Composition comprising a thermoplastic polymer and a synergistic mixture of determined amino ethers and finely particled phosphinates

Abstract

Compositions containing, as component (A), a finely particled phosphinic acid salt of formula (I) and/or a finely particled diphosphinic acid salt of formula (II) and/or the polymers thereof, as component (B), an aminoether of formula (III), and as component (C), a thermoplastic polymer.

Claims

1. A composition comprising as component (A) a finely divided phosphinic acid salt of formula (I), diphosphinic acid salt of formula (II), and polymers thereof, ##STR00006## wherein R.sup.1, R.sup.2 are identical or different and are H, C.sub.1-C.sub.6-alkyl, linear or branched aryl or combinations thereof; R.sup.3 is C.sub.1-C.sub.10-alkylene, linear or branched, C.sub.6-C.sub.10-arylene, -alkylarylene or -arylalkylene; M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, a protonated nitrogen base or a combination thereof; m is 1 to 4; n is 1 to 4, x is 1 to 4, having a particle size d.sub.50 of less than 20 μm; as component (B) an amino ether of formula (III), ##STR00007## wherein n may be less than or equal to the number of carbon atoms in E and E is C.sub.1- to C.sub.1000000-alkyl or C.sub.5-C.sub.6-cycloalkyl, wherein the alkyl chain may comprise alkyl substituents, aromatic substituents and polar groups as substituents and may be interrupted by alkene units heteroatoms or a combination thereof; wherein G1 and G2 may be identical or different and independently of one another are hydrogen, halogen, NO.sub.2, cyano, CONR.sub.5R.sub.6, (R.sub.9)COOR.sub.4, C(O)—R.sub.7, OR.sub.8, SR.sub.8, NHR.sub.8, N(R.sub.18).sub.2, carbamoyl, di(C.sub.1-C.sub.18-alkyl)carbamoyl, C(═NR.sub.5)(NHR.sub.6), C.sub.1-C.sub.18-alkyl; C.sub.3-C.sub.18-alkenyl; C.sub.3-C.sub.18-alkynyl, C.sub.7-C.sub.9-phenylalkyl, C.sub.3-C.sub.12-cycloalkyl or C.sub.2-C.sub.12-heterocycloalkyl; C.sub.2-C.sub.18-alkyl interrupted by at least one O atom, by —NR.sub.5— or a combination thereof; C.sub.6-C.sub.10-aryl; phenyl oder naphthyl, in each case substituted with C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-alkylthio, halogen, cyano, hydroxy, carboxy, COOR.sub.21, C(O)—R.sub.22, C.sub.1-C.sub.4-alkylamino or di(C.sub.1-C.sub.4-alkyl)amino; or G1 and G2 together with the carbon atom to which they are bonded form a C.sub.3-C.sub.12-ring; T′ is hydrogen, a primary C.sub.1-C.sub.18-alkyl, a secondary C.sub.3-C.sub.18-alkyl, a tertiary C.sub.4-C.sub.18-alkyl or a phenyl group, each of which is unsubstituted or substituted with halogen, OH, COOR.sub.21 or C(O)—R.sub.22; or C.sub.5-C.sub.12-cycloalkyl or C.sub.5-C.sub.12-cycloalkyl interrupted by at least one O or —N(R.sub.18)—; or a polycyclic alkyl radical having 7 to 18 carbon atoms, or the identical radical interrupted by at least one —O— or —N(R.sub.18)—; or T′ is C-(G.sub.1)(G.sub.2)-T″; T″ is hydrogen, halogen, NO.sub.2, cyano or a monovalent organic radical having 1 to 50 carbon atoms; or T″ and T′ together form a divalent organic connecting group which, together with the sterically hindered amine nitrogen atom and the quaternary carbon atom substituted with G.sub.1 and G.sub.2, form an optionally substituted five- or six-membered ring structure, and R.sub.4 is hydrogen, C.sub.1-C.sub.18-alkyl, phenyl, an alkali metal ion or a tetraalkylammonium cation; R.sub.5 and R.sub.6 are independently of each other hydrogen, C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkyl substituted with hydroxy or, taken together, form a C.sub.2-C.sub.12-alkylene bridge or a C.sub.2-C.sub.12-alkylene bridge interrupted by —O—, —N(R.sub.18)— or a combination thereof; R.sub.7 is hydrogen, C.sub.1-C.sub.18-alkyl or C.sub.6-C.sub.10-aryl; R.sub.8 is hydrogen, C.sub.1-C.sub.18-alkyl or C.sub.2-C.sub.18-hydroxyalkyl; R.sub.9 is C.sub.1-C.sub.12-alkylene or a bond; R.sub.18 is C.sub.1-C.sub.12-alkyl or phenyl, unsubstituted or substituted by halogen, OH, COOR.sub.21 or C(O)—R.sub.22; R.sub.21 is hydrogen, an alkali metal atom or C.sub.1-C.sub.18-alkyl; R.sub.22 is C.sub.1-C.sub.18-alkyl; and as component (C) a thermoplastic polymer.

