METHOD FOR PRODUCING FLAME RETARDANT POLYURETHANE FOAMS USING HALOGEN-FREE FLAME RETARDANTS

• US 20170306122A1
• Filed: 11/18/2015
• Published: 10/26/2017
• Est. Priority Date: 11/18/2014
• Status: Active Grant

• Current Assignee: Covestro Deutschland AG
• Original Assignee: Covestro Deutschland AG
• Inventors: Meyer-Ahrens, Sven, Reiter, Stephan, Cavlan, Engin, Gossner, Matthus
• Granted Patent: US 10,563,032 B2
• Time in Patent Office: Days
• CPC Class Codes: C07F 9/12 with hydroxyaryl compounds
• CPC Class Codes: C08G 18/4837 and other oxyalkylene units
• CPC Class Codes: C08G 18/4866 having a low unsaturation value
• CPC Class Codes: C08G 18/7621 being toluene diisocyanate including isomer mixtures
• CPC Class Codes: C08G 2101/00 Manufacture of cellular products
• CPC Class Codes: C08G 2110/0008 flexible
• CPC Class Codes: C08G 2110/005 < 50kg/m3
• CPC Class Codes: C08G 2110/0083 prepared using water as the sole blowing agent
• CPC Class Codes: C08J 2205/06 Flexible foams
• CPC Class Codes: C08J 2375/04 Polyurethanes
• CPC Class Codes: C08J 9/0038 containing phosphorus
• CPC Class Codes: C08K 5/0066 Flame-proofing or flame-retarding additives
• CPC Class Codes: C08K 5/523 with hydroxyaryl compounds
• CPC Class Codes: C08L 75/04 Polyurethanes
• CPC Class Codes: C09K 21/12 containing phosphorus

Abstract

The present invention relates to a process for producing flame-retarded polyurethane foams, in particular flexible polyurethane foams, using halogen-free flame retardants, wherein the resulting flame-retarded polyurethane foams exhibit low emission values coupled with good mechanical properties. The present invention further relates to halogen-free flame retardants.

Claims

1. A process for producing polyurethane foams comprising preparing a reaction mixture comprising a component comprising

a) at least one compound which comprises isocyanate--reactive hydrogen atoms,

b) water and/or a physical blowing agent,

c) auxiliary and additive substances,

d) at least one halogen-free flame retardant comprising

d.1) a phosphoric ester corresponding to formula (I)

2. The process as claimed in claim 1, wherein component a) comprises at least one compound which comprises isocyanate-reactive hydrogen atoms and has a hydroxyl number according to DIN 53240 of ≧

5 mg KOH/g to ≦

250 mg KOH/g.

3. The process as claimed in claim 1, wherein the halogen-free flame retardant d) comprises a compound d.1) corresponding to formula (I), wherein m represents 3, one of the radicals R₁, R₂, R₃, R₄ or R₅ is a C₆- to C₁₂-aryl radical or C₂H₂Ph radical and the remaining radicals represent a hydrogen atom, or wherein m represents an integer of 1 to 3, R₁, R₃ and R₅ are identical and each represent a C₅- to C₁₂-aryl radical or C₂H₂Ph radical, and R₂ and R₄ each represent a hydrogen atom, or a compound d.2) corresponding to formula (II), wherein n represents an integer from 1 to 4, and one of the radicals R₆, R₇, R₈, R₉ or R₁₀ is selected from the group consisting of a hydrogen atom, a straight chain, branched or cyclic C₁- to C₁₀-alkyl radical, a C₅- to C₁₂-aryl radical, a C₂H₂Ph radical, an O-alkyl radical having C₁ to C₅-carbon atoms, and an O-aryl radical having C₆ to C₁₂-carbon atoms or COOR₁₁ wherein R₁₁ represents a C₁- to C₅-alkyl radical, and the remaining radicals R₆, R₇, R₈, R₉ or R₁₀ represent a hydrogen atom.

4. The process as claimed in claim 1, wherein the halogen-free flame retardant d) comprises a compound d.1) corresponding to formula (I), wherein m is an integer from 1 to 3, R₁, R₃ and R₅ are identical and each represent a C₆-aryl radical or a C₂H₂Ph radical and R₂ and R₄ represent a hydrogen atom, or a compound d.2) corresponding to formula (II), wherein n represents an integer from 1 to 4, and one of the radicals R₆, R₇, R₈, R₉ or R₁₀ is selected from the group consisting of a hydrogen atom, a straight-chain, branched or cyclic C₁- to C₆-alkyl radical, a C₆-aryl radical, a C₂H₂Ph radical, an O-alkyl radical having C₁ to C₃-carbon atoms, and an O-aryl radical having C₆-carbon atoms or COOR₁₁ wherein R₁₁ represents a C₁- to C₃-alkyl radical, and the remaining radicals R₆, R₇, R₆, R₉ or R₁₀ represent a hydrogen atom.

