CS227914B1 - Method of blowing agent deodoration - Google Patents

Description

The invention relates to a simple method of deodorizing blowing agents, wherein the conditions are chosen such that the application of a wide range of technically available sulfonated lignin compounds results in a substantial increase in product quality as well as greater safety in the handling, transport and storage of blowing agents.

The blowing agents based on 1,5-endomethylan-3,7-dinitroso-1,3,5,7-tetraazacyclooctane are one of the most widespread rubber auxiliaries of this kind. Their function is related to the thermal reactivity of 1,5-endomethylan-3,7-dinitroso-1,3,5,7-tetraasacyclooctane, in an earlier literature called N, N'-dinitrosopentamethylanetetramine, code-named DNPT.

Upon thermal decomposition of this substance, which is an N-Manicheva base in terms of chemical structure, primary fragments, probably of the aetylanimine type, are formed. These fragments combine with each other, respectively. chemical interactions with the components of the rubber mixture then form unspecified, unpleasant smelling nitrogen compounds. The smelly substances remain after decomposition in rubber products, which is one of the apatose ap11, blowing agents based on 1,5-endomethylene-3,7-dinitroso-1,3,5,7-tetraazacyclooctane.

Elimination of the unpleasant odor of thermolysis products of 1,5-endomethylan-3,7-dinitroso-1,3,5,7-tetraazacyclooctane world-wide manufacturers ensure in a fair way. The oldest and most commonly used methods of deodorization reported in the current company literature are based on the use of fine grain urea or a mixture of urea with polyols.

The main disadvantage is the negative influence of urea on stability! Ν, Ν'-dinitrosopentemethylenetetremine, therefore a deodorant of this type must be stored separately from the blowing agent. The use of urea deodorant also sometimes causes the urea to diffuse to the surface of the product. Therefore, substances other than urea have been tested. The company literature thus refers to aelaain, similar to the French patent S. 2,416,243, which discloses its use in an amount of 0.05-0.4%. In this case, it should be appreciated that aelaain is more expensive than urea and also significantly reduces the stability of Ν, Ν'-dinitrosopentamatylenetatramine. Somewhat more suitable deodorizing additions of N, N'-dinitrosopentamethylenetetramine have been shown to be lower formaldehyde condensates with urea or malamine, i.e., diaethylolactone, respectively. triethylolaelaain (U.S. Patent 121,445). part of the blowing agent with said condensate was paraffin oil and ethylene glycol.

This type of deodorant has been improved by the application of a 2-molar urea condensate with 1 mole of formaldehyde in an alkaline medium (U.S. Patent 154,357). approx. 35 ° C. Thus, when the literature discloses the deodorization of urea-formaldehyde condensates (U.S. Ser. 196,956 and 196,957), it is meant that the lower water-soluble products of urea-formaldehyde reaction in an alkaline medium (essentially a mixture of mono- and dimethylolureas, e.g. whose first predominance).

The application of urea-formaldehyde condensates obtained by an alkaline-catalyzed reaction has a number of disadvantages. In terms of self-deodorant synthesis, this is a relatively long reaction time a. In particular, from the point of view of the physical stability of the blowing agent, it is tangling and hardening, since methylureas cure over time (due to the decomposition products of N, N'-dinitrosopentamethylenetetramine) - exhibit the properties of a urea-formaldehyde adhesive.

From the point of view of handling, storage and transport of the blowing agent, the mono- and diaethylolureas have a negative effect on the thermal stability of the product: overheating of a sample weighing at least 25 kg, containing 55% by weight. Ν, Ν'-dinitrosopentamethylenetetraine at a temperature of 46-50 ° C inevitably leads to its self-inflammation. Other carbaid derivatives (urea) have also been proposed to eliminate the odor of 1,5-endoaethylene-3,7-dinitroso-1,3,5,7-tetraazacycloctane thermolysis products such as urea. nitro- and cyanoguanidine (Japanese Pat. No. 73-37,346), or guanidine nitrate and guanidine thiocyanate (French Pat. No. 2,354,360 and German Pat. No. 2,723,446). Of the s-triazine derivatives, the use of cyanuric acid and trihydrazino-s triazine is protected (Japanese Pat. No. 73-37,347). Of great note is the use of tetrahydroiaidazo- [4,5-d] -laidazole-2,5- (1H, 3H) -dione (cf. Aut. No. 227 909).

