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CN-122029225-A - Flame retardant compositions with improved electrical properties and hydrolytic stability

CN122029225ACN 122029225 ACN122029225 ACN 122029225ACN-122029225-A

Abstract

Flame retardant compositions with improved electrical properties and hydrolytic stability, their use for polymers, and additional applications in electrical and electronic components. In particular, the flame retardant composition comprises an alkyl phosphinate, a hydroxyapatite and a carbodiimide, and optional components such as nitrogen-containing synergists, sterically hindered phenols and phosphorylated fatty acid esters.

Inventors

  • E. M. Leshner
  • S. Herold
  • SCHLOSSER ELKE

Assignees

  • 科莱恩国际有限公司

Dates

Publication Date
20260512
Application Date
20241016
Priority Date
20231030

Claims (13)

  1. 1. A flame retardant composition comprising: as component A, 40 to 99.9% by weight of phosphinates of the formula (I), Wherein the method comprises the steps of R 1 、R 2 , identical or different, are linear or branched C 1 -C 6 -alkyl, M is Mg, ca, al, sb, sn, ge, ti, zn, fe, zr, ce, bi, sr, mn, li, na, K and/or a protonated nitrogen base, M is 1 to 4; 0.1 to 30% by weight of hydroxyapatite as component B; as component C, from 0 to 50% by weight of a nitrogen-containing synergist selected from the group consisting of condensation products of melamine, reaction products of melamine with phosphoric acid, and melamine cyanurate; 1 to 10% by weight of a carbodiimide as component D; 0 to 10% by weight of a sterically hindered phenol as component E, and 0 To 50% by weight of a phosphorylated fatty acid ester as component F; Wherein the sum of the components is always 100% by weight.
  2. 2. The flame retardant composition of claim 1, wherein M is aluminum, calcium, titanium, zinc, tin, or zirconium.
  3. 3. The flame retardant composition of claim 1 or 2, wherein component B comprises 5 to 25 weight percent of the flame retardant composition.
  4. 4. The flame retardant composition of any of the preceding claims, wherein component C comprises 5 to 45 weight percent of the flame retardant composition, and wherein component C is selected from melamine cyanurate, melamine polyphosphate, and melem.
  5. 5. The flame retardant composition of claim 1, wherein component D is a polymeric carbodiimide.
  6. 6. The flame retardant composition of any of the preceding claims, wherein component E comprises from 1 to 10 weight percent of the flame retardant composition.
  7. 7. The flame retardant composition of claim 6, wherein component E is selected from pentaerythritol tetrakis (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), ethylene bis (oxyethylene) bis (3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate), and ethylene glycol bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate ].
  8. 8. A flame retardant composition according to any preceding claim wherein component F comprises from 5 to 45% by weight of the flame retardant composition.
  9. 9. The flame retardant composition of claim 8, wherein component F comprises an alkylated triphenyl phosphate and glyceride based ester.
  10. 10. A flame retardant polymer composition comprising the flame retardant composition of any of the preceding claims and a thermoplastic polymer P, wherein the flame retardant composition comprises 2 to 50 wt% of the flame retardant polymer composition.
  11. 11. The flame retardant polymer composition according to claim 10, comprising: 5 to 50 wt% of the flame retardant composition of any of claims 1-9; 50 to 98% by weight of a thermoplastic polymer P, and 0 To 40% by weight of reinforcing agents or fillers R.
  12. 12. The flame retardant polymer composition according to claim 11, wherein the thermoplastic polymer P is selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, poly-1, 4-cyclohexanedimethanol terephthalate, polyhydroxybenzoates, block polyether esters derived from polyethers having hydroxyl end groups, and polyesters modified with polycarbonates or methacrylate-butadiene-styrene.
  13. 13. Use of the flame retardant polymer composition according to any of claims 10-12 in or for plug connectors, current carrying components in power supply distributors (residual current protection), circuit boards, potting compounds, plug connectors, circuit breakers, lamp housings, LED housings, capacitor housings, coil elements and ventilators, ground contacts, plugs, housings for use in/on printed circuit boards, plugs, flexible circuit boards, engine hoods or textile coatings, in particular for various cables, cable jackets or cable insulations.

