Amplifiers adhesion rubber

 

The invention relates to ORGANOMETALLIC compounds, to compositions containing them and their use. Vulcanicola rubber mixture contains natural rubber, one or more conventional components, rubber compound and at least one ORGANOMETALLIC compound as an adhesion promoter of the General formula X(OMA'p)m(OMB'q)nwhere X represents aluminum, titanium, zirconium or silicon, alkyl - or kilcranny or dialkyl-, diaryl - or alkylidene; M is cobalt or Nickel; And a' is the radical of aliphatic carboxylic acid having 7-15 carbon atoms; a' is the radical of an aromatic carboxylic acid having 7-15 carbon atoms or an aliphatic or aromatic aryloxyalkanoic acid with 8 to 15 carbon atoms; p and q is independently from 0.5 to 1.5; m+n=x, where x represents the valence of X, m/n is equal to 0.67-9.0 and n is 0.2 to(x-1). Rubber consists of a rubber mixture comprising at least one adhesion promoter and one or more additives. The technical result consists in increasing the adhesion of rubber to steel Corda was with a brass coating and keep it during aging under conditions of steam or saline environment. 2 C. and 8 C.p. f-crystals, 1 table.

This izobreteniya, containing three atoms of divalent metal such as cobalt, which is attached via oxygen atoms to the boron atom or phosphorus containing radicals of aliphatic monocarboxylic acids attached to the metal. These known compounds are used as additives to the rubber mixtures to enhance the adhesion of rubber to metal.

They put in a form which is easily handled and which, in particular, is not inherent stickiness or viscosity.

In the present invention proposed new connections, which have advantages compared with the above-mentioned known compounds and which, in addition, yet enhance the adhesion of rubber to steel Corda was with a brass coating and retain such adhesion during aging under conditions of steam or saline environment in comparison with the known containing cobalt compounds.

In accordance with the present invention proposed ORGANOMETALLIC compound for use in order to enhance the adhesion of rubber to metal, having the General formula X(OMA'p)m(OMB'q)nin which X represents aluminum, titanium, zirconium, alkyl - or aryl and silicon; M represents a cobalt or Nickel, preferably cobalt(II); And' represents the radical of aliphatic carboxylic acids (General formula RCOO) with 7-15 carbon atoms; a' represents the radical of an aromatic carboxylic acid (General formula R) with 7-15 carbon atoms or arylacetamides aliphatic or aromatic carboxylic acid with 8 to 15 carbon atoms; p and q are independently from 0.5 to 1.5, preferably 1.0 to; n+m= x, where x is the valency of X, m/n typically ranges from 0.67 to 9,0, preferably from 1.5 to 4.0; typically, n ranges from 0.2 to (x-1), preferably from 0.5 to 3, and particularly preferably from 0.5 to 1.4.

If X is an alkyl and/or aryl-substituted compound of silicon, an alkyl group preferably is a group having from 1 to 4 carbon atoms, particularly preferably stands, while the aryl group is preferably phenyl. Typical examples include methylchromone, dimethylene, diphenylcresyl and methyl-, phenolchemie.

Aliphatic of Carbonara acid (A N) is preferably a monocarboxylic acid, for example n-heptane acid, 2,2-dimethylpentane acid, 2-ethylpentane acid-dimethylcarbamoyl acid, 2,4,4-trimethylpentane acid, n-nonanoyl acid, 2,2-dimethylheptane acid, 6,6-dimethylheptane acid, 3,5,5-trimethylammonium acid, n-dekanovu acid, 2,2-dimethyloctane acid, 7,7-dimethyloctane acid, n-undecanoyl acid, isodecanol acid, cekanova acid or a mixture of 2,2,2-trialkylborane acids, known as neodecanoate acid.

To aromatic acids ('- N) may include, for example, benzoic acid, alkyl-, alkoxy, amino-, halogen-, thio -, or replacement of benzoic acid, such as 2-, 3 - or 4-methylbenzoic acid, salicylic acid, 3,5-diisopropylsalicylic acid, 3,5-di-tert-butylsilane acid, o-aminobenzoic acid or 4-chlorbenzene acid, phthalic acid, terephthalic acid, cinnamic acid or the majority of complexes of aromatic acids containing cyclic system. If'-N is aryloxyalkanoic acid, it preferably represents phenoxytoluene aliphatic or aromatic acid, particularly preferably phenoxyacetyl acid and phenoxypropionic acid.

ORGANOMETALLIC compound can be associated with a borate of an element of group IA or IIA of the periodic activities is estvovati in concentration, for example, up to 20% by weight of metal joining. To suitable borates include sodium borate, potassium borate, calcium borate and magnesium borate.

