DD146957A1 - PROCESS FOR STABILIZING ORGANIC POLYMERES BY PHOSPHORIC ACID AMIDES - Google Patents

Abstract

The aim of the invention is a process for the stabilization of organic polymers by phosphoric acid ester amides against thermo-oxidative degradation. The inventive sterisch hindered Phosphorsaeureesteramide have good color and Hydrolysestabilitaet and are effectively effective as thermal stabilizers at high temperatures. The compounds according to the invention correspond to the general formula (formula) in which X is O, NH or S and R &sub1;!, R & ind2! and R & ind3! open-chain, cyclic substituted or unsubstituted aliphatic or aromatic radicals.

Description

Title of the invention

Process for stabilizing organic polymers by phosphoric acid amides

Fields of application of the invention

The invention relates to an improved process for stabilizing organic polymers against oxidative, thermal, photochemical and hydrolytic degradation by ester amides of phosphoric acid. In addition, the compounds according to the invention increase the stability of organic polymers to ozone and to act as flame retardants of organic polymers. Organic polymers are subject to degradation phenomena caused by both the manufacturing process and environmental factors such as temperature, light, oxygen, ozone, moisture and more. Therefore, organic compounds are added which can prevent or delay one or more of these degradation processes. For this reason, there is a great practical interest in developing such stabilizers, which allow the longest possible lifetime of organic polymers with the same performance properties. In this case, the most complex possible effect of the stabilizers as light stabilizers, chain-stopping pder preventive antioxidants'angestrebt to keep the content of the organic polymers of additives as low as possible.

Characteristic of the known solutions

Phosphorus compounds, in particular esters of phosphorous acid and also of phosphoric acid, are known as good stabilizers for organic polymers, in particular against thermooxidative degradation.

The activity of these classes of compounds as stabilizers is attributed to their action as Hydroperoxidzersetzer, chain terminators, complexing agents and also as a light stabilizer. In particular, esters of hindered phenols show good activity as antioxidants (US Pat. No. 3,415,906). The introduction of free amino groups into organic phosphites (US Pat. No. 4,006,117) as well as organic phosphates (US Pat. No. 3,956,428) causes good efficacy of these derivatives as antioxidants even at lower temperatures. The use of steramides of phosphoric acid as stabilizers for rubber and lubricating oils (US 3,903,002, US 3,819,748) is also known.

Although the derivatives of organic phosphites or phosphates, especially in the presence of amino groups, have excellent activity as chain-breaking and preventive antioxidants, the use of these compounds brings some disadvantages.

Thus, the hydrolytic stability of these compounds is very low in many cases, and it often comes to a strong Eigenyerfärbung the polymer by the stabilizer. Thus, the application of these classes of compounds is limited to organic polymers which, when used, do not impose color stability requirements, e.g. Rubber, lubricating oils and the like

Object of the invention

The aim of the invention is to increase the thermooxidative stability of organic polymers.

Explanation of the essence of the invention

The object of the invention is to effectively suppress the thermo-oxidative degradation of organic polymers. According to the invention, this object is achieved in that the organic polymer sterically hindered ester of Phos-. phosphoric acid are added as stabilizers and flame retardants, with compounds; be used according to the general formulas I to IV; ·

worm.

and R,

in which R ₁ -, and R

216,577

R ₁ O. S

¹ > PZ R ₂ O

(D

ο ^x

•O

P-Z

(II)

Il> »v ^ ^w \

X and ·

P-OR ₆

Ί £ Γ

(III)

No)

independently of one another are C 1 -C _{2 2} -alkyl, phenyl, benzyl, C ₇ -C ₂₀ -alkylphenyl, cycloalkyl, C ₃ -O ₆ -hydroxyalkyl or hydroxyphenyl in the formula I, and

Is hydrogen, C ^ -O ₁₈ alkyl, C ₅ -O _{3 is} cycloalkyl, phenyl, benzyl, C ^ -C ₁₂ alkylphenyl, in the formula III, and

Are hydrogen or C 1-8 alkyl in the formula IY, and

C ₁ -C ₁₈ AlIQTl, phenyl, benzyl, C ₃ -C ₁₆ aralkyl,

C ₁ -C ₁₂ alkylphenyl in the formula IV,

and

a residue consisting of residues A and B

can

^VR 8

ν-R ₁₂

independently of one another, are hydrogen, C ₁ -C ₃ alkyl, cycloalkyl, phenyl, C ₇ -C ₂₀ alkylphenyl or aralkyl in the formula A, and

are independently hydrogen, C ₁ -C ₃ alkyl, preferably methyl in the formula B, and

2U 577

Is hydrogen, alkyl, hydroxy, amino, ethoxy, carbethoxy, hydroxyalkyl in formula (B), and

Oxygen or sulfur in formulas I to IY, and

a divalent radical consisting of the radicals of the formulas G, D, E and F in the formulas II, III and IV,

in which

and

E.