2. The mixture as claimed in claim 1, wherein R.sup.1, R.sup.2 are identical or different and are methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, phenyl or a combination thereof.

3. The mixture as claimed in claim 1, wherein R.sup.3 is methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene or n-dodecylene; phenylene or naphthylene; methylphenylene, ethylphenylene, tert-butylphenylene, methylnaphthylene, ethylnaphthylene or tert-butylnaphthylene; phenylmethylene, phenylethylene, phenylpropylene or phenylbutylene.

4. The mixture as claimed in claim 1, wherein the average particle size d50 of component (A) is less than 10 μm.

5. The mixture as claimed in claim 1, wherein the average particle size d50 of component (A) is less than 5 μm.

6. The mixture as claimed in claim 1, wherein E is C.sub.60- to C.sub.1000000-alkyl.

7. The mixture as claimed in claim 1, wherein in component (A) R.sup.1 and R.sup.2 are each ethylene.

8. The mixture as claimed in claim 1, wherein in component (A) M is aluminum.

9. The mixture as claimed in claim 1, wherein component B is a reaction product of a fatty acid 2,2,6,6-tetramethylpiperidin-4-yl-hexadecanoate and 2,2,6,6-tetramethylpiperidin-4-yl-octadecanoate with an oxidized polyethylene of the formula ##STR00008## wherein C.sub.15/17 are the main components and the alkyl radical at the N—O— has an average molecular weight of about 2000.

10. The mixture as claimed in claim 1, wherein the mixture comprises 0.2 to 10 wt % of component (A), 0.1 to 5 wt % of component (B) and 85 to 99.7 wt % of component (C).

11. The mixture as claimed in claim 1, wherein the mixture comprises 0.5 to 5 wt % of component (A), 0.2 to 2 wt % of component (B) and 93 to 99.3 wt % of component (C).

12. The mixture as claimed in claim 1, wherein the mixture comprises 0.2 to 2 wt % of component (A), 0.5 to 2 wt % of component (B) and 96 to 99.7 wt % of component (C).

13. The mixture as claimed in claim 1, wherein the thermoplastic polymer is a polyolefin.

14. The mixture as claimed in claim 1, wherein the mixture is processed into a transparent sheeting of 50-500 μm in thickness.

15. A molded article, film or fiber produced with the mixture as claimed in claim 1.

Description

EXAMPLES

Employed Inventive Materials

(1) Component A

(2) Exolit® OP 935, aluminum salt of diethylphosphinic acid, referred to hereinbelow as Depal d50 2-3 μm, particle size d95<10 μm, particle size d50 2-3 μm, Clariant, Frankfurt, DE

(3) Component B

(4) Hostavin® NOW: 2,2,6,6-tetramethylpiperidin-4-yl-hexadecanoate and 2,2,6,6-tetramethylpiperidin-4-yl-octadecanoate, reaction product with an oxidized polyethylene wax, Clariant, Frankfurt, DE, referred to hereinbelow as HALS-NO wax.

