In situ polymerized flame retardant, preparation method thereof, and molding composition comprising thereof

Patent metadata

Field	Value
Publication number	US-12534573-B2
Application number	US-202017609409-A
Country	US
Kind code	B2
Filing date	Apr 10, 2020
Priority date	May 9, 2019
Publication date	Jan 27, 2026
Grant date	Jan 27, 2026

Abstract

The invention discloses an in situ polymerized flame retardant, derived from the following monomers: a diacid monomer A: where A1 is terephthalic acid, A2 is a phosphorus aromatic ring-containing reactive flame-retardant diacid monomer, A1+A2=100 mol %, A1=50 to 90 mol %, A2=10 to 50 mol %; and a diamine monomer B: one or more of diamine monomers containing 4 to 36 carbon atoms. In the present invention, a novel flame retardant is obtained by in situ polymerization of the phosphorus aromatic ring-containing reactive flame-retardant diacid monomers in semi-aromatic polyamide oligomers, which has advantages of no precipitation in the semi-aromatic polyamide and no influence on other properties of the semi-aromatic polyamide and has an excellent flame-retardant property.

First claim

What is claimed is:

1. An in situ polymerized flame retardant, wherein the in situ polymerized flame retardant is derived from the following monomers:
a diacid monomer A consisting of a diacid monomer A1 and a diacid monomer A2, wherein the diacid monomer A1 is terephthalic acid, the diacid monomer A2 is a phosphorus aromatic ring-containing reactive flame-retardant diacid monomer, a total content of the diacid monomer A1 and the diacid monomer A2 is 100 mol %, a content of the diacid monomer A1 is 60 to 85 mol %, and a content of the diacid monomer A2 is 15 to 40 mol %; and
a diamine monomer B including one or more of diamine monomers containing 4 to 36 carbon atoms,
wherein the phosphorus aromatic ring-containing reactive flame-retardant diacid monomer is at least one member selected from the group consisting of 3-hydroxyphenylphosphinyl propanoic acid, bis(p-carboxyphenyl)phenyl phosphine oxide, bis(p-carboxyphenyl)methyl phosphine oxide, bis(p-carboxyphenyl)ethyl phosphine oxide, and [(6-oxido-6H-dibenzo-(c,e)(1,2)-oxaphosphorin-6-ketone)methyl]-butanedioic acid,
wherein a relative viscosity of the in situ polymerized flame retardant is 1.2 to 1.5, under a test condition being in 98% concentrated sulfuric acid at 25° C.±0.01° C., with a concentration of the in situ polymerized flame retardant being 10 mg/mL.

2. The in situ polymerized flame retardant according to claim 1 , wherein the diamine monomer B is at least one member selected from the group consisting of 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,14-tetradecanediamine, 1,16-hexadecandiamine, 1,18-octadecanediamine, 1-butyl-1,2-ethylenediamine, 1,1-dimethyl-1,4-butanediamine, 1-ethyl-1,4-butanediamine, 1,2-dimethyl-1,4-butanediamine, 1,3-dimethyl-1,4-butanediamine, 1,4-dimethyl-1,4-butanediamine, 2,3-dimethyl-1,4-butanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 2,5-dimethyl-1,6-hexanediamine, 2,4-dimethyl-1,6-hexanediamine, 3,3-dimethyl-1,6-hexanediamine, 2,2-dimethyl-1,6-hexanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 2,4-diethyl-1,6-hexanediamine, 2,2-dimethyl-1,7-heptanediamine, 2,3-dimethyl-1,7-heptanediamine, 2,4-dimethyl-1,7-heptanediamine, 2,5-dimethyl-1,7-heptanediamine, 2-methyl-1,8-octanediamine, 3-methyl-1,8-octanediamine, 4-methyl-1,8-octanediamine, 1,3-dimethyl-1,8-octanediamine, 1,4-dimethyl-1,8-octanediamine, 2,4-dimethyl-1,8-octanediamine, 3,4-dimethyl-1,8-octanediamine, 4,5-dimethyl-1,8-octanediamine, 2,2-dimethyl-1,8-octanediamine, 3,3-dimethyl-1,8-octanediamine, 4,4-dimethyl-1,8-octanediamine, and 5-methyl-1,9-nonanediamine.

3. A preparation method of the in situ polymerized flame retardant according to claim 1 , comprising the following steps: weighing the diacid monomer A, the diamine monomer B, a catalyst, and deionized water into a high-temperature high-pressure reactor, after gas aerating and exchange to make atmosphere in the reactor as nitrogen, heating up to 160 to 180° C., reacting at a constant temperature for 0.5 hours, continuing to heat up to 200 to 210° C., and reacting at a constant temperature for 0.5 hours, continuing to heat up to 240 to 250° C., reacting at a constant temperature for 1 hour, draining for about 0.5 hours and discharging to obtain the in situ polymerized flame retardant.

4. A polyamide molding composition composed of the in situ polymerized flame retardant according to claim 1 , wherein in parts by weight, the polyamide molding composition comprises the following components:
40 to 100 parts of a semi-aromatic polyamide; and
5 to 45 parts of the in situ polymerized flame retardant.