All of these substances are particularly advantageous from an economic point of view. Cyanuric acid as a protogenic substance decreases the stability of N, N'-dinitrosopentaaethylenetetraine, nitroguanldine and guanidine nitrate are explosives. For the sake of completeness, it is necessary to add that in Japanese patent no. 73-92,541 is protected to remove free formaldehyde from rubber products by the use of guanldine, its N-methyl-, Ν-ethyl-, N-aaino- and N-nitro derivatives.

From the above calculation of the substances used as deodorants in swearing with N, N'-dinitrosopentamethylenetetramine, it can be seen that from a molecular structural point of view and all of them are subject to N-Manich condensation with a structurally suitable component. This fact confirms the already expressed assumption that the primary fragment! thermolysis of 1,5-endomethylene-3,7-dinitroso-1,3,5,7-tetraazacyclooctene are intermediates with a methyleneimino group in the molecule.

These fragments can be reacted with these additives by a N-Manich condensation mechanism and then with other components of the rubber composition to form non-malodorous products. This principle applies to the use of water-soluble and / or insoluble formaldehyde condensation products with urea (cf. cf. 227 904).

Although the use of a deodorant on this basis results in less influence on the stability of the resulting blowing agent in an unfavorable sense, as in the case of methylolurea type condensate, its serious drawback is the relatively low deodorizing activity, which is increased by activation, i. j. by treatment with compounds capable of forming N-Manich bases, in particular from the group of acid amides and / or amines, preferably urea, guanidine, thiourea and melamine (cf. no. 227 912).

Some of the aforementioned drawbacks of the deodorant ingredients used are overcome by the present invention.

According to the present invention, the process of deodorizing blowing agents, in particular based on 1,5-endomethylan-3,7-dinotroso-1,3,5,7-tetraazacycloctoctan, is carried out by producing a blowing agent aa with sulfonated lignin compounds, preferably 11-n-sulphonic acids and / or α-Tm-1 and / or their products with reactive urea-formaldehyde condensate, added to the kernel or sequentially in an amount of 0.05 to 20% by weight, calculated on all blowing agent components.

The advantage of this invention is that the applied sulfonated lignin compounds are both technically readily available and their addition has not been particularly effective in reducing stability. On the basis of the results, it can further be concluded that during storage the compositions containing the deodorant additive are not susceptible to agglomerate or sinter in such a way that at least a portion of the blowing agent converts to relatively agglomerated hard lumps against the desired spreading blowing agent.

The source of sulphonated lignite compounds is mainly pulp production. These processes involve chemical reactions of lignin and boiling chemicals. The essence of these reactions is the splitting of the lignin-cellulose complex and the macromolecule of lignin, while increasing its solubility due to the hydrophilic groups formed. Lignosulfonic acids react inside the cell wall with cations of cooking solutions to form lignosulfonates, which then diffuse Tahko into the cooking medium.

The material of the acidic cooking liquor is an aqueous solution of inorganic and organic compounds having a dry weight of 9 to 14% by weight. About 65% of the dry matter content is lignin compounds, 25% carbohydrate moieties, including simple pentoses, and hexoses, aldonic and alduronic acids, hemcelluloses and the remaining 1d% are inorganic compounds such as sulfur dioxide, sulfites and sulfates of sodium, magnesium, calcium and ammonium and the like. The carbohydrate content can be varied e.g. by a biological treatment, after which the reducing carbohydrate content is reduced to a value of 0.1 to 0.2% by weight. on the sulphite liquor.

There are a number of methods for the isolation of llgnosulfonic acids from sulfite leaches, for example, membrane separation, adsorption, electrochemical, salting-out, chemical precipitation and the like. The lignin sulfone compounds as a deodorant may be used in the form of lignosulfonic acid. It should be noted that the lignosulfonic acid contained and the sulfite liquor is a highly polydisperse material.

Its average molecular weight ranges from several hundreds to several hundreds of thousands. Obeene is known to have low molecular weight frequencies of lignosulfolaevyen eu more eulfanevane and have an almost linear macromolecular chain structure. As the molecular haetneet increases, the relative descent of the sulfosphere in the lignin macromolecule decreases per monomer unit and the lignin fragments acquire a three-dimensional structure.

Most preferably, the lignosulfonic acid is in the form of its sodium, calcium, magnesium salts and the like. standalone or withstand. The lignosulfonic acid precipitation products have received great attention. respectively. a salt thereof, a weekend of prepared by condensation of amide derivatives of carbonic acid or thickening with aldehydes.

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Dozodorant yeah maybe poulit eye firm. More preferred is the use in the form of a paste, auaponsio or solution.

