Ftorjelastomery composition

 

(57) Abstract:

Usage: when processing forecasters containing bromine in the polymer chain. The inventive ftorjelastomery composition comprises at least three components: a polymer, a peroxide curing agent and an additive that reduces the allocation of highly toxic volatile products processing - methylbromide, ethylbromide, etc., the Mass ratio of the additive to the peroxide curing agent is 0,18-1,42 per 100 wt.h. the polymer. Additive chosen from the group of compounds comprising maleic anhydride, derivatives maleamide, derivatives of diphenylguanidine, benzothiazole and its derivatives, derivatives of teorama. 7 table.

The present invention relates to forecasters compositions.

Curing organic peroxides forecasters containing as centres of curing along the polymer chain and/or at the end atoms of bromine or iodine is well known. In such forecaster bromine or iodine are introduced into the macromolecule elastomer by using at the stage of polymerization of brominated or yugirovannykh of comonomers, such as in particular fibromyalagia olefins, brominated or yugirovannykh ferminia as transmitters chain.

When peroxide curing mainly use organic peroxide aliphatic or cycloaliphatic type, or a saturated or unsaturated alkylaromatic type, such as, for example:

2,5-dimethyl-2,5-di(tert-BUTYLPEROXY)hexene-3,

2,5-dimethyl-2,5-di(tert-BUTYLPEROXY)hexane,

dicumylperoxide, tert-butylperbenzoate,

ethyl-3,3-di-(tert-BUTYLPEROXY)butyrate,

1,1-bis(tert-BUTYLPEROXY)-3,3,5-trimethylcyclohexane,

which in the process of curing promote the release of methyl or ethyl radicals. These radicals, connecting with bromine or iodine contained in the fluoroelastomer made, can contribute to the formation of the above-mentioned methyl or ethylbromide or iodides, which are highly toxic and probably carcinogenic volatile products.

Therefore, although the cured product obtained by peroxide curing forecasters, bromine or iodine, show excellent properties and characteristics that are at least partly better properties forecasters, hardened by ions, peroxide curing the above-mentioned products poses a serious danger to the health of operators and the

Thus, the purpose of the present invention is to overcome the above-mentioned serious shortcomings by adding to the curable mixtures of substances can significantly reduce the allocation methyl - or ethylbromide or iodides in the curing process.

The closest analogue of the present invention is a reference to the use of organic fofanah compounds and peroxides for curing forecasters in Encyclopedia of Chemical Technology, Kirk-Othmer, 3rd edition, T. 8, 1979, page 506.

Indeed, it has been unexpectedly found that certain types of substances introduced into the mixture in moderate amounts, usually from 0.1 to 3 weight.parts per 100 weight. parts of fluoroelastomer made that could significantly reduce the allocation of these toxic products without any noticeable changes in curing or characteristics of the product of vulcanization. The mechanism of action of the additives of the present invention, probably based on the fact that they can be combined with a methyl or ethyl radical, resulting from an organic peroxide, resulting in the formation of new radicals capable of further reaction cross-linkage. This prevents any formation of methyl-t actually suitable as additives in accordance with the invention. Indeed, many compounds that are able to reliably block of methyl and ethyl radicals and which sharply reduce the allocation of the above-mentioned bromides and iodides, adversely affect the curing process, with the result that he becomes too slow and inefficient and leads to products of vulcanization of very poor quality.

Products suitable as additives in accordance with the present invention are selected from compounds belonging to the following classes:

a) benzothiazole and its derivatives of General formula:

< / BR>
in which X represents H,

< / BR>
< / BR>
in particular benzothiazole, 2-mercaptobenzothiazoles, benzothiazole disulfide, morpholine-2-benzothiazolesulfonamide, cancerchemotherapy.

b) derivatives Melamid General formula:

< / BR>
in which A= H, or together with T forms a bond, T is a group-OH,

< / BR>
or together with A forms a link;

represents H, alkyl (C1-C6the halogen atom, the nitro-group and when T makes a connection with A, R can also be:

< / BR>
C) derivatives of Turnov General formula:

< / BR>
in which Y represents a

< / BR>
R' represents alkyl, C1-C4that is as General formula:

< / BR>
in which R1represents a hydrogen atom, alkyl, C1-C6in particular compounds in which R1represents H or methyl. In addition, other compounds such as maleic anhydride, diarylprymidine and derivatives of diazo - and triazacyclononane proved to be suitable as additives.

In accordance with the present invention supplements when they are used in amounts generally from 0.1 to 3 weight. parts per 100 weight. parts of elastomer (p. h. g) and in particular from 0.2 to 2 p.h. g, in addition to a significant reduction in emissions of the toxic products of methyl - or ethylbromide or iodide, in some cases, 90% give the curable compositions of the following characteristics:

the increased time required for the occurrence of burnout (burnout) and consequently increasing the security of processing,

the decrease in viscosity of the mixture (Mooney) and therefore improved processability,

a modest impact on the speed and output cross-linkage 180oC.

All of the above additives can be prepared by the known methods described in the technical literature.

Forecaster, applies to the present image is to quote the following. Copolymers CH2=CF2with perferrable and optional with perforations, as well as with performancewise ethers containing small amounts of bromine or iodine, which are introduced by copolymerization of a small amount of brominated or yugirovannykh monomers, such as brominated olefins, perforrmance-performancewise ethers, or by the use of chain transfer, consisting of bromine - or italicising connections.

Mixture-based forecaster, cured by peroxides, which can be added in accordance with the present invention, in addition to the organic peroxide include conventional components, such as carbon black and other reinforcing fillers associated with peroxide curing agents (for example, triallylisocyanurate), oxides or hydroxides of metals (such as lead oxide, zinc oxide) and processing tools.

