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JP-7854942-B2 - Improved polyether ester

JP7854942B2JP 7854942 B2JP7854942 B2JP 7854942B2JP-7854942-B2

Inventors

  • エレーニ カライアンニ

Assignees

  • セラニーズ・ポリマーズ・ホールディング，インコーポレーテッド

Dates

Publication Date
20260507
Application Date
20210615
Priority Date
20200615

Claims (20)

  1. (1) At least one polymer selected from copolyether esters, polyamide elastomers, thermoplastic polyolefin elastomers, styrene elastomers, thermoplastic polyurethanes, and thermoplastic vulcanized products, (2) Aluminum diethylphosphinate ("DEPAl") , (3) Zinc diethylphosphinate ("DEPZn") and (4) A flame-retardant polymer composition comprising 2 to 20% by weight of a phosphate selected from aluminum phosphite, zinc phosphite, and mixtures thereof, wherein the weight percentage is based on the total weight of the composition.
  2. (1) at least one copolyether ester, (2) Aluminum diethylphosphinate ("DEPAl"), (3) Zinc diethylphosphinate ("DEPZn") and (4) A flame-retardant copolyether ester composition comprising 2 to 20% by weight of a phosphate selected from aluminum phosphite, zinc phosphite, and mixtures thereof, wherein the weight percentage is based on the total weight of the composition.
  3. The composition according to claim 1 or 2, wherein the copolyether ester is produced by reacting a C2 - C6 diol with an aromatic diacid moiety and a poly(alkylene oxide) diol.
  4. The composition according to any one of claims 1 to 3, wherein the copolyether ester is prepared using a poly(alkylene oxide) diol selected from poly(ethylene oxide) diol, poly(propylene oxide) diol, poly(tetramethylene oxide) diol ("PTMEG"), and a mixture of two or more thereof.
  5. The composition according to any one of claims 1 to 4, wherein the copolyether ester is prepared using a C2 - C6 diol selected from ethylene glycol, propylene glycol, butylene glycol, and mixtures of two or more thereof.
  6. The composition according to any one of claims 1 to 5, wherein the copolyether ester is prepared using an aromatic diacid selected from terephthalate, isoterephthalate, and mixtures thereof.
  7. The composition according to any one of claims 1 to 6, wherein the copolyether ester is made from butylene glycol , terephthalate, and PTMEG.
  8. The composition according to any one of claims 1 to 7, wherein the total amount of DEPAl and DEPZn is 5 to 40% by weight based on the total weight of the composition.
  9. The composition according to any one of claims 1 to 7 , comprising 5 to 20% by weight of DEPAl and 5 to 20% by weight of DEPZn based on the total weight of the composition.
  10. The composition according to any one of claims 1 to 7 , comprising 8 to 15% by weight of DEPAl and 8 to 15% by weight of DEPZn based on the total weight of the composition.
  11. The composition according to any one of claims 1 to 7 , comprising 8 to 15% by weight of DEPAl and 2 to 6% by weight of DEPZn based on the total weight of the composition.
  12. The composition according to any one of claims 1 to 7 , comprising 15 to 25% by weight of DEPAl and 15 to 25% by weight of DEPZn based on the total weight of the composition.
  13. A composition according to any one of claims 1 to 12, comprising aluminum phosphite [CAS56287-23-1].
  14. A composition according to any one of claims 1 to 12 , comprising zinc phosphite [CAS14332-59-3].
  15. A composition according to any one of claims 1 to 12 , comprising aluminum phosphite [CAS56287-23-1] and zinc phosphite [CAS14332-59-3].
  16. The composition according to any one of claims 1 to 15, wherein the total phosphate concentration is 20% by weight or less based on the total weight of the composition.
  17. The composition according to any one of claims 1 to 16, wherein the total phosphate concentration is 5 to 10% by weight based on the total weight of the composition.
  18. (1) at least one copolyether ester, (2) 5 to 20% by weight of aluminum diethylphosphinate (" DEPAl ") (3) 5-20% by weight of zinc diethylphosphinate (" DEPZn ") (4) A flame -retardant polymer composition comprising 2 to 10% by weight of a phosphate selected from aluminum phosphite [CAS56287-23-1], zinc phosphite [CAS14332-59-3] and mixtures thereof, wherein the weight percentage is based on the total weight of the composition .
  19. The composition according to any one of claims 1 to 18, having a Line of Influence (LOI) of 20 or more when measured using a test rod in the shape of a rectangular bar with dimensions of 125 mm in length and 13 mm in width, and an average thickness of approximately 1.7 ± 0.1 mm, in accordance with the test method ISO 4589-1/-2.
  20. The composition according to any one of claims 1 to 19, having a line of intake (LOI) of 23 or more when measured using a test rod in the shape of a rectangular bar with dimensions of 125 mm in length and 13 mm in width, and an average thickness of approximately 1.7 ± 0.1 mm, in accordance with the test method ISO 4589-1/-2.

