DE1442434A1 - Coagulating and soil conditioning agents - Google Patents

Description

Coagulants and soil conditioning agents

The invention relates to a coagulant for sedimentation and excretion of substances dissolved or suspended in water and a soil conditioning agent to improve the physical and dynamic properties of soil types.

It is already known that polyvinyl alcohol (hereinafter abbreviated to PYl) that of clay minerals and various inorganic Compounds adsorbed as a coagulating and sedimentation agent to remove contaminants dissolved or suspended in water or as a soil conditioning agent or stabilizer to improve the physical and dynamic properties, such as air permeability, water permeability, Water retention, erosion resistance, easy cultivation, impermeability, shear strength and the like, to use · However, it was not able to achieve a sufficient and sufficient effect »Especially with from volcanoes Containing volcanic ash or volcanic earth thrown out Volcanic gravel this effect could only be achieved aefawacli with PVJ alone, so that the combination for such palls

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With a swellable, (Jitter tone required, is. according to it was found that an acetalized PYA mixed with aldehyde and aminoaldehyde both excellent sedimentation and has clarifying effects as well as soil conditioning effects, whereby it is also extremely beneficial without any additive for volcanic Soils can be used.

G-mixed acetalized PTA is made by reacting PVA with various amino aldehydes and various aldehydes in the presence of mineral acids such as hydrochloric acid, sulfuric acid, etc., educated. The degree of acetalization can be determined by the reaction conditions, i.e. the amount of aldehyde, the reaction temperature, the acid concentration, etc., can be controlled. Aldehydes suitable for this purpose are aliphatic ^ aldehydes (formaldehyde, Acetaldehyde, butyraldehyde, decylaldehyde, dodecylaldehyde, etc.) and their derivatives, as well as aromatic aldehydes such as benzaldehyde, and substituted aldehydes. Suitable amino aldehydes

are aliphatic amino aldehydes such as aminobutyraldehyde, ρ-C hexyl-

/ aminobutyraldehyde, dimethylaminopivaldehyde and the like, as well as aromatic Aminoaldehydes such as p-aminobenzaldehyde, p-dimethylaminobenzaldehyde and the like «

The starting material subjected to the mixed acetalization PVA can be either fully saponified? VA, partially saponified

alcohol PVA or denatured PVA copolymerized with allyl alcohol, isopropeny ^ or methyl vinyl ether * It is also possible to carry out the acetalization and saponification reactions directly with polyvinyl acetate as the starting material *

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. These acetalized polyvinyl alcohols have various types physical and chemical properties of PTX, however, according to the invention it could be determined that they are beyond that are extremely effective coagulants and soil conditioning agents. In particular, this effect increases with the number the carbon atoms of the aldehydes used for acetalization This effect is particularly good with more than seven carbon atoms. On the other hand, the degree of acetalization is increased by the The number of carbon atoms is limited because of the associated hydrophobicity, since the water solubility is maintained

must stay from. Accordingly, when using aldehydes with a high carbon number acetalized PVA, an improvement in the water solubility at low temperatures is desirable.

On the other hand, in the case of PVA acetalized with aminoaldehyde, the water solubility increases as the degree of acetalization increases because of the hydrophilic character of the amino group. Amino acetalized PVA has cation properties because of the amino group and is adsorbed by clay particles with natural negative charge, so that it acts as a coagulant and soil conditioning agent grows. Accordingly, a TVA acetalized with an aldehyde having a high carbon number can be used in its Water solubility at low temperatures and, moreover, improved in its coagulability by aminoacetalization will. Furthermore, the upper soil layer under natural conditions in the soil is formed with the formation of clay bodies Practice subjected to drying and moistening, being observed It is important that the drying or drainage process is extremely effective in stabilizing the soil structure

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is. The mechanism by which high molecular weight compounds die Making grains water-resistant by drying is such that the drainage creates a capillary pressure between the soil particles causes them to approach each other. This causes the crosslinking between the soil particles through the high molecular weight Connection and, as a result of drainage, the binding forces between the soil particles and the high molecular weight compound as well as between the high molecular weight compounds among each other. TJm, by such means, the degree of water resistance au increase, the bond between the high molecular weight compounds and between them and the soil parts should be never be diminished in water. Such an irreversible change with grain formation through high molecular weight compounds is important for the binding of the soil particles having aminoaeetalized polyvinyl alcohol with water-resistant substituents and great coagulation ability of the Effect of the formation of water-resistant grains grows stronger.

As described above, the acetalized PVA mixed by aldehyde and aminoaldehyde has increased its own effect and eliminates its defects, increasing the effects of the coagulants and soil conditioning agents accordingly.

The common coagulants and soil conditioning agents are in volcanic soils, as they cover large parts of Japan, practically completely ineffective. According to the invention it was found that aminoacetalized polyvinyl alcohols because of . 809812/0703

their cationic aminoacetal group from volcanic soils are adsorbed. However, the OH-G group of the polyvinyl alcohols not adsorbed by volcanic soils, so that the effect of aminoaeetalisfertem PYA on volcanic soils is not is always sufficient · If therefore the adsorption on volcanic soils by an aminoacetal group and also by a group with great eoagulation ability is produced, a very strong effect can be observed in volcanic soils will. According to the invention, however, it has been ensured that an acetalized by a mixture of aldehyde and aminoaldehyde PYX by far the best effect on volcanic soils Has·

The above-described acetalized P ¥ A mixed with aldehyde and amino aldehyde is a highly effective and excellent one Coagulants and soil conditioning agents for both non-Vulians as well as for volcanic soils.

