DE2850200A1 - ESPECIALLY AGRICULTURAL MATERIAL MIXTURES AND METHOD FOR THEIR PRODUCTION - Google Patents

Description

Mixtures of substances and processes for their production particularly suitable for agriculture

The invention relates to a mixture of substances that one or several water-sensitive substances such as a water-soluble substance and a finely divided organic one Contains substance in which the rate of dissolution of the water-soluble substance is significantly reduced and can be used with particular advantage in agriculture, horticulture and the like.

The mixture of substances according to the invention contains an organic finely divided material in which the particles or Groups of particles are coated with a polymeric material, making them water-repellent, and a water-sensitive one Material.

The water-sensitive material is usually a water-soluble one Material even if the solubility is only on the order of a few parts per million.

For the purposes of the invention, for example bitumen, tar and homopolymers are suitable as polymeric materials and copolymers of the following monomers:

a) Vinyl esters of aliphatic acids with 1 to 18 carbon atoms, in particular vinyl propionate and "vinyl versatate"

(Manufacturer Shell).

b) Acrylic and methacrylic acid esters of alcohols with 1 to 18 carbon atoms, in particular methyl acrylate, ethyl acrylate, Butyl acrylate, 2-ethylhexyl acrylate and methyl

25 methacrylate.

909821/0 707

c) mono- and diethylenically unsaturated hydrocarbons, for example styrene, and aliphatic dienes, for example butadienes.

d) Unsaturated carboxylic acids, for example acrylic acid, methacrylic acid, crotonic acid, fumaric acid and itaconic acid

acid.

e) Esters of unsaturated carboxylic acids with alcohols which contain a further functional group, for example Glycidyl methacrylate, hydroxyethyl acrylate and

1O hydroxypropyl acrylate.

f) vinyl monomers, for example vinyl acetate, acrylamide, Acrylonitrile, methylol acrylamide and methacrylamide.

As organic finely divided materials, waste products, for example sawdust or bagasse, or cut grass, compost, paper pulp and the like can be used.

The material chosen must be compatible or indifferent to the medium in which it is to be used. Sawdust has the advantage that it is a cover (mulch) for the ground, so that a mass with polymer Containing coated sawdust and a fertilizer serves a dual purpose, namely 1) slow release effect of fertilizer and 2) keep moisture in the soil.

The polymer can be applied to the organic material as an emulsion, dispersion or solution. The water sensitive Material can be included in the polymer emulsion, dispersion or solution or with the organic Material can be mixed before the application of the polymer, or it can be mixed with the already coated

909821/0707

organic material can be mixed. The speed of dissolution or other function depends on the method of incorporation of the water-sensitive material away.

The mixture of substances can be compressed and shaped into briquettes. It can also be made in the form of a loose mixture will. In another embodiment of the invention the polymer is added in such an amount that, after drying, a free-flowing or rieseifiable Mass is obtained. In some applications an undried mixture can be used, whereby the water-repellent properties develop during the natural drying of the product.

In order to obtain a free-flowing mass, the finely divided organic material, preferably with a polymer preparation which contains a polymer, in an amount treated, which corresponds to about 0.1 to 5 parts of polymer per 100 parts of the finely divided material. The amount is chosen so that it is ensured that the individual particles are water-repellent or non-wettable, but are free-flowing or pourable.

It is evident that different types and structures of organic material require different amounts of polymer to achieve the desired properties. This amount can be determined empirically.

The treated particles may be visually indistinguishable from the untreated particles, but the influence of the treatment becomes noticeable when the particles are moistened: the untreated particles are wetted while the treated particles are not wetted. The treated particles are thus extreme advantageous for mixing, for example, with highly soluble

909821/0707

fertilizers to reduce the amount dissolved in the first wetting, or in a storm, causing Damage to the plants is prevented and the fertilizer is made available over a longer period of time.

The effect of the wettability can be achieved through treatment with a surfactant, wetting agent or a high concentration of soluble salts.

The amount of water-sensitive material used depends on the particular application. On a weight / Weight-basis, the volume-to-weight ratio is very large, as the encased organic material is a has a much lower density than the water-sensitive materials.

The organic finely divided material can have a particle size between 10 and 700 μm.

