CS255376B1 - Activating agent - Google Patents

Abstract

The essence solutions is a the use zeolites, with gauge surface 5 until 300. m 2 . g _1 . than activator "in are you here " to reduction temperature. the decomposition du blowing agents on the· a base; l, 5-methano-3J7-dinit- Rozoy-l, 3,5,7-tetraazacyklooktánu and / or. azo.- dikarbónamidu. and deodorising released fumes in process formation rubber or plastics in-roducts. solution is a possible used at production blowing agents, respectively. production rubber; and plastics; materials.

Description

The invention relates to the use of zeolite for activation and / or activation. deodorizing rubber or plastics mixtures.

One of the negative properties of some substances commonly used in the rubber and plastics industries is the fact that in the processing process these additives escape from the mixture in the form of odorous fumes. Of particular note are the unpleasantly odorous organic nitrogen compounds formed during the decomposition of blowing agents, in particular on the basis of 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane (I) and azo-di- carbonamide (II) formulas:

ON-N CH, N-NO

I 1 I

CH ^ · N 'CN _Z

U)

NH2 — CO — N = N — CO — NH2 (Π)

E.g. the intermediates of thermolysis of 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane are methyleneimine fragments which produce an unpleasant odor by reaction between themselves and / or with the sulfur and other components of the rubber mixture. The formation of odorous compounds is removed by additives capable of acting as components in N-Mannich condensations. In this sense, urea and its derivatives are most commonly applied, as well as a mixture of fine grain urea with ethylene glycol or glycerin (AA Berlin, FA Sutov: Chimija i technologija gazonapolnenych vysokopolimerov, Izdat. Nauka, Moscow, 1980; J. Simonik, J. Balusek: bulletin, VUGPT, Gottwaldov, March-April, 1977, p. 55).

The presence of ethylene glycol, sometimes also boric acid, in deodorized mixtures and the concomitantly protected application of cyanuric acid as a deodorant (Japanese Pat. No. 73 37 347) suggests that the formation of odorous products can also be blocked by protogenic substances in which 5-methano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane (i.e., 120-160 ° C) does not show any significant evaporation.

A disadvantage of the known state is the fact that, when stored, you may reach the stratified blowing mixture, furthermore most of the deodorants used are toxic and their effects are specific.

These drawbacks are overcome by the present invention which, as an activator, is in situ to reduce the decomposition temperature of blowing agents based on 1'-methano-5'-dinitroso-1S, 2'-tetraazacyclooctane and / or azo-dicarbonamide, and deodorizing the released flue gases used in the process of forming rubber or plastics products used zeolite, with a specific surface area of 5 to 300 m ² . g ^_1 .

An advantage of the present invention is the easy availability of the activating and deodorizing additive. Its use will increase the economic efficiency of the production of rubber and plastics materials by saving expensive auxiliary additives, especially activators, fillers, blowing agents and energy.

The nontoxic additive reduces the decomposition temperature of the blowing agent, affects the rate of vulcanization and removes odors of pollutants from lightened and vulcanized systems, respectively.

Of the more than 200 known types of zeolites, only about ten, e.g. from natural clinoptilolite, mordenite, shabazite, erionite; from synthetic zeolite A in Na-, K- and Ca-forms, X in Na-, Ca- and Ba-forms, Y in Na-, Ca- and NHd- forms, synthetic mordenite in Na- and H- forms, omega in Na- - and H-forms and ZSM zeolites.

While zeolites of the clinoptilolite type on modernite are the only natural zeolites found in Slovakia that constitute economically significant accumulations. They are the zeolites with the highest Si content, have high chemical and thermal stability.

Zeolites are aqueous aluminosilicates of alkali metals (Na, K, Li) and alkaline earths (Ca, Mg, Ba, Sr) of the general formula:

(M2 ^+, M ^{2 +)} H. Al2O3. g S1O2. from H ₂ O, where M ⁺ , M ² * · are monovalent and divalent cations; g and g are moles.

Tufas with the dominant clinoptilolite are the most widespread and investigated. They have been shown to have the most versatile use. In addition to the Si / Al (1,5-6) ratio, its cationic form, which determines thermal stability, ion exchange ability and adsorption capacity, is also of major importance.

The unexpected effect of zeolites is that they increase stability when blended with the active blowing agent component, while decomposing (reducing the decomposition temperature of the blowing agent) in the rubber blend and adjusting the vulcanization rate.

The variability of the zeolite composition has no significant effect on the protected effect, since its specific surface area, which has no significant dispersion, is used. The chemical composition of zeolite is usually guaranteed by the manufacturer. Nevertheless, it is necessary to monitor the content of some undesirable ingredients, e.g. sulfur oxides and rubber poisons, so as not to exceed a harmful amount with regard to the storage safety and quality of the products concerned.

The favorable amount of zeolite applied is usually up to 60% by weight. and only rarely need to add more.