C - C-R

R ₁₇ (C)

18

16

R.

(E)

.0-CH _2,

16 (D)

are independently hydrogen, C 1 -C 6 alkyl or C 1 -C 4 hydroxyalkyl in the formulas (C) and (D), and

are independently hydrogen, C ₁ -Cg alkyl, C ₁ -Cc hydroxyalkyl or carbalkoxy groups in the formula (D), and

are independently hydrogen, C 1 -C 6 alkyl, C ₅ -C ₈ cycloalkyl or C ₇ -C ₉ aralkyl in formula (E), and

a radical consisting of the previously described radicals of the formula A and B in the formula F means.

_ ₅ _. 216,577

Compounds of formula I are e.g.

Phosphoric acid diphenyl ester tert-butyl amide Phosphoric acid diphenyl ester di-tert-butyl amide Phosphoric acid diphenyl ester di-cyclohexyl chloride Phosphoric acid diphenyl ester anilide

Phosphoric acid ediphenyl ester N-ethy lane ilide Phosphoric acid ediphenyl ester 2, 4-, 6-tr imethylanilide Phosphoric acid diphenyl ester 4-benzo2y-2,2,6,6-tetraethylpipe-

Phosphoric acid diphenyl ester piperidide ^: '

Phosphoric acid edi-tert-butyric he di-tert-butyl-amide phosphoric di-tert-butyl ester anilide phosphoric acid di-tert-butyl ester 2,4 ·, 6-tr-imethylanilide phosphoric acid di-tert-butyl ester piperidide phosphoric acid di tert. butyl ester ^z J-benzoxy-2,2,6,6-tetramethyl piperidide

Compounds of formula II are e.g.

2-Anilino-2-oxo-1,3-2-dioxaphospholane 2- (2,6-dimethylanilino) -2-oxo-1,3,2-dioxaphospholane 2- (2,4-, 6-trimethylanilino) -2 -oxo-1,3 »2-dioxaphospholane 2- (2, ^, 6-trimethylanilino) -2-oxo-benzo-1,3,2-dioxaphospholine 2- (2, ^, 6-trimethylanilino) -5-diniethy 1-2-OXO-1,312-dioxaphosphorinane ^J

Bis-2-anilino-bis-2-oxo-1,3,2-dioxaphosphorinane 2- (bis-tert-butylamino) -2-oxo-benzo-1,3,2-dioxaphospholine 2-0ctylamino-2-oxo benzo-1,3,2-dioxaphospholine 2- (bis-cyclohexylaiaino) -2-oxo-benzo-1,3,2-dioxaphospholine 2-piperidino-2-oxo-benzo-1,3,2-dioxaphospholine

Compounds of general formula III are e.g.

2,2 ^f -Anilino- (bis-2-oxo-benzo-1,3,2-dioxaphospholine) 2,2 ^l - (2,6-dimethylanilino) - (bis-2-oxo-benzo-1,3, 2-dioxaphospholin

2,2 '- (2,4,6-tri-tert-butylanilino) - (bis-2-oxo-benzo-1,3,2-dioxaphospholin

2,2 ^l -cyclohexylamino- (bLS-2-oxo-benzo-1,3,2-dioxaphospholine 2,2'-tert-butylanino- (bis-2-oxo-benzo-1,3,2-dioxaphospholine

. 216,577

- D - ·

2,2 ^l - (2,6-dimethylanilino) - (bis-2-oxo-1,3,2-dioxaphospholane 2,2 ^f - (2,6-dirriethylanil-lno) -bis (-2-oxo-5-dimethyl -1,3,2-dioxaphosphorinane

2,2 ^f - (p-phenylenediamino) - (bis-2-oxo-benzo-1,3,2-dioxaphospholane

Compounds of general formula IV are e.g.

