DE2543650C2 - Use of phenolamine resins for the stabilization of rubbers and vulcanizates - Google Patents

Description

20th

The invention relates to the use of phenolic resins as antioxidants for stabilization of rubbers and vulcanizates.

To protect rubbers from aging during their extraction from latex or from solution while During processing and storage, it is essential to use antioxidants. From the point of view of High molecular weight antioxidants, especially phenolic resins, are of great interest in practical applications

30th

For the stabilization of polymers, processes are known in which phenolaldehyde resole (GB-PS 8/7 128) and novolak resins (GB-PS 10 02 258, SU-PS 191 108) can be used.

However, when these resins are used, the desired practical result is not achieved. the Novolak resins are poorly compatible with emulsion rubbers in the latex stage, which means that some of the Novolak resins get into sewage. The use of resole resins is because of their high reactivity difficult. At a temperature of 60 to 90 ° C, the resole resins turn into ineffective Condensates around.

With the help of these two types of phenolic resins it is therefore not possible to achieve the desired goal. namely to protect the rubber against aging with high effectiveness.

Because of such fundamental difficulties, the method for stabilizing rubbers has become not realized in this way using phenol-formaldehyde resins. 1;

Although phenol-formaldehyde resins are relatively cheap, not 2) volatile, and readily available, they are from the 3) mentioned reasons for the stabilization of rubbers not suitable. 5S

In DE-OS 20 23 441 a method for 4) Manufacture of plasticizers, especially for the 5) processing of natural and synthetic elastomers, described, in which the plasticizer by an, incomplete prepolycondensation reaction zwU Approximately 100 parts by weight in phenol production by the »cumene process as by-products obtained polyalkylphenol resins in exhausted or unexhausted state or on obtained from these, Distillation fractions collected between 160 ° and 400 ° G and 2 to 20 parts by weight of hexamethylene tfainin, formaldehyde or another organic Polycondensable aldehyde can be produced.

In Examples 10 and 12 of this prior publication It is stated that the manufactured products due to the low content of phenol derivatives with small Molecular weight and the presence of complex phenol derivatives in the phenol component of the Distillation fraction leads to the production of products with a pronounced antioxidant effect, or that the plasticizers have a pronounced antioxidant character due to their complex phenolic composition and protect the elastomers especially against the damaging effects of light, but this does not indicate what the An explanation is also due to the book »Ulimann, Encyklopädie der technical chemistry ", Volume 13, pages 434 to 436, not given, because for the synthesis of the previously explained plasticizers are used only new products and after distilling off five Fractions remaining residue consists not only of cumylphenol, but this residue contains a large amount of -methylstyrene dimer (up to 40%) and a certain amount of other products and thus corresponds to a so-called »exhausted Resin". Cumylphenol mixed with a-methylstyrene dimer cannot be used to make phenolamine resins for the purpose of the present invention because, among other reasons, unsaturated compounds such as a-methylstyrene dimers are attached to the Participate in the formation of the reaction product. The resulting product is used to stabilize Rubbers and vulcanizates not suitable

The references to the antioxidant effect in DE-OS 20 23 441 thus indicate that what this effect is due to, nor does this publication specify in which Extent elastomers are protected from oxidation.

In the extraction of the main mass of rubbers, antioxidants such as N-phenyl-2-naphthylamine (hereinafter referred to as "agent D"), p-phenylenediamine derivatives (diphenyl-p-phenylenediamine, dialkyl-p-phenylenediamine - hereinafter referred to as » Means W «denotes -. Alkylaryl substituents of p-phenyldiamine), 2,6-dialkylphenol derivatives. mainly 2,6-di-tert-butyl-4-methylphenol and some phosphites. ? .. B. Polyhard (= tri (nonylphenyl) phosphite) is used.

All attempts to find other stabilizers which would fully meet the practical requirements, namely:

high efficiency.
Accessibility.

simple technological design of the extraction of the respective antioxidant and its introduction into polymers.
Intoxication and equity,
Non-volatility at higher temperatures.

711 did not lead to a positive result.

The state of the art of working out the problem of Stabilization are discussed in detail in the following publications:

I. 1- Helps stabilize synthetic materials against light and warmth, Leningradj 1972,

2, - stabilizers, accelerators, vulcanizing agents, Propellants abroad, catalog, publishing house "Tambo * werPraWda" 1972.

3. Pospisil, Antioxidanty Praha, 1968.

4. Y. Scott Atmospheric Oxidation and Antioxidant Aml, New-York1965, No. 9.

5. Synthesis and study of the effectiveness of chemicals for polymer work stages, expenses 1-4, Verlag Tabow, NIICHIMPOLYMER, 1964-1970.

6. Chemical additives for polymers, Handbuch, Moscow Verlag »Chemie«, 1973.

7. Inhibition of oxidation processes in polymers by means of stabilizer mixtures, NIITEL, Moscow 1970.

8. Information bibliographical scoreboard for stabilizers, Accelerators and vulcanizing agents for polymers, issues - 1-18, NIITECHIM, Moscow.

