DE1268103B - Use of aqueous preparations of unsaturated polyesters for binding finely divided carbon - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

Number:
File number:
Registration date:
Display day:

ClOl

German class: 10 b-3/04

1 268 103
P 13 68 103.7-45
March 19, 1964
May 16, 1968

It is known to press finely divided coal, in particular anthracite, with pitch as a binder. However, the briquettes thus obtained have various disadvantages. Once the smoke caused by the burning of the pitch, disturbing, on the other hand, the calorific value of the briquettes by the pitch component, the / ₀ is in the order of 7 ° to 10 °, reduced.

It has now been found that these disadvantages are avoided by using finely divided materials for the binding Charcoal or charcoal-like materials, aqueous preparations of unsaturated polyester are used, those from ", ^ - unsaturated dicarboxylic acids and aliphatic polyalcohols with at least 2 ether oxygen atoms in the chain.

According to a preferred embodiment of the present invention, the unsaturated Polyester used without the simultaneous use of polymerizable vinyl monomers, but what for Special purposes the use of such polymerizable vinyl and / or vinylidene monomers - appropriate in minor quantities - does not exclude. Also on the use of the usual peroxidic Polymerization initiators can generally always be used when air has access to the polyester is possible to be dispensed with.

The polyesters to be used according to the invention are preferably used in aqueous solution. Depending on the chemical nature of the polyester, an aqueous dispersion in Come into consideration.

In general, a water-polyester ratio has been found within the limits of 30 to 70 ° / ₀ polyester, calculated water-polyester mixture as appropriate.

Polyesters to be used in the context of the present invention are with respect to the polycarboxylic acid component expediently from «, ^ - unsaturated Dicarboxylic acids, such as especially maleic acid and fumaric acid, built up because of their easy accessibility. In addition, there are also other «, / 9-unsaturated Carboxylic acids, such as itaconic or mesaconic acid or derivatives of the aforementioned acids, are suitable.

The aliphatic polyalcohols with at least 2 ether oxygen atoms in the chain are preferably used, for. B. tri-, tetra-, penta-, hexa-, hepta-, octaethylene glycol and tri-, tetra-, penta-, hexa-, hepta-, octapropylene glycol. The adducts of ethylene and / or propylene oxide or tetrahydrofuran with di- or polyalcohols, ζ are also suitable. B. the adducts of 2 to 10 moles of ethylene or propylene oxide on 1,2-per-use of aqueous preparations of
unsaturated polyesters for bonding
finely divided coal

Applicant:

Paint factories Bayer Aktiengesellschaft,

5090 Leverkusen

Named as inventor:

Dr. Karlheinz Andres, 5000 Cologne-Flittard;

Dr. Horst Wieden, 4047 Dormagen

pylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, 2,2-Dimethylpropanediol-1,3, trimethylolpropane, glycerol, hexanetriol, etc. There are also such Suitable polyols z. B. have allyl or benzyl ether groups in the molecule.

The production of this polyester takes place, for. B. preferably by thermal condensation at temperatures between 150 and 200 ° C. It is advisable to carry out the reaction yourself in an inert atmosphere, otherwise swelling easily occurs. It is often also beneficial to take the final phase of condensation perform under reduced pressure. When using bifunctional alcohols containing ether groups, it is advantageous to carry out the condensation with approximately equivalent amounts of acids and alcohols. Used However, branched polyols containing ether groups, such as the adduct of 3 moles of ethylene oxide, are used 1 mole of trimethylolpropane will result in the condensation

better carried out with a larger excess of polyols (at least 1 mol Triol).

In addition to these glycols, customary aliphatic Glycols, such as ethylene glycol, 1,2-propylene glycol, 1,3 - butylene glycol, 2,2 - dimethylpentanediol (l, 3), can also be used proportionally as ester build-up components.

The polyesters can be with aromatic polyhydroxy compounds such as hydroquinone and tert-butyl catechol, stabilize in amounts of 0.005 to 0.2 ° / _0th

The use according to the invention of the labeled polyesters is based on their compatibility with water. This depends mainly on the number of ether oxygen atoms in the macromolecule. The greater the number of ether oxygen atoms, the more water is absorbed. A polyester made

809 549/57

Claims (1)

