JPWO2020132075A5

JPWO2020132075A5 -

Info

Publication number: JPWO2020132075A5
Application number: JP2021535891A
Authority: JP
Publication date: 2022-11-30
Anticipated expiration: 2039-12-18

Claims

1. A process for preparing a phosphorus-containing flame retardant, comprising: preparing a mixture comprising a metal or suitable metal compound and a stoichiometric excess of unsubstituted or alkyl- or aryl-substituted phosphonic acid relative to said metal or said suitable metal compound. , reacting at a reaction temperature,
- said metal is capable of forming a polycation, or said suitable metal compound has the formula _Mp ⁽⁺⁾ _yXq , where M is a metal and (+)y is a metal cation where y is 2 or greater, X is an anion, and the values of p and q provide a charge-balanced metal compound);
- the molar ratio of said unsubstituted or alkyl- or aryl-substituted phosphonic acid to said metal or said suitable metal compound in said mixture is greater than 4:1;
- the reaction temperature is 105°C or higher;
- said unsubstituted or alkyl- or aryl-substituted phosphonic acid is in a molten state at said reaction temperature;
Method.

1. A process for preparing a phosphorus-containing flame retardant, comprising: preparing a mixture comprising a metal or suitable metal compound and a stoichiometric excess of unsubstituted or alkyl- or aryl-substituted pyrophosphonic acid relative to said metal or said suitable metal compound. , reacting at a reaction temperature,
- said metal is capable of forming a polycation, or said suitable metal compound has the formula _Mp ⁽⁺⁾ _yXq , where M is a metal and (+)y is a metal cation where y is 2 or greater, X is an anion, and the values of p and q provide a charge-balanced metal compound);
- the molar ratio of said unsubstituted or alkyl- or aryl-substituted pyrophosphonic acid to said metal or said preferred metal compound in said mixture is greater than 2:1;
- said unsubstituted or alkyl- or aryl-substituted pyrophosphonic acid is in a molten state at said reaction temperature;
Method.

2. The method of claim 1, wherein the reaction temperature is about 150[deg.]C or higher.

The method of claim 1, wherein said reaction temperature ranges from about 140°C to about 260°C.

3. The method of claim 2, wherein the reaction temperature is about 40[deg.]C or higher.

3. The method of claim 2, wherein the reaction temperature ranges from about 60°C to about 260°C.

5. The method of any one of claims 1, 3 and 4, wherein said molar ratio is 8:1 or greater.

8. The method of claim 7, wherein said molar ratio ranges from about 10:1 to about 50:1.

7. The method of any one of claims 2, 5 and 6, wherein said molar ratio is 4:1 or greater.

10. The method of claim 9, wherein said molar ratio ranges from about 5:1 to about 25:1.

3. The method of claim 1 or 2, wherein the mixture comprises metals capable of forming 2+, 3+ or 4+ polycations.

The mixture has the formula M _p ^(+)y X _q (where M is a metal, (+)y represents the charge of the metal cation, y is 2, 3 or 4, and X is an anion). 3. The method of claim 1 or 2, comprising a suitable metal compound represented by , where the values of p and q provide a charge-balanced metal compound.

13. The method of claim 12, wherein y is three.

14. The method of claim 13, wherein M is selected from Al, Ga, Sb, Fe, Co, B, and Bi.

15. The method of claim 14, wherein M is Al or Fe.

4. The claim wherein said reaction mixture comprises said suitable metal compound, said suitable metal compound being selected from metal oxides, halides, alkoxides, hydroxides, carbonates, carboxylates, or phosphonates. The method according to 1 or 2.

17. The method of claim 16, wherein M in the formula _Mp ^(+)yXq _is Al.

The suitable metal compounds are alumina, aluminum trichloride, aluminum trihydroxide, aluminum isopropoxide, aluminum carbonate, aluminum acetate, iron(III) oxide, iron(III) chloride, iron(III) isopropoxide, and 18. The method of claim 17, selected from iron(III) acetate.

wherein said unsubstituted or alkyl- or aryl-substituted phosphonic acid is represented by formula (I)

(wherein R is H, C _1-12 alkyl, C _6-10 aryl, C _7-18 alkylaryl, or C _7-18 arylalkyl, and said alkyl, aryl, alkylaryl, or arylalkyl is , unsubstituted or substituted with halogen, hydroxyl, amino, C _1-4 alkylamino, di-C _1-4 alkylamino, C _1-4 alkoxy, carboxy or C _2-5 alkoxycarbonyl)
2. The method of claim 1, represented by:

Said unsubstituted or alkyl- or aryl-substituted pyrophosphonic acid has the formula (Ia)

(wherein R is H, C _1-12 alkyl, C _6-10 aryl, C _7-18 alkylaryl, or C _7-18 arylalkyl, and said alkyl, aryl, alkylaryl, or arylalkyl is , unsubstituted or substituted with halogen, hydroxyl, amino, C _1-4 alkylamino, di-C _1-4 alkylamino, C _1-4 alkoxy, carboxy or C _2-5 alkoxycarbonyl)
3. The method of claim 2, represented by:

21. The method of claim 19 or 20, wherein R is unsubstituted C _1-12 alkyl, C ₆ aryl, C _7-10 alkylaryl, or C _7-10 arylalkyl.