The present invention is based on the object for the stabilization of rubbers and Vulcanization to indicate an antioxidant that is free from the disadvantages mentioned above and at its use an effective protection of the rubbers and vulcanizates during their extraction and processing and storage is ensured

This task is achieved through the use of phenolamine resins, the condensation products of Hexamethylenetetramine with alkyl, alkylene, dialkyl, aryl-alkyl and halogen-substituted phenols or Dioxydiphenylalkanes, oxybenzoic acids and mixtures of the resins mentioned with antioxidants from the series of ek. Amines, diamines, 2,6-dialkyl derivatives of phenol, phosphorus and sulfur-containing compounds, as antioxidants for the stabilization of rubbers and vulcanizates solved.

The phtnolamine resins mentioned are extremely effective and outperform the known stabilizers stabilizing effectiveness.

A great advantage of the phenolamine resins proposed for use is the property that To increase the adhesive power of the rubber compounds and the vulcanizates considerably.

The effectiveness of the phenolamine resins exceeds that of the phenol-formaldehyde resins by virtue of their presence an additional reaction center, namely an amino group.

The phenolic amine resin can be added to the rubber in an amount of 0.02 to 10%.

For the practical stabilization of rubbers, a dosage of 0.2 to 0.4% is often necessary. Phenolic amine resin is sufficient.

The phenolamine resins do not contain unstable methylol groups like the resole resins. This enables them to be treated at high temperatures of 80 to 100 ^° C. and beyond, the resin does not change in the process, and a convenient method for introducing phenolamine resin into rubber can be implemented.

Preferred examples of antioxidants are condensation products of hexamethylenetetramine with p'Kresol, or mixtures of cresols, p-tert-Bu-% ipheii oil, Hexylphenol, octylphenol, nonylphenol, dodecylphenol, xylene oil, dimethylvinyiäthinyl-4 "oxyphenylmethane, Phenol alkylated with styrene, cumylphenol, salicylic acid, p-oxybenzoic acid, diphe ' nylölpropane, mixture of alkylphenol or arylalkyU phenol or halophen oil

The phenolamine resins dissolve in organic solvents and are well compatible with rubbers and can be easily introduced into them technologically. The resins can be used individually or in Mixture with known antioxidants from the series of secondary amines, diamines, 2,6-dialkylphenoid derivatives, Phosphites and sulfur-containing compounds are used.

The following phenoleonine resins are used as stabilizers suggested that by condensation of hexamethylene tratramine (hexamine) with para-cresoi, para-tert-butylphenol, Hexylphenol, octylphenol, nonylphenol, dodecylphenol, bromophenol, xylenol, diphenylolpropane. Salicylic acid, para-hydroxybenzoic acid, cumyiphenol, phenol, alkylated with styrene, with a mixture of Pl onols, para-tert-butylphenol and salicylic acid will.

The phenolamine resins proposed for stabilizing rubbers and vulcanizates can be set out by the following general formula:

OH

CH ₂ NHCH ₂ - ^

wherein Ri, R ₂ , R3 and R4 represent alkyl with a number of 1 to 12 carbon atoms, alkeninyl, arylalkyl, hydroxyarylalkyl, halogen, carboxyl group.

When Ri and R4 are hydrogen and R ₂ and R3 are CH ₃ · tert. C ₄ H, · Cl · NO ₂ ■ dimethylvinyläthinylmethyl, such resins are described in the literature (A. Zinke, G. Ligenner, G. Weiss, W. Lenpold-Löwenthal, monthly books for chemistry, 84, 1098/1950) , (SU-PS 2 29 798 and 3 22 346).

If the substituents of Ri. R ₂ , R3 and R4 are alkyls with a number of carbon atoms of Cs-Ci ₂ ; Arylalkyls, for example phenylethyl, cumyl; Hydroxyarylalkyls, for example hydroxyphenylpropyl; Are carboxyl group, these resins are not described in the literature.
Resins obtained by condensing hexamethylenetetramine and a mixture of alkylphenol with 1 to 12 carbon atoms in the alkyl radical or arylalkylphenol and hydroxybenzoic acid are also new.

In Examples 1-4 typical cases of the synthesis of the new phenolamine resins are given, in examples 5-31 a method for stabilizing Kartschuken is compared with proposed resins treated to the known phenol-formaldehyde resins and other known antioxidants.

example 1

A mixture containing 97 g (0.5 mol) of octylphenol with a molecular weight of 194 and 14.0 g (0.1 mol) Hexamethylenetetramine, heat in a reaction flask with mixing to 140-145 ° C. the Condensation, which begins at this temperature, is caused by self-heating of the reaction mixture up 165 ° C and an intense development of ammonia accompanied After completion of the reaction (20-30 min),

the cessation of the development of ammonia testifies to this, the reaction mass is placed in a porcelain bowl * be poured. The Harr solidifies quickly and turns into a brittle amber-colored product. After disintegration

It is a light yellow powder with a dropping point of 94 ° C. The resin yield is 107 g. The resin is easily soluble in benzene, toluene, hexane, cyclohexane. The characteristics of the resin are in listed in Table 1.