Description

Flame retardant compositions with improved electrical properties and hydrolytic stability Technical Field The present invention relates to flame retardant compositions having improved electrical properties and hydrolytic stability, their use for polymers, and flame retardant polymers comprising the flame retardant compositions. Background To meet the industrial flame retardancy requirements, one or more flame retardants are typically incorporated into the polymeric material. In modern formulations, non-halogenated flame retardant systems are often favored due to their ability to produce low smoke density and less toxic smoke compositions during combustion, as well as other environmentally advantageous features. Among non-halogenated flame retardants, salts of phosphinic acids (also known as phosphinates) have been established as particularly effective flame retardants, especially in thermoplastic polymer applications, as disclosed in DE-A-2252258 and DE-A-2447727. Nevertheless, the high concentrations of phosphinate flame retardants in thermoplastic polymers, which are necessary to ensure satisfactory flame resistance, may inadvertently affect the stability of the flame-retardant polymer during melt processing of the polymer at high temperatures due to the reactivity of these flame retardants. To counteract this adverse effect, synergistic combinations of phosphinates with specific nitrogen-containing compounds (most notably melamine derivatives) have been established. These combinations have shown enhanced flame retardant efficacy in various polymers, exceeding the performance of phosphinates used alone, as mentioned in WO 2002/28953 A1, DE 197 34 437 A1 and DE 197 37 727 A1. U.S. Pat. No. 7,420,007 B2 discloses compositions of dialkylphosphinic salts containing small amounts of selected telomers, which exhibit excellent applicability as polymeric flame retardants. After incorporating the telomer-containing flame retardant into the polymer matrix, the resulting polymer undergoes only a negligible degree of degradation. Furthermore, WO 2014/135256 A1 discloses polyamide compositions comprising salts of dialkylphosphinic salts and phosphorous acid, which notably achieve improved thermal stability, reduced migration tendency and good electrical and mechanical properties. In view of the wide range of applications of flame retardant polymer compositions in industrial environments, there remains a continuing need to design new synergistic combinations of phosphinate flame retardants and their synergist(s). Such synergistic combinations should be aimed at producing polymers featuring enhanced flame retardancy, good electrical and mechanical properties, and long lasting hydrolytic stability under humid conditions. It is therefore an object of the present invention to provide novel phosphinate-containing flame retardant compositions to help obtain flame retardant polymers having the above-mentioned property profile. Disclosure of Invention The present invention provides a flame retardant composition comprising: 40 to 99.9% by weight of phosphinate of the formula (I) as component A Wherein the method comprises the steps of R 1、R2, identical or different, are linear or branched C 1-C6 -alkyl, M is Mg, ca, al, sb, sn, ge, ti, zn, fe, zr, ce, bi, sr, mn, li, na, K and/or a protonated nitrogen base, M is 1 to 4; 0.1 to 30% by weight of hydroxyapatite as component B; As component C, from 0 to 50% by weight of a nitrogen-containing synergist selected from the group consisting of condensation products of melamine, reaction products of melamine with phosphoric acid and melamine cyanurate; 0 to 10% by weight of a carbodiimide as component D; 0 to 10% by weight of a sterically hindered phenol as component E, and 0 To 50% by weight of a phosphorylated fatty acid ester as component F; wherein the sum of the components is always 100% by weight. Component a generally comprises 50 to 95 wt%, preferably 55 to 90 wt% of the flame retardant composition. M is preferably aluminum, calcium, titanium, zinc, tin or zirconium, more preferably aluminum. R 1 and R 2 are identical or different and are preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl and/or isohexyl. A particularly preferred example of component A) is Al diethylphosphinate. Other examples of component a) include ethylbutylphosphinate, dibutylphosphinate, ethylhexyl phosphinate, butylhexylphosphinate, ethyloctylphosphinate, sec-butylethylphosphinate, (1-ethylbutyl) butylphosphinate, ethyl (1-methylpentyl) phosphinate, di-sec-butylphosphinate (di-1-methylpropylphosphinate), propyl (hexyl) phosphinate, dihexylphosphinate, hexyl (nonyl) phosphinate, and dinonylphosphinate. The hydroxyapatite component B generally comprises from 0.1 to 30 wt%, preferably from 5 to 25 wt%, more preferably from 5 to 15 wt% of the flame retardant composition. Hydroxyapatite, sometimes referred to in the art as "HAp", is a naturally occurring mi