Novolac curing agent with alkoxysilyl group, method for preparing the same, composition containing the same, the cured product, and use thereof

Patent metadata

Field	Value
Publication number	US-10519274-B2
Application number	US-201515110677-A
Country	US
Kind code	B2
Filing date	Jan 9, 2015
Priority date	Jan 9, 2014
Publication date	Dec 31, 2019
Grant date	Dec 31, 2019

Abstract

A new novolac curing agent with an alkoxysilyl group exhibiting excellent heat resistance such as a low CTE and an high Tg when a composite is formed, a preparing method of the same, a composition including the same, a cured article, and an use thereof, are provided. The new novolac curing agent having an alkoxysilyl group of Formulae I-1 to I-4, a preparing method of the new novolac curing agent by alkenylation and alkoxysilylation of the novolac curing agent, a preparing method of the new novolac curing agent by alkoxysilylation of a novolac curing agent, a composition including a novolac curing agent having an alkoxysilyl group of Formulae I-1 to I-4, a cured article and a use thereof, are provided. A composite including a novel novolac curing agent having an alkoxysilyl group exhibits a low CTE and a high glass transition temperature.

First claim

The invention claimed is:

1. A novolac curing agent with at least one alkoxysilyl group selected from the group consisting of Formulae I-1, I-3 and I-4,

in Formula I-1, Z is one selected from the group consisting of Formulae 1B to 1F:

in Formula I-4, p is 1 or 2, and X is

and in

R is a linear or branched alkyl group of C1-C10,
in Formulae I-1, I-3 and I-4, at least one of A's has Formula A2 or A3, wherein in the case that at least one of A's is A2, the remainder of A's is Formula B2 or hydrogen, and in the case that at least one of A's is A3, the remainder of A's is hydrogen, and n is an integer of 1 or more,
—(CH 2 ) m —SiR 1 R 2 R 3   [Formula A2]

—CONH(CH 2 ) m —SiR 1 R 2 R 3   [Formula A3]

in Formulae A2 and A3, at least one of R 1 to R 3 is a linear or branched alkoxy group of 1 to 5 carbon atoms, the remainder thereof is a linear or branched alkyl group of 1 to 10 carbon atoms, and m is an integer from 3 to 10,
—(CH 2 ) l —CH═CH 2   [Formula B2]

in Formula B2, l is an integer from 1 to 8,
wherein the novolac curing agent with at least one alkoxysilyl group selected from the group consisting of Formulae I-1, I-3 and I-4 is used as a curing agent in a composition comprising an epoxy resin and the curing agent.

2. A preparing method of a novolac curing agent with at least one alkoxysilyl group selected from the group consisting of Formulae I-1, I-3 and I-4, the preparing method comprising:
a first step of preparing one of intermediates of Formulae IB-1, IB-3 and IB-4 by reacting one of starting materials of Formulae IA-1, IA-3 and IA-4 and an alkenyl compound of Formula II in the presence of a base and an optional solvent; and
a second step of preparing one of compounds of Formulae I-1, I-3 and I-4 having a structure of Formula A2 by reacting one of intermediates of Formulae IB-1, IB-3 and IB-4 and alkoxysilane of Formula IIIA in the presence of a platinum catalyst and an optional solvent,

in Formula IA-1, X is one selected from the group consisting of Formulae 2B to 2F:

in Formula IA-4, p is 1 or 2, X1 is

and in

R is a linear or branched alkyl group of C1-C10,
in Formulae IA-1, IA-3 and IA-4, n is an integer of 1 or more,

in Formula IB-1, Y 1 is one selected from the group consisting of Formulae 3B to 3F:

in Formula IB-4, p is 1 or 2, and X2 is

and in

R is a linear or branched alkyl group of C1-C10,
in Formulae IB-1, IB-3 and IB-4, at least one of D's is Formula B2, the remainder thereof is hydrogen, and n is an integer of 1 or more,
—(CH 2 ) l —CH═CH 2   [Formula B2]

in Formula B2, l is an integer from 1 to 8,
X—(CH 2 ) l —CH═CH 2   [Formula II]

in Formula II, l is an integer from 1 to 8, and X is Cl, Br, I, —O—SO 2 —CH 3 , —O—SO 2 —CF 3 , or —O—SO 2 —C 6 H 4 —CH 3 ,
HSiR a R b R c   [Formula IIIA]

in Formula IIIA, at least one of R a to R c is a linear or branched alkoxy group of C1-C5, and the remainder thereof is a linear or branched alkyl group of C1-C10,

in Formula I-1, Z is one selected from the group consisting of Formulae 1B to 1F:

in Formula I-4, p is 1 or 2, and X is

and in

R is a linear or branched alkyl group of C1-C10,
in Formulae I-1, I-3 and I-4, at least one of A's is Formula A2, the remainder of A's is Formula B2 or hydrogen, and n is an integer of 1 or more,
—(CH 2 ) m —SiR 1 R 2 R 3   [Formula A2]

in Formula A2, at least one of R 1 to R 3 is a linear or branched alkoxy group of 1 to 5 carbon atoms, the remainder thereof is a linear or branched alkyl group of 1 to 10 carbon atoms, and m is an integer from 3 to 10,
—(CH 2 ) l —CH═CH 2   [Formula B2]

in Formula B2, l is an integer from 1 to 8,
wherein the novolac curing agent with at least one alkoxysilyl group selected from the group consisting of Formulae I-1, I-3 and I-4 is used as a curing agent in a composition comprising an epoxy resin and the curing agent.

3. A preparing method of a novolac curing agent with at least one alkoxysilyl group selected from the group consisting of Formulae I-1, I-3 and I-4, the preparing method comprising:
an alkoxysilylation step of preparing one of compounds of Formulae I-1, I-3 and I-4 with a structure of Formula A3 by reacting one of starting materials of Formulae IA-1, IA-3 and IA-4 and alkoxysilane of Formula IIIB in the presence of an optional base and an optional solvent,

in Formula IA-1, X is one selected from the group consisting of Formulae 2B to 2F:

in Formula IA-4, p is 1 or 2, and X1 is

and in

R is a linear or branched alkyl group of C1-C10,
in Formulae IA-1, IA-3 and IA-4, n is an integer of 1 or more,
OCN—(CH 2 ) m —SiR 1 R 2 R 3   [Formula IIIB]

in Formula IIIB, at least one of R 1 to R 3 is a linear or branched alkoxy group of 1 to 5 carbon atoms, the remainder thereof is a linear or branched alkyl group of 1 to 10 carbon atoms, and m is an integer from 3 to 10,

in Formula I-1, Z is one selected from the group consisting of Formulae 1B to 1F:

Assignees

• Korea Inst Ind Tech

Inventors

• Chun Hyun-Aee
• Kim Yun-Ju
• Park Su-Jin
• Park Sook-Yeon
• Tak Sang-Yong
• Park Sung-Hwan

Classifications

• H10W74/47

  comprising organic materials, e.g. plastics or resins · CPC title

• H10W74/40

  characterised by their materials · CPC title

• C08J2363/02

  Polyglycidyl ethers of bis-phenols · CPC title

• C09J163/04

  Epoxynovolacs · CPC title

• C09D161/14

  Modified phenol-aldehyde condensates · CPC title