Table 1

Characteristic of the resin

No. Designation of the code number value of the

Code number

IO

1. Appearance powder,

light yellow

2. Molecular weight 728

3rd drop point according to Ubbelohde, ³ C 94

4. Dumas nitrogen content,% 6.5

5. Solubility in g / 100 ml toluene 83

Hexane 80

Hexane-cyclohexane mixture 85
(15:85)

20th

25th

40

Example 3

A mixture containing 37 g (0.175 mol) of 4-cumylphenol (product of the alkylation of phenol with α-methylstyrene!) With a melting point of 68-71 ° C. and 4.9 g (0.035 mol) of hexamethylenetetramine is heated with mixing until 135 ° C. The condensation occurring at this temperature is accompanied by self-heating of the reaction mixture to 150 ^° C. and an intensive evolution of ammonia. When the reaction has ended, as evidenced by the cessation of the evolution of ammonia, the reaction mixture is poured into a porcelain key. The solidified resin is a solid, brittle product of amber color. After comminution, the resin is a light yellow powder having a dropping point of 101 ⁰ C. The resin yield was 40 g. The resin dissolves well in cyclohexane. The characteristics of the resin are shown in Table 2.

Table 2

Characteristic of the resin

Example 2

A mixture containing 42 g (0.212 mol) of alkylation product of phenol with styrene (mixture of phenylethylphenols) with a boiling point of 140-150 ° / 5 mm and a molecular weight of 198 and 4.94 g (0.035 mol) of hexamethylenetetramine is heated in a reaction flask for 50 minutes at 130 ^° C. The condensation is accompanied by a strong evolution of ammonia. After cooling, the resin is a very viscous liquid of golden yellow color. The molecular weight of the resin is 550, the nitrogen content -4.1%.

No.
running

Designation of the code number

Value of the code number

15th

Appearance Example 4 Powder, light yellow Molecular weight 880 Drop point according to Ubbelohde, ° C 101 Nitrogen content according to Dumas,% 4.5 Solubility in cyclohexane in 11th g / 100 ml

In a reaction flask, see with a thermometer and stirrer, one fills 60 g (0.4 g mol) of para-tert-butylphenol, 10 g (0.071 g mol) of hexamethylenetetramine and 7.8 g (0.056 mol) salicylic acid

The reaction mixture is warmed up to a temperature of 15O ⁰ C the reaction is accompanied by a vigorous evolution of ammonia. The mixture is maintained at 150 ⁰ C for one and a half hours, then poured into heated 7ustand in a bowl. The resulting mass solidifies in the form of a solid, brittle amber-colored resin. The dropping point is 140 ° C.

Resins based on other substituents of phenol or their mixtures won.

Example 5

In 200 g of Buna S with a bound styrene content of 25% and stretched, with 15% of naphthenic aromatic oil 0.7 g (0.35) of the condensation product of hexamethylenetetramine with paratert-butylphenol are placed on rollers introduced.

The sample produced was subjected to heat aging in the open air at 100 ⁰ C for 24 hours, while the changes in the Defohärte and characterizing viscosity were checked.

In addition, the test piece in the oxygen medium at 14O ⁰ C is oxidized and the induction period of the oxidation, and the change of the base resistance is then determined in the induction period.

For the purpose of comparison, test pieces with 0.35% novolak-phenol-formaldehyde resin, resci-para-octylphenol-formaldehyde resin were carried out analogously (Agent A) and 0.35 and 1.3% N-phenyl-2-naphthylamine (Agent D) testifies and tests. The test results are given in Table 3.

Table 3

Influence of various antioxidants on the stability of the rubber

running Antioxidants Dosage, Induk Grurid toughness after d.
; induc-
functional
period Heat aging at 100 P.
after
Aging ⁰ C No. functional
period,
Min before
Alteruni 2.07 Defo hardness,
Before d.
Aging 520 Basic
toughness
after d.
Aging 1. Condensation product
Butylphenol with hexamine 0.35 69 1.99 0.7 640 370 2.01 2. Phenol formaldehyde
Novolak resin 0.35 10 1.51 2.07 640 410 1.6 3. Phenol formaldehyde
Resole Resin Agent A. 0.35 18th 1.93 0.97 540 370 1.91 4th Medium D 0.35 1.5 1.85 LO7 640 37G 1.3 5. Medium D 1.3 27 1.93 64ü 1.52

From Table 3 it can be seen that the condensate agent D, which improves the effectiveness of protection of

tion product of para-terL-butylphenol with hexame 25 rubber against oxidation and aging in the air

ethylene tetramine surpasses all phenol-formaldehyde resins and elevated temperatures.

Example 6

035% phenolamine resin is introduced into the rubber with characteristics according to Example 5 on the tests of this rubber in comparison with, which is indicated by the control specimens, the phenol formal condensation of para-cresol with hexamethylenetetradehyde resins and agent D,
min is obtained. Table 4 shows the information 35

Table 4

Influence of antioxidants on the stability of rubber on heat aging

running Antioxidants Dosage, Indicators from aging Code numbers 1 reason 1 No. % laugh toughness Aging, 100 ⁰ G, 2.07 P. Defo hardness, reason 24 hours ü P. toughness Defo hardness, 1.6 I. Product of the condensation of the cresol 0.35 640 2.23 P. 1.91 'I. with hexamine 640 1.3 P. 2. Phenolic aldehyde resin 0.35 640 1.51 1.52 B. 3. Phenolic Aldehyde Resin Agent A 0.35 640 1.93 370 i 4th Medium D 0.35 640 1.85 410 β
P. 5. Medium D 640 1.93 370 370

As can be seen from Table 4, the phenolic amine resin is significantly more effective than other antioxidants.