If sawdust that was previously impregnated with a 0.4% emulsion of a styrene-acrylic acid copolymer and then has been dried, has been dry-mixed with an organic compound fertilizer in a weight ratio of 1.5: 1.0, the mixture proved to be water-repellent. When this mixture is buried in sand and continuously covered with water was leached, the rate of fertilizer loss from this mixture was considerably slower than that Losses with a common fertilizer.

The mixture of substances according to the invention can be fertilizers, Herbicides, insecticides, bactericides or other pesticides or other agricultural Contain chemicals.

909821/0707

example 1

An emulsion of a copolymer of styrene and 2-ethylhexyl acrylate was diluted with water so that the polymer content Was 0.4%. 3 g of sawdust was mixed with 14 g of this diluted emulsion. The crowd then became dried at 55 ° C.

10

In the dry state, the water repellency of the treated sawdust was checked before 3.8 g of des Sawdust were mixed with 2.5 g of calcium ammonium nitrate. In a comparative experiment, 3.8 g became ordinary Dry sawdust mixed with 2.5 g lime ammonium nitrate.

The two fertilizer-containing mixtures were buried in a mass of ordinary sea sand, whereupon Excess water was poured on the surface. The different amounts of fertilizer used with the different Treatments with continuous leaching were measured as electrical conductivity. The following results were obtained:

20th

Electrical conductivity (Micromho per cm χ 10)

Dry overnight

- 7th

25th

30th

35

Fertilizer in the pre-treated sawdust

% of the total conductivity

Fertilizer in the untreated sawdust

% of the total conductivity

237 550 593 864 520 419

6 21 37 61 75 86

413 1080 897 703 157 33

13 45 72 94 98 99

909821/0707

The results show that by pretreating the sawdust the speed of fertilizer release is reduced. This is particularly evident in the leach 7 after drying overnight, where the percolate has 14% of the total electrical conductivity, while this is only 0.7% in the comparison test.

Example 2
18 g of calcium ammonium nitrate were dissolved in 81 g of water. 1 g of a 56% solids emulsion of a copolymer of vinyl acetate and 2-ethylhexyl acrylate was added to the solution. 14 g of this mixture was mixed with 3 g of sawdust. The mass was dried at 50 ° C. overnight. For comparison, this experiment was repeated exactly, but using 92 g of water and no polymer emulsion was added.

When a drop of water was applied to these variously treated mixtures, it was found that it was immediately absorbed in the comparison sample, while it was immediately absorbed in the case of the invention, with the polymer treated material is only absorbed after about 15 minutes became. The dried materials were separately covered with samples of 200 g sea sand each and repeatedly leached . The conductivities of the successive per-

25 colates are listed in the following table.

909821/0707

Electrical conductivity (micromho per cm χ 10)

Leaching 2 3 4 5 6

after

Drying overnight

KAS dissolved in 10 water + sawdust

% of the total conductivity

χ.

KAS dissolved in a copolymer emulsion containing 0.5% solids + Sawdust

% of the total conductivity

3700 357 68 24

16

88 97 99 99 100

423 857 563 411 323 15 46 66 81

92

KAS = calcium ammonium nitrate

The results show that the dissolved salts through the treatment with the polymer are much slower than through the sample, which does not contain any polymer, can be released.

Example 3

Bagasse was air dried and then ground to a powder in a hammer mill. 100 g of this powder were mixed well with 100 g of a 0.5% solids dispersion of a copolymer of vinyl acetate and 2-ethylhexyl acrylate. The mixture was then thoroughly dried in the oven at 70 ⁰ C. As soon as this material showed the ability not to allow a drop of water applied to it to penetrate, the powder was

909821/0707

which amounts of granulated lime ammonium nitrate are dry mixed. Samples of 10 g each of the powder in an intimate mixture with the calcium ammonium nitrate were then pressed under a pressure of 60 MPa. The tablets obtained that 45 mm in diameter and 4 mm thick were buried in sea sand. The speeds, with from which soluble salts were removed from the tablets, were treated with ordinary calcium ammonium nitrate and the loose, compared to free-flowing, water-repellent bagasse powder. The relative electrical conductivities of consecutive Percolates of 50 ml each are listed in the following table.

