HALOGEN-FREE FLAME RETARDANT THERMOPLASTIC POLYURETHANE ELASTOMER COMPOSITION AND PRODUCT AND FLAME RETARDANT PACKAGE THEREOF

• US 20190330449A9
• Filed: 09/30/2015
• Published: 10/31/2019
• Est. Priority Date: 09/29/2015
• Status: Active Grant

• Current Assignee: Wanhua Chemical Group Co., Ltd. (Wanhua Industrial Group Company Limited)
• Original Assignee: Wanhua Chemical Group Co., Ltd. (Wanhua Industrial Group Company Limited)
• Inventors: FU, Xiaoliang, HUANG, Qishan, ZHAI, Zhibin, YANG, Li
• Granted Patent: US 11,613,627 B2
• Time in Patent Office: Days
• CPC Class Codes: C08K 2003/322 Ammonium phosphate
• CPC Class Codes: C08K 2003/323 Ammonium polyphosphate
• CPC Class Codes: C08K 2003/324 Alkali metal phosphate
• CPC Class Codes: C08K 2003/325 Calcium, strontium or barium phosphate
• CPC Class Codes: C08K 2003/326 Magnesium phosphate
• CPC Class Codes: C08K 2003/327 Aluminium phosphate
• CPC Class Codes: C08K 2003/328 Phosphates of heavy metals
• CPC Class Codes: C08K 3/04 Carbon
• CPC Class Codes: C08K 3/32 Phosphorus-containing compounds
• CPC Class Codes: C08K 5/34922 Melamine; Derivatives thereof
• CPC Class Codes: C08K 5/34924 containing cyanurate groups; Tautomers thereof
• CPC Class Codes: C08K 5/521 Esters of phosphoric acids, e.g. of H3PO4
• CPC Class Codes: C08L 75/08 from polyethers
• CPC Class Codes: C09K 21/04 containing phosphorus
• CPC Class Codes: C09K 21/10 containing nitrogen
• CPC Class Codes: C09K 21/12 containing phosphorus

Abstract

A halogen-free flame retardant thermoplastic polyurethane elastomer composition and product and flame retardant package thereof comprised thermoplastic polyurethane and halogen-free flame retardant package. The halogen-free flame retardant comprises inorganic phosphorus-based flame retardant and can further comprise expandable graphite, melamine or derivatives thereof and organic phosphorus-based flame retardant. The composition is environmentally friendly and safe, the comprehensive mechanical properties thereof are excellent, does not drip during the burning test, passed UL94 with rating of V0−1.5 mm, and the limiting oxygen index thereof can be up to 35%.

Claims

1. A halogen-free flame retardant thermoplastic polyurethane elastomer composition comprising a thermoplastic polyurethane and a halogen-free flame retardant package comprising, based on the weight of the thermoplastic polyurethane:

Inorganic phosphorus-based flame retardant;

6-95 wt %;

Expandable graphite;

0-20 wt %;

Melamine or derivatives thereof;

0-65 wt %;

Organic phosphorus-based flame retardant;

0-45 wt %.

2. The halogen-free flame retardant thermoplastic polyurethane elastomer composition according to claim 1, characterized in that the halogen-free flame retardant package comprises, based on the weight of the thermoplastic polyurethane:

Inorganic phosphorus-based flame retardant;

6-95 wt %;

Expandable graphite;

1-20 wt %;

Melamine or derivatives thereof;

0-65 wt %;

Organic phosphorus-based flame retardant;

0-45 wt %.

3. The halogen-free flame-retardant thermoplastic polyurethane elastomer composition according to claim 1, characterized in that the halogen-free flame retardant package comprises, based on the weight of the thermoplastic polyurethane:

Inorganic phosphorus-based flame retardant;

6-95 wt %;

Expandable graphite;

0-20 wt %;

Melamine or derivatives thereof;

1-65 wt %;

Organic phosphorus-based flame retardant;

0-45 wt %.

4. The halogen-free flame-retardant thermoplastic polyurethane elastomer composition according to claim 1, characterized in that

the halogen-free flame retardant package comprises, based on the weight of the thermoplastic polyurethane:

Inorganic phosphorus-based flame retardant;

6-95 wt %;

Expandable graphite;

1-20 wt %;

Melamine or derivatives thereof;

1-65 wt %;

Organic phosphorus-based flame retardant;

0-45 wt %;

Preferably, the halogen-free flame retardant package comprises, based on the weight of the thermoplastic polyurethane;

Inorganic phosphorus-based flame retardant;

11-65 wt %;

Expandable graphite;

1-9 wt %;

Melamine or derivatives thereof;

8-50 wt %;

Organic phosphorus-based flame retardants;

5-35 wt %;

Further preferably, the halogen-free flame retardant package comprises, based on the weight of the thermoplastic polyurethane;

Inorganic phosphorus-based flame retardant;

18-45 wt %;

Expandable graphite;

3-7 wt %;

Melamine or derivatives thereof;

14-38 wt %;

Organic phosphorus-based flame retardant;

10-25 wt %.