2-Phenoxy-2-oxo-benzo-1,3,2-diazaphospholine 2- (2,6-di-tert-butyl-4-methylphenoxy-2-oxo-benzo-1,2,2-diazaphospholine -Phenoxy-2-oxo-1,3,2-diazaphospholane 2- (2,6-di-tert-butyl-4-methylphenoxy-2-oxo-1,3,2-diazaphospholine)

The compounds I to IV are prepared by reacting the corresponding phosphoric acid ester monochlorides (G) or dichlorides (H)

Λ /

P-Gl R-O-P ^

R-O .01

obtained with the relevant amines. The phosphoric acid ester monochlorides or dichlorides (G) and (H) are known or easily prepared by generally known methods. The reaction with the amines takes place in the presence of a tertiary amine, such as triethylamine or pyridine, to neutralize the resulting hydrochloric acid. Diethyl ether, dioxane, dimethylformamide, methylene chloride, chloroform, tetra, benzene, toluene, pyridine or aqueous sodium carbonate solution are particularly suitable as solvents.

In special cases, the reaction can be carried out without solvent. The resulting amides of phosphoric acid are mostly solid, in some cases also as a liquid. Solid products are recrystallized in particular from alcohol, hexane, cyclohexane, benzene or petroleum ether. Liquid compounds are purified by distillation in vacuo. All synthesized products were characterized by elemental analysis and NMR spectroscopy.

_ ₇ _ 216 5 77

The compounds of formulas I to IV are used as stabilizers and flame retardants for organic monomers and polymers

 For example, such are:

1. polyolefins, e.g. Polyethylene, polypropylene, polyisobutylene, polybutene-1, polyisoprene, polybutadiene and polystyrene, as well as copolymers of the monomers of said homopolymers such as e.g. Styrene, butadiene copolymers, propylene-isobutylene copolymers

2. Halogenhaltige vinyl polymers such as polyvinyl chloride, polychloroprene and chlorinated rubber

3. polyacrylates, polymethacrylates, polyacrylonitrile and their copolymers with other vinyl compounds such as acrylonitrile, butadiene, styrene. ,

4-, polyvinyl alcohol, polyvinyl acetate

5. Polyethylene oxide, polypropylene oxide and copolymers thereof

6. Polyurethanes and polyureas

7. polyamides and copolyamides derived from licarboxylic acid diamides or lactans

8. polyesters derived from dicarboxylic acids and dialcohols or

Derive lactones, e.g. Polyäthylenglykolkrephthalat.

9. phenol-formaldehyde and melamine-formaldehyde resins

10. Natural polymers such as cellulose, gum and the like.

11. Natural and synthetic organic polymers which are pure monomers or mixtures of such, for example mineral oils, oils, waxes and fats.

The compounds of the formulas I to IV are added to the substrates in a concentration of 0.005 to 5% by weight, calculated on the material to be stabilized. Preference is given to 0.02 to 0.5 wt.% Of the compounds incorporated. The incorporation can be carried out, for example, by admixing at least one of the compounds of the formulas I to IV and, if appropriate, further additives according to the .in. Technique conventional methods before or during processing.

, 216

- ο -

The compounds of the formulas I to IY can also be added to the polymerization before or during polymerization, it being possible to obtain by a possible incorporation into the polymer chain stabilized substrates in which the stabilizers are not volatile or extractable.

The compounds of the formulas I to IV can be used both alone and in combination with other known stabilizer classes; e.g. With: ·

1, antioxidants, like

2,6-di-tert-butyl-4-methylphenol 2,6-di-tert-butyl-4-hydroquinone 2.2 ^J ~ thiobis- (6-tert-butyl-4-methylphenol) ·.

2,2- ^F- methylene-bis (6-tert-butyl-4-methylphenol) .beta .- (3 1 5-di-tert-butyl-4-hydroxyphenyl) -propionsäureäthylester

3,5-di ~ tert. ~ Butyl-4rhydroxybenzylphosphonsäurediäthyJI, ester

Phenyl-2-naphthylamine

2, light stabilizers, such as

2- (2 ^f -hydroxyphenyl) -benzotriazole 2,4-Bis- (2'-l-iydroxy-phenyl) -6-alkyl-s-triazine 2-hydroxybenzophenone cc-Cyano-.beta.-methyl-p-methoxycinnamic acid methyl ester -Nickeldibutyldithiocarbamat

sebacate bis (2,2,6,6-tetramethylpiperidide)

3 # Preventive antioxidants, like

N, N-diacetyl ^f adipic mercaptobenzimidazole

Lauryldithiopropionate. -

Tri- (nonylphenyl) phosphite

⁹ "216 577

embodiments

_t The making and using the compound according to the invention fertilize is described in detail in the following examples.

