795Si3", with the rest of the steps remaining unchanged.

[0245] The results are shown in Table 1.

[0246] Comparative Example C1

[0247] Repeat the procedure described in Example E1, except that component (B) is not added to component (A).

[0248] The results are shown in Table 1.

[0249] Comparative Example C2

[0250] Repeat the procedure described in Example E2, except that component (B) is not added to component (A).

[0251] The results are shown in Table 1.

[0252] Table 1

[0253]

[0254] 1 Unassessed

[0255] The invention is further characterized by the following key points:

[0256] 1. A poly(diorganosiloxane) having the general formula (I)

[0257] R a R 1 3-a Si-O-(R d R 1 2-dSi-O-) b -SiR c R 1 3-c (I)

[0258] in,

[0259] R is the same or different, and represents

[0260] -Aliphatic hydrocarbon group with a single valence and linked by a SiC bond, or

[0261] -Aromatic hydrocarbon groups without phenolic hydroxyl groups linked by SiC bonds, with a single valence.

[0262] R 1 Are they the same or different, and indicate

[0263] A monovalent aromatic hydrocarbon group having at least one phenolic hydroxyl group,

[0264] a can be 2 or 3, with 2 being the preferred choice.

[0265] b is an integer from 1 to 10, preferably from 1 to 7, and more preferably from 1 to 4.

[0266] c can be 2 or 3, with 2 being the preferred value.

[0267] d is 1 or 2, preferably 2.

[0268] The condition is that each poly(diorganosiloxane) molecule of general formula (I) contains one or two R groups. 1 Preferably, two groups R 1 .

[0269] 2. According to point 1, the poly(diorganosiloxane) wherein the monovalent, aliphatic hydrocarbon group R linked by SiC bond further includes ether (≡COC≡), hydroxyl (-OH) and / or epoxy (=COC=) groups.

[0270] 3. According to point 1, the poly(diorganosiloxane) wherein the monovalent, phenol-free aromatic hydrocarbon group R, linked by a SiC bond, is interrupted by at least one heteroatom.

[0271] 4. The poly(diorganosiloxane) according to point 3, wherein the at least one heteroatom is selected from the group consisting of: O, S, N, P, preferably O.

[0272] 5. The poly(diorganosiloxane) according to any of the foregoing points is a solid or liquid at 23°C and 1013 hPa, preferably a liquid.

[0273] 6. The poly(diorganosiloxane) according to any one of the foregoing points has a weight-average molar mass Mw of 300 to 2000 g / mol, preferably 300 g / mol to 1000 g / mol, more preferably 300 g / mol to 700 g / mol.

[0274] 7. The poly(diorganosiloxane) according to any of the foregoing points, having a number-average molar mass Mn of preferably 300 g / mol to 1500 g / mol, more preferably 300 g / mol to 1000 g / mol, and even more preferably 300 g / mol to 700 g / mol.

[0275] 8. A poly(diorganosiloxane) according to any of the foregoing points, wherein R is selected from the group consisting of the following:

[0276] -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl;

[0277] - Self-base, such as positive self-base;

[0278] -Henyl base, such as positive heptyl base;

[0279] -Octyl, such as n-octyl and isooctyl, such as 2,4,4-trimethylpentyl and 2,2,4-trimethylpentyl;

[0280] -Renji, such as Zheng Renji;

[0281] -decyl, such as n-decyl; dodecyl, such as n-dodecyl;

[0282] -Hexadecyl, such as n-hexadecyl;

[0283] -Octadecanyl, such as n-octadecyl;

[0284] -Cycloalkyl groups, such as cyclopentyl, cyclohexyl, cycloheptyl, and methylcyclohexyl;

[0285] -Alkenyl groups, such as vinyl, allyl, cyclopentenyl, and cyclohexenyl; and

[0286] -Epoxy groups, such as 3-glycidoxypropyl, ethylene-2-yl, and 2-(3,4-epoxycyclohexyl)ethyl.