5. The halogen-free flame-retardant thermoplastic polyurethane elastomer composition according to claim 1, characterized in that the inorganic phosphorus-based flame retardant is an inorganic phosphate and/or an inorganic hypophosphite;

preferably, the inorganic phosphate is selected from the group consisting of ammonium polyphosphate, triammonium pyrophosphate, ammonium pyrophosphate, magnesium ammonium phosphate, aluminum phosphate, magnesium phosphate, zinc phosphate, and a mixture of two or more thereof;

the inorganic hypophosphite is selected from the group consisting of lithium hypophosphite, sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, zinc hypophosphite, magnesium hypophosphite, iron hypophosphite, aluminum hypophosphite, lanthanum hypophosphite, yttrium hypophosphite, cerium hypophosphite, and a mixture of two or more thereof;

More preferably, the inorganic phosphorus-based flame retardant is selected from the group consisting of calcium hypophosphite, zinc hypophosphite, magnesium hypophosphite, iron hypophosphite, aluminum hypophosphite, lanthanum hypophosphite, yttrium hypophosphite, cerium hypophosphite, and a mixture of two or more thereof;

further the preferred is calcium hypophosphite and/or aluminum hypophosphite.

6. The halogen-free flame retardant thermoplastic polyurethane elastomer composition according to claim 1, characterized in that the organic phosphorus-based flame retardant has the structural formula of

7. The halogen-free flame-retardant thermoplastic polyurethane elastomer composition according to claim 1, characterized in that the initial expansion temperature of the expandable graphite is 200°

C to 800°

C, preferably 190°

C to 600°

C , further preferably 210 to 500°

C;

The average particle diameter of the expandable graphite is 5 μ

m to 150 μ

m, the expansion multiple of the expandable graphite is 20 to 500, preferably 25 to 100, and further preferably 30 to 250.

8. The halogen-free flame retardant thermoplastic polyurethane elastomer composition according to claim 1, characterized in that the melamine or derivatives thereof are melamine and/or melamine cyanurate, preferably melamine cyanurate.

9. The halogen-free flame-retardant thermoplastic polyurethane elastomer composition according to claim 1, characterized in that the weight-average molecular weight of the thermoplastic polyurethane is from 60,000 to 800,000, preferably from 90,000 to 450000;

its hardness is from Shore-A45 to Shore-D80, preferably from Shore-A65 to Shore-D54.

10. The halogen-free flame-retardant thermoplastic polyurethane elastomer composition according to claim 1, characterized in that the weight ratio of the halogen-free flame retardant package to the thermoplastic polyurethane elastomer in the composition is 0.06-1:

1, preferably 0.20-0.80;

1, further preferably 0.25-0.45;

1.

15. An article comprising the halogen-free flame retardant thermoplastic polyurethane elastomer composition of claim 1.

16. The halogen-free flame-retardant thermoplastic polyurethane elastomer composition according to claim 2, characterized in that the inorganic phosphorus-based flame retardant is an inorganic phosphate and/or an inorganic hypophosphite;

preferably, the inorganic phosphate is selected from the group consisting of ammonium polyphosphate, triammonium pyrophosphate, ammonium pyrophosphate, magnesium ammonium phosphate, aluminum phosphate, magnesium phosphate, zinc phosphate, and a mixture of two or more thereof;

the inorganic hypophosphite is selected from the group consisting of lithium hypophosphite, sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, zinc hypophosphite, magnesium hypophosphite, iron hypophosphite, aluminum hypophosphite, lanthanum hypophosphite, yttrium hypophosphite, cerium hypophosphite, and a mixture of two or more thereof;

More preferably, the inorganic phosphorus-based flame retardant is selected from the group consisting of calcium hypophosphite, zinc hypophosphite, magnesium hypophosphite, iron hypophosphite, aluminum hypophosphite, lanthanum hypophosphite, yttrium hypophosphite, cerium hypophosphite, and a mixture of two or more thereof;

further the preferred is calcium hypophosphite and/or aluminum hypophosphite.

