DE1668328A1 - Process for stabilizing polymers - Google Patents

Description

f AtENTANWXLTt ^ w

DR-ING ₁ H. FlNCKE ^; βmunch «* _S , ^ A ft DIPL.-INQ, H. BOHR ΜΟΚ-Λαβ. «^ 1, 0. DIPL.-ING. S. STAEQER ■

Mapje 21606 - BrvK
Gases Β 20060

BES Ο HREIB IT K © M

to the godfather of

Company HiIERIAI GHEMIGAIi INDUSTHIBS ^^ LIMITES »iondoii S ₀ W ₀ 1, Qiroßbrltaniiiea

"Process aar S-teftilization of Bolymeren ¹ *

PRIORIf B? EK 5 17. ΜΜϊ »1967 tmd 8 · Mäws 1968

The invention relates to a method of improvement the stability of polymers against heat, calibration and oxidation »

According to the invention there is a method of stabilization

■ *

109836/1569

proposed by polymers, which is thereby carried out, that one in the said polymer a Phoephorigsäuremonoester of the formula

0 HO-P-H

where R represents an alkyl, alkenyl, cycloalkyl, aryl or aralkyl group, or a substituted derivative thereof »

The Phoephorigaäuremonoeter are also known, for example, as WaeeeratoffphoBphonate or alkyl phosphonic acids and can also be represented by the ionic RO-P (OH) ₂ . As far as the present invention is concerned, no dead flea is found between the two formulas. ^:

For example, natural polymers should be mentioned as polymers and synthetic guwai, polymers of diolefins, micropolymers from dielefins and from ethylene iso-unsaturated monomers, Polymers of ethylenically unsaturated compounds such as methyl methacrylate, vinyl chloride, acrylonitrile, vinylidene chloride and vinyl acetate, especially polyolefins such as polyethylene, polypropylene, poly-4 - «* thyipenten * 1 and copolymers of the same

109836/1569 bath

166832a

with other olefins, copolymers, vie ζ.B wobbled ₀ acrylonitrile / styrene Mieciipolyiasre, mi echpolymeri Aorylnitril / butadiene / StyroI resins ,, polyamides such "B _e polyhexamethylene adipamide, polyesters such as polyethylene terephthalate or PoIyphenylenterephthalat, polyurethanes and polyethers.

For example, all groups represented by R should be "rmähnt": methyl, ethyl, propyl, η-butyl, isoaayl, n-Heptyl, n-Oetyl, Lauryl, Allyl, Crotonyl, Cyclohexyl, Phenyl, Uaphtby !, lolyl »Φ-Ohlcaepnenyl, 4-lfethoiyphenyl, 2-tert» -butyl-5-methylphenyl, beneyl, t- ^ PoryliEthyl »3,5-3> i-tert-butyl-4-hydroxyüenjsyl, ^^ ydroacy - ^ - bönBOylpheiiyl, 5 * (ben2oyloxy) -phenylt 5 »^ - ^ i-tert.-bBtylphÄnyl, 2-hienylphenyl, 2-chloroethyl and 2,2-Id- (hydroxyethyl) -al] cyl, such as 2,2-di- (nydroxyaethyl) -butyl and analogs including those in which the alkyl group a long-chain alkyl group, and a * © ahXieBlich Derirete, as ■ .B. the AöylderiTate of the same; divalent groups, such as β.B. 2,2-Di- (hydroymethyl) -trine thyl * *, pnenylene, biphenylpropa «. (all can with ewei Phosphonearic residues Iraabiniert) and groups by Esterification of at least a part of the Hyäroaylgruppen in polyhydric alcohols such as s, B. GIy ο er in, pentaerythritol, Dipentaerythritol, sugar, phloroglucinol, 2,6-dihydroxymethyl-4-n-thylphenol and poly-vinyl alcohol can be obtained.

109836/1560

BATH ORIGINAL

The 2,2-di- (hydrox; ^ ethyl) -alkyl compounds and the derivatives of these mentioned above are members of one new bond class.

The phosphorous acid monoester can be incorporated into the polymer through ^ ede conventional procedures can be incorporated, for example by mixing the ester with the polymer in powder form and subsequent grinding, if necessary at elevated temperature; by adding a solution of the ester in a volatile Solvent to the polymer powder and subsequent evaporation of the solvent; through extrusion & ompondingi or by treating the polymer in 2Όηα of a yarn or Textiles with an aqueous suspension of the monoester, optionally together with the application of other finishes.