[0287] 9. A poly(diorganosiloxane) according to any of the foregoing points, wherein R is selected from the group consisting of the following:

[0288] -Aryl groups, such as phenyl, biphenyl, cumylphenyl, benzylphenyl, naphthyl, anthraceneyl, and phenanthrene;

[0289] -Alkyl groups, such as tolyl, xylyl, and ethylphenyl;

[0290] -Aryl groups, such as benzyl, cumyl, α-phenethyl and β-phenethyl;

[0291] -Alkoxyaryl, such as methoxyphenyl;

[0292] -Aryloxyaryl, such as phenoxyphenyl;

[0293] -Hydroaryl groups, such as fluorophenyl, chlorophenyl, bromophenyl, and trifluoromethylphenyl; and

[0294] - Heterocyclic aromatic groups, such as pyridyl, pyrazinyl, quinolinyl, furanyl and (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-10-yl)ethyl.

[0295] 10. A poly(diorganosiloxane) according to any of the foregoing points, wherein R is a monovalent alkyl or aryl group having 1 to 8 carbon atoms linked by a SiC bond, preferably methyl or phenyl, especially methyl.

[0296] 11. A poly(diorganosiloxane) according to any of the foregoing points, wherein R 1 Selected from compounds described by formula (II):

[0297] (II)

[0298] in,

[0299] R 4 R 5 R 6 R 7 and R 8 In their respective cases, each group independently represents a hydrogen atom, a hydroxyl group, or a hydrocarbon group that optionally has a hydroxyl group and is optionally interrupted by at least one heteroatom and has 1 to 18 carbon atoms.

[0300] The condition is that in formula (II), at least one group R 4 R 5 R 6 R 7 Or R 8 It is a phenolic hydroxyl group or contains a phenolic hydroxyl group.

[0301] 12. According to point 11, the poly(diorganosiloxane), wherein R 4 R 5 R 6 R 7 and R 8In each case, a hydrogen atom, a hydroxyl group, or optionally a hydroxyl group and optionally a hydrocarbon group having 1 to 8 carbon atoms is independently represented.

[0302] 13. Poly(diorganosiloxane) according to points 11 or 12, wherein R 6 It represents a hydroxyl group, and the group R 4 R 5 R 7 and R 8 In each case, a hydrogen atom is represented independently or optionally, a hydrocarbon group having 1 to 12 carbon atoms is bonded together via an oxygen (-O-) unit.

[0303] 14. A poly(diorganosiloxane) according to any one of points 11 to 13, wherein the group R 6 It represents a hydroxyl group, and the group R 4 R 5 R 7 and R 8 In each case, it independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

[0304] 15. A poly(diorganosiloxane) according to any one of points 11 to 14, wherein R 6 It represents a hydroxyl group, and the group R 4 R 5 R 7 and R 8 It represents a hydrogen atom.

[0305] 16. A poly(diorganosiloxane) according to any of the foregoing points, wherein R 1 Selected from the following group, which consists of the following items: hydroxyphenyl [-C6H4(OH)], hydroxy(methyl)phenyl [-C6H3(OH)(CH3)], hydroxy(dimethyl)phenyl [-C6H2(OH)(CH3)2], hydroxy(ethyl)phenyl [-C6H3(OH)(CH2CH3)], hydroxy(methyl)(isopropyl)phenyl [-C6H3(OH)(CH3)(CH(CH3)2)], hydroxy(methoxy)phenyl [-C6H3(OH)(OCH3)], hydroxy(phenoxy)phenyl [-C6H3(OH)(OC6H5)], (hydroxyphenyl)phenyl [-C6H4(C6H4(OH))], hydroxynaphthyl [-C 10 H6(OH)], hydroxy(phenyl)phenyl[-C6H3(OH)(C6H5)], hydroxy(benzyl)phenyl[-C6H3(OH)(CH2(C6H5))] and (hydroxycumyl)phenyl[-C6H3(C(CH3)2)(C6H4(OH))] groups,

[0306] Preferably selected from the group consisting of: hydroxyphenyl, hydroxy(methyl)phenyl, hydroxy(dimethyl)phenyl, hydroxy(ethyl)phenyl, and hydroxy(methyl)(isopropyl)phenyl.

[0307] Specifically selected from hydroxyphenyl.

