NO168529B - PROCEDURE FOR THE PREPARATION OF S - (-) AND R - (+) - N- (QUINUCLIDINYL-3) AMIDES. - Google Patents

Description

Mineral mixing.

The present invention relates to a mineral mixture comprising 1 a finely divided mineral and; Intimately mixed with the mineral, an amine salt s- om improves sar.menpakr.i n.g segen creators and, compression ons strengths. of it- finely divided: mineral.

When treating minerals, use; common.show a painting.s-op is as; ion when the mineral occurs in an untreated or partially treated state to reduce it to a relatively small particle size. It is undesirable in this painting step to see the nest. particle-shaped: mineral to cnsted particle sitor' at a relatively high speed. A painting aid is used; frequent, with such grinding; treatment' to support the grinding either by increasing the production speed or by increasing the fineness of the particles at the same production speedj without having adverse effects on any of the properties of the painted product. Division, of the particles during the painting! of the minerals reveals fresh or rich surfaces that have great energy. The surface forces of the ground particles last for some time after grinding and lead to compression or compaction and/or poor flowability if they are not reduced. Mineral particles that have been compressed by vibration, e.g. when they are transported in a silo wagon, they often become semi-rigid and will not flow if considerable mechanical force has been applied. Therefore, it is also desirable to use an additive

to prevent this.

The term "compaction" is used here to refer to the agglomeration or sticking together of particles resulting e.g. from storage or transport in bulk. Cohesion results from surface forces, the majority of which are assumed to ! be obtained during the grinding of the minerals. "Compression index" is a relative term that indicates numerically, how likely a particulate material is to begin to flow after it has been stored or transported in bulk. "Compression index ratio" is the relative; compression index for an untreated sample compared to a treated sample. This ratio is used to allow comparison between different samples of the same mineral. Compress- ! ring index is determined in the following manner: 100 g of the mineral is placed in a 250 ml Erhlenmeyer bottle placed on top of a variable vibrator. The bottle containing the mineral is vibrated for 15 seconds, after which it is removed from the vibrator and placed in a shaking device with the axis of the bottle lying horizontally. The bottle is then rotated around its axis until the mineral which is compressed at the bottom of the bottle breaks down. The bottle is turned at l80<o>,s angles with approx. 100 revolutions per minute.- The number of 180° revolutions required for the mineral sample to break down indicates the compression index. The greater the energy required to break up the layer, the higher the compaction index. It has now been found that amine salts of aryl hydroxy compounds, e.g. e.g. phenol, will act as an aid in the grinding and compaction inhibitors for minerals. The mineral mixture according to the invention is thus characterized in that the amine salt is an amine salt of an aryl hydroxy compound where the hydroxy group is the salt-forming functional group and is present in an amount of 0.001 to 1 tsp by weight, preferably 0.00 to 0.5 tsp by weight, based on the weight of the mineral. The starting materials can be pure chemicals or materials containing impurities. The methods for producing the additives are known in the field. Preferably, equimolar amounts of the amine and the aryl hydroxy compound are used.

Preferably, the arylhydroxy compound consists of a phenyl or naphthyl radical which is substituted with a hydroxy radical and is otherwise unsubstituted or substituted with one or more nitro, halogen, preferably chlorine, alkyl, preferably containing 1 to 5 carbon atoms, especially methyl -, aryl-, amino- or alkoxy-, preferably with 1 to 5 carbon atoms, radicals.

Preferably, the amine is a compound of the formula:

where R"*" means a hydrogen atom or a substituted or unsubstituted alkyl-, e.g. hydroxyalkyl, or aryl-, e.g. alkaryl, radical; R 2 means a hydrogen atom or a substituted or unsubstituted alkyl-, e.g. hydroxyalkyl, radical, and RJ means a hydrogen atom, a hydroxyl radical or a substituted or unsubstituted alkyl-, e.g. hydroxyalkyl, or aryl radical;

or

where

means a substituted or unsubstituted pyrro-

lidinyl-, pyrrolinyl-, pyrrolyl-, morpholinyl-, piperidinyl-'