Suitable denominations of the monoesters are 0.005 to 5 percent by weight and equivalent ™ preferably 0.05 to 1 wt .- ^, based on the polymer ·

The stabilizing effect of the monoeter is found in many pollen

improved if you add sulfides to the polymer, such as e.g. Dilauryl- or Diootadecyldithiop: * opionate or -thio dibutyrate, Bi β-hydroxy aryl sulfide, wi <* ζ „Β. Bi8- (2-hydroxy-

5-methylbenzyl) sulfide, Bi beneyl) sulfide, a ^ '

Metalldialkyldithiophsophate, TriallqrltrithiophoBphite or BATH ORIGINAL

109836/1569

Phenols, such as ζ „Β. 2,6-di-tert-butyl-4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1,5,5-letra -kis- (5-tert-butyl-4-hydroxy-2-methylphenyl) -pentane, pentaerythrityl-β- (4-hydroxy-3,5-di-tert-butylphenyl) -propio- ^ a * f 1 »115 , 5-Tetra-kia- (3 ~ methyl-4-hydroxy-5-tert «butyl phenyl) pentane, 4,4 * -thiobl-C 3-methyl-6-tert-but: ylphenol), 1, 3> 5-Trimethyl-2,4,6-tris- ( 3 * * 5 * -di-tert-butyl-4-hydroxy "beneyl) -benEOl, Octadecyleetes? From β-3» 5-Bi-tert-T > ui: yl-4-hydroxyphenylpropionic acid and phenol / aldehyde condensates are incorporated.

Suitable amounts of these sulfides or phenols are zvdsohen 0.05 to 5 GeTO.- £ and Torsugeweiee between 0.1 to 0.5 Cfew · - $>, based on the polymer ·

Other customary additives can also be present in the polymers *, such as β.B. other stabilizers such as senstaiasol and dihydroanthraoene, antioxidants, crosslinking agents, Treibaittol, Weiohmaoher, fillers, lubricants, anti-static gowns, pigments, UV absorbents, e.g. 2-Hydroiybensophenone, 2-Hydroxyphenylbenetriazole, nickel complexes of compounds, such as, for example, Bialkyldithlocarbemate, Bis-phenol-sulfide, 2-hydroxyphenylketoxime and metal soaps.

The process according to the invention makes a more effective one Protection against degradation or discoloration caused by heat, Licnt

10S836 / 1569

or cause oxidation, go create. In particular, for example, polypropylene is protected against oxidation, in particular against oxidation catalyzed by ketallion ions, never copper or cobalt ions. Polyolefins with a higher melting point, such as, for example, poly-4-methylpentene-i, are stabilized against thermal degradation during melting and extrusion or during another deformation process. Furthermore, the tendency of the polymer or polymer composition, si discolor during processing or during 'the aging suppressed ·

The monoesters used in the process according to the invention can be produced in a wide variety of ways. For example, an alcohol or a phenol is reacted with PhoephortrichlorId, whereby a Blohlorphosphit is obtained, which is hydrolyzed, for example, by water sum Kemoester will; Bialkyl phosphites partially know la alkaline solution

<5i are hydrolyzed to obtain monoesters; Athy Lenoxyd (or another Alky learning oxy d) is introduced into Phoephertri-chloride, vad the Oichlorphoephit obtained is hydrolyzed by water, whereby the ß-Chloräthylmonoeter clay Phaophorigsäure is obtained; cyclic phosphites köaaea. In one or, if necessary, in other stages eu feydrolysiert the monoesters «heS? a. _v, for example, a bicyolisches Trimethylolfolkaapheephlt is suersi; «Um hydro ^ yaethylsubetitul ·» - '

BAD 108836 / ^ 5 6 ^

tan dimethyloIaIkanphoBphit and then hydrolyzed to the 2,2-dihydroxyxoethylalkylmonoester of phosphorous acid «

The invention is illustrated in more detail by the following examples. The examples are not in a restrictive sense to take ο All! Parts and percentages are given in weight printed out unless otherwise stated.

example 1

Stabilizers, as indicated in the following table, are dissolved in 5 parts of ethyl alcohol (or acetone) and 4-5 parts of trichlorotrifluoroethane are added. The LC solution is shown below of a powdered copolymer of 98 £ 4-methylpentene-1 and 2, f n-Deoen-1 sugegeben (prepared by the method of British Patent 1,001,801), "because ad · Geeisch is stirred at 50 ⁰ C until the entire LSsuneittel is removed

Hemogenisation line of Qealsohs obtained in the "catfish is an electrically geheiaten Press · ausgeftlhrt at 260 ⁰ C la, wherein separately 3 · pressings of one minute duration are carried out in each case. These mixtures are then combined into one

Tendon lsi »see r at 280 ⁰ C using a fluted τοη

Tested under -2 kg on the Stespel and a / standard nozzle, and dae

109836/1569

BATH ORIGINAL

*- 8th -

The weight of the polymer pressed out in one minute is determined at regular intervals / ^ tPminutsn A higher number indicates poorer melt stability and vice versa,

All of the above times around Chile also have a 5 minute duration Preheat period of the polymer in the knife before use the weight of 2 kg.