The bagasse treated with the polymer decreases both in loosely mixed form and in the pressed state dramatically reduces the rate of removal of the soluble salts. The aggregated material seems to be more effective because with a ratio of 1: 1 only 53% (relative to the comparison sample) of the salts are removed after six leachings while out of the loose, pourable mixture

20 98% can be removed.

909821/0707

2.5 g
10 g Electric Bagasse Conductivity in micromho χ KAS * +
treated Bagasse 10 ³ / cm ^{3 only} *
CHEESE loose Bagasse I. Date, KAS * +
treated 1: 4 5 g
10 g relationship 1: 2 10,000 4150 1: 1 1
-Λ Leach No. only
CHEESE* relationship ver
seals ver
seals 10 g KAS * +
10 g treated 100 42 ver
seals I. 3550 loose 236 loose 590 relationship 4250 3100 2650 11/18/77 1 100 7th 720 12th 100 51 27 % of control,
cumulative 373 224 800 15th 2250 95 577 2050 11/18/77 2 100 6th 26th 2900 27 100 55 33 % of control,
cumulative 43 925 544 34 1225 21st 3900 103 8 ro 11/18/77 3 100 29 40 273 38 100 82 40 co
cn
CD % of control,
cumulative 95 404 555 36 1550 11 995 1050 11/21/77 4 100 39 53 875 52 100 89 47 % of control,
cumulative 11 630 371 44 498 11 738 518 11/21/77 5 100 53 62 564 56 100 94 51 % of control,
cumulative 11 353 178 49 176 294 11/22/77 6 100 62 66 136 58 53 % of control,
cumulative 125 50 65 ^only *
CHEESE* 4850 100 5,800 100 88 100 29 100 72 100 11 100

KAS = calcium ammonium nitrate

Example 4

Chips from the South African pine were dried and ground into sawdust (less than 300 μm). In 1100 g of this 5,000 g of a 28 g dry polymer were used as sawdust containing dispersion of a copolymer of Stir in vinyl acetate and 2-ethylhexyl acrylate. After good Mixing the material, the mixture was dried in the oven at 50.degree.

Wells were made in the treated sawdust and in one Comparative sample of the sawdust created. 5 ml of water was added to each well. This water was in the Comparative sample of the sawdust soaked in one minute, while it was still in the treated material after 10 hours had not penetrated.

The experiment was repeated, but using bagasse, a By-product of the sugar cane industry. It consists of the stem fibers, which after removal of the Juice left behind. The bagasse was ground to a fine powder and in the same way as the sawdust treated. The same degree of water repellency was found.

Example 5

The same material as that described in Example 4 The experiment used was sprinkled on the surface of water in a 500 ml beaker.

A comparative sample of untreated sawdust was shown in used another beaker.

After an hour, all of the sawdust in the comparison cup was soaked with water and sank to the ground, while the treated sawdust was still floating on the surface after a week and had not sunk to the bottom.

909821/0707

Example 6

The treated material prepared according to Example 4 was proportioned with crystalline potassium chloride fertilizer from treated sawdust to potassium chloride of 1: 1 and from 3: 1 mixed. Comparative mixtures with the same proportions of ingredients but using Common sawdust were also produced.

Samples of these mixtures, each containing 2 g of potassium chloride, were buried in 200 g of sea sand, which was placed in plastic cups, in the bottoms of which holes were pricked, was contained. Each treatment was carried out on triplicate samples. Aliquots of 50 ml of water were allowed to trickle through each container in turn. The concentrations of the salts in the percolates were determined by measuring their electrical conductivity.

3 3 Electrical conductivity (micromho χ 10 / cm)

Ratio 1: 1 treated
sawdust Ratio 4: 1 treated
sawdust Percolate
No. Con
trolls 363 Con
trolls 187 1 147 1700 no
Fluid
ability
through 550 2 2467 1083 2500 1267 3 130 147 747 767 4th 21st 34 121 543 5 16 17th 39 271 6th 13th 16

909821/0707

The non-wettable sawdust slowed the rate at which the potassium chloride was leached out. The more Protective modified sawdust is present, the more effectively the leaching is reduced. For example the conductivity in leach 2 was about 2500 χ 10 micromho / cm in the comparison samples, 1700 10 micromho / cm at the ratio of 1: 1 and 550 10 micromho / cm at the ratio of 4 parts protective sawdust to 1 part potassium chloride.