Example 7

Phenolamine resin, which is obtained by condensation of hexamethylenetetramine with 3,4-xylenol, is introduced into the rubber with characteristics according to Example 5.
The test results are shown in Table 5 in comparison with the phenolic aldehyde resin and agent D.

ίο

table 5

Influence of the resins on the stability of the rubber

running antioxidant Dosie Induc- Basic toughened wedge Heat aging at 100 "C, No. tion, functional 24 hours % period, Exit after d. Defo forces, ρ reason Min. viscosity induc Exit After toughness functional
period viscosity aging after
Aging

1. Product d. condensation of 3,4-xylon oil with hexamine

2. Phenol formaldehyde resin

3. Phenol-formaldehyde Resole Resin Agent A.

4. Means D

5. Means D

0.35

44

2.31

1.25

640

560

1.98

0.35 10 1.51 0.7 640 370 1.6 S. 0.35 18th 1.93 1.07 640 410 1.91 j 0.35 15th 1.85 0.97 640 370 1.52 :
■ 1.30 27 1.93 1.07 640 370 1.52

Example 8

In the rubber having the characteristic according to Example 5, phenolamine resin is introduced, which was produced by the Kondensa- * / ön of hexamethylenetetramine with para-bromophenol.
The test results are shown in Table 6.

Table 6

Influence of the phenolamine resin on the stability of the rubber

running Antioxidants Dosie induc- Basic tenacity After d. Heat aging at 100 ° C To reason No. tion, functional ; Induk in 24 hours Aging toughness % period, before ions
period Hardness 570 after
Aging min. Aging 2.97 before 1.98 Aging 1. Product d. condensation 0.35 69 1.99 640 370 of bromophenol with 0.97 i 370 1.3 Hexamine 1.07 1.52 2. Medium D 0.35 15th 1.85 640, 3. Medium D 1.3 27 1.93 640

Example9

There were rubber test pieces with the characteristics of Example 5 with 0.35% of the condensation product of para-tert-butylphenol with hexamethylenetetramine and 1 J4% agent D; with 0.35% phenol-formaldehyde resin and 1.4% Means D; obtained with 0.35% agent A and 1.4% agent D and with 1.4% Neozone D.

The specimens were subjected to mechanical working in rolling at a temperature of 140 ⁰ C, while the change in was controlled Defohärte

The results are shown in Table 7.

11 12

Table 7

Influence of antioxidants on the stability of the rubber during mechanical heat treatment in rollers

earth. Antioxidants Dosage,% Processing Defo hardness, gs To No. duration, min before Aging Aging 410 1. Product of the condensation of the step butyl 0.35 30th 590 phenols with hexamine Medium D U4 195 2. Phenol-formaldehyde novolak resin 0.35 20th 680 Medium D 1.4 220 3. Means A 0.35 20th 680 Medium D 1.4 195 4th Midday l Γ) 1.4 20th 680

From Table 7 it can be seen that the mixture of the condensation product tert-butylphenol with hexamethylenetetramine and agent D protects the rubber from destruction during mechanical processing better than mixtures of phenol-formaldehyde resins with agent D or agent D alone.

Example 10

6 I industrially produced latex of the divinyl-Λ-methylstyrene rubber analog of the rubber of the type 1712 with a dry substance of 20% is the condensation product of the octylphenol with hexamethylenetetramine added in an amount of 7.5 g and 336 g ■ i naphthenic aromatic oil. The manufacture of the Rubber is carried out in a conventional process, that is, using sodium chloride and Sulfuric acid.

Control test pieces of rubber with antioxidants, a mixture of agent D and diphenyl-para-phenylenediamine; Diphenyl paraphenyl diamine (Dialkyl-p-phenylenediamine derivative = medium W) and phenol-formaldehyde novolak resin.

The stability of the rubber is assessed after the Mooney viscosity has been maintained when processing rubber in rollers at 140 ^° C. for 20 minutes. The processing was subjected to 200 g of rubber in rollers with a slot of 1 mm between the rollers, with the dimensions of the rollers 320 × 160 mm and a fraction of 1: 1.24. Table 8 shows the results obtained with different doses of antioxidants.

Table 8

Preservation of the Mooney viscosity of the rubber with different dosages of the antioxidant

dationsmittei in the mechanical heat treatment.

running antioxidants

No.

1. Condensation product d. Oktyiphenols m. Hexamethylenetetramine

2. Agent D + diphenyl-para-phenylenediamine

3. Medium W

4. Phenol-formaldehyde resin (novolak resin)

Dosage,% conservation the mooney Viscosity at Editing, 0.5 77 1.0 76 1.2 31 0.3 0.5 33 1.0 47 1.0 47

As can be seen from Table 8, this exceeds Phenolamine resin from octylphenol with hexamethylenetetramine means both the phenol-formaldehyde resin as well as other antioxidants.

