DD264446A1 - METHOD FOR STABILIZING HIGH POLYMERS, LOW-MOLECULAR ORGANIC COMPOUNDS AND OILS - Google Patents

Abstract

The invention relates to a process for the stabilization of high polymers, low molecular weight organic compounds and oils. It aims to increase the durability of organic materials in their manufacture and use. The aim is to use cost-effective, low molecular weight, volatile and migrating stabilizers at elevated temperature and in the presence of extracting solvents for long-term stabilization. According to the invention, as inhibitors, molecular complexes of calix-n-arenes with cost-effective, low molecular weight inhibitors are used, which are added to the substrates during the post-processing or during the production of molding materials. The novel stabilizers are used in a concentration of 0.01 to 0.7 parts by weight in% and are particularly suitable for stabilizing polyolefins and olefin copolymers, ABS, polyamides, polyesters and polyurethanes against degradation by oxidation, heat and light.

Description

, 6

are, be included, applied.

6. The method according to claim 1, characterized in that molecular complexes containing as molecular complex partner Dialkylthiodipropionate the general formula R ¹⁵ · O · CO · CH ₂ · CH ₂ -S-CH ₂ · CH ₂ -COOR ¹⁵ ,

in which H ^{15 is} an alkyl radical having 1 to 18 carbon atoms.

7. The method according to claim 1, characterized in that molecular complexes containing as molecular complex partner amines of the general formulas

in which R ¹⁶ , R ¹⁷ and R ^{18 are} H, alkyl, cycloalkyl, aryl, aralkyl, alkylaryl radicals, R ^{19 is} H, alkyl, cycloalkyl, hydroxyalkyl or alkoxyalkyl groups, A is H, -OH, NH ₂ , alkyl, aryl, aralkyl, alkylaryl, cycloalkyl groups and B = O, S, NR ¹⁶ are included.

8. The method according to claim 1, characterized in that molecular complexes which contain as molecular complex partners mixtures stabilizing acting low molecular weight compounds according to claims 2 to 7, are applied.

9. The method according to claim 1 to 8, characterized in that the molecular complexes in a concentration of 0.05 to 0.5 parts by mass in%, based on the amount of substrate used.

Field of application of the invention

The invention relates to the use of inhibitors for stabilizing high polymers, low molecular weight organic compounds and oils against degradation by oxidation, heat and light.

Characteristics of the known prior art

The thormooxidative and photooxidative stability of high polymers, low molecular weight organic compounds and oils is controlled by sterically hindered phenols, by aminic antioxidants, Hydroperoxidzersetzer such as organophosphites and thioethers, UV absorbers on 2 Hydroxybonzophenon- and Benztriüzolbdsis, hindered amines (HALS) and quenchers

(Metal chelates) improved. It is also known that selected mixtures of sold antioxidants (e.g., historically hindered phenols and hydroperoxide decomposers, organophosphites and HALS) are synergistically incorporated into polymers in inhibiting performance. For example, it is known from various proposals that calix -, n - arenes exhibit synergistic effects when co-incorporated with other ther and photooxidative inhibiting stabilizers (cf also USP 4,617,336).

Such economically favorable precursors of low molecular weight, such as, for example, 2,6-di-tert-butyl-p-kiesol, 2,2 ', 6,6'-tetramethylpiperidine or bis (1) e. ö'-TetramethylpiperidinoMJs ^ buCat volatilize already selecting the processing or other thermal stress (such as in motor oils η), migrate within a short period of use from the polymers to be protected, or weird exirdhiert from them by water, so that no long-term stabilization comes about.

It is very disadvantageous that even in stabilizer combinations the volatile, low molecular weight and migrating stabilizers leave the substrate to be protected rapidly and are lost for long-term stabilization.

Z il the invention

The aim of the invention is the Eigonschaftsprofil of high polymers, low molecular weight organic compounds and oils by inhibiting thermo- and photo-oxidative processes at elevated temperature and in the presence of extracted solvent acting such. As water, even by means of inexpensive low molecular weight stabilizers over the longest possible Gobrauchsdauer to obtain.

Explanation of the essence of the invention

It is an object of the invention to reduce the mobility of the low molecular weight stabilizers in the polymers to be protected from autoxidation, so that they are at higher temperatures by their volatility, by migration to the surface of the polymer or by extraction by water or other liquids in contact with the polymer for the inhibition process can not go lost.