The use of zeolites in accordance with the present invention has not been described in the literature to date and is illustrated by the following examples.

Example 1

Technical 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane containing

4.9 wt. 1,3,5-trinitroso-1,3,5-triazacyclohexane, zeolite-clinoptilolite with the following specification:

Average chemical composition loss on ignition (1000 ° C) 6.74 to 10.19%

SiO2 60.63 to 71.76%

AI2O3 11.47 to 12.85%

Alkylthio; s 0,30 to 0.33% FeiOj 1,65 to 1,72% CaO 3.50 to 4.36% Mg O 0.50 to 1,26% MnO tracks up 0.01% Nazo 0.55 to 0.70% K2O 2.26 to 3.02% P2O5 0.02 to 0.05% SO3 0.03 to 0.09%

Spectral analysis revealed 400 ppm of Ba, 350 ppm of Sr, 13 ppm of Pb, 3 ppm of Cu and traces of As, Hg, Cd, F, Cr, in samples of zeolite rock ground to a fineness below 0.09 mm containing approximately 53% clinoptilolite Sn, Bi, Ga, Ni, Li, Y, Yb.

Physico-mechanical properties Specific gravity Specific gravity Rock hardness Rock agility according to VTI Compressive strength of rock (cat 50X50X50 mm) Specific surface (Absorption method Effective surface [from water adsorption

222 to 2,440 kg. nr ³

850 to 1,950 kg. ιτγ ³

1.5 to 2.0 degrees by Mohsa

1.205, t. j. medium to good grindable

20.3 to 49.7 MPa F) 25 to 30 m ² . g ^J r) 120.33 to 140.66 m ² , g ¹

Bulk density of rock (4-7% moisture):

fraction kg. m ~ ³ ground (0 to 0.2 mm) 670 to 1 mm 945 to 4 mm 1 090

0.2 to 2 mm 830 to 950

0.5 to 1 mm 845

2.5 to 3.15 mm 905 to 5 mm 760 to 850 to 16 mm 780 to 30 mm 810

Granulometry of the sample used particle size above 20 µm 22.9% below 20 µm 77.1% and water-soluble reaction products of urea with formaldehyde in an alkaline medium - a mixture of mono- and dimethylurea (Dezo 6). A mixture containing 53 wt. % of nitroso derivatives, 31 wt. % zeolite, 5 wt. Dezo 6 and 11 wt. water.

By means of differential thermal analysis (DTA), the prepared mixture shows a water evaporation peak at 112 ° C, an onset of decomposition of 125.5 ° C, and a first exo peak at 172.3 ° C.

The gas number of the mixture is 176 cm ³ . g ^-1 .

This mixture is further specified by activation energies and air induction periods; the reference blowing agent is a commercial mixture of Chempor PC-55 (containing 55% by weight of technical 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane; 45% by weight Dezo 6).

Table 1

Explosion characteristics

The blowing agent mixture of Example Chempor PC-55

Activating energy (kj mol ^-1 )

Induction period ls)

Tau 100 ° C Tau 150 ° C Tau 190 ° C

note:

Tau - inductive period

Chempor PC-55 has a water evaporation peak at 110-115 ° C, an onset of decomposition of 76-80 ° C and a first exo-peak at 167-173 ^° C,

Example 2

The blowing agent of Example 1 is applied to lighten polyvinyl chloride (PVC) based products. In a kneader heated to a temperature of 120 to 140 ° C, 62.1 kg of polyvinyl chloride E-PVC (emulsion type of K-hoduote 67 +1), 3.0 kg of zeolite (spec. As in Example 1) were mixed, 2 kg of lead stearate, 0.6 kg of stearin (Astra) and 2.3 kg of blowing agent according to Example 1. 17.9 kg of phthalate dioctes, 6.0 kg of dioctyladipate and 6.9 kg of chloro-paraffin are then added equally. The composition is mixed at 130 ° C and then cooled to 40-60 ° C. The processing of this composition is carried out on a twin screw extruder with a 100 X 2 mm die at temperatures of 130 to 160 ° C. The resulting extrudate has a uniform porous structure and is odorless.

Example 3

A first composition is prepared consisting of 100 kg of an emulsion polyvinyl chloride having a K-value of 70, 77 kg of a mixed triarylphosate based on phenol and isopropylphenols (Retar 131), 14 kg of micronized limestone, 2 kg of dibutyltin maleate. 12 (SiO 2) 12. 27 H ₂ O (HAB A 40), 4.4 kg azodicarbonamide and 2.2 kg lead stearate. The paste is aged for 24 hours and vented under vacuum.

A second composition is prepared consisting of 100 kg emulsion polyvinyl chloride having a K-value of 70, 60 kg dioctyl phthalate and 2 kg dibutyltin maleate. The paste is aged for 24 hours and vented under vacuum.