Example ί 1

The condensation product of Oktyiphenols with hexamethylenetetramine is as a suspension in the latex of the 1712 rubber was introduced. The suspenders of the antioxidant is prepared according to the following recipe:

1. Product of the condensation of the

Octvlphenols and hexamethylenetetramine 402 kg

2. Potash soap of synthetic

Fatty acids 12 kg

3. water 5 m ³

The mixture is passed through a colloid mill leave, after which a fine, stable, transportable suspension is obtained

In the rubber latex in an amount of 120 m ³ with a dry substance of 20%, which contains 1.2% agent D, a suspension of the phenolic amine resin based on 0.7% of the rubber is introduced. Latex and oil emulsions are fed to the kneader with subsequent separation of the polymer. The drying of the

Rubber takes place without difficulty in a dryer at a temperature of 95-100 ° C; it is no destruction of the polymer to be recorded.

Table 9 shows the results of the stability of the rubber mentioned in the case of mechanical heat treatment in rollers at 140 ° C. for 20 minutes and heat aging
cited.

at 100 ° C for 24 hours

Table 9

Stability of rubber during mechanical heat treatment in rolls and at

the heat aging

Mechanical Heat treatment Heat aging According to Be Beib Initial Mooney viscosity Starting plot plot, % viscosity After Beibe viscosity action action,%

63.5

72.4

62

As can be seen from Table 9, the concentration product of octylphenol protects with hexamethylenetetramine reliably protects the polymer from aging.

Example 12

A 24% solution of the condensation product of octylphenol is added to the polyisoprene rubber calculated with hexamethylenetetramine in toluene, added 0.8 g per 100 g of rubber; previously contained the

Rubber 0.4% Medium D.

The polymer was precipitated in Wasserentgasungs method and at 70-8O ⁰ C for 10 - dried for 16 hours. Table 10 gives details of the change in Mooney viscosity on heat aging of the polymer with phenolamine resin and the stabilizing control system (agent D + diphenyl-para-phenylenediamine).

Table 10

Change in Mooney viscosity on heat aging of the polyisoprene rubber

running Antioxidant Dosage,% Duration of treatment No. in a thermostat be. 100 ⁰ C · h 0 6 1. Medium D 0.4 77.5 72 Product of condensation d. 0.8 Octylphenols with hexamine 2. Medium D 0.4 75.5 70.5 Diphenyl-rrara-phenylenediamine 0.34

As can be seen from the table, the product of the condensation of the para-nonylphenoi "

Phenolic amine resin added well even to the extremely unstable 50 with hexamethylenetetramine. The specimen

Polyisoprene rubber. of the starting rubber with phenolamine resin

. -I ₁ kept in the air at 140 ° C for 30 minutes.

Example 13 Table 11 shows the values of the Walles ^ starting

200 g of rubber with the characteristics of the example plasticity and the aging and read index

5, which contains 1.2% Neozone D, is listed in the roll with 1 g of 55 Plasticity Preservation (PRJ)

Table 11

Preservation of the Walles plasticity of the rubber with the product of the condensation of the

n-Nonylphenol with hexamine

Jfd. Antioxidant
No.

Walles plasticity

Initial plasticity

1. Means D

2. Product of KcMensasioa de *:
Konylphesois rrsi s Texaimö

4L23

0.22

To
Aging

0.05
G, 20

PRJ,

27
95

As can be seen from Table 11, the Rubber is almost completely preserved in the presence of phenolamine resin and largely with agent D. destructed

Example 14

0.7 g of the product of the condensation of hexamethylenetetramine and dodecylphenol are introduced into 200 g of oil-extended butadiene-styrene rubber with the characteristics of Example 5. The rubber gained one set of WärmeaJterung at 140 ^c C for 30 minutes. The preservation of plasticity index (PRJ) is 92%, the control specimen with agent D has a preservation of plasticity index of 27%.

i6

Example 15

The statistical Buna S with a content of bound styrene of 18% is added in rollers means D in an amount of 1.1% into the second rubber test piece - product of the condensation of dimethylvinyläthinyl-4-oxyphenylmeihans with hexamethylenetetramine (1.1%) , in the third specimen - M ^; ttel D (0.8%) and the condensation product of dimethylvinylethinyl-4-oxyphenylmethane with hexamethylenetetramine (0.3%) were added. The test pieces produced were oxidized in an oxygen medium at 140.degree. C., and the induction period of the oxidation was determined. The results are summarized in Table 12

Table 12

Influence of the phenolamine resin on the stability of the rubber during oxidation

Current antioxidant system
No.

Dosage,%

Induction period,
Min.

1. Medium D 1.1

2. Condensation product of Dimethylvinylätliinyl- IJ 4-oxyphenylm \ ithans with hexamine

3. Dimethylvinyläthinyl- 0.3 condensation product 4-oxyphenylmethane with hexamine + agent D 0.8

78
147

425

From Table 12 it can be seen that the mixture of the condensation product of dimethylvinylethinyl-4-oxyphenylmethane with hexamethylenetetramine and agent D is highly effective and significant the effectiveness each of the components outperforms.