5. The process as claimed in claim 1, wherein the halogen-free flame retardant d) comprises a compound d.1) corresponding to formula (I), wherein m is an integer from 1 to 3, R₁, R₃ and R₅ are identical and each represent a C₆- to C₁₂-aryl radical, or C₂H₂Ph radical and R₂ and R₄ represent a hydrogen atom, or a compound d.2) corresponding to formula (II), wherein n represents an integer from 1 to 2, one of the radicals R₆, R₇, R₈, R₉ or R₁₀ is selected from the group consisting of a hydrogen atom, an O-alkyl radical having C₁ to C₅-carbon atoms, or COOR₁₁ wherein R11 represents a C₁- to C₅-alkyl radical, and the remaining radicals R₆, R₇, R₈, R₉ or R₁₀ represent a hydrogen atom.

6. The process as claimed in claim 1, wherein the halogen-free flame retardant d) comprises a compound d.1) corresponding to formula (I), wherein m is an integer from 1 to 3, R₁, R₃ and R₅ are identical and represent C₂H₂Ph radical and R₂, R₄ represent a hydrogen atom, or a compound d.2) corresponding to formula (II), wherein n represents an integer from 1 to 2 and the radicals R₆, R₇, R₈, R₉ or R₁₀ are identical and each represent a hydrogen atom.

7. The process as claimed in claim 1, wherein the halogen-free flame retardant d) comprises a mixture of compounds d.1) corresponding to formula (I), wherein represents an integer from 1 to 3, R₁, R₃ and R₅, are identical and represent C₂H₂Ph radical and R₂, R₄ represent a hydrogen atom or a compound d.2) corresponding to formula (II), wherein n represents an integer from 1 to 4, and the radicals R₆, R₇, R₈, R₉ or R₁₀ are identical and each represent a hydrogen atom.

8. The process as claimed in claim 1, wherein the halogen-free flame retardant d) comprises a compound d.1) corresponding to formula (I), wherein m is an integer from 1 to 3, R₁, R₃ and R₅ are identical and each represent C₂H₂Ph radical and R₂, R₄ each represent a hydrogen atom and wherein component d.1) is in the form of a mixture of compounds where m=3 in an amount of 20 to 26 wt %, where m=2 in an amount of 25 to 35 wt % and where m=1 in an amount of 45 to 55 wt %, or a compound d.2) corresponding to formula (II), wherein n represents an integer from 1 to 2 and the radicals R₆, R₇, R₈, R₉ or R₁₀ are identical and represent a hydrogen atom.

9. The process as claimed in claim 1, wherein per 100 parts by wt of component a), component b) is employed in an amount of 0.5 to 25 parts by wt, component c) is employed in an amount of 0.05 W to 10 parts by wt and component d) is employed in an amount of 1 to 30 parts by wt.

10. The process as claimed in claim 1, wherein production of the polyurethane foam is effected with an index of 50 to 250.

11. The process as claimed in claim 1, wherein an isomer mixture of 2,4- and 2,6-tolyiene diisocyanate is employed as component e).

12. A flame-retarded polyurethane foam obtainable by the process as claimed in claim 1.

13. The flame-retarded polyurethane foam as claimed in claim 12, wherein the polyurethane foam is a flexible polyurethane foam,

14. An article comprising polyurethane foam as claimed in claim 12 in the automobile, construction and/or furniture industries.

16. The article of claim 14, wherein said article comprise an automobile part, a construction part or a furniture part.

15. A flame retardant comprising d.1) phosphoric ester of formula (I)

17. The flame retardant of claim 15, comprising:

d.1) the phosphoric ester corresponding to formula (I) wherein;

m represents an integer from 1 to 3,

R₁, R₂, R₃, R₄, R₅ each independently represent a C₆ aryl radical, an O-alkyl radical having C₁ to C₃-carbon atoms, an O-aryl radical having C₆ carbon atoms, and/or COO₁₁ where R₁₁ represents a C₁ to C₃-alkyl radical,

and

wherein at least one of the radicals R₁, R₂, R₃, R₄, R₅ is distinct from hydrogen;

or

d.2) the phosphoric ester corresponding to formula (II)

wherein;

n represents an integer from 1 to 2,

R₆, R₇, R₈, R₉, R₁₀ each independently represent a straight-chain, branched or cyclic C₁- to C₆-alkyl radical, a C₆-aryl radical, an O-alkyl radical having C₁ to C₃-carbon atoms, an O-aryl radical having C₆-carbon atoms, and/or COOR₁₁ where R₁₁ represents a C₁ to C₃-alkyl radical.

18. The flame retardant of claim 15, comprising:

d.1) the phosphoric ester corresponding to formula (I) wherein;

m represents an integer from 1 to 3,

R₁, R₂, R₃, R₄, R₅ each independently represent an O-alkyl radical having C₁- carbon atoms, and/or COOR₁₁ where R₁₁ represents a C₁-alkyl radical,

and

wherein at least one of the radicals R₁, R₂, R₃, R₄, R₅ is distinct from hydrogen;

or

d.2) the phosphoric ester corresponding to formula (II) wherein;

n represents the integer 1,

R₆, R₇, R₈, R₉, R₁₀ each independently represent an O-alkyl radical having C₁-carbon atoms, and/or COOR₁₁ where R₁₁ represents a C₁-alkyl radical.