10 Example 7

1000 g of dry bagasse from the sugar cane industry were mixed with 1000 g of a 5 g dry polymer Mixed dispersion of a copolymer of vinyl acetate and 2-ethylhexyl acrylate. The mass was dried at 50.degree and then pounded and ground in a mortar. A drop of water placed on the mass showed that the mass had become unwettable.

The following four mixes were made:

(a) 2.5 g urea with 2.5 g modified bagasse

(b) 2.5 grams of urea with 5.0 grams of modified bagasse

(c) 2.5 grams of urea with 7.5 grams of modified bagasse

(d) 2.5 grams of urea with 2.5 grams of untreated bagasse powder.

Three samples of each of these mixtures were covered with sandy soil in 5 l plastic pots with drainage holes in the Ground was included. Two grams of superphosphate, two grams of potassium chloride and four kernels of corn were mixed in each pot. the Pots were always well watered.

After 6 weeks the plants were harvested and weighed. Four more corn kernels, 2 g superphosphate and 2 g potassium chloride were added again and the same experiment repeated. No further nitrogen fertilizer was made added. After 6 weeks the trial was stopped for a

909821/0707

third harvest repeated. The yield results for the three harvests are given in the table below.

Ratio of cellulose flour to urea

Yields as green weight 3

in g harvests

■ overall

Harvest harvest harvest velvet
1 2 3

untreated flour

: Urea = 1: 1 72.6

10 treated flour

: Urea = 1: 1 99.2

treated flour

: Urea = 2: 1 89.8

treated flour
15: urea = 3: 1 90.1

54.7 57.6 184.9

90.7 62.8 252.7

62.4 69.5 221.7

62.7 58.7 211.5

In all cases, the cellulose flour modified with the polymer resulted in higher yields than with the mixture obtained from untreated flour and urea. At the ratio of 1: 1, the treatment with the polymer resulted 36.7% more vegetation compared to the three harvests.

Example 8

Dry sawdust from South African pine was mixed with a dispersion containing 0.5% solid polymer a copolymer of styrene and butyl acrylate and increasing concentrations of ammonium sulfate mixed, until it was completely damp. (1100 g of sawdust with 5000 g of diluted dispersion, the 25 g of dry polymer and contained 0, 500, 1000 and 2000 g of ammonium sulfate.)

Three samples of each of these mixtures, which contained the equivalent of 5.7 g of ammonium sulfate, were lightly compacted, so that they dried into briquettes. The briquettes at the

909821/0707

10% ammonium sulfate solution was therefore 4 times larger than the briquettes for which the 40% solution was used.

The briquettes were buried in sandy soil contained in 5 1 pots with holes drilled in the bottoms was. Two grams of superphosphate, two grams of potassium chloride, and four kernels of corn were added to each pot. The pots were well watered, and after 6 weeks the plants were harvested. The income received is shown below.

Concentration of ammonium sulfate

in a mixture with modified yield as green weight, sawdust (total amount in all
Cases 5.7 g) ^g

100% (control sample) 67.1

64% 83.2

15 47% 93.2

31% 94.0

In all cases, sawdust treated with polymer produced significantly higher yields than the comparison sample, which only contained ammonium sulfate, achieved.

20 Example 9

In a 3-fold field experiment with maize the following treatments were compared:

A. 50 kg N / ha as usual ammonium sulphate, total amount applied to the seed.

B. 50 kg N / ha as usual ammonium sulfate, but applied in two equal parts: 25 kg N / ha in the Sowing and 25 kg N / ha 6 weeks later.

9 0 9821/0707

C. 50 kg N / ha as urea (109 kg) with 120 kg pretreated, dry mixed water-repellent sawdust. The total amount of this mixture was used when sowing applied in a drilled furrow at a distance of about 5 cm along the seeds placed in the ground -

The wood flour was made water repellent by adding 120 kg Wood flour with 560 liters of an emulsion of a styrene-2-ethylhexyl acrylate copolymer containing 2.24 kg of dry polymer were mixed.

The nitrogen content of the leaves in the flower, the grain yield, the total yield of plants and the calculated total nitrogen uptake (leaf N% χ total plant yield) at harvest are mentioned below.