Description

Cross-reference of related applications This application claims priority to U.S. Provisional Patent Applications No. 63/039,098, No. 63/039,133, and No. 63/039,171, filed on 15 June 2020 under Section 365 of the U.S. Patent Act, each of which is incorporated herein by reference in its entirety. This invention relates to copolyether esters, particularly to flame-retardant copolyether esters. Several patents, patent applications, and publications are referenced herein to provide a more detailed description of the context of the technical field to which this invention relates. The entire disclosures of each of these patents, patent applications, and publications are incorporated herein by reference. Copolyether esters are a group of elastomer polyesters having a hard segment containing polyester blocks and a soft segment containing long-chain polyetherdiols. They are widely used in applications requiring resilience and elasticity. Typical copolyether esters are produced by reacting one or more diacid moieties with short-chain diols and long-chain polyetherdiols. Copolyether esters exhibit excellent elasticity, maintenance of mechanical properties at low temperatures, and good fatigue performance. Non-halogenated flame retardants ("NHFR") copolyether esters are continuously in demand. Dialkylphosphinates are well-known non-halogenated flame retardant molecules. U.S. Patent No. 7,420,007 [Clariant Produkte (Deutschland) GmbH] describes formula (I): (In the formula, R1 and R2 are either the same or different, and are linear or branched C1 - C6 alkyl groups.) M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K, and/or a protonated nitrogen base, and m is 1 to 4. The use of dialkylphosphinates as flame retardants in numerous different polymers, such as polyether esters, is described. U.S. Patent Application Publication No. 2013/0190432 describes the use of aluminum diethylphosphinate in combination with an aluminum salt of phosphite as a flame retardant in nylon-6,6, nylon-6T/6,6, nylon-4,6, copolyether esters, and PBT. The use of flame retardants in polymer resins can significantly reduce flammability, but unfortunately, it can result in high smoke generation when exposed to heat or flames. This is a concern because smoke can significantly contribute to injury and mortality in fires. Definition and abbreviation: PBT Poly(butylene terephthalate) PTMEG Polytetramethylene ether glycol copolyether ester or TPC Thermoplastic elastomer resulting from the reaction of at least one diol, at least one diacid, and at least one poly(alkylene oxide) diol DEPAl Aluminum diethylphosphinate DEPZn Zinc diethylphosphinate phosphite As used herein, it is synonymous with “salt of phosphorous acid” or “salt of phosphonic acid” of aluminum and/or zinc. The inventors have surprisingly discovered that when a copolyether ester is combined with 2 to 16% by weight of a phosphate selected from DEPAl, DEPZn, and aluminum salts of phosphite, zinc salts of phosphite, and mixtures thereof, a composition with good flame retardancy and reduced smoke generation when exposed to heat and/or flame is obtained. The inventors have also surprisingly found that adding a phosphate selected from aluminum phosphite, zinc phosphite, and mixtures thereof to a flame-retardant copolyether ester composition containing DEPAl and DEPZn reduces smoke generation from the composition when exposed to heat and/or flame. DEPAl and DEPZn are well known for imparting flame retardancy to polymer formulations. The inventors have found that the addition of phosphate reduces smoke generation. Since the addition of phosphate appears to slightly reduce the flame retardancy imparted by DEPAl and DEPZn, the phosphate must be added in an amount that reduces smoke generation without excessively impairing flame retardancy. The inventors have found that adding 2 to 16% by weight of phosphate, based on the total weight of the composition, yields acceptable flame retardancy and smoke reduction. Copolyether esters suitable for the compositions of the present invention are polymers produced by reacting a C2 - C6 diol with an aromatic diacid moiety and a poly(alkylene oxide) diol. The poly(alkylene oxide)diol is preferably selected from poly(ethylene oxide)diol, poly(propylene oxide)diol, poly(tetramethylene oxide)diol ("PTMEG"), and mixtures thereof. Poly(propylene oxide)diol and poly(tetramethylene oxide)diol can be linear or branched. If they are branched at a terminal hydroxyl-containing carbon, they are preferably end-capped with ethylene glycol or poly(ethylene oxide)diol. Poly(propylene oxide)diol and poly(tetramethylene oxide)diol ("PTMEG") and mixtures thereof are particularly preferred, with PTMEG being particularly preferred. The C2 - C6 diol is preferably selected from ethylene glycol, propylene glycol, butylene glycol, and mixtures thereof, with butylene glycol being particularly preferred. The aromatic diacid is preferably selected from terephthalate, isote