The first prepared composition is applied at a thickness of 2 mm on a release paper with a silicone emulsion surface coating, provided with a spatial pattern, and pregelatinised at 135 ° C for 2 minutes. A second 0.25 mm thick composition is applied to the pregelatinized layer into which fiber particles based on 61.61 are introduced.

36.05

475.42 332.16 73.13

297.94

71.40

28.92 lyamide 6 and a fineness of 17 dtex and a length of 2.2 millimeters in a 5 kV DC electric field. cm ' ¹ . The flocculated formation is gelatinized and lightened at 175 ° C for 5 min. After cooling and clearing the excess flake, the sheet formed is separated from the separation pad.

Example 4

Procedure as in Example 1 except that a mixture of 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane with azo-dicarbonamide is added instead of 4.4 kg of azo-dicarbonamide. 1 - 1.

Example 5

Prepare a mixture consisting of 50 phr of chloroprene rubber (type W), 50 phr of styrene-butadiene rubber (SBR-1500), 27 phr of sulfur-crosslinked vegetable oil, 5 phr of zinc oxide, 2.5 phr of magnesium oxide, 1.5 phr of stearic acid, 3.0 phr paraffin, 1.5 phr phenyl- í-naphthylaroin, 27 phr carbon black (N-539), 40 phr zeolite (Spec. As in Example 1), 20 phr calcium carbonate, 34 phr aromatic oil, 2 phr sulfur, 2,2'-dibenzthiazyl disulfide, 1.0 dsk of 2-mercaptoimidazoline, 0.3 dsk of 2-mercaptobenzothiazole, 0.6 dsk of tetramethylthiuram disulfide, 6.7 dsk of 1,5-methano-3,7-dinitroso-1 , 3,5,7-tetraazacyclooctane (Chempor PC-65) and 3.0 dsk of calcium oxide.

Note: dsk - quantity per 100 mass. parts of rubber.

Example 6

Prepare a blend consisting of 100 dsk rubbers (32 dsk EPDM and 68 dsk SBR 1500], 14 dsk sulfur-cross-linked vegetable oil, 5.5 dsk zinc oxide, 2.0 dsk stearic acid, 5.5 dsk paraffin, 29 dsk carbon black, 51 dsk CaCCb, 40 parts of aromatic oil, 9 parts of zeolite (spec. As in Example 1), 3.5 parts of sulfur, 1 part of 2-mercaptobenzothiazole, 1 part of 1,3-diethylthiourea,

1,4 dsk of N-cyclohexyl-2-benzothiazyl sulfenamide, 6,5 dsk of 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane (Chempor PC-65 and 4,0 dsk of calcium oxide) The blends according to Examples 5, 6 were prepared on conventional rubber plants and processed into finished products by conventional processing technologies - on continuous vulcanization equipment (LCM lines, microwave heating, shear head lines, air vulcanization heat).

The treatment of the mixture was carried out at reduced temperature and the working environment as well as the finished technical rubber products removed the unpleasant odor, in particular from the methylene-imine-type fragments from the decomposition of 1,5-methano-3,7-dinitroso-1,3,5, 7-tetraazacyklooktánu.

Example 7 '<3

100 kg of hutadiene-styrene latex with a non-volatile component content of 53% by weight and a styrene content of 27% by weight are mixed in the homogenizer. calculated on a non-volatile component, 1.4 kg succinate-based surfactant containing 35 ^p / o wt. of active ingredient, 2.5 kg of azodicarbonamide, 1 kg of a 30 percent aqueous alkylbetaine solution, kg of emulsion paste-forming polyvinyl chloride powder with a K-value of 70, 10 kg of zeolite (spec. as in Example 1), 15 kg of a curing dispersion containing % wt. containing sulfur, mercaptobenzothiazole, zinc oxide, zinc diethyldithiocarbamidate, sodium dimethyldithiocarbamidate, 2,6-di-tertiary butyl-3-methyl; phenol and sodium 3-naphthalenesulfonate / formaldehyde condensate in the following component ratio 3.75: 0.38: 5.07: 1.4: 1: 2.76: 0.35; 0.5 kg of ammonium nitrate dissolved in 3 kg of 25% ammonia. The coating composition thus prepared is applied to a nonwoven interwoven fabric produced on a Malimo ^R machine with a weight of 160 g. m ² , unilaterally combed, consisting of a 65:35 polyester-cotton blend. The coated fabric is subjected to a heat exposure of 160 ° C and subsequently spatially patterned with a pattern roller with a tread depth of 1 mm.

Claims (1)

SUBJECT Use of zeo-it, with a specific surface area of 5 to 300 m ² . g " ¹ , as an" in situ "activator for reducing the decomposition temperature of the 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazaase of cyclooctane and / or azo-dicarbonamide, and deodorizing the released fumes in the process of forming rubber or plastic products.