22. The method of claim 21, wherein R is unsubstituted C _1-6 alkyl.

21. The method of claim 19 or 20, wherein R is methyl, ethyl, propyl, isopropyl, butyl, or t-butyl.

24. A phosphorus-containing flame retardant produced according to the method of any one of claims 1 to 23, wherein the empirical formula (III)

(In the formula,
R is H, an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group;
M is a metal and y is 2 or 3, thus M ^(+)y (where (+)y represents the charge formally imparted to the cation) is a metal cation;
a, b, and c represent the proportions of mutually corresponding components in the compound and satisfy the charge balance equation 2(a)+c=b(y);
c is not zero)
A phosphorus-containing flame retardant, comprising a compound of

25. The phosphorus-containing flame retardant of claim 24, wherein y is 3, a is 1, b is 1, and c is 1.

26. A flame retardant polymer composition comprising (i) a polymer and (ii) a phosphorus-containing flame retardant according to claim 24 or 25.

the polymer comprises one or more of polyolefin homopolymers or copolymers, rubbers, polyesters, epoxy resins, polyurethanes, polysulfones, polyimides, polyphenylene ethers, styrene polymers or copolymers, polycarbonates, acrylic polymers, polyamides, or polyacetals; 27. The flame retardant polymer composition of claim 26.

28. The flame retardant polymer composition of claim 27, wherein the polymer comprises one or more of styrene polymers or copolymers, polyolefin homopolymers or copolymers, polyesters, polycarbonates, acrylic polymers, epoxy resins, polyamides, or polyurethanes. thing.

29. The flame retardant polymer composition of Claim 28, wherein the polymer comprises polyalkylene terephthalate, high impact polystyrene (HIPS), epoxy resin, or polyamide.

30. The flame retardant polymer composition of Claim 29, wherein the polymer comprises a glass-filled polyalkylene terephthalate, a glass-reinforced epoxy resin, or a glass-filled polyamide.

30. The flame retardant polymer composition of claim 29, wherein said polymer comprises polyphthalamide.

30. The flame retardant polymer composition of Claim 29, wherein the polymer comprises polyamide 46, polyamide 6, polyamide 66, polyamide 4T, or polyamide 9T.

wherein the polymer is polyamide MXD,6, polyamide 12,T, polyamide 10,T, polyamide 6,T/6,6, polyamide 6,T/D,T, polyamide 6,6/6,T/6,I, 30. The flame-retardant polymer composition of claim 29, comprising polyamide 6/6,T or polyamide 6,T/6,I.

The polymer is polyphenylene ether/styrene resin blend, acrylonitrile butadiene styrene (ABS), polyvinyl chloride/ABS blend, methacrylonitrile/ABS blend, α-methylstyrene containing ABS, polyester/ABS, polycarbonate/ABS, impact resistant 27. The flame retardant polymer composition of claim 26, comprising modified polyester or impact modified polystyrene.

35. The flame-retardant polymer composition of any one of claims 26-34, further comprising (iii) one or more compounds selected from additional flame retardants, synergists, and auxiliary flame retardants. .

The one or more compounds are halogenated flame retardants, alkyl or aryl phosphine oxides, alkyl or aryl polyphosphine oxides, alkyl or aryl phosphates, alkyl or aryl phosphonates, alkyl or aryl phosphinates, salts of alkyl or aryl phosphinic acids , carbon black, graphite, carbon nanotubes, siloxane, polysiloxane, polyphenylene ether, melamine, melamine derivatives, melamine condensation products, melamine salts, metal hydroxides, metal oxides, metal oxide hydrates, metal borates , metal carbonates, metal sulfates, metal phosphates, metal phosphonates, metal phosphites, metal hypophosphites, metal silicates, and mixed metal salts. A flame retardant polymer composition as described.

The one or more compounds are aluminum tris(dialkylphosphinate), aluminum hydrogen phosphite, benzylphosphine oxide, polybenzylphosphine oxide, melam, melem, melon, melamine phosphate, melamine metal phosphate, melamine cyanurate, melamine Borate, talc, clay, calcium silicate, aluminosilicate, aluminosilicate as hollow tube, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, boron phosphate, calcium molybdate, exfoliated vermiculite, zinc stannate, Zinc hydroxystannate, zinc sulfide, zinc borate, zinc molybdate, zinc phosphate, magnesium oxide, magnesium hydroxide, aluminum oxide, aluminum oxide hydroxide, aluminum trihydrate, silica, tin oxide, antimony oxide (III and V), antimony (III and V) oxide hydrates, titanium oxide, zinc oxide, zinc oxide hydrate, zirconium oxide, and zirconium hydroxide. thing.