Example 16

In the oil-extended Buna S with the characteristic of Example 5 mixtures of medium D with different phenol-formaldehyde resins and the product of condensation of the DimethylvinyIäthinyI-4-oxyphenylmethan introduced with hexamethylenetetramine The sample patterns produced are subjected to a mechanical treatment in rolling at 140 ⁰ C for 20 minutes . Before and after aging, the values of the plastic-elastic properties of the rubber were checked.

The results are shown in Table 13.

Table 13

Change in the plastic-elastic properties of rubber during mechanical treatment in rollers

lfd system of antioxidants

Dosage, defo hardness, regen- plasticity elastic
% ρ manageability. Reduction,

mm mm

Medium D 1.4 1.95 0.9 0.56 1.17 I. Product of the condensation of dimethyl 0.35 580 2.5 0.37 2.36 1 vinyläthinyl-4-oxyphenylmethans with i Hexamine i Medium D 1.4 i Phenol formaldehyde novolak resin 0.35 195 0.8 0.54 0.97 I. Medium D 1.4 I. Phenol-formaldehyde resoil resin ι Means A 0.35 220 1.0 0.56 1.03 I. Medium D 1.4 ϊ
J Plastic-elastic properties of the 680 3.1 0.32 2.75 Rubber before treatment 230 265/145

From Table 13 it can be seen that the mixture of means D with the product of the condensation of the DimethylvinyIäthinyI-4-oxyphenylmethane with hexamethylenetetramine according to its effectiveness, the mixtures of agent D with phenol-formaldehyde resins and des Significantly outperforms by means of D alone

Example 17

In the synthetic isoprene rubber, the mixture of agent D with the product of

Condensation of dimethylvinyathynyl-4-oxyphenylmethane with hexamethylenetetramine (hexamine) and the mixture of agent D with Ν, Ν'-diphenyl-para-phenylenediamine introduced into rollers at a temperature of 60-70 ° C. The sample samples produced were exposed to heat aging for 3 days at 100 ° C. The change in the characteristic Viscosity checked every 24 hours; the results are summarized in Table 14

Table 14

Change in the basic toughness of the rubber with heat aging

Current system of antioxidants

Dosage, heat aging in 3 days at 100``.

Starting. After after after

1 day 2 days 3 days

1. Agent D 0.65 Diphenyl-para-phenylenediamine 0.3

2. Medium D 0.65 product d. Condensation of the dimethyl vinyl 0.3 äthinyl-4-oxyphenylmethane with hexamine

3. Medium D 0.65 product d. Condensation d. Dimethylvinyl-1,0-ethinyl-4-oxyphenylmethane with hexamine

2.66 1.98 1.53 1.44

2.45 2.12 1.96 1.79

2.58 2.28 2.27 2.17

From Table 14 it can be seen that the mixture of D with the product of the condensation of the Dimethylvinyl-4-oxyphenylmethane with hexamine after its effectiveness the well-known mixture of agent D with N.N'-diphenyl-para-phenylenediamine significant surpasses

Example 18

In those extended with 15% naphthenic oil Buna S is introduced into rollers with phenolic amine resin obtained by the condensation of hexamethylenetetramine (Hexamine) was obtained with cumylphenol as in Example 3.

Phenol-formaldehyde novolak resin is used in control samples and means D introduced

Table 15 shows the changes in the physical-mechanical characteristics of the rubber test pieces during mechanical treatment of rubber in rollers at 140 ° C 20 minutes listed.

Table 15

Change in the properties of the rubber during mechanical heat treatment

in rollers

running antioxidant
No.

Dosage,% dimensional stability in h

Defo hardness

Regenerability

1. Medium D 1.5 29 29 2. Phenol formaldehyde resin 0.3 29 26th 3. Product of the condensation of the cumyl 0.1 78 88 phenols with hexamine 4th the same 0.3 94 100 5, the same 0.5 91 100

The results presented in Table 15 prove that the introduction of phenol amine resin in the rubber makes it possible to increase its stability greatly, the retention of ¹ Defoliärte of Kau * tschüks center D and phenol formaldehyde resin is under-mentioned conditions only 29%,

Example 19

In the Buna S Type 1500 in latex phase were different dosages of phenolafhinhafz introduced according to Example 18. For the purpose of comparison, under analogous conditions, Pheriol formaldehyde resin is used in

The rubber was introduced. The induction periods were introduced (τ), the values of which are given in Table 16.

Table 16

Influence of the resins on the stability of the rubber on oxidation with oxygen

running
No.

Antioxidants

Dosage, (13CVC),% Min.

1. Phenol-formaldebyd resin 0.3 12

2. the same 0.6 15

3. Product of the condensation 0.3 17 of the cumylphenol with

Hexamine

4. the same 0.6 50

5. desgi. 3.0 110

The results shown in Table 16 testify to the advantages of the phenolamine resin over it the control antioxidant in terms of its effectiveness

Example 20

In the Buna S, which is obtained with organolithium catalysts, phenolic resin according to Example 18 and control antioxidant e'- .. The test details for the rubbers after oxidation at 130 ° C are in the table at a temperature of 70-75 ° C 17 listed

Table 17

Influence of the resins on the stability of the rubber

the oxidation with oxygen

running
No.