This object is achieved by a process for the stabilization of high polymers, low molecular weight organic compounds and oils - in particular polyolefins and olefin copolymers, ABS, polyamides, polyesters and polyurethanes, but also lubricants such as motor oils - golöst against degradation by oxidation, heat and light by incorporation of inhibitors in which, according to the invention, they are used as stabilizer molecule complex of the low molecular weight stabilizers with c / cic multinuclear methylphenol compounds "calix-n-arenes".

As a molecular complex partner for the calix (n) arene according to the invention sterically hindered phenols of the general formula

alkyl groups with 4 to 8 carbon atoms attached via tertiary carbon atoms in R ⁸ and R ⁷ , cycloalkyl groups with 6 to 12 carbon atoms bonded via tertiary carbon atoms, aryl groups or alkylaryl groups bonded via tertiary carbon atoms and R ⁸ Alkyirosts,

- (CH ₂ LO · CO R ⁵ ,

- (CH ₂ L-NH CO R ⁵ or- (CH ₂ LO R ^5,

or sterically hindered Zwoikernphenole the general formulas

OH

In which Z

A ¹⁰

, - Either way., -,

R * and R ¹⁰ = H, alkyl, cycloalkyl, aryl or aralkyl groups are used.

Further orfirdungagemäße Motekülkomploxpartner are 2-hydroxibonzophenone or Bonztriazolderivate the all): emeinon

formoln

in which R "= H or halogen, or organophosphito of the general formula

12

, 0 - R O - R

13

0 - R ^U

in the R ' ² , R ¹³ and R ¹⁴ = alkyl, Aralkylgrupnn or

or Oialkyltliiodipropionate the general formula R ¹⁵ • O • CO • CH ₂ • CHy-S-CH ₇ -CH ₂ -COOR ' ⁵ ,

in which R ^{15 is} an Aikylrest having 1 to 18 carbon atoms.

Likewise very well suited for the formation of molecular complexes are aminic antioxidants of the general For no

R ¹⁶ P. ' ⁷

cH

ir those

R ¹⁶ , R ¹⁷ and R ' ⁸ =

H, alkyl, cycloalkyl, aryl, aralkyl, alkylaryl,

H, alkyl, cycloalkyl, hydroxyalkyl or alkoxyalkyl group,

H, -OH ₁ -NH ₂ , alkyl, aryl, aralkyl, alkylaryl, cycloalkyl groups and

O, S, NR ⁹

Similarly, it is useful to formulate with the colixarone Jie stabilizing molecular coxomplox with mixtures of the listed nledormolocular molecular complementin ornithosis-like Weiso to express synergistic effecto / wisciiori various low molecular weight stabilizer.

The organomagazine Molokülkomploxo also in Korr binotlon with andoron well-known Plosthilfsstotfon wio Antioxidantißn. LichtschutzHoffoffon, lubricants and antistatic agents used.

Dio orfindungsgomäßen Molokülkomploxo been oinor in concentration from 0.01 to 0.7% in Massoantoilon, but insbosondoro of O ₁ OD Biso, 5 parts by mass in%, bozogen the Substratmon _'d n, and dio bokennton additives in oinor concentration of 0, 01 to 2 massiles in%, in particular from 0.0B to 1 Massoanti in%, bozogon on the Substratmengo used. The erfindungrjsrjomäß Molekularkomploxo bildon used siel) only if they were prepared prior dor incorporation into the substrate in dor boschriobonen Woiso. Despite the relative motion stability of the molecular cochompxo, dio in gobundon inhibitors act surprisingly strong. Whereas the component of stabilizer combinotlonone in customary w oiso in the form of mechanical mixtures of a twin-screw extruder in the polymer melt oingoarboitot, the molecule complexes do not. The more volatile, low molecular weight stabilizers gohon daboi by pre-mg mg vorloron and cause no Langzeitstabilislorung.

embodiments In the examples, the following molecular cochomponents were used:

a) 5 g Tetra-4torl.-butylciilix (4) -nron and 1.7g 2,6Ditüi1.-bulylporosol wordon with 10ml methanol for 10min to Sicidon orhitzt and anschlioßond the methanol - finally under vacuum - evaporated.