The one or more compounds are aluminum tris(dimethylphosphinate), aluminum tris(diethylphosphinate), aluminum tris(dipropylphosphinate), aluminum tris(dibutylphosphinate), methylene diphenylphosphine oxide substituted polyaryl ether , xylylenebis(diphenylphosphine oxide), 1,2-bis-(9,10-dihydro-9-oxy-10-phosphaphenanthrene-10-oxide)ethane, 4,4'-bis(diphenylphosphinylmethyl) 38. The flame retardant polymer composition of claim 37, selected from -1,1'-biphenyl, melam, melem, melon, and dimelamine zinc pyrophosphate.

27. The flame-retardant polymer composition of Claim 26, further comprising one or more compounds selected from hydrotalcite clays, metal borates, metal oxides, and metal hydroxides.

40. The flame retardant polymer composition of claim 39, wherein the metal of said metal borates, metal oxides and metal hydroxides is zinc or calcium.

The one or more compounds are melam, melem, melon, melamine cyanurate, melamine polyphosphate, melamine poly(metal phosphate), poly-[2,4-(piperazin-1,4-yl)-6-( 36. The flame retardant polymer composition of claim 35, selected from morpholin-4-yl)-1,3,5-triazine]/piperazine, aluminum hypophosphite, and aluminum diethylphosphinate.

The one or more compounds are zinc borate, zinc stannate, polysiloxane, kaolin, silica, magnesium hydroxide, zinc molybdate complex, zinc molybdate/magnesium hydroxide complex, zinc molybdate/silicic acid 36. The flame retardant polymer composition of claim 35, selected from magnesium complexes, calcium/zinc molybdate complexes, zinc phosphate complexes, and melamine-poly(zinc phosphate).

The one or more compounds are melam and zinc borate, zinc stannate, zinc molybdate complex, zinc molybdate/magnesium hydroxide complex, zinc molybdate/magnesium silicate complex, calcium molybdate. 36. The flame retardant polymer composition of claim 35, comprising any one or more materials selected from /zinc complexes, zinc phosphate complexes, and zinc oxide.

The one or more compounds are melon and zinc borate, zinc stannate, zinc molybdate complex, zinc molybdate/magnesium hydroxide complex, zinc molybdate/magnesium silicate complex, calcium molybdate 36. The flame retardant polymer composition of claim 35, comprising any one or more materials selected from /zinc complexes, zinc phosphate complexes, and zinc oxide.

Empirical formula (IIIa)

(wherein R is H, an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group)
flame-retardant materials, including compounds of

46. The flame retardant material of claim 45, wherein R is H or alkyl.

46. The flame retardant material of claim 45, wherein R is C _1-6 alkyl.

46. The flame retardant material of claim 45, wherein R is methyl or ethyl.

46. The flame retardant material of claim 45, wherein R is methyl.

50. Flame retardant material according to any one of claims 45 to 49, wherein the compound of empirical formula (IIIa) constitutes at least 75% by weight of the flame retardant material.

51. Flame retardant material according to claim 50, wherein the compound of empirical formula (IIIa) constitutes at least 90% by weight of the flame retardant material.

52. A flame retardant polymer composition comprising (i) a polymer and (ii) a flame retardant material according to any one of claims 45-51.

52. A method of increasing the flame retardancy of a polymer, comprising combining the flame retardant material of any one of claims 45-51, optionally with one or more additional flame retardants, synergists or flame retardants. A method comprising the step of incorporating into a polymer resin together with an adjuvant.

26. A method of increasing the flame retardancy of a polymer, comprising the phosphorus-containing flame retardant material according to claim 24 or 25, optionally together with one or more additional flame retardants, synergists, or auxiliary flame retardants. , the method comprising the step of incorporating into a polymer resin.

Empirical formula (III)

(In the formula,
R is H, an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group;
M is a metal and y is 2 or 3, so M ^(+)y(+)y (wherein (+)y represents the charge formally imparted to the cation) is a metal cation;
a, b, and c represent the proportions of mutually corresponding components in the compound and satisfy the charge balance equation 2(a)+c=b(y);
c is not zero)
A crystalline compound of

56. The crystalline compound of claim 55, wherein y is 3.

56. The crystalline compound of claim 55, wherein M is aluminum or iron.

R is unsubstituted C _{1～61 to 6} 58. The crystalline compound of any one of claims 55-57, which is alkyl.

59. The crystalline compound of claim 58, wherein R is methyl or ethyl.