ORGANOMETALLIC compound may also be associated with microcrystalline wax and/or recycled oil and/or hydrocarbon resins, and/or with resorcine-formaldehyde resin.

ORGANOMETALLIC compounds may be introduced as amplifiers adhesion in rubber mixtures for promazyvanija containing rubber and normal components of the rubber mixtures. The rubber mixture can be reinforced with steel with brass plated, and then vulcanized.

ORGANOMETALLIC compound is present, generally in amounts of from 0.2 to 2 weight. hours at 100 weight. including rubber, and preferably ORGANOMETALLIC compound is approximately 0,224 weight. including cobalt metal per 100 weight. including rubber.

ORGANOMETALLIC compounds in accordance with the present invention can be obtained by combining the heating of the mixture in the desired proportions: (1) acids A N D N, which is injected at elevated concentrations relative to the radicals And' and', as defined above, (2) donor cobalt or Nickel, such as oxides, Gigi acid and (4) acid, capable of forming volatile ester with radicals, lower alcohols present in said complex ester, for example acetic acid or propionic acid, and distillation mentioned volatile complex ester, preferably under reduced pressure. All acid (1) and (4) and donor metal (2) must respond before the addition of ester (3). The reaction temperature is usually in the range from 50 to 250oC.

The invention is illustrated by the following examples. In examples 1-4 describes the obtaining of new ORGANOMETALLIC compounds.

EXAMPLE 1.

The solution of cobalt propionate with neodecanoate (891 g) in mineral spirit was heated to 50oWith mechanical stirring. Added propionic acid (44 g) and benzoic acid (72.5 g). The reaction mass was stirred for 10 minutes and added hydroxide cobalt (57 g). The reaction mixture is slowly heated to 195oWith and perform the distillation of water (24 g) and white spirit (446 g), and to complete the distillation used the vacuum. In the reaction mixture at 170oWith added methyltriethoxysilane (126,1 g) and supported reaction using the reverse of the refrigerator for 4 hours before fulfilled about what ispolzovanie vacuum.

Product (540 g) was a brittle solid substance blue generalized formula
MeSi[OCo(neodecanoate)1,0]2,16[CCA(benzoate)1,0]0,84
and contained 22,9% (wt./weight.) cobalt.

EXAMPLE 2.

The solution of cobalt propionate with neodecanoate (817 g) with 9.8% of cobalt in mineral spirit was heated to 40oWith under stirring. Added propionic acid (44 g) and benzoic acid (71,8 g). The reaction mass is added hydroxide cobalt (55,4 g). The reaction mixture was heated to 190oWith and perform the distillation of water and white spirit (with a total weight 415 g), and to complete the distillation used the vacuum.

Slowly added triisopropoxide aluminum (132 g) and heated the reaction mass to 190oBy doing the Stripping propionate complex isopropyl ether as his education.

The reaction temperature is slowly raised to 240oIn order to drive away the last remnants of ester, and to complete the distillation used the vacuum. Just received 159 g Isopropylamine.

Product (533 g) was a brittle solid substance blue generalized formula
Al[CCA(neodecanoate)1,0]2,1[OCo(benzoate)1,0]for 0.9
and contained 20.8%of acid (188 g), benzoic acid (88 g) and toluene (200 g) and was heated to 50oWith mechanical stirring. Added hydroxide cobalt (233 g) and raised the temperature to 90oWith obtaining low-viscous blue liquid. Continued heating further for removing water from the reaction mass using the apparatus of Dean-stark, raising the reaction temperature up to 190oAnd removing the last traces of solvent under vacuum, receiving 91 g of water and 206 g of toluene. To the reaction mass at 160oWith slowly added tetrabutyltin (205 g) and maintained the reaction at a temperature of irrigation 160oC for 3 hours. By distillation removed butylphosphonate when heated to 230oWith, and to complete the distillation used the vacuum.

Product (624 g) was a brittle solid substance blue generalized formula
Ti[CCA(neodecanoate)1,0]2,8[CCA(benzoate)1,0]1,2
and contained 22,5% (wt./weight.) cobalt.

EXAMPLE 4.

In a reaction flask equipped with a mechanical stirrer, was loaded neodecanoate acid (193 g), benzoic acid (62 g) and toluene (420 g). To this mass was added to the cobalt hydroxide (156 g) and propionic acid (130 g).

Slowly raised the temperature to 120oFor complete distillation used the vacuum. To the reaction mass slowly added tetraethylorthosilicate (85 g) and maintained the reaction at a temperature of irrigation 145oC for 2 hours before removing ethylpropane (136 g) by distillation by heating to a final reaction temperature of 230oWith, and to complete the distillation used the vacuum. Product (416 g) was a brittle solid substance blue generalized formula
Si[CCA(neodecanoate)1,0]2,75[CCA(benzoate)1,0]1,25
and contained 22,8% (wt./weight.) cobalt.