The quality and quantity of other adjuvants are among the parameters that influence the amount of deodorant to be added. The content of lignosulfonates in the non-aqueous blowing agent (phlogmatized mineral oil) is up to 20% by weight. However, in the case of a blowing agent having a water content and an insoluble urea-formaldehyde condensate, this content is not more than 5% of tingling. With this in mind, the amount of deaodorizing additive is within the range of 0.05 to 20% by weight, exceptionally, the upper limit of the addition of the additive is exceeded. The sulfonated lignin compounds, in addition to their own deodorizing capacity, also have a high activating capacity by acting on additives based on poorly soluble and / or insoluble urea-formaldehyde condensates.

The application of sulfonated lignin compounds in the mind of the present invention has not been described in the literature and is documented by the following examples.

Ex, k 1 and d 1

1,5-ondomatylan-3,7-dinitroso-1,3,5,7-tetraazacyclooctane containing 2.2 wt. 1,3,5-trinitrole-1,3,5-triazacyclohexane and a urea-methylurea complex deodorant containing 69.1 wt. solids. A mos is prepared in a kneader containing 63.6 wt. % By weight 1,5-endomotylan-3,7-dinltrose-1,3,5,7-tetraazacyclooctane; % Of 1,3,5-trinitroso-1,3,5-triazacyclohexane, 24.2 wt. % urea-methylurea complex and 10.8 wt. water. This mixture, produced industrially in Czechoslovakia, is specified by means of explosion activation energies for temperature range 190 to 220 ° C (II. Novotný:

Proceedings of ICT, Pardubice, 1961 - I, p. 195), which · 39.87 kJ.mol ^- '. For 250 days of storage, the original pasty moss has a consistency of hard nits and lumps.

Example 2

Of 1,5-endomethylene-3,7-dinitroso-1,3,5,7-tetraazacyclooctane of the same quality as in Example 1, Ligrasol and mineral oil (bearing oil grade B-1), it is prepared in a kneader with a composition of 63, 6 wt. % 1,5-endaethylene-3,7-dlnitroso-1,3,5,7-tetraazacyclooctane; % Of 1,3,5-trinitroso-1,3,5-triazacyclohexane, 20 wt. % Ligrasol and 15 wt. minor oil.

This pasty yellow mixture sl maintains its consistency even after 250 days of curing at 25 ° C. The activation energy flash point, determined as in Example 1, the E «60.06 kJ mol ^- '.

Example 3

From a 1,5-endomethylan-3,7-dinitroso-1,3,5,7-tetraazacyclooctane grade as in Example 1, a VD (30% lignosulfenan solution) and a water-insoluble urea-formaldehyde condensate, a mixture of 63.6 was prepared. % wt. 1,5-endomethylan-3,7-dlnitroso-1,3,5,7-tetraazycyclooctene, 1.4 wt%, 1,3,5-trinitroso-1,3,5-triazacyclohexane, 20 wt% water-insoluble urea-formaldehyde % condensate, 4.5 wt. % lignosulfenate and 10.5 wt. water. This loose mixture retains its consistency even after 250 days of storage. The explosion activation energy, determined as in Example 1, is E = 67.34 kJ ^/ mol.

Example 4

From a 1,5-endomethylene-3,7-dinitroso-1,3,5,7-tetraazacyclooctane grade as in Example 1, a water-insoluble urea-formaldehyde condensate, Ligrasol and water, a mixture of 63.6 wt. 1,5-endomethylene-3,7-dinitroso-1,3,5,7-tetraazacyklooktánu,

1.4 wt. % Of 1,3,5-trinitroso-1,3,5-triazacyclohexane; % water-insoluble urea-formaldehyde condensate, 10 wt. % Ligrasol and 15 wt. water. This pasty mixture retains its consistency after 250 days of storage. Activation energy flash point, determined as in Example 1, E = 95.72 kJ mol ^- '.

Example 5

A mixture is prepared from 1,5-endomethylene-3,7-dinitroso-1,3,5,7-tetraazacyclooctane grade as in Example 1, kaolin and mineral oil. with a content of 78.3 wt. % By weight 1,5-endomethylene-3,7-dinitroso-1,3,5,7-tetraazacyclooctane; % 1,3,5-trinitroso-1,3,5-triazacyclohexane, 15 wt. % kaolin and 5 wt. mineral oil. This loose mixture retains its consistency even after 250 days of storage and is industrially produced in Czechoslovakia. The explosion activation energy, determined as in Example 1, is E = 58.7 kJ.mol ^-1 .