b) 7.5g Tetra-4-tort-butylcalix- [6] -arenbzw. 10 g of t-butyl-calix-iej-arone and 1,2 g4-hydroxy-2,2 ' ₁ 6, o'-tolram (ethylpiperidine or 1,2 g 4-amino-2,2', 6, G'-totramothylpiperidine or 1.5g of 4-acetomino-2,2 ', 6,6'-totramothylpiporidine or 2.1g of bonzoylamino-2,2', 6,6'-tetramethylpiphoridine-N-oxyl or 2,1g Bonzoyloxi-2,2 ', 6,6'-totramothylpiporiditvN-oxyl wordon with 10ml 1 oluen 10min heated to the Siedon and anschlioßond the toluene - finally in vacuo - evaporated.

Example 1 to 8

Dio orfindungsgomäßon Molokülkomploxe from 4-tert-Bulylcalix- | 4) -aron and 2,6-di-t ') rt.-butyl-pc-rosol (Vorftift a) wordon on a laboratory mill at 105 ⁰ C to 140X or a Laboroxtrudcr boi oingemischt 18O ⁰ C to 200'C Zylindonnmporatur in dio Polymoron and on a press of don Walzfollon or granules, films of 0.05mm Dicko goproßl. At (Jon slides is determined by measuring the oxygen to take place under isobaric conditions boi 173 ^C C dio dio duction oxidation.

example polymer inhibitor concentration induction (Maüsoantoilo poriodo (min) in %) 1 PE-ND without 0 19 2 PE-ND 2,4-Ditort.butyl-pcrosol 0.2 17 0.4 19 0.6 17 3 PE-ND 4-tort-butyl-calix [4 | arene 0.2 62 0.4 93 0.6 126 4 PE-ND Molokülkomplüx after a 0.2 97 0.4 131 0.6 179 5 LIdPE without 0 13 6 LLdPE 2,6-di-tert-butyl-p-crosol 0.4 14 7 LLdPE 4-tort.-butyl calixl4! -Jron 0.4 78 8th LLdPE MolokülkofT'.plox after ü 0.4 122

Examples 9 to Π

That is to say, molocule comploxo which is in accordance with the invention is incorporated into the polymer protective substrate according to method b wordon wio in donor examples I to 8, and grafted into films. Dio Folionstücko weidon with gofiltcrtom Xononbogoniicht untor Borognung with dostilliortom water (allo 30min for 0.5min) in oonom Xonotostgorät 450 bowittort.

The anticorrosive process was followed by an IR-Spe! Motor by absorbing the extinction of the CO valence oscillation at 1720 cm '. Dio sample is seen as damaged as soon as the extinction of 0.1 nm is correct.

Bokpioi

Polymor

Inhibitor Conjontrotion (Mdssoontollo

Hours (h) Eco-o.i

PEND PEND PEND

PEND

PEND

PEND PEND

PEND

PEND

PEND LLdPE LLdPE LLdPE

without

l-tort.-BulylcaUx-iel-flron

Molokülkomplox after b

4-tort.-butylcalix- | 6 | aron and

4-Acatamino-2,2 ', e, 6'-totramothylplpor! Din

Reconstruct Molokülkomplox

4t.-Butylcallx- | 6 | -aron and

4-Btn; oylamino-2,2 ' ₁ 6,6 ^>

lotromothylplporldin-N-oxyl

Molokülkomplox after bans

• Itorl. -butylcalix IOI nronund

4Hydroxl-2,2 ', 0,6'-tolromothylpl | erldin)

4-tort butylcolix-iiron

Molokülkomplox after ο out

4 tort -Butylcalix -iei-aron and

4-Bonioyloxi-2,2 ', e, fi'-

totramothylplpnrldin-Noxyl

Mo'okülkomploxnochhoiis

') -tort.-Dii \ ylco! ix- | 8 | -of ar) and

4Acotamlno?, 2 ', 0,6'-totramnthylplporldin

Molokülkomplox after b

4-tert-butylcalix- (81-arone and

4Amino-2,2 ', SS' 0 'totramothylp: porJdln

4Amino-2,2 ', 6,6'-totromothylplporidin

r.lüio

<Ltort.-Uutylcolix- (6 | o on

Molokülkomp ¹ · ":.! (IchI) off

4-torl-Btitylcalix- [6 | -oron and

4-amino-2,2 ', 6, e'-tütrümothylplporldin

400 110C IGOO

1900

2400

0.3 0.3 350 17G0 0.3 1500 0.3 2300 0.3 0.0 fi 370 0.3 0.3 1,000 2,000

Claims (2)