Antioxidants

Dosing induction, % period,

1. Phenol-formaldehyde resin 0.5 40

2. Product of condensation 0.5 196 of cumylphenol with

Hexamine

The duration of the induction period of the oxidation of rubber with phenol amine resin exceeds 5 fold the induction period of the oxidation of this rubber • n when using phenol formaldehyde resin.

Example 21

In the oil-extended Buna S with the characteristics according to Example 5, this is carried out in rolls by the Condensation of the hexamethylenetetramine with phenol obtained resin, alkylated with styrene according to Example 2, introduced.

Rubber which contains 1.5% by weight of agent D is used as a control sample are the heat aging in an air thermostat at 100 ° C for 24 hours, the processing in Rolling exposed at 140 ° C for 20 minutes and checked for oxidation at 140 ° C. The test results are listed in Tables 18 and 19

Table 18

Effect of the phenolamine resin on the stability of the rubber under conditions de. Oxidation with

Oxygen (14 (TC) and heat aging (100 ° C)

running antioxidant

No.

Dosage,% induction period. Min

Walles plasticity

Initial plasticity

To
Aging

Conservation,

1. Means D

2. Phenolic amine resin

1.5

0.5

0.22
0.23

0.11
0.21

50 93

Table 19

Effect of the phenolamine resin on the stability of the rubber under mechanical conditions

Heat treatment in rolls

running characteristics
No.

Medium D (1.5%)

Starting. After treatment

Conservation,

Resin (0.5%)
Starting.

After treatment

Conservation,

1, defo hardness, ρ

2, regenerability, mm

3, Karrer plasticity

4, elastic regenerability, mm

530 185 35 * 30 490 93 2.4 0.8 33 2.4 2.2 92 0.38 0.59 155 0.38 0.41 107 2.85 1.99 70 2.85 2.76 97

The specified characteristics show that the use of phenolamine resin enables high stability to achieve the rubbers under conditions of their heat aging and mechanical heat treatment,

Example22

In the Buna S with the characteristic of Example 5 different dosage 4-cumyl phenol and product of the reaction of hexamethylenetetramine with cumylphenol is introduced into rolls at a temperature of 6O ⁰ C. DU Kautschukprobe3tücke be processed in rolling at 140 ⁰ C for 20 minutes. Table 20 shows the results of these tests

Table 20

The retention of the defo hardness during the mechanical heat treatment of the rubber

running Antioxidant Dosage,% Conservation of No. Rubber hardness according to mechanise 'he Heat treatment, 1. Control specimen without antioxidant S. middle 2. * f "\ ^ ÜJxi y ι JJ Ii 2 0 O ι 0.2 22nd 3. the same 1.0 36 4th Phenolic amine resin 0.2 90

As can be seen from Table 20, the Introduction of phenolic amine resin to maintain 90% rubber hardness after mechanical treatment, while when using 4-cumylphenol this is only retained to 36%.

Example 23

In the Buna S with the characteristics according to Example 5, phenolamine resin is fed in an amount in rollers of 0.5%, according to Example 4 by condensation of the hexamethylenetetramine with the mixture of para-tert-butylphenol was obtained with salicylic acid. The Plasticity Conservation Index (PRJ) is after aging at 140 ° C. for 30 minutes for this rubber 91%; the control specimen with agent D (1.2%) has an index of preservation of plasticity of 47%.

Example 24

In two test pieces from Buna N, antioxidants are placed in rollers at a temperature of 70-80 ° C introduced: agent D in an amount of 2.5% and product of the condensation of hexamethylenetetramine with 4-cumilphenol in an amount corresponding to 1.0%.

The effectiveness of these antioxidants was tested by oxidation of the samples produced at 140 ⁰ C. The test results are shown in Table 21.

Table 21

Influence of the phenolamine resin on the stability of the rubber when it is oxidized with oxygen

| fd,
fir.

Antioxidants

Dosage,%

Induction period, min,

Medium D 2.5 11

Product, der Kiiädensatiöri 1.0 87

of cumylphenol with

Hexamine

As can be seen from the table, the product of the condensation of cumylphenol with hexamine is almost complete 8 times more effective even at a lower dosage than agent D.

Example 25

The butadiene-α-methylstyrene rubber, which has been expanded with 15% naphthenic aromatic oil, is fed into rollers Phenolamine resin in an amount of 0.3% obtained by condensation of diphenylolpropane with hexamethylenetetramine was won. The rubber turns into a rubber mixture in nothing! rush after prepared according to the following recipe:

rubber 100 Stearic acid 1.5 Zinc oxide (Jl Altax 3 sulfur 2

The vulcanization is carried out at 143 ° C. for 60 minutes; the thickness of the panels is 0.3 mm. The constant of the speed of stress relaxation at 130 ° C. in the air is determined for the test pieces produced. For gums with resins these P, 34 ■ 10- ³ was, r for control sample "': i NeoZone D -0.43 x 10" ^3. From this it can be seen that phenolic amine resin is better than a standard antioxidant - Neozone D protects vulcanizuie from aging.