[0308] 17. A poly(diorganosiloxane) according to any one of the foregoing points, corresponding to one of the following formulas (IIIa), (IIIb), (IIIc), (IV) to (XII), preferably formulas (IIIa), (IIIb), (IIIc), (VI), (X) and (XI), more preferably formulas (IIIa), (X) and (XI).

[0309] (IIIa)

[0310] (IIIb)

[0311] (IIIc)

[0312] (IV)

[0313] (V),

[0314] (VI)

[0315] (VII)

[0316] (VIII)

[0317] (IX),

[0318] (X),

[0319] (XI),

[0320] Where R 9 Selected from the following group, which consists of the following items: Me, Ph, VI, H, especially Me,

[0321] (XII)

[0322] Where Me is methyl and Ph is phenyl.

[0323] m is an integer from 2 to 11, preferably from 2 to 8, and more preferably from 2 to 5;

[0324] n is an integer from 1 to 10, preferably from 1 to 7, more preferably from 1 to 4, and o is an integer from 1 to 10, preferably from 1 to 7, more preferably from 1 to 4, provided that the sum of n + o is 2 to 11, preferably from 2 to 8, more preferably from 2 to 5.

[0325] 18. A method for preparing poly(diorganosiloxane) according to any one of points 1 to 17, the method comprising the following steps in a specified order:

[0326] (A) Provides an aromatic hydrocarbon compound having the chemical formula (XIII).

[0327] R 1 -X (XIII),

[0328] in,

[0329] R 1 This indicates a monovalent aromatic hydrocarbon group having at least one phenolic hydroxyl group, and

[0330] X represents F, Cl, Br or I, preferably Cl, Br or I, more preferably Cl or Br;

[0331] (B) Protecting R with a suitable protecting group 1 The at least one phenolic hydroxyl group in -X;

[0332] (C) The protected compound R obtained after step (B) 1 -X reaction to form organometallic compound R 1 -M, wherein M preferably represents Li, Mg-X or Zn-X, especially Li and Mg-X;

[0333] (D) React the organometallic compound obtained after step (C) with a siloxane having the chemical formula (XIV).

[0334] R a Y 3-a Si-O-(R d Y 2-d Si-O-) b -SiR c Y 3-c (XIV)

[0335] in,

[0336] R is the same or different, and represents

[0337] -Aliphatic hydrocarbon group with a single valence and linked by a SiC bond, or

[0338] -Aromatic hydrocarbon groups without phenolic hydroxyl groups linked by SiC bonds, with a single valence.

[0339] Y is the same or different, and

[0340] Represents Cl, MeO, EtO, or O i Pr, especially Cl,

[0341] a can be 2 or 3, with 2 being the preferred choice.

[0342] b is an integer from 1 to 10, preferably from 1 to 7, and more preferably from 1 to 4.

[0343] c can be 2 or 3, with 2 being the preferred value.

[0344] d is 1 or 2, preferably 2; and

[0345] (E) Deprotect the protected poly(diorganosiloxane) obtained after step (D);

[0346] To obtain a poly(diorganosiloxane) according to any one of points 1 to 17.

[0347] 19. The method according to point 18, wherein in step (B) a suitable protecting group is selected from benzyl, benzyl derivatives, allyl, tetrahydropyran (THP), methoxymethyl (MOM), silyl ethers such as trimethylsilyl, p-methoxybenzyl, benzyloxymethyl, preferably benzyl and allyl, more preferably benzyl.

[0348] 20. According to point 18 or 19, the reaction in step (C) to form the organometallic compound is carried out in the following manner:

[0349] When M represents Li, let R 1 -X reacts with organolithium compounds, especially n-BuLi; or

[0350] When M represents Mg-X, make R 1 -X reacts with Mg to form Grignard compounds; or

[0351] When M represents Zn-X, make R 1 -X reacts with Zn to form organozinc compounds.

[0352] 21. The method according to any one of points 18 to 20, wherein deprotection in step (E) is achieved by hydrogenolysis or under acidic conditions, preferably by hydrogenolysis.

[0353] 22. The use of poly(diorganosiloxane) as a modifier in organic resins according to any one of points 1 to 17 is preferred as a toughening modifier, a hydrophobic agent, or a modifier for improving flame retardancy, thermal oxidation properties, dielectric properties, moisture resistance, chemical resistance, and / or processing properties.