Stabilizer composition

Speed of extrusion per Hinute (g χ 10 ² ) after heating in the knife during

10 min «

O _p 25 $ antioxidant sold under the trademark "Irganox 1010" and 0.25 $> 2,2-dihydroxymethylbutyl ster of phosphorous acid

$ 0.25> Irganox 1010 and 0.25 1>2; 6-di-tert-butyl-4-n »thyl phenol

* $> Irganox 1010 and 0.25 diphenylisodecyl phosphite

2.20 3.3 5.3

15 min. 20 min.

2.40

8.5

6.6

2.54 25 8.7

The 2,2-dihydroxymethylbutyl monoester of phosphorous acid used above is prepared as follows:

302 parts of trimethylolpropane are ucter stirring to 309 parts of phosphorus trichloride, which is cooled to 0 ⁰ C were added. After 1.5 hours, the temperature is increased over a period of time from 5 hours to 70 ⁰ O and 12 hours at this value

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- Q -

held. Trimethylolpropane phosphite is isolated by distillation at room temperature between 110 and 1H ⁰ C under a pressure of 15 mm Hg. Upon standing, this material as colorless crystals, melting at 56 ⁰ C provides.

3.6 parts of water north at room temperature to 32.4 parts of trimethylolpropane specified, and the mixture is then heated for 1 hour at 70 ⁰ C, is removed whereupon jegliohea residual water by allowing to stand in a Vakuumexicator for 48 hours. The thus obtained 2,2-Dihydroxymethylbutylmonoester of phosphorous ^sa * »* · analysis contained gemäft 17 _f 1 $ phosphorus and 6.7 £ Waß3eratoff ;, the theoretical figures are 17.2 # 7.2 ^ phosphorus and hydrogen. The infrared spectrum showed absorption bands at 2.9 and 9 »5 μ, which are characteristic of hydroxymethyl groups, a sharp band at 4.15 n, which is inferior to the PH groups, and broad absorption bands in the vicinity of τβη 4 , 5, 6.0, 8.1 and 10.1 n which display phosphoric acid groups.

The stabilizers given in the table below are dissolved in a minimal amount of ethanol (or acetone) and diluted with trihydrofluoroethane. You on this

109838/1569

Solution thus obtained is added under stirring to PolypropylenpulYer "which is held in a container at 50 ⁰ G, and stirring is continued as long has been obtained until a homogeneous Hasse, which is free of solvents. This mixture is "yerpreßt in a steam heated press at 180 ⁰ C, so that disks τοη be obtained about 0.75 mm thickness. Piping plates are then baked in an air at 150 ⁰ C, which is equipped with a Zirkulationeventilator, aged, and the tent up to the beginning of embrittlement, which is determined by inspection, is determined. The results obtained are given below - they show the protective effect of the products according to the invention against a deterioration of polypropylene catalyzed by copper.

.BAD CFHGlNAI-

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Polypropylene

191.3 »Trie» (5 «tert · - buty 1- "" -hydroxy-2-r.3thylph "nyl) -butane

100

100

100

100

100

100

100

Ml * uiyldithiopropion * t 0.25 0.25 0.25 0.25 0.25 0.25 0.5 0.5 ffrianonylphogp hit - 0.5 0.5 - ·

2 ₁ 2-DihydroxyiMthyl »butylaonoest · * from PhosphorigeÄur ·

15 2,6,6-tetrahydroxylh

y by Phosphorige & ure

Copper tearate

Time (hours) up to E '.? Inn dor

336

0.1

0.5 0.5

0.1

380

0.1

3 «» i »

"" 87

AGO

0.5 0.5

o.5 0.5

0.1

10ö

0.25 0.28 0.25 0.25 0.25 0.25 0.5 0.5 0.5 0.5 0.5

C ₉ 5

05

515

lötj

0.5 0 _s 5

05 0.1

109836 / $ 15 *

X σ>

- 12 -

Example 3

it

55 parts of phosphorus trichloride are added dropwise at -5 ⁰ O to 5 CyS parts of diphtaerythritol, and the mixture is gradually ^{warmed to 75 0} G. This temperature is maintained for 12 hours, during which nitrogen is bubbled through to remove hydrogen chloride. 14 * 4 parts of water are added, and the Gemisoh is ^{heated to 90 0} O for half an hour. 17.0 parts of a white solid are formed and identified as 2,2,6,6-tetrahydroxymethyl -4-o3caheptamgthylen ~ bis ismonoester of Phoephorigsa'-are.