(5) Flamestab® NOR 116: 1,3-propanediamine, N,N″-1,2-ethandiylbis, reaction product with cyclohexane and the peroxidized N-butyl-2,2,6,6-tetramethyl-4-piperidinamine-2,4,6-trichloro-1,3,5-triazine reaction product, CAS No. 191680-81-6, from BASF, Ludwigshafen, DE

(6) Component C

(7) Sabic LDPE 2102 Z 500, low-density polyethylene, MFR 1.7-2.2 g/10 min, from Sabic, Geleen, the Netherlands, referred to hereinbelow as LDPE

(8) Comparator:

(9) Exolit® OP 1230, aluminum salt of diethylphosphinic acid, referred to hereinbelow as Depal d50 30 μm, particle size d95<100 μm, particle size d50 about 30 μm

(10) Aflammit® PCO 800: melamine salt of a phosphonic acid, Thor, Speyer, DE

(11) Mixing of the polymer (component C) and the additives (components A, B and others) was performed in an Arenz KL 1 single-screw extruder at a temperature of 180-210° C. at 100 rpm.

(12) The production of blown films of 200/400 μm in thickness was performed on a Collin BL 180/400 blown film line at 160-200° C.

(13) Determination of the low flammability of the sheetings was performed according to DIN 4102 B2 with test specimens having dimensions of 190*90 mm which are vertically clamped and subjected to flame exposure at their lower edge with 20 mm-high flames from a gas burner for 15 seconds. The test is passed if over a period of 20 seconds the tip of the flames does not reach a reference mark on the test specimens which is disposed at a distance of 150 mm from the flame-exposed lower edge.

(14) Table 1 shows the fire test results for the sheetings of 200 and 400 μm in thickness with Exolit OP 935 and Hostavin NOW alone (V1 and V2) and the inventive combinations of Exolit OP 935 and Hostavin NOW (B1-B3). The fire test DIN 4102 B2 is only passed for 200 and 400 μm with a combination of both products.

(15) TABLE-US-00001 TABLE 1 Fire tests according to DIN 4102 B2 on 200 and 400 μm LDPE sheetings. Examples V1 V2 B1 B2 B3 LDPE 98 98 98 98 98 HALS-NO wax 2 1 1.5 0.5 Depal d50 2-3 μm 2 1 0.5 1.5 DIN 4102 fire test 200 μm no no yes yes no DIN 4102 fire test 400 μm no no yes yes no

(16) TABLE-US-00002 TABLE 2 Comparator formulations Example B2 B3 V3 V4 V5 LDPE 98 98 98 HALS-NO 1.5 1.5 0.5 wax Flamestab 1.5 0.5 NOR 116 Aflammit 0.5 2.5 2.5 PCO 800 Depal d50 0.5 0.5 2-3 μm DIN 4102 yes yes no yes yes B2 200 μm transparency clear clear cloudy cloudy cloudy odor no unpleasant no no unpleasant color colorless yellowish colorless colorless yellowish

(17) Table 2 compares the inventive combination of finely divided phosphinate salt and amino ether with a combination of phosphonate and with an amino ether according to WO 2010/026230 (V3, V4, V5). Transparent sheetings are obtained only through the inventive combination of finely divided phosphinate with amino ether. Employing HALS-NO wax further prevents discoloration and unpleasant odor during processing.

(18) It is apparent from table 3 that only the combination of amino ether with finely divided phosphinate (B4, B5) affords transparent polyethylene sheetings.

(19) TABLE-US-00003 TABLE 3 Comparison of finely divided and normal particle size Depal Example V6 B4 V7 B5 V8 LDPE 100 98 98 98 98 HALS-NO wax 1 1 Flamestab NOR 116 1 1 Depal d50 3 μm* 1 1 Depal d50 30 μm** 1 1 % transmission 88 87 85 87 85 transparency (doubled) 66 63 59 66 59 DE*ab 0.03 0.33 0.76 0.29 0.81 Haze (D1003-97) © 16 16 20 16 35

(20) The haze number is a measure for clouding of the sheetings. The inventive combinations of NOR HALS with finely divided Depal show markedly lower clouding values compared to the comparative examples with normal Depal particle size. The sheetings with finely divided Depal further show improved mechanical properties (tensile test). The transparency of the sheetings with finely divided Depal is markedly higher than with standard material. DE*ab denotes the degree of discoloration compared to a white standard. The inventive examples show markedly reduced discoloration compared to the comparative examples. The use of finely divided Depal additionally has a positive effect on fire characteristics. While all four examples from table 3 meet the B2 classification, the sheetings with finely divided Depal show markedly shorter afterflame times and smaller destroyed regions.