5. The polyamide molding composition according to claim 4 , wherein in a diacid monomer of the semi-aromatic polyamide, a content of terephthalic acid is 50 to 100 mol %; a diamine monomer of the semi-aromatic polyamide is selected from one or more of a diamine having 4 to 36 carbon atoms; the diamine having 4 to 36 carbon atoms is selected from at least one of 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,14-tetradecanediamine, 1,16-hexadecandiamine, 1,18-octadecanediamine, 1,36-trihexadecanediamine, and other linear aliphatic diamines; 1-butyl-1,2-ethylenediamine, 1,1-dimethyl-1,4-butanediamine, 1-ethyl-1,4-butanediamine, 1,2-dimethyl-1,4-butanediamine, 1,3-dimethyl-1,4-butanediamine, 1,4-dimethyl-1,4-butanediamine, 2,3-dimethyl-1,4-butanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 2,5-dimethyl-1,6-hexanediamine, 2,4-dimethyl-1,6-hexanediamine, 3,3-dimethyl-1,6-hexanediamine, 2,2-dimethyl-1,6-hexanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 2,4-diethyl-1,6-hexanediamine, 2,2-dimethyl-1,7-heptanediamine, 2,3-dimethyl-1,7-heptanediamine, 2,4-dimethyl-1,7-heptanediamine, 2,5-dimethyl-1,7-heptanediamine, 2-methyl-1,8-octanediamine, 3-methyl-1,8-octanediamine, 4-methyl-1,8-octanediamine, 1,3-dimethyl-1,8-octanediamine, 1,4-dimethyl-1,8-octanediamine, 2,4-dimethyl-1,8-octanediamine, 3,4-dimethyl-1,8-octanediamine, 4,5-dimethyl-1,8-octanediamine, 2,2-dimethyl-1,8-octanediamine, 3,3-dimethyl-1,8-octanediamine, 4,4-dimethyl-1,8-octanediamine, 5-methyl-1,9-nonanediamine, and other linear aliphatic diamines; diaminocyclohexane, methyl diaminocyclohexane, isophorondiamine, norbornane dimethylamine, tricyclodecane dimethylamine, and other alicyclic diamines.

6. The polyamide molding composition according to claim 4 , wherein for the semi-aromatic polyamide, when measured in 98% concentrated sulfuric acid at 25° C.±0.01° C., a relative viscosity of the semi-aromatic polyamide resin with a concentration of 10 mg/ml is 1.7 to 2.8.

7. The polyamide molding composition according to claim 4 , wherein in parts by weight, the polyamide molding composition further comprises at least one of a reinforcing fiber, a filler, an additive, and a processing aid.

8. The in situ polymerized flame retardant according to claim 1 , wherein the phosphorus aromatic ring-containing reactive flame-retardant diacid monomer is selected from [(6-oxido-6H-dibenzo-(c,e)(1,2)-oxaphosphorin-6-ketone)methyl]-butanedioic acid.

9. A preparation method of the in situ polymerized flame retardant according to claim 2 , comprising the following steps: weighing the diacid monomer A, the diamine monomer B, a catalyst, and deionized water into a high-temperature high-pressure reactor, after gas aerating and exchange to make atmosphere in the reactor as nitrogen, heating up to 160 to 180° C., reacting at a constant temperature for 0.5 hours, continuing to heat up to 200 to 210° C., and reacting at a constant temperature for 0.5 hours, continuing to heat up to 240 to 250° C., reacting at a constant temperature for 1 hour, draining for about 0.5 hours and discharging to obtain the in situ polymerized flame retardant.

10. A polyamide molding composition comprising the in situ polymerized flame retardant according to claim 5 , wherein in parts by weight, the polyamide molding composition comprises the following components:
40 to 100 parts of a semi-aromatic polyamide; and
5 to 45 parts of the in situ polymerized flame retardant.

11. The polyamide molding composition according to claim 6 , wherein for the semi-aromatic polyamide, when measured in 98% concentrated sulfuric acid at 25° C.±0.01° C., the relative viscosity of the semi-aromatic polyamide resin with the concentration of 10 mg/ml is 2.0 to 2.3.

Assignees

• Kingfa Science & Technology Co

Inventors

• Chang Huan
• Huang Xianbo
• Ye Nanbiao
• Cao Min
• Zhang Chuanhui
• Jiang Sujun
• Xie Mingchen
• Yan Kun
• Peng Zhongquan

Classifications

• C08L2205/025

  containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure · CPC title

• C08L2201/02

  Flame or fire retardant/resistant · CPC title

• C08L77/06

  Polyamides derived from polyamines and polycarboxylic acids (C08L77/10 takes precedence) · CPC title

• C08G69/42 Primary

  Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen (C08G69/12, C08G69/32 take precedence) · CPC title

• C08G69/265

  from at least two different diamines or at least two different dicarboxylic acids · CPC title