The infrared spectrum shows bands leading to -CBUOH groups

(3300 can "" ¹ ), P-OH groups (2100-2300, 1580-1750 and 1000 «Γ ¹ ), P-0 groups (1220 cm) and iP-H groups (2420 c» "" ¹ ) belong.

Example 4 .

140 parts Phosphortriohlarid, during a period of time of 1 hour at 20 ⁰ C to bucket Iiösung τοη 67 »5 ropes pentaerythritol in 150 ml of chloroform were charged and gradually heated to 70 ° 0 and then kept for 3 hours at this Teaperatur. Hydrogen chloride is removed from the reaction mixture by means of a stream of nitrogen. The chloroform is removed under vacuum, 90 parts of pentareythrityldiohlorophosphite being returned.

BATH 1Q9836 / 1S69

Ble ilen · 36 Ter.le Waaser are added to the solid, and it is ^{heated to 90 0} C for 4 hours, 102 parts of a colorless viscous liquid are obtained, the all 2,2-difcyiroxymethylene-bis-monoesters of phosphoric acid are identified « The infrared spectrum shows bands in the -CEgOH groups (3300 cm ** ¹ ), P-OH groups (2100-2300, 1600-1700 and in the vicinity of 1000 cm " ¹ ),:?« 0 groups ( 1200 ca "" ¹ ) and PH groups (2400 cm) belong to "

Example 5

3-Methyl-6-t-butylphenylphoephonic acid (A), prepared from ^ methyl-6-t-butylpheaylphosphorus dichloride (bp 110 to 115 ^G C / 2 mm Eg) by hydrolysis with cold water, was converted into the powdered copolymer of 98 £ 4 -Methyl pent en-1 and 2 i> n-decene-1 incorporated, and strar by the method described in Example 1. The speed of the polymer extrusion in the melt knife at 260 ^° C. was as follows:

Stabilizer co-mingling: speed of extrusion

~ 3e minute fg χ 10 ^z ) after Sr-

during warming in the Hesser

to min. 15 min, 20 MSU.

0. £ 5 ί Irganox 1010 + 0.1 φ Α 5.7 7.2 7.6

0, t5 ¹ A Iriianox '010 φ 0.25 ^ A 2.2 2.5 2.6

Ο, -; ¹ »/ ü '^ müt 'OtO> 0.1 7> 4 +
0.26 ? DiViXW ^ ι!, Ti oat ηφΙβΆΆΐ * _t 2 4.0 4.6

■) i '■ * .'■> r ^% u, \ r. ·· - 0! ι

56 Tocile phosphorus trichloride zv during a period of time of 3 hours. is added to a stirred suspension of 54 ropes of trihydrate ethylolpropane in 52 parts of toluene, a large stream being continuously passed through the reaction mixture. The temperature is maintained at 33 to 37 ° C. during the reaction and for a further 2 hours, cooling being required during the first part of the addition and heating during the latter part , 5 parts of water are added over 30 minutes while maintaining the flow of nitrogen through the tubes. The temperature will

during the addition to 30 to 35 ° C and raised then for 2 hours at 60 ⁰ C, wherein during the first salvation the addition nut cooling and later heating is ig. The temperature is then increased to 8O ⁰ C, and the toluene asl the other volatile materials are removed under a pressure of 25 mercury. The 2 _> 2 ^> -Di (hydr3xyaethjl) tutyl ester of phosphorous acid, which was prepared with the Pro

product is identical, remains behind.

Beiapiel?