Example 26

In 200 g of butadiene-styrene rubber having the characteristic of Example 5 is inserted one gram of the condensation product of Bexamethylentetramins with ortho-hydroxybenzoic (salicylic) acid in rolling at 60 ⁰ C. The test piece produced is subjected to the mechanical heat treatment in rolls with an air gap of 1 mm at 140 ° C. for 20 minutes.

After the treatment, the rubber hardness with the resin mentioned is 80% and with the control specimen with Neozone D to 35%. The product of the condensation of hexamethylenetetramine with para-

Hydroxybenzoic acid leads to an analogous result.

Example 27

In the 1500-type butadiene-styrene rubber in the latex phase, phenolamine resin is introduced which by condensation of hexamethylenetetramine with octylpheno! according to example 1, starting from 0.2%, 0.5% and 1%, was recovered. Only agent D in an amount of 1% is included in the control specimen on the rubber. After the rubber has been separated and dried, it becomes rubber mixtures prepared in parts by weight according to the following recipe:

rubber

Stearic acid

Zinc oxide

Altax

sulfur

100
1.5
5
3
2

10 The vulcanization is by! Conducted 43 ⁰ G for 60 minutes.

The vulcanizates are exposed to the Wärrheälterung at 100 ⁰ C in an oven for 3 and 5 days.

Table 22 contains information about the change in the tensile strength and the related elongation of the respective specimens listed.

Table 22

Aging of the vulcanizates in the presence of phenolic amine resin

running antioxidant
No.

Dosage, ° / l tensile strength, kp / cm ²

Duration, days

0 3 5

Related elongation,%

Duration, days

0 3 5

1. Product of condensation d. Octyl 0.2 260 233 243 600 535 540 1 phenols with hexamine i 2. the same 0.5 260 349 215 650 580 500 3. the same 1.0 260 217 220 630 490 490 4th Medium D 1.0 260 198 173 570 424

As can be seen from the table, the phenolamine resin protects the vulcanizate from heat aging better than D.

Example 28

The butadiene-alfa-methylstyrene rubber specimens, the analog of the rubber of type 1712 were admitted:

Antioxidant

35 dose content
tion, of resin,
Amine, %%

PRJ,

Mixture of agent W 0.6
with phenolamine resin

40

a) Mixtures of the secondary amine product from the condensation of diphenylamine and acetone (Antioxidant agent B) with phenolamine resin, which is produced by condensation of hexamethylenetetramine was obtained with octylphenol according to Example 1;

b) Mixture of the secondary amine - para-phenylenediamine derivative (Antioxidant Agent W) - with the same phenolamine resin. The exam results on heat aging according to the index of plasticity maintenance are given in Table 23 cited

Table 23

Effectiveness of the mixtures of phenolamine resin with agent B and agent W

0 22nd 0.2 81 0.4 87 0 37 0.2 67 0.4 87

45

Antioxidant

Dosage,
Amine, %

salary
of resin,

PRJ,

Mixture of means B
with phenolic amine resin

0.6

0 20th 0.2 58 0.4 90 0 21 0.2 50 0.4 90

As can be seen from Table 23, are already increasing

the small additions of phenolic amine resin significantly increase the effectiveness of the known antioxidants from the series of the secondary amine, respectively

so diamins.

Example 29

200 g of butadiene-styrene rubber of the 1500 type are poured into rollers. 0.2 g of phenolamine resin is passed through Condensation of the nonylphenol with hexamethylenetetramine was recovered, and 2 g of 2,6-di-tert-butyl-4-methylphenol (Ionol) to it. The rubber becomes the Heat aging exposed at 140 ° C for 60 minutes. The plasticity retention index is in this case 97%, in the case of control specimens with the resin alone 90% and with Ionol alone 75%.

Example 30

200 g diluted with 15% aromatic naphthenic oil Butadiene-styrene rubber is placed in rollers with 0.2 g of phenolamine resin, which is composed of hexamine and octylphenol was recovered, and 24 g of tri (nonylphenyl) phosphite

(Polyhard) too. The rubber is heat aging on control specimens of the rubber with resin

exposed at 14O ⁰ G for 30 minutes. The index alone 85% and with Polyhard alone 40%.
the retention of plasticity of the rubber is 99%,

Example 31

100 g of butadiene-styrene rubber of type 1712 are added to thiodipropionate. The index of plasticity conservation

0.4 g of phenolamine resin, which is composed of hexamine after aging of the rubber at 140.degree. C., is placed in rollers

and octylphenol was recovered, untf- O _n Sg dilauryl for 30 minutes 90%.

Claims (3)

Patent claims: 1. Use of phenolic amine resins, the condensation products of hexamethylenetetramine with alkyl, alkenyl, dialkyl, arylalkyl and halogen substituted Phenols or dioxydiphenylalkanes, oxybenzoic acids and mixtures of the mentioned Resins with antioxidants from the series of sec. Amines, diamines, 2,6-dialkyl derivatives of phenol, Represent phosphorus and sulfur-containing compounds as antioxidants for stabilization of rubbers and vulcanizates. 2. Use according to claim 1 in an amount of 0.02 to 10%. 3. Use according to claim 1 or 2 in an amount of 0.2 to 0.4%.