The following examples are given to illustrate but not to limit the present invention.

Assessment of the allocation of methyl bromide under the conditions of curing is usually conducted according to the following method.

Opportunities for dosing ejecta oC in a closed reactor for 30 minutes at a pressure of 0.5 ATA in nitrogen atmosphere. The mixture is then cooled to 40-50oC and added as an internal standard 1 cm3dichlorotetrafluoroethane (A114, so Kip.4oC).

The gas phase is stirred and subjected to gas chromatographic analysis; column porapak TOyT=100oC.

In contrast, in example 2, the actual allocation occurring under practical conditions of curing at 170oC, is determined by measuring methyl bromide in air samples taken above the mold.

Used elastomer:

P. 1 ternary copolymer of 66,2 mol. CH2CF2, 18.2% of performability, 15.2% of tetrafluoroethylene containing propertieswindow simple ether in a quantity equal to 0.65 weight. bromine.

P. 2 ternary copolymer of CH2CF2(54,1 mol.), 22.2% of performability, 22.9% of tetrafluoroethylene containing propertieswindow simple ether in a quantity equal to 0.54 weight. bromine.

Components of mixtures, in addition to the additives according to the invention, are as follows (in weight parts per 100 weight. parts ternary copolymer):

-2,5-dimethyl-2,5-di-tert-butylperoxide at 45% inert filler (and 75% inert filler, 4 pieces,

the lead oxide, 3 parts,

carbon black MT 30 parts.

Assessment of the propensity to curing is carried out by determining the torque element (MH-ML) using ODR oscillating disk rheometer (type Monsanto) according to ASTM D2084/81.

The measurement is carried out at 180oC, maximum torque MH define in 12 minutes "sector 3".

Example 1

Testing was performed using a triple polymer P. 1. The elastomer without the additive according to the invention was made in the curing process the value of D torque equal to 71.

In some trials a weak decrease in the allocation of methyl bromide were caused by insufficient amount of additive: by increasing this amount in the range cited above interval, it is possible to improve the effect (see, for example, tests 7 and 8, PL. 1).

Test 21 is a comparative test is a variant of products that dramatically reduce the allocation of methyl bromide, but at the same time they prevent or greatly reduce the curing time.

Example 2

The tests were carried out in order to check the correspondence between the reduced allocation is the group of made in the curing process in the mold at 170oC operating conditions (determined by analysis of a sample of air taken above formed products immediately after extraction of the vulcanizate from the form). Used additive was mercaptobenzothiazole (MTBS), the test was performed without additives, in order to have a comparison of the values of the rotating moment D and the allocation of methyl bromide.

Used elastomer was described above copolymer type R. 2. The results (see tab. 2) are the average of the five definitions of air samples.

Example 3

Characteristics of the curable mixtures and product vulcanization.

These characteristics were compared with the same products without additives and in the following tables.

In particular, from table 3 it is obvious that a mixture containing the additive according to the invention show a significantly longer time to burn, reduce the Mooney viscosity when warping (135oC) and a decrease in Mooney viscosity at 121oC; these characteristics are indicative of better processing AIDS mixture.

Table 4 contains some characteristic value, which is the Example 4

Tests are shown in table 6, show that the decrease in the allocation of methyl bromide and the tendency of curing is changed by varying the polymer type and content of bromine.

In all trials, are shown in table 6 used additive was phenylmaleimide:

< / BR>
Other components of the mixture were (p.h. g): Loparco 3; TAIC 4; lead oxide 3; carbon black 30.

Examples 5 9

In all examples, the polymer is P1and the additive is METS in the amount of 0.5 hour to 100 hours of the polymer, the formula of which is given in the table. 3.

As the peroxides used:

in examples 5 and 6, Luporco 101XL, which is 2,5-dimethyl-2,5-di-tert. butyl-peroxy-hexane at 45% inert filler (see page 9 of the description of the application) and which is aliphatic peroxide;

example 7 use of 2,5-dimethyl-2,5-di-tert. butyl peroxy-hexyne-3, which is another aliphatic peroxide;

example 8 use dicumylperoxide, which is alkylaromatic peroxide;

in example 9 using 1,1-bis/tert.BUTYLPEROXY/-3,3,5-trimethylcyclohexane, cycloaliphatic peroxide.

Other additives in each example are TAIC (triesta polymer.

The following is a modification of the dispensing allocation CH3Br. The nature of the ingredients and the results are shown in table 7.

The vulcanization is carried out at 180oC with peroxides examples 5, 6 and 7, at 170oC with peroxide of example 8 and 160oC with peroxide of example 9.

Ftorjelastomery composition comprising the fluorine-containing polymer having a bromine in the polymer chain, peroxide curing agent, characterized in that the polymer contains a copolymer of vinylidenefluoride with HEXAFLUOROPROPYLENE and/or without tetrafluoroethylene with brainlove simple ether, as a peroxide curing agent it contains aliphatic, cycloaliphatic or alkylaromatic peroxide, the composition further comprises an additive selected from the group of compounds of the following structural formula:

a) derivatives maleamide:

< / BR>
where R is H, CH3, -Cl, -NO2;

b) maleic anhydride;

g) derived diphenylguanidine

< / BR>
where R1C1-C6-alkyl, -N;

d) benzothiazole and its derivatives

< / BR>
where

< / BR>
< / BR>
e) derivatives turama

< / BR>
where

< / BR>
where R2-C2H5,

when the next mass attributed the

 

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