or piperazinyl radical, and "5 means a hydrogen atom -or an alkyl or hydroxyalkyl radical; or Y - R1^, where Y means a pyridyl, pyrinidlnyl or pyrldizinyl; R^ means a halogen atom or an alkyl or hydroxyl radical, and n is '0 to 5- Suitable amines include, for example, ammonia, ethylamine, di-ethanolamine, monoethanolamine, triethylamine, triethanolamine, .ani-line, D-toluidine, m-phenylenediamine, dimethylaniline, diphenylamine, 2,^,6-tribromoaniline , N-phenylhydroxylaniin, B-phenethylamln, morpholine, pyridine, piperidine, pyrrole, pyrroline, pyrrolidine., pyridazine, pyrimidine, N-methylmorpholine, <l!>+-{2-aminoethoxy)-ethylmorpholine, dimethylpyridine, dirr.ethylethylpyrrole and piperazine.

The term "mineral" is used here to indicate naturally occurring inorganic minerals, such as phosphate minerals, partially processed minerals such as concentrated iron ore, and mixtures of minerals, such as cement clinker or ceramics. Examples of suitable minerals include beryllium oxide, limestone, gypsum, clay and bauxite. Cement, particularly Portland cement, is the mineral of choice. Portland cement represents a class of hydraulic cements and essentially consists of two calcium silicates and a smaller amount of calcium alunainate. These cements are produced by heating an intimate mixture of finely divided calcareous material (limestone) and clayey material (clay) to form a clinker. The clinker is ground by adding approx. 2% gypsum or another form of calcium sulfate, to achieve the desired hardening properties in the final cement. It is to the clinker that the scar salt is preferably added to increase the grinding efficiency and to inhibit subsequent compaction in the final cement.

The additives used in the present invention are used in either dry or liquid form. Appropriately, the additive is present in an aqueous solution to allow accurate measurement of the mineral. In cases where the additive is not particularly soluble in water, it can be used in liquid form by emulsifying it with a suitable functionalizing agent, e.g. sodium dodecylbenzene sulfonate. The addition is either carried out before the grinding or the additive is introduced into the grinding mold at the same time as the mineral. If the additive is used exclusively for reduction of compaction or for fluidization purposes, e.g. when the mineral is to be transported by a transport system, in particular a pneumatic air system, it is added at any suitable place in the treatment.

The additive is used effectively over a relatively wide area. The preferred area is approx. 0.001 to 1% based on the weight of the mineral, i.e. the weight of solid additives based on the weight of solid minerals (referred to here as solid to solid). In a particularly preferred embodiment, the amount of additive used is approx. 0.00^ to 0, Ch %. Higher amounts are used if the grinding takes place to a relatively high surface area, and the amount of additive is only limited by the desired surface area and the degree of desired fluidity.

The additive according to the present invention is preferably used as the only aid in grinding, but it should be understood that it can also be used with a mixture of one or more such aids or in a mixture with other additives.

The following examples illustrate the invention.

Example 1.

The following table indicates the effectiveness of triethanolamine phenoxide, prepared by mixing equimolar amounts of triethanolamine and phenol, as a painting aid. The data are from Portland cement type I ground in a laboratory steel ball mill with 3<*>+03 revolutions at 99°C.

in

Example 2.

A grinding aid was prepared by mixing 3<*>+ by weight of a 50-5° mixture of phenol and cresol with 65.9 parts by weight of a 50-50 mixture of morpholine and triethanolamine. Grinding efficiency was determined on Portland cement type 1 ground in a laboratory mill with ^9^1 revolutions at 110°C. At an amount of 0.012% based on the weight of the cement, an increase in bladder surface area of 6.75% over the control was determined.

In the following. tables show results from compaction index samples and mortar compressive strength tests respectively. The additives according to the present invention are also used with satisfactory results when grinding other minerals other than cement, such as phosphate rock and iron ore.

in.

Claims (2)

1., Mineral mixture comprising a finely divided mineral and mixing intimately with the mineral, an amine salt which: improves the packing properties and compressive strength of the finely divided mineral, characterized in that the amine salt is an amine salt of an aryl hydroxy compound where hydroxy groups . is the salt-forming functional group and is present in an amount of 0.001 to 1 wt, preferably 0.00 to 0.0% by weight, based on the weight of the mineral. 2. Mixture according to claim 1, characterized in that the amine salt is triethanolamine phenoxide or a reaction product of morpholine and; triethanolamln with phenol and kre sol..