Treat
lung N content
in the leaf,
O
■ o Grain carry
(t / ha at
12.5% N ₂ O) Total-
plants-
yield
(t / ha,
incorrectly
greed for
Damp
speed) calculated
Total-
nitrogen-
intake / ha A. 2,428 7.142 14,558 35.4 B. 2.656 7,099 16.634 44.2 C. 2.861 7.518 19.033 54.5

The results show that the fertilizer mixed with the water-repellent wood flour had higher values were achieved for all four measured criteria.

The calculated total nitrogen uptake was 54% higher than with the comparative treatment, in which all nitrogen was also used during the sowing.

909821/0707

Example 10
The following two fluids were made:

A) 1g "Malasol" (emulsifiable insecticidal concentrate

based on mercaptothion)

5 10Og water

101 g

B) 1 g "Malasol" 100 g water

1 g of a 50% polymer solids dispersion of a copolymer of styrene and 2-ethyl

hexyl acrylate

102 g

25 ml aliquots of the above liquids were mixed well with 10 g wood meal samples. The mixtures were in the heating cabinet with forced ventilation dried at 50 ° C.

After drying, the treated wood meal samples were buried in 200 g of sea sand, which was in plastic cups (280 cm), in the bottom of which holes were punched, was included. Consecutive aliquots of water of 50 ml each was then poured onto the surface of the sand. The electrical conductivity of the trapped individual Percolates were measured. Each test with the wood meal samples treated with liquids A) and B) was carried out 4 times. The results of the conductivity measurements on the successive percolates are given in the following table.

909821/0707

Percolate
No. Liquid A
+ Wood flour Liquid B
+ Wood flour Mixture B as
cumulative
Percentage of
Mixture A 1 Electric
(Mikromho χ conductivity
OK ³ / cm ³ ) 33% 2 40 13th 53% 3 20th 19th 81% 4th 13th 27 95% 5 11 21st 100% 6th 9 13th 102% 7th 9 11 104% 8th '9 11 105% 8th 10

The results show that the soluble insecticide from the ordinary wood flour faster than that with the styrene-2-ethylhexyl acrylate copolymer treated wood flour is leached.

The experiment described above was carried out using "25% extermathion", a mercaptothion containing insecticidal in the form of a wettable powder, repeated. The same delay in insecticide leaching was observed.

Example 1 1 The following two solutions were prepared:

A)

1 g of a flowable dispersion of the herbicide "Atrazine" containing 50% active ingredient

100 g of water

101 g

9821/0707

B) 1g of a flowable containing 50% active ingredient

Dispersion of the herbicide "Atrazine" 100 g of water

1 g of a 50% polymer solids dispersion of a styrene-2-ethylhexyl acrylate copolymer

102 g

Aliquots of 25 ml each of the above-mentioned solutions were mixed well with 10 g each of wood flour. The mixtures were dried ^{at 50 °} C. in a heating cabinet with forced ventilation.

After drying, the treated wood meal samples were each buried in 200 g of sea sand, the one in plastic cups (280 cm), in the bottom of which holes were made, was included. Consecutive aliquots of each 50 ml of water was then poured onto the surface of the sand. The electrical conductivity of the trapped individual percolates were measured. The experiments with the wood meal samples treated with solutions A) and B) were Carried out 4 times. The results of the measurement of the conductivity of the successive percolates are mentioned in the following table.

909821/0707

Percolate

No.

Mixture Λ
+ Wood flour

Mixture B + wood flour

Electric conductivity

3 3 (micromho χ 10 / cm)

Mixture B as a cumulative percentage of Mixture A

1 18th 2 22nd 3 18th 4th 12th 5 10 6th 9 7th 9 8th 9

15 17 17 14 12 10 10 10

83% 80% 84% 90% 94% 96% 97% 98%

The above results show that after leaching three times with 50 ml of water each time, the total amount of soluble Material removed from the wood flour treated with the polymer, only 84% of that from the ordinary Amount removed from wood flour. This soluble material is believed to be almost entirely derived from the herbicide viewed.

Example 12

Wood chips from the South African pine were crushed to sawdust (less than 300 μm). 5000 g of a dispersion of vinyl acetate-2-ethylhexyl acrylate copolymer containing 28 g of dry polymer were stirred into 1100 g of this sawdust. After mixing well, the material was dried in the oven at 50 ° C.