[0354] 23. According to the application of point 22, wherein the resin is selected from epoxy resins, cyanate ester resins, phenolic varnish resins, phenolic resins, UP resins, vinyl ester resins and BT resins, particularly from cyanate ester resins.

Claims

1. A poly(diorganosiloxane) having the general formula (I) R a R 1 3-a Si-O-(R d R 1 2-d Si-O-) b -SiR c R 1 3-c (I) in, R is the same or different, and represents - Monovalent, aliphatic hydrocarbon groups linked by SiC bonds, or - Monovalent aromatic hydrocarbon groups without phenolic hydroxyl groups linked by SiC bonds. R 1 Are they the same or different, and indicate A monovalent aromatic hydrocarbon group having at least one phenolic hydroxyl group, a is 2 or 3. b is an integer from 1 to 10. c is 2 or 3. d is 1 or 2. The condition is that each poly(diorganosiloxane) molecule of general formula (I) contains one or two R groups. 1 .

2. The poly(diorganosiloxane) according to claim 1, It has a weight-average molar mass Mw of 300 to 2000 g / mol, and / or It has a number-average molar mass Mn ranging from 300 to 1500 g / mol.

3. The poly(diorganosiloxane) according to any one of the preceding claims, having a PDI in the range of 0.8 to 1.

5.

4. The poly(diorganosiloxane) according to any one of the preceding claims, wherein, R selects a group consisting of the following items: - Alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl; - Self-base, such as positive self-base; - Geng base, such as positive Geng base; - Octyl, such as n-octyl and isooctyl, such as 2,4,4-trimethylpentyl and 2,2,4-trimethylpentyl; - Renji, such as Zheng Renji; - Decyl, such as n-decyl; dodecyl, such as n-dodecyl; - Hexadecyl, such as n-hexadecyl; - Octadecyl, such as n-octadecyl; - Cycloalkyl groups, such as cyclopentyl, cyclohexyl, cycloheptyl, and methylcyclohexyl; - Alkenyl, such as vinyl, allyl, cyclopentenyl and cyclohexenyl; - Epoxy groups, such as 3-glycidoxypropyl, ethylene-2-yl, and 2-(3,4-epoxycyclohexyl)ethyl; - Aryl groups, such as phenyl, biphenyl, cumylphenyl, benzylphenyl, naphthyl, anthraceneyl, and phenanthrene; - Alkyl aryl, such as tolyl, xylyl and ethylphenyl; - Aryl groups, such as benzyl, cumyl, α-phenethyl and β-phenethyl; - Alkoxyaryl, such as methoxyphenyl; - Aryloxyaryl, such as phenoxyphenyl; - Halogenated aryl groups, such as fluorophenyl, chlorophenyl, bromophenyl, and trifluoromethylphenyl; and - Heterocyclic aromatic groups, such as pyridyl, pyrazinyl, quinolinyl, furanyl and (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-10-yl)ethyl.

5. The poly(diorganosiloxane) according to any one of the preceding claims, wherein, R is a monovalent alkyl or aryl group with 1 to 8 carbon atoms linked by SiC bonds.

6. The poly(diorganosiloxane) according to any one of the preceding claims, wherein, R 1 Selected from compounds described by formula (II): (II), in, R 4 R 5 R 6 R 7 and R 8 In their respective cases, each group independently represents a hydrogen atom, a hydroxyl group, or a hydrocarbon group that optionally has a hydroxyl group and is optionally interrupted by at least one heteroatom and has 1 to 18 carbon atoms. The condition is that in formula (II), at least one group R 4 R 5 R 6 R 7 Or R 8 It is a phenolic hydroxyl group or contains a phenolic hydroxyl group.