Example 6

From the 1,5-endomethylene-3,7-dinitroso-1,3,5,7-tetraazacyclooctane grade as in Example 1, the plasticizer VD (30% aqueous lignosulfonate solution), a blend containing 78.3 wt. % By weight 1,5-endomethylene-3,7-dinitroso-1,3,5,7-tetraazacyclooctane; % 1,3,5-trinitroso-1,3,5-triazacyclohexane, 6 wt. % lignosulfonate and 14 wt. water. This loose mixture retains its consistency even after 250 days of storage. The explosion activation energy determined as in Example 1 is E = 63.38 kJ.mol ^-1 .

Example 7

From a 1,5-endomethylene-3,7-dlnitroso-1,3,5,7-tetraazacyclooctane grade as in Example 1, a mineral oil (bearing oil grade B-1) and a lignosulfonate / urea-condensate condensation product, a mixture of 78.3 wt. % By weight of 1,5endomethylene-3,7-dinitroso-1,3,5,7-tetraazacyclooctane; % By weight of 1,3,5-trinitrole-1,3,5-triazacyclohexane; % of a lignosulfonate condensation product with an azo-formaldehyde precondensate and 10 wt. mineral oil. This loose mixture retains its consistency even after 250 days of storage. The explosion activation energy, determined as in Example 1, is E = 56.65 kJ.mol ^-1 .

Example 8

Using blowing agents prepared according to Examples 1 to 7, 7 test rubber mixtures are prepared under standard conditions. The amount of blowing agent added per 1000 g of the rubber mixture is shown in Table 1.

T a b u 1 k a 1

The blowing agent of Example 1

Amount of blowing agent 24

3

24

5

18

7

18

Note: The blowing agents according to Examples 1 to 5 are in control

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When admixed into the rubber mixture, the bonding of the mixture to the roller was observed in accordance with Examples 4 and 6. The blowing agents prepared according to Examples 2, 3 and 7 are mixed into the rubber mixture comparable to the control blowing agents.

The evaluation of the vulcanization properties carried out on a Qottfert elastograph at 155 ° C is shown in Table 2.

Table 2

The blowing agent according to the example «min (Nm) * Saax 15 ' (Nm) * bl (Min) * v90 (Min) 1 0.14 0.85 1.8 4.2 2 0.12 0.57 2.7 7.6 3 0.08 0.37 7.3 8.8 4 0.10 0.46 6.4 9.3 5 0.12 0.75 2.5 6.8 6 0.08 0.36 7.5 9.0 7 0.14 0.79 2.2 5.8

Note; M _ain “max. Torque ^M max 15 ' ^{= maxilll} torque at 15 minutes t _bl * process safety ^ v90 ^and monkey vulcanization time

It is apparent from the table that blowing agents prepared according to Examples 3, 4 and 6 at least affect the vulcanization of the rubber composition.

To investigate the growth properties of the rubber blend with blowing agents prepared according to Examples 1 to 7, a test plate is pressed on a 250 x 200 mm block at 155 ° C and a vulcanization time of 12 minutes from each test mixture.

The measured values of the whims of the test plates are shown in Table 3.

Table 3

The rubber blend β blowing agent according to the example

Plate size (mm)

7

360 x 295 362 x 295 360 x 295 360 x 290 360 x 295 350 x 283 350 x 285

From the measured dimensions of the test plates it can be seen that the growth capabilities of the blowing agents according to Examples 1 to 4 are comparable. In the case of blowing agents according to Examples 6 and 7 I do not achieve! however, the control blowing agent values of Example 5.

When grounding blowing agents according to Examples 2, 3, 4, 6 and 7 into a white rubber compound, it is found that these blowing agents do not affect the color shade of the final product.

The deodorizing properties of the blowing agents of Examples 2, 3, 6 and 7 are fully comparable to the control blowing agent of Example 1. When the blowing agent of Example 4 is applied, a slight odor can be felt when incorporated into the rubber composition.

Claims (1)

OBJECT OF THE INVENTION !. Process for deodorizing blowing agents, in particular based on 1,5-endomethylene-3,7-dinitroso-1,3,5,7-tetraazacycloctocane, characterized in that in the production and / or application of the blowing agent, 3-sulphonated lignin compounds, preferably 11gnosulfone compounds, are used acids and / or their salts and / or their products with reactive urea-formaldehyde condensates added at one time or successively in an amount of 0.05 to 20% by weight, calculated on all the blowing agent components. Method for deodorizing blowing agents according to claim 1, characterized in that a sulphite extract from sulphite wood treatment is used as the raw product or treated as a powder, suspension and / or concentrated solution as raw material of ilgnosulfonic acids and / or salts thereof.