A) 10 g samples of this dry, polymer-treated sawdust were mixed with 10 g of dry "25% extermathion" (Commercially available mercaptothione-containing insecticide in the form of a wettable powder).

909821/0707

B) As comparison samples, 10 g samples of the untreated sawdust were mixed with 10 g "25% extermathion".

The various sawdust mixtures described above were buried in 200 g of sea sand, the one in 280 ml plastic containers was included. Holes have been poked in the bottoms of these containers, resulting in aliquots of 50 ml of water each were poured one after the other onto the surfaces of the sand. Each percolate was collected individually and subjected to the measurement of electrical conductivity. The results for eight leaches with each 50 ml are given in the following table.

Percolate Mixture A Mixture B Mixture B as No. Electric
(Mikromho conductivity
χ OK ³ / cm ³ ) cumulative
Percentage of
Mixture A 1 57 8th 14% 2 40 11 20% 3 22nd 22nd 34% 4th 14th 47 66% 5 11 32 83% 6th 11 17th 88% 7th 9 12th 91% 8th 8th 10 92%

While the largest amount of soluble material that was removed in a leaching out of the mixture ordinary sawdust with insecticide was dissolved during the first leaching, this is the case with the polymer pre-treated sawdust only applies to leaching No. 4. Even after eight leaches the mixture gave containing the water-repellent sawdust released more herbicide than the mixture of herbicide with ordinary sawdust.

909821/0707

Claims (11)

Claims 1. Mixture of substances for use in particular in the Agriculture, containing, in addition to a water-sensitive material, an organic finely divided material, in which the particles are encased in small groups of particles with a polymeric material that forms the particles makes it non-wettable. 2. Mixture of substances according to claim 1, characterized in that that as a finely divided organic material there is a waste material from the sawdust, wood flour, bagasse, contains shredded grass, paper pulp and compost existing group. 3. Mixture of substances according to claim 1 or 2, characterized in that that the enveloping polymeric material is selected from the group (a) vinyl esters of aliphatic acids with 1 to 18 carbon atoms, 9 0 9 621/0707 Telephone: (0221) 131041 Telex: 8882307 dopa d -Telegram: Dompalenl Cologne 285-200 (b) esters of acrylic acid and methacrylic acid with alcohols with 1 to 18 carbon atoms, (c) mono- and diethylenically unsaturated hydrocarbons and aliphatic dienes, (d) unsaturated carboxylic acids, (e) Esters of unsaturated carboxylic acids with alcohols which contain a further functional group, and (f) vinyl monomers. 4. Mixture of substances according to claim 3, characterized in that a polymer of monomers from group (a) vinyl propionate and vinyl versatate is used as the polymeric material, of group (b) methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and methyl methacrylate, group (c) styrene and butadienes, group (d) acrylic acid, methacrylic acid, crotonic acid, fumaric acid and Itaconic acid, group (s) glycidyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate and group (f) vinyl acetate, acrylamide, acrylonitrile, methylol acrylamide and methacrylamide. 5. A method for producing mixtures of substances according to claim 1 to 4, characterized in that an emulsion, dispersion, solution or similar preparation of a polymer which is or becomes non-wettable gives an organic finely divided material, the product if necessary, dries and mixes a water-sensitive material. 6. The method according to claim 5, characterized in that the water-sensitive material before the addition of the Polymer preparation with the organic finely divided material mixes. 909821/0707 2Hb iJ 200 7. The method according to claim 5, characterized in that the water-sensitive material of the polymer preparation clogs. 8. The method according to claim 5, characterized in that the coated finely divided material is dried and then mixes with the water sensitive material. 9. The method according to claim 5 to 8, characterized in that the product after drying to form an aggregate condensed. 10. The method according to claim 5 to 8, characterized in that the finely divided material with a polymer preparation treated, which contains the polymer in such an amount that about 0.1 to 5 parts of polymer per 100 parts of finely divided material are present, the amount being chosen so that it is ensured that the individual particles become unwettable, but are free-flowing and free-flowing. 11. Use of the mixture of substances according to claim 1 to 10 for Treatment of agricultural cultivation areas in such a way that the mixture of substances is transferred to the cultivation area dry state or in such an undried state Condition in which the polymer, after natural drying, imparts its non-wettability to the particles. 21/0707