claims: 1. A process for the stabilization of high polymers, low molecular weight organic compounds and oils - especially polyolefins and olefin, ABS, polyamides, polyesters and polyurethanes - against degradation by oxidation, heat and light by incorporation of inhibitors, di (optionally combined with other known plasticizers as antioxidants, light stabilizers, lubricants, antistatic agents, which are then used in a concentration of 0.01 to 2.0 parts by mass in%, in particular 0.05 to 1.0 parts by mass in%, based on the Substratatrnenge, characterized in that as a stabilizer in a concentration of 0.01 to 0.7 parts by weight in%, based on the Substraimenge, molecular complexes of compounds of the group of cyclic Mehrkernmothylenphenolverbindungen "calix [n] arenes" of the general formula 3 3 in the y «- Ο * - which is partly or completely replaced by - C ^ - 0 - C ^ - 0 R
or - ό - is replaced, R ¹ = H, alkyl, cycloalkyl, acyl or aryl radicals, R ² = H, alkyl, cycloalkyl, aryl radicals, - (CH ₂ ) _m -O · COR ^b or- (CH ₂ ) _m -NH · COR ⁵ , R ³ and R ⁴ = H, alkyl, cycloalkyl or aryl radicals, R ⁵ = H, alkyl, cycloalkyl, aryl or alkylaryl groups, η - 2 to 1: 2 and m = O to; 18 are. and inhibiting low molecular weight compounds as molecular complex partners, wherein the molecular complexes are prepared by raising the molecule complex partner on the calixarene from organic solvents and then evaporating the same or by co-fusing the calixarene with the molecular complex partner become. According to the invention "calix [n] arenes" of the general formula used in the y = i - that, in whole or in part, through R ³ R ³ I y = -C-O-C- or Il -C- Is replaced, R ¹ - Hjalkyl-cycloalkyl, acyl or aryl radicals, R ² = H, ζ »alkyl, cycloalkyl, aryl radicals, - (CH ₂ LO • COR ⁵ or - (CH ₂ ) _in -NH • COR ⁶ , R ³ and R ⁴ = H, alkyl, cycloalkyl, or aryl radicals,
R ^{5 is} H, alkyl, cycloalkyl, aryl or alkylaryl groups, n = 2 to 12 and m = Obis 18. Before the molecular complex is incorporated into the substrate to be protected against autoxidation, the molecule complex partners are applied to the calixarenes from organic solvents and the solvent is then evaporated off. Solvents are in particular volatile aliphatic or aromatic hydrocarbons, alcohols of C ₁ -C ₅ , ketones, chlorinated hydrocarbons. However, it is also possible to obtain the molecular complexes by processing together the low molecular weight stabilizers with the calix [n] arsenic prior to processing. 2. The method according to claim 1, characterized in that molecular complexes containing as molecular complex partner sterically hindered phenols of the general formula in the R ⁶ and R ⁷ via tertiary carbon atoms bonded alkyl groups having 4 to 8 carbon atoms, bonded via tertiary or secondary carbon atoms cycloalkyl groups having from β to 12 carbon atoms, aryl groups or via tertiary carbon atoms bound Alkylaiylgruppen and
R ⁸ = alkyl radicals, - (CH ₂ LO.COR ⁵ , (CH _? ) _M -NH.COR ⁵ or - (CH ₂ L.OR ⁵ are used.) 3. Process according to Claim 1, characterized in that molecular complexes which contain sterically hindered dinuclear phenols of the general formulas as molecular complex partners OH I
- C _, _ SO - or - SO ₂ _, where Z = Rio R ⁹ and R ¹⁰ = H, alkyl, cycloalkyl, aryl or aralkyl groups are included. 4. The method according to claim 1, characterized in that molecular complexes containing as molecular complex partner 2-hydroxybenzophenone or benzotriazole derivatives of the general formulas OH R ( in which R ¹¹ = H or halogen, are used. 5. The method according to claim 1, characterized in that molecular complexes, as the Molekomplexpartncr organophosphites of the general formula 12 0 - R
in the R ¹² , R ¹³ and R ¹⁴ = alkyl, aralkyl groups or