17. The halogen-free flame-retardant thermoplastic polyurethane elastomer composition according to claim 3, characterized in that the inorganic phosphorus-based flame retardant is an inorganic phosphate and/or an inorganic hypophosphite;

preferably, the inorganic phosphate is selected from the group consisting of ammonium polyphosphate, triammonium pyrophosphate, ammonium pyrophosphate, magnesium ammonium phosphate, aluminum phosphate, magnesium phosphate, zinc phosphate, and a mixture of two or more thereof;

the inorganic hypophosphite is selected from the group consisting of lithium hypophosphite, sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, zinc hypophosphite, magnesium hypophosphite, iron hypophosphite, aluminum hypophosphite, lanthanum hypophosphite, yttrium hypophosphite, cerium hypophosphite, and a mixture of two or more thereof;

More preferably, the inorganic phosphorus-based flame retardant is selected from the group consisting of calcium hypophosphite, zinc hypophosphite, magnesium hypophosphite, iron hypophosphite, aluminum hypophosphite, lanthanum hypophosphite, yttrium hypophosphite, cerium hypophosphite, and a mixture of two or more thereof;

further the preferred is calcium hypophosphite and/or aluminum hypophosphite.

18. The halogen-free flame-retardant thermoplastic polyurethane elastomer composition according to claim 4, characterized in that the inorganic phosphorus-based flame retardant is an inorganic phosphate and/or an inorganic hypophosphite;

preferably, the inorganic phosphate is selected from the group consisting of ammonium polyphosphate, triammonium pyrophosphate, ammonium pyrophosphate, magnesium ammonium phosphate, aluminum phosphate, magnesium phosphate, zinc phosphate, and a mixture of two or more thereof;

the inorganic hypophosphite is selected from the group consisting of lithium hypophosphite, sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, zinc hypophosphite, magnesium hypophosphite, iron hypophosphite, aluminum hypophosphite, lanthanum hypophosphite, yttrium hypophosphite, cerium hypophosphite, and a mixture of two or more thereof;

More preferably, the inorganic phosphorus-based flame retardant is selected from the group consisting of calcium hypophosphite, zinc hypophosphite, magnesium hypophosphite, iron hypophosphite, aluminum hypophosphite, lanthanum hypophosphite, yttrium hypophosphite, cerium hypophosphite, and a mixture of two or more thereof;

further the preferred is calcium hypophosphite and/or aluminum hypophosphite.

19. The halogen-free flame retardant thermoplastic polyurethane elastomer composition according to claim 2, characterized in that the organic phosphorus-based flame retardant has the structural formula of

20. The halogen-free flame retardant thermoplastic polyurethane elastomer composition according to claim 3, characterized in that the organic phosphorus-based flame retardant has the structural formula of

11. A halogen-free flame retardant package comprising,

Inorganic phosphorus-based flame retardant:

6-95 parts by weight;

Expandable graphite;

0-20 parts by weight;

Melamine or derivatives thereof;

0-65 parts by weight;

Organic phosphorus-based flame retardants;

0-45 parts by weight.

12. The halogen-free flame retardant package according to claim 11, characterized in that the halogen-free flame retardant package comprises,

Inorganic phosphorus-based flame retardant:

6-95 parts by weight;

Expandable graphite;

1-20 parts by weight;

Melamine or derivatives thereof;

0-65 parts by weight;

Organic phosphorus-based flame retardants;

0-45 parts by weight.

13. The halogen-free flame retardant package according to claim 11, characterized in that the halogen-free flame retardant package comprises,

Inorganic phosphorus-based flame retardant:

6-95 parts by weight;

Expandable graphite;

0-20 parts by weight;

Melamine or derivatives thereof;

1-65 parts by weight;

Organic phosphorus-based flame retardants;

0-45 parts by weight.

14. The halogen-free flame retardant package according to claim 11, characterized in that the halogen-free flame retardant package comprises,

Inorganic phosphorus-based flame retardant:

6-95 parts by weight;

Expandable graphite;

1-20 parts by weight;

Melamine or derivatives thereof;

1-65 parts by weight;

Organic phosphorus-based flame retardant;

parts by weight;

Preferably, the halogen-free flame retardant package comprises,

Inorganic phosphorus-based flame retardant;

11-65 parts by weight;

Expandable graphite;

1-9 parts by weight;

Melamine or derivatives thereof;

8-50 parts by weight;

Organic phosphorus-based flame retardants;

5-35 parts by weight;

Further preferably, the halogen-free flame retardant package comprises,

Inorganic phosphorus-based flame retardant;

18-45 parts by weight;

Expandable graphite;

3-7 parts by weight;

Melamine or derivatives thereof;

14-38 parts by weight;

Organic phosphorus-based flame retardants;

10-25 parts by weight.