Example 1 to 10

According to the following general procedure, the compounds of general formula I listed in Table 1 are used

R ₁ OO

PZ shown. R ₂ O

0.1 mol of the phosphoric acid ester monochloride in question are dissolved in 100 ml of DMF under nitrogen and exclusion of moisture at room temperature. The resulting "solution is mixed with a mixture of 0.1 mole of the corresponding amine and 0.1 mole of tertiary amine, eg triethylamine, in 30 ml of J) IIE at such a rate that the temperature of the Reaktions.es 30-40 ⁰ C does not exceed. After completion of addition of the amine 3 is stirred at 70-80 ⁰ G. Then the hydrochloride of the tertiary amine formed is filtered off and the filtrate was concentrated. the resulting solids are purified by recrystallization from methanol, benzene or hexane. Conveniently also proves working in pyridine as a solvent and hydrogen chloride.

Table 1 . I ₁ H ₂ If Z Mp ( ⁰ C) Example I no. // - 1If- -NH (tG ₄ H) -NH (C ₆ H ₁₁ ) -NH (C ₆ H ₅ ) -NH (C ₆ H ₄ CH ₃ ) 116 1 -C • t TT 1 TT O 5 -NH (C ₆ H ₂ (CH ₃ ).) 104-05 129-30 138-40 2 -C 3 -C 4 -C J ₆ H ₅ -piperidyl 171-72 5 -C ³ 6 ^H 5 -N (iC ₄ H ₉ ) ₂ 78-79 6 -C 118-19 7 -C , -NH (C ₆ H ₂ (CH ₃ ) ₃ ) 140 8 -C j- - NH (C ₆ H ₅ ) 153-54 9 -1 121-22 10

2U 577

Example 11 to 18

In otherwise the same procedure as in Examples 1 to 10, 0.1 mol of a cyclic phosphoric diester monochloride of the general formula

/ O _n O

y _n _; p-ci

reacted with 0.1 mol of a primary or secondary amine of the general formulas A and B. ·

Examples of the compounds of the general formula II 'shown in this way

/ O _x SY / PZ (II)

are included in Table 2.

Table 2 example

Mp ( ⁰ C)

E N G E R E G E

-NH (G ₈ H ₁₇ )

-N (G ₆ H ₅ ) ₂

82-83 145-46 147-50 120-21 Oil

178-79 133-34 143-45

Example 19

In otherwise the same procedure as in Examples 1 to 20, 0.2 mol of 2-chloro-2-oxo-benzo-1,3,2-dioxaphospholin reacted with 0.1 mol of 2,6-dimethylaniline. The resulting product 2.2 ^f - (2,6-dimethylanilino) -bis-2-o2co-benzo-1,3,2-dioxaphospholin has a melting point of 193-95 ⁰ · G. '. .

-11- 21 <S 577

Example 20

In otherwise the same procedure as in Example 1 to 10, 0.2 mol of 2-chloro-2-2-oxo-benzo-1,3,2-dioxaphospholine with 0.1 mol of 2,4,6-tri-tert. The resulting product 2,2 ^f - (2,4,6-tri-tert-butyl-anilino) - (bis-2-oxo-benzo-1,3,2-dioxaphospholine has a melting point of 213 -14- ⁰ C on.

Example 21 to 24

In otherwise the same procedure as in Example 1 to 10, 0.1 mol of a Phosphorsäureesterdichlorids of the general

Formula _n . ,

n.Cl

^{6 X} C1

reacted with 0.1 mol of a cyclic diamine. Examples of the compounds of general formula IV thus prepared are shown in Table 3. '

- OR ₆ (IV)

Table 3

Example Rz ₁ = R _n - Ϊ R ₁ - F p ( ⁰ O)

No. ⁴ ^ °

21 H σ -C ₆ H ₅ 196 22 H C - (C ₆ H ₂ (CH ₃ ) (tC ₄ H ₉ ) ₂ ) 261 23 H e -C ₆ H ₅ 185 24 H e - (C ₆ H ₂ (CH ₃ X t C ₄ H _g ) ₂ ) 235

Example 25

Influence of the compounds according to the invention on the autoxidation of polypropylene.

The oxygen uptake was monitored during the oxidation of isotactic polypropylene (MW 510,000, ash content 0.29%, titanium dioxide).

