Siloxane-modified cyclotriphosphazene halogen-free flame retardant, preparation process and use thereof

Patent metadata

Field	Value
Publication number	US-10400173-B2
Application number	US-201715475471-A
Country	US
Kind code	B2
Filing date	Mar 31, 2017
Priority date	Oct 20, 2016
Publication date	Sep 3, 2019
Grant date	Sep 3, 2019

Abstract

The present invention provides a siloxane-modified cyclotriphosphazene halogen-free flame retardant, and a preparation method and a use thereof. The siloxane-modified cyclotriphosphazene halogen-free flame retardant has the structural formula as shown in Formula I. In the siloxane-modified cyclotriphosphazene halogen-free flame retardant of the present invention, three kinds of structures of siloxane, aryl phosphorus oxygen compound and cyclotriphosphazene are built in one molecular formula, which combines the advantages of three structures, improves the compatibility between the flame retardant and resins, has a high flame retardant efficiency and a better char formation and can greatly increase the flame retardancy and stability of resin cured products.

First claim

The invention claimed is:

1. A siloxane-modified cyclotriphosphazene halogen-free flame retardant, wherein the flame retardant has the structural formula as shown in Formula I:

wherein the groups of X 1 -X 6 are each independently selected from

 or —O—R′, and at least two groups therein are

 R 1 is a substituted or unsubstituted arylene: R 2 is selected from the group consisting of methenyl,

 wherein R a is a substituted or unsubstituted C1-C5 alkyl group; R b is a substituted or unsubstituted aryl group; R 3 is a group containing aryl phosphorus oxygen structure; Rs in the groups of X 1 -X 6 is independently selected from siloxane group or hydrogen, and Rs in the groups of X 1 -X 6 are not hydrogen at the same time; R′ is a substituted or unsubstituted aryl group.

2. The siloxane-modified cyclotriphosphazene halogen-free flame retardant according to claim 1 , wherein R 1 is selected from the group consisting of

3. The siloxane-modified cyclotriphosphazene halogen-free flame retardant according to claim 1 , wherein R 3 is selected from the group consisting of

4. The siloxane-modified cyclotriphosphazene halogen-free flame retardant according to claim 1 , wherein the siloxane group is selected from the group consisting of

or a combination of at least two selected therefrom, wherein R 4 is selected from the group consisting of

and —CH 2 CH 2 CH 2 NH—CH 2 CH 2 —NH 2 ; R 5 is selected from C1-C5 alkyl groups.

5. The siloxane-modified cyclotriphosphazene halogen-free flame retardant according to claim 1 , wherein R′ is selected from the group consisting of substituted phenyl, unsubstituted phenyl, substituted naphthyl, unsubstituted naphthyl, substituted alkylphenyl, unsubstituted alkylphenyl, substituted cycloalkylphenyl, unsubstituted cycloalkylphenyl, substituted nitrophenyl, unsubstituted nitrophenyl, substituted nitrogen-containing heterocyclylphenyl, unsubstituted nitrogen-containing heterocyclylphenyl, substituted aryloxyphenyl, and unsubstituted aryloxyphenyl, or a combination of at least two selected therefrom.

6. The siloxane-modified cyclotriphosphazene halogen-free flame retardant according to claim 1 , wherein the flame retardant is selected from the group of the compounds having the following formulae a-g, or a combination of at least two selected therefrom:

wherein six Rs in Formula a are each independently

wherein six Rs in Formula b are each independently

 or H, but not H at the same time;

wherein six Rs in Formula c are each independently

wherein six Rs in Formula d are each independently

wherein Rs in Formulae are

wherein three Rs in Formula f are each independently

wherein three Rs in Formula g are each independently

7. A process for preparing the siloxane-modified cyclotriphosphazene halogen free flame retardant according to claim 1 , wherein the process comprises the following steps:
(1) reacting aldehyde- or keto-substituted aryl phenol shown in Formula II and any optional aryl phenol shown in Formula III with hexachlorocyclotriphosphazene to obtain the cyclotriphosphazene compound as shown in Formula IV, wherein the reaction formula is as follows:

(2) reacting the cyclotriphosphazene compound as shown in Formula IV obtained in step (1) with phosphorus-containing aromatic compound containing P—H bonds as shown in Formula V to obtain the cyclotriphosphazene compound containing hydroxyl and aryl phosphorus oxygen structure as shown in Formula VI, wherein the reaction formula is as follows:

(3) reacting the cyclotriphosphazene compound containing hydroxyl and aryl phosphorus oxygen structure as shown in Formula VI obtained in step (2) with siloxane monomer as shown in Formula VII to obtain the siloxane-modified cyclotriphosphazene halogen-free flame retardant as shown in Formula I, wherein the reaction formula is as follows:

wherein the groups of Y 1 -Y 5 are each independently selected from R 6 —R 1 —O— and —O—R′, and at least one is R 6 —R 1 —O—; R 1 is a substituted or unsubstituted arylidene; R 6 is aldehyde group or

 R 7 is a substituted or unsubstituted C1-C5 alkyl or a substituted or unsubstituted aryl; R′ is a substituted or unsubstituted aryl; the groups of Z 1 -Z 5 are each independently selected from

 or —O—R′, and at least one is

 R 2 is selected from the group consisting of methenyl,

 wherein R a is a substituted or unsubstituted C1-C5 alkyl; R b is a substituted or unsubstituted aryl; R 3 is a group containing aryl phosphorus oxygen structure; the groups of X 1 -X 6 are each independently selected from

 or —O—R′, and at least two groups are

 R 4 is selected from the group consisting of

 and —CH 2 CH 2 CH 2 —NH—CH 2 CH 2 —NH 2 ; R 5 is selected from the group consisting of C1-C5 alkyl groups; R′ is a substituted or unsubstituted aryl; Rs in X 1 -X 6 are independently selected fro

Assignees

• Shengyi Technology Co Ltd

Inventors

• Wang Yongzhen
• He Yueshan
• Yang Zhongqiang
• Xu Yongjing

Classifications

• D06M15/673

  containing phosphorus and nitrogen in the main chain · CPC title

• C08L27/02

  not modified by chemical after-treatment · CPC title

• C08K5/5406

  containing elements other than oxygen or nitrogen · CPC title

• C08K5/5399

  Phosphorus bound to nitrogen · CPC title

• C07F9/659

  having three phosphorus atoms as ring hetero atoms in the same ring {(C07F9/65812 takes precedence)} · CPC title