(π) JOQ £ a.Äi) ^ :. i * iiW: ui ^J iiumIivrep8 we-lsr «. 5 MJ.mi ^!: ■: - ■ ·! in a

i u 9: '3 B / * & S 3

e. "be ¹ at a temperature of 7O ⁰ C milled 1έ3 resulting ^ EIL is cut and: In a äampfbeiisizten platen press for 3 minutes at 14O ⁰ C (jspreßt and cooled under pressure Sauerstoffabsorp ti onsme ABRIDGMENT S be a manometric method at 10O ⁰ C. carried out, and the times for the absorption of 0.5, 1.0 and 1.5 · - ^ oxygen are determined,

(O) 3The procedure is repeated, except that 0.5 g of 2,2-I »i- (hydroxymethyl) butyl ester of phosphoric acid are incorporated into the gum on the mill in the usual manner. The results are as follows:

mixture Time to absorb oxygen
at 100 ⁰ C (hrs.) $ 1.0 1.5 ^ Gumni alone (a)
Gruaani + Ester (b) 0.5 # f
f
4.75 j 6.5
26 j 31.5 9
34.5

Example 8

Pressed sheets of polypropylene, which are the following

109836/1569

_BAD oBi

contain specified additives, are replaced by the in Beiapiel 2 described method produced. 3) ie pressed plates are checked by visual inspection and. mf-t using a Hardy spectrophotometer tested for light transmission at a wavelength of 380 mn.

mixture Appearance Permeability (#). at 380 nn Polypropylene + 0.5 i> pale yellow-brown 76 1,1,3 ~ tris (5-tert-butyl- 4 ~ hydroxy-2-methylphenyl) -
butane Polypropylene + $ 0.5> colorless 81 1,1,3-ΐΠβ- (5-tert-butyl- 4-hydroxy-2-methylphenyl) - butane + $ 0.5> 2.2-di- (hydr oxyrne thyl) -but ylmano- phosphorous acid esters

PAHäffTAN PROVERBS:

109836/1569

Claims (17)

1 · Method of stabilizing polymers, dadaroh characterized in that a phosphorous acid monoester is incorporated into the polymer the piglet RO-P-H OH ■ where K is an alkyl, alkenyl, cycloalkyl, aryl or aralkyl group represents, or incorporates a substituted derivative thereof 2. The method according to claim 1, characterized in that the polymer iet a polyolefin. I5. Method according to claim 2 _r, characterized in that the polyolefin is polypropylene 4. The method according to claim 2 _9, characterized in that the polyolefin is a polymer or Misschpolymer ron 4-Methylponl; en-l. 5 * Φβτί'ίύΐι'Ίη after one of the Anoprtßhe 1 blii i-, thereby 109Ö36 / IS63 characterized "that H is an aryl group". 6, method according to one of address 1 to 4, thereby characterized in that R is a 2.2 »di ~ (hydrO3cymethyl) ~ aryl group or a derivative thereof. 7. The method according to any one of the preceding »claims, characterized in that the mono-meter is used in an amount of 0.005 to 5.0% by weight and preferably from 0.05 to 1.0% by weight, based on the polymer. 8ο Method according to one of the preceding claims, characterized characterized in that a sulfide is also incorporated into the polymer. 9. The method naoh one of claims 1 to 7, characterized gekesrtseielinet that the polymer also incorporated a phenol will. 10 · The method jmoh β ine a of claims β or 9, characterized in that the sulfide or the phenol in a stage »from 0.05 to 5» 0 or 5i and preferably from 0.1 to »0, 5 i> _t sucked on the polymer, is incorporated. 11 »HibsphorigsäiiremonoöBtör der Pormel 109838/1569 HO-P-H OH . S is an alkyl, alkenyl, cycloalkyl, aryl or aralkyl group means, as well as the substituted derivatives thereof 12. Pho3phorig8äuremonoester according to claim 11, characterized ™ characterized in that R is an aryl group? is. 13. Phosphorous acid monoester according to claim 11, characterized characterized in that R is a 2,2-dihydroxymethylalkyl group or is a! derivative of it. 14. Phosphorous acid monoester according to claim 11, characterized in that R is a divalent group _r which is combined with two phosphonic acids. 15. Process for the production of Phosphorigsäuremoxioe star Whether one of claims 11 and 14, denoted by, that jean a phenol or an alcohol with phosphorus trichicride remaining to divide a Dichlorphoephits and implement the / beiaitt Chlorine atoms removed by hydrolysis. 16. Terfehren sur production of phosphorous acid monoesters Claim I3, characterized. without knowing that one has a tri- 109836/1569 1668320 i? r-ii? fr; äylo! älkanpho3pMt «κ-.er a derivative thereof hydrolyzed 17. "Verfahron aur production of Bi oaphorigaäureiaonoe star according to claim 13 * dadrurdi gekennac · pays that a cyclic s Hydroxyme sbyl dime thy lolalkanpiicaphit or a derivative lavon hydrolj'ßiert · Hf INC »UIPLiNCH ... PWL-MMIlIAIfrM 109836/1569