577

halt ?, 0.017 %, aluminum content 0.11 ' % and atactic fraction 0.68 %) at 180 ⁰ G in the presence of phosphoric acid ester amides (0.05 mol / kg and 0.025 mol / kg polypropylene) was followed.

As a measure of the effectiveness of these compounds as antioxidants, the induction period type and the relative autoxidation rate S were used. As a comparison with Tripheny! Phosphate (TPPO) or '2,6-di-tert-butyl-4-methylphenol (BHT) stabilized samples were taken into account (Table 4).

Table 4 t _Ip / example No. ₀ 40 without 55 TPPO 210 BHT 205 3 230 VJL 180 9 220 11 260 13 295 16 120 19 415 22 520 24

S ^r

0.49 0.49 0.78 0.65 0.72 0.69 0.75 0.71 0.80 0.46 0.39

Claims (5)

wherein
and in which
R "and R and R. 12 independently of one another O _{1 is} -O ₂ alkyl, phenyl, benzyl, C 0 -C 20 alkylphenyl, oxyalkyl, O ₂ -Og hydroxyalkyl or hydroxyphenyl, and may be a radical consisting of the radicals of the formula A and B. - R (B) are independently hydrogen, O ₁ -Og alkyl, cycloalkyl, phenyl, O ₇ -O ₂₀ alkylphenyl or aralkyl in the formula A, and are independently hydrogen, O _{1 is} -O ₂ , alkyl, preferably methyl in the formula B, and Is hydrogen, alkyl, hydroxy, amino, alkoxy, Aroxy, Garbäthoxy or hydroxyalkyl in the formula B, and Oxygen or sulfur in formula I, or compounds of the general formula II are added; X
^ 0 ' P-Z (II) worm
Y '- * - 2U 5 77 a divalent radical consisting of the radicals of the formulas C, D, E and. M 6 (C) -Y (D) ^L 18 in which " ^R 16 and R _1g and Z-P ' , O-CH. O-OH. .CH ₂ - GH ₂ - (F) are independently V / asser material, O ₁ -Og alkyl or O ₁ -C ₈ hydroxyalkyl in the formulas C and D, and are independently hydrogen, C ₁ -C ₈ alkyl, C ₁ -C ₈ hydroxyalkyl or carbalkoxy in the formula D, and are independently hydrogen, C ₁ -C ₈ cycloalkyl, C ₇ -Cg aralkyl or aryl in the formula E, and Oxygen or sulfur in formula II is and . a radical consisting of the previously described radicals of formula A and B after point. or compounds of general formula III are added; PNP ^ ^R 3 III · - * - 216 577 wherein R is hydrogen, C ₁ -C ₂ alkyl, C ₅ -O ₃ cycloalkyl, Phenyl, benzyl, C ₁ -C ₁₂ alkylphenyl and C / j-Cg aralkyl, and X after. Point 1 is oxygen or sulfur, and 1 X after point 1 a bivalent radical, consisting from the remainders of the formulas C, D, Ξ and F means » or compounds of general formula IV are added, Rz ₁ . wherein R ₄ and Sr are independently hydrogen or Cj -G _1, alkyl, and R _{6 is} C ₁ -C ₂₄ alkyl, phenyl, benzyl, C ₅ -C ₈ cyclo alkyl, C ₁ -G ₆ hydroxyalkyl, C ₂ -C ₁₆ aralkyl, C ₁ -C ₁₂ alkylphenyl or hydroxyphenyl, and X after point 1 is oxygen or sulfur, and Y after point 1 a bivalent radical, consisting from the radicals of the general formulas C, D, E and F. 2 »" Process for the stabilization of organic polymers with compounds of the general formulas I to XV according to item 1 as antioxidant, antiozonant, light stabilizer and flame retardant. 3. A process for stabilizing organic polymers by adding compounds of general formulas I to IV according to item Λ alone or in combination with other chain-terminating and preventive antioxidants and light stabilizers. ο ι ΛΜ 1Q pi i! * fi t ^ k f-5 ^ f ii T ^  -λ- 21 6 5 77 4 "Process for stabilizing organic polymers such as e.g. Polyolefins, in particular polypropylene, polyisoprene, polybutadiene, polyvinyl chloride, polyester alcohol, for example, polyethylene glycol terephthalate, polyamides, polyurethanes, and natural and synthetic polymers such as rubber, mineral oils, waxes and fats by compounds of general formulas I to XV in concentrations of 0.002 to 5% by weight, preferably 0.02 to 0.5% by weight, based on the material to be stabilized.