The rubber mixture in accordance with the present invention includes a rubber plus one or more ordinary included in the rubber compound components such as pigments, fillers, diluents, accelerators, antioxidants, vulcanization agents, etc. and, as adhesion promoter, ORGANOMETALLIC compound in accordance with the present invention. Prepared rubber mixture having the following composition in weight.h.:
Natural rubber SMR 10 - 100
Peptization (Renacit 12)a)- 0,05
Carbon black MAF (vozdushno,7
Insoluble sulfur - 4,0
a)Zinc salt of pentachlorothiophenol,
b)N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine,
c)N,N-DICYCLOHEXYL-2-benzothiazolesulfenamide.

Vulcanized compositions prepared by using the above rubber compound and amplifiers adhesion listed below. Amplifiers adhesion added to the rubber mixture in the mixing process in a laboratory mixer with a volume of 15 liters and laminated into a sheet on a laboratory rolling mill with Z-shaped corrugation rolls. All the formulations were vulcanizable at a temperature of 90oWith plus for eight minutes at 153oC.

The adhesion test was performed using a modified tests at static stretching on the basis of the methodology of the American society of testing materials ASTM D2229 using the length of the cover 10 mm Used standard tire cord steel with brass coating having the structure 2+2 = X 0,25 for Bekaert'y, each cord had a covering of brass with an average copper content of 63.5 per cent. The amount of coating was determined in Newtons/10 mm the Results are shown in the table.

Modes of aging:
Par 16 hours at 121oWith
Humidity 7 days at 70oC and a relative humidity of 95%
), shown in these tables show that the rubber mixture containing ORGANOMETALLIC compound in accordance with the present invention shows significantly improved adhesion of rubber to metal in comparison with the known compounds of breedekloof. This improvement is especially noticeable during aging in the pair. In addition, new ORGANOMETALLIC compounds exhibit equivalent properties at lower usage than the corresponding breedekloof.

In one embodiment, the ORGANOMETALLIC compound was applied to the substrate, for example, from the oil solution of the compounds. The substrate, typically consisted of a silicon dioxide or a silicate of a metal of group IA or IIA, such as sodium silicate, potassium silicate, magnesium silicate or calcium silicate.


Claims

1. Vulcanicola rubber compound containing natural rubber, one or more conventional components, rubber compound and at least one ORGANOMETALLIC compound as an adhesion promoter General formula

X(OMA'p)m(OMB'q)n1

where X represents aluminum, titanium, zirconium or silicon, alkyl - or kilcranny a radical of aliphatic carboxylic acid having 7-15 carbon atoms;

In' represents the radical of an aromatic carboxylic acid having 7-15 carbon atoms or an aliphatic or aromatic aryloxyalkanoic acid with 8 to 15 carbon atoms;

p and q are independently from 0.5 to 1.5;

m+n=x, where x is the valency of X, m/n is from 0.67 to 9.0 and n is from 0.2 to (x-1).

2. Rubber mixture according to p. 1, where M represents Co(II).

3. The rubber mixture under item 1 or 2, where' represents the radical of benzoic acid, 2-, 3 - or 4-methylbenzoic acid, salicylic acid, 3,5-diisopropylsalicylic acid, 3,5-di-tert-butylsilane acid, o-aminobenzoic acid, cinnamic acid, PHENOXYACETIC acid and phenoxypropionic acid.

4. Rubber mixture according to any one of paragraphs. 1-3, where a' is a radical neodecanoic acid, soundcanvas acid, cekanova acid or 2-ethylcaproic acid.

5. Rubber mixture according to p. 4, where m/n is from 1.5 to 4.0.

6. Rubber mixture according to any one of paragraphs.1-5, where the ORGANOMETALLIC compound is associated with up to 20 wt.% Borat metal of groups IA or IIA of the Periodic table of elements.

7. Rubber mixture according to any one of paragraphs.1-5, where the ORGANOMETALLIC compound is associated with microcrystalline wax, with the new mixture according to any one of paragraphs.1-5, where the ORGANOMETALLIC compound is applied on the silicon dioxide or a silicate group IA or IIA.

9. Rubber mixture according to any one of paragraphs.1-8, containing from 0.2 to 2.0 weight.h. mentioned ORGANOMETALLIC compound per 100 weight.h. rubber bracelet.

10. Rubber consisting of vulkanizetas rubber mixture according to any one of paragraphs.1-9, reinforced steel with a brass coating.

Priority PP. 1-10 10.10.1997 and 24.10.1997.

 

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