3 4 made from equimolar amounts of maleic acid and whole is then pressed into cylindrical bodies according to a polyethylene glycol with 8 ether oxygen atoms, Example 1. Which is then still vorist compatible with water unlimited, while at handene water through 24stundiges drying when using a polyethylene glycol ether with only 3 50 ⁰ C removed. Oxygen atoms, the compressive strength of the moldings was added only 58 ° / ₀ water 5 is an average of 41 kgf / cm ^2. will. . ·. . , ~ - The curing of the polyester can be done with radical example 3 formern be carried out as catalysts. 3 parts of a polyester made from 1 mole These include organic peroxides such as dibenzoyl maleic anhydride and 1.1 moles of a Polyäthylenperoxid, methyl ethyl ketone peroxide, particularly forthcoming io glycol having 8.3% OH (but is stabilized with 0.05 ° / ₀ Hydrozugt cyclohexanone peroxide. Suitable quinone) are in 12 parts of an aqueous cyclofor moreover also azo compounds of the azo hexanone peroxide solution type (1%) dissolved and with lOOTeibutyric acid dinitrile. The application-technical balls of finely divided coal are intimately mixed. Subsequently, Sonders significant cure at room temperature 15 parts of a 3 ^o / o · cobalt (II) sulfate solution is achieved by the use of accelerators incorporated in the mixture 15 °. The whole thing is then z. B. araliphatic tertiary amines or metal pressed into cylindrical bodies (according to Example 1). Compounds such as titanium (III) and cobalt (II) compound then fertilize the remaining water, in combination with peroxides. Removed by drying at 50 ^° C. for 24 hours. The surprisingly result of such metal compounds in the compressive strength of the moldings is on average unsaturated polyesters, which are at least 3 ether-20 52 kp / cm ² . have oxygen atoms in the alcohol component, BeisüieI4 even without radical formers at room temperature to .. ■
Crosslinking, 2.5 parts of a polyester made from 1 mole As finely divided coal and coal-like materi- fumaric acid and 1.2 mol of a diol with 12.8 ° / "OH, alien comes z. B. coal (hard coal, lignite, 25 obtained by reacting 1 mole of 1,4-butanediol Anthracite) in the form of dust or in granular and 4 mol ethylene oxide (stabilized with 0.08% tert-like Form of different grain sizes into consideration. Butyl catechol), are in 4 parts of an aqueous It is possible to work at room temperature, cyclohexanone _{peroxide solution (1.6 ° / 0} ig) dissolved and, however, intimately mixed with the 100 g of finely divided charcoal for faster removal. Subsequently, water-aftertreatment at elevated temperature-30 are ßend 7 parts of a 10 ° / ₀ aqueous Korataren, z. B. in. Range from 50 to 12O ⁰ C, proven. balt (II) sulfate solution incorporated into the mixture. The whole given in the following examples is then divided into cylindrical bodies are parts by weight, unless otherwise measured Example 1 is pressed. Then it will notices is. existing water by drying for 24 hours Example 1 ^{35 5} O ⁰ C removed. The compressive strength of the bricks averages 73 kp / cm ² . 4 parts of a polyester made from 1 mole. Maleic anhydride and 1.2 moles of a polyethylene example glycol with 17 ° / ₀ OH (stabilized with 0.05 ° / ₀ hydro- 4 parts of a polyester, made from 3 mol quinone), are in. 5 parts of an aqueous cyclo- 40 maleic anhydride and 4.5 mol of a diol with hexanonperoxidlösung (l, 6 ° _/ ig) and treated with 100 TEI 19.2% OH, obtained by reacting 3 moles len finely divided coal intimately mixed. Then ethylene oxide and 4.5 moles of trimethylolpropane (stabilized , 5.5 parts of a ll ° / o aqueous cobalt (II) - Siert with 0.05 ° / ₀ hydroquinone, be in 6 parts sulfate solution incorporated into the mixture. The whole water dissolved and intimately with 100 g of finely divided coal is then mixed at a pressure of 400 kg / cm ² to form cylinder 45. Then 4 parts of a 20% drical bodies with the dimensions diameter: cobalt (II) sulfate solution incorporated into the mixture, 3.6 cm, height: 5 cm pressed. Then the whole thing becomes cylindrical bodies any water still present is compressed by drying according to Example 1 for 24 hours. Then the at 50 ⁰ C removed. The compressive strength of the moldings still present water by drying for 24 hours is over 100 kp / cm ² . The compressive strength of a 50 at 50 ⁰ C is removed. The compressive strength of the bricks body of the same size, from the same amount averages 44 kp / cm ² . In contrast, water obtained without a binder is
only 6.7kp / cm ² . Patent claims: Example 2 _Tr . ",. 55 1. Use of aqueous preparations of 5 parts of a polyester, made from 1 mole of polyesters from ", ^ - unsaturated dicarboxylic acids maleic anhydride and 1.1 moles of a polyethylene and those polyols that contain at least 2 ether glycols with 11.3 ° / ₀ OH (stabilized at 0.05 ° / ₀ hydro- oxygen atoms in the molecule, for the quinone), are dissolved in 5 parts of water and bound with finely divided coal. 100 parts of finely divided coal intimately mixed. An 60 2. Use of polyesters according to claim 1 Finally , 5 parts of a 20 ⁰ I ₀ IgQn cobalt (H) - together with heavy metal salts and / or radisulphate solution are incorporated into the mixture. The caulking as a hardener. 809 549/57 5.68 © Bundesdruckerei Berlin