7. The poly(diorganosiloxane) according to any one of the preceding claims, wherein, R 1 Choose from the following groups: hydroxyphenyl [-C6H4(OH)], hydroxy(methyl)phenyl [-C6H3(OH)(CH3)], hydroxy(dimethyl)phenyl [-C6H2(OH)(CH3)2], hydroxy(ethyl)phenyl [-C6H3(OH)(CH2CH3)], hydroxy(methyl)(isopropyl)phenyl [-C6H3(OH)(CH3)(CH(CH3)2)], hydroxy(methoxy)phenyl [-C6H3(OH)(OCH3)], hydroxy(phenoxy)phenyl [-C6H3(OH)(OC6H5)], (hydroxyphenyl)phenyl [-C6H4(C6H4(OH))], hydroxynaphthyl [-C 10 H6(OH)], hydroxy(phenyl)phenyl[-C6H3(OH)(C6H5)], hydroxy(benzyl)phenyl[-C6H3(OH)(CH2(C6H5))] and (hydroxycumyl)phenyl[-C6H3(C(CH3)2)(C6H4(OH))] groups, Preferably, it is selected from the group consisting of: hydroxyphenyl, hydroxy(methyl)phenyl, hydroxy(dimethyl)phenyl, hydroxy(ethyl)phenyl and hydroxy(methyl)(isopropyl)phenyl.

8. The poly(diorganosiloxane) according to any one of the preceding claims, which corresponds to one of formulas (IIIa), (IIIb), (IIIc) and (IV) to (XII). (IIIa), (IIIb), (IIIc), (IV), （V）， (WE), (VII), (VIII), (IX), （X）， (XI), Where R 9 Choose from the following groups: Me, Ph, VI, H. (XII), Where Me is methyl and Ph is phenyl. m is an integer from 2 to 11; n is an integer from 1 to 10, and o is an integer from 1 to 10, provided that the sum of n and o is 2 to 11.

9. A method for preparing a poly(diorganosiloxane) according to any one of claims 1-8, the method comprising the following steps in a specified order: (A) Provides an aromatic hydrocarbon compound having the chemical formula (XIII). R 1 -X (XIII), in, R 1 This indicates a monovalent aromatic hydrocarbon group having at least one phenolic hydroxyl group, and X represents F, Cl, Br, or I; (B) Protecting R with a suitable protecting group 1 At least one phenolic hydroxyl group in -X; (C) The protected compound R obtained after step (B) 1 -X reaction to form organometallic compound R 1 -M, wherein M preferably represents Li, Mg-X or Zn-X, especially Li and Mg-X; (D) React the organometallic compound obtained after step (C) with a siloxane having the chemical formula (XIV). R a AND 3-a Si-O-(R d AND 2-d Yes-O-) b -Sir c AND 3-c (XIV), in, R is the same or different, and represents - Monovalent, aliphatic hydrocarbon groups linked by SiC bonds, or - Monovalent aromatic hydrocarbon groups without phenolic hydroxyl groups linked by SiC bonds. Y is the same or different, and Represents Cl, MeO, EtO, or O i Pr, a is 2 or 3. b is an integer from 1 to 10. c is 2 or 3. d is 1 or 2; and (E) Deprotect the protected poly(diorganosiloxane) obtained after step (D); To obtain the poly(diorganosiloxane) according to any one of claims 1-8.

10. The method of claim 9, wherein the suitable protecting group in step (B) is selected from benzyl, benzyl derivatives, allyl and tetrahydropyran.

11. The method according to claim 9 or 10, wherein the reaction that forms the organometallic compound in step (C) is carried out in the following manner: When M represents Li, let R 1 -X reacts with organolithium compounds; or When M represents Mg-X, make R 1 -X reacts with Mg to form Grignard compounds; or When M represents Zn-X, make R 1 -X reacts with Zn to form organozinc compounds.

12. The method according to any one of claims 9 to 11, wherein the deprotection in step (E) is achieved by hydrogenolysis or under acidic conditions.

13. The use of poly(diorganosiloxane) as a modifier in organic resins according to any one of claims 1-8, preferably as a toughening modifier, a hydrophobic agent, or a modifier for improving flame retardancy, thermal oxidation properties, dielectric properties, moisture resistance, chemical resistance, and / or processing properties.

14. The use according to claim 13, wherein the resin is selected from epoxy resin, cyanate ester resin, phenolic varnish resin, phenolic resin, UP resin, vinyl ester resin and BT resin.

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