“JThe present coagulant and soil conditioning agent can xxxxx combined with! anon mineral particles that are predominantly consist of swellable lattice clay, e.g. monmorinite (bentonite), vermiculite, etc., extremely effective, but it can just as well used in a mixture with other low molecular weight compounds or inorganic and organic fibrous substances. will. In addition, the mixed acetalized PVA is for substances dissolved in water or for suspended organic particles, after being adsorbed by an adsorbent such as bentonite can be used for effective coagulation and sedimentation.

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It can also be used as a soil conditioning agent on farms and in gardens and gardens with seeds or fertilizers are mixed. For the rest, bathing can also be done with an aqueous suspension of the under discussion Means for strengthening light and weak soils or for Prevent 'water leakage from them being soaked.

When swellable mesh clays to prevent water leakage to be used on rice fields or at earthworks ^ the present remedy can be combined with these in order to destroy them to prevent.

The invention is illustrated below with the aid of a few examples, which, however, are in no way restrictive.

example 1

A 1 $ aqueous kaolinite suspension was made with sodium hydroxide solution brought to pH 6 and with a suitable amount of a mixed acetalized polyvinyl alcohol with a p-Cyclohexylaminobutylaeetalisierungsgrad of 9.5 MoI- ^ (hereinafter Called HBA-G-rad) and a degree of n — deeyl acetalization of

added 5 mol-fo and a degree of polymerization of 100 / The eoagulation effect was measured by the relative irradiation at 30 C after the course of one hour (at room temperature). In addition, a n-decylacetalisierter PVA fo for comparison with a degree of acetalization of 2.3 mol and a polymer - sationsgrad of 1700 dealt with "The acetalized with n-decyl BVA completely dissolve only in boiling water,

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while the mixed acetalized PVA of n-decylaldehyde and HBA was completely dissolved in room temperature water. Of the mixed acetalized PYA also showed better coagulating effect.

Example 2

The coagulating effect of n-heptylacetalized PYA with a degree of aeetalization of 5.3 mol- $ and a degree of polymerization of 1700, a PVA with a degree of 2-ethylhexylaeetalization of 5 # 7 mol- # and a degree of polymerization of 1700 and a like acetalized PVA with HBA a degree of 9.5 mol #, an n-Decylacetalisierungsgrad of $ 5 mol and a polymerization degree of 1700 were tested in the same manner as in example 1. · the results are ig refer _e 2 3?. Older heptalized PVA and 2-ethylhexyl acetalized PVA were only slightly dissolved in boiling water, while the mixed acetalized PVA could be completely dissolved in water at room temperature, the coagulation effect of the latter also being considerably better.

Example 5

"Kuroboku" grains with a grain size of less than 0.1 mm, made by Wagahira-machi, Kagoshima Prefecture, Japan, were used as volcanic soil. To 25 ml of a 2.4 $ Volcanic earth suspension were mixed acetalated in appropriate amounts PVA with a degree of n-decyl acetalization of 5 mol-? 6, an HBA örad of 14 MoI- ^ and a degree of polymerization of

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1700 and one with a degree of n-decyl acetalization of 5 Hol- $, an HBA degree of 9.5 mol-tfo and a degree of polymerization of 1700 were added. Each of the sedimentation volumes was
after one step "determined at room temperature. The results are shown in Table 1 below
show that the clarifying effect with the sedimentation volume
increases.

Table 1 • • 6 min 10 min 15 minutes 0 ^ 85 0.2.9 1.0 Added Amount of one 1.7 1.7 ■ 1.7 middle dry soil 1.9 1.9 1.9 sample added
th means <fo Sedimentation volume at 1.7 1.7 1.7 Without addition 0 different time intervals 1.7 1.7 1.85 Mixed aceta- 0.025 3 min 1.85 1.85 1.85 lized PVA
with an n-De- 0.05 1.7 1.7 1.7 cylacetalisie-. 0.10 1 ₅ 7 degree of
5 mole #, one 0.25 1.95 1.8 1.8 1.8 KBA degree from
9.5 Wol-fo 0.5 1.8 1.5 1.5 1.5 Mixed aceta- 0.025 1.8 1.9 1.9 1.9 lized PYA 2.0 2.0 2.0 1.95 with an n-decyl 0.05 1.7 aoetalization 0.10 degree of 5 mol- $
and an HBA degree 0.25 1.8 from 14 moles: - # 0.5 1.5 1.95 2.05

Me clarifying effect is not only for non-volcanic, but
especially large for volcanic soils

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Example 4

To a solution of 1 ^ Titanoxydsuspension was mixed on the basis of a titanium oxide 1 $ acetalized polyvinyl alcohols with a n-Deeylacetalisierungsgrad MOI of 5 ^, an HBA-G-rad of 9 »$ 5 mol and a degree of polymerization of 1700, the added titanium oxide balled up on it and settled down while the supernatant liquid cleared.

Example 5

Air dried kaolinite of less than 20 / u was used as a sample. An aqueous solution of 200 ml of mixed acetalized PVA with a degree of normalization of 10 mol- $, an HBA degree of 9.7 mol- $ and a degree of polymerization of 1700 and a mixed acetalized PVA with a n-decyl acetalization degree of 5 mol-96 , an HBA- & rad of 9 »5 Mo 1- $ and a degree of polymerization of 1700 100 g of soil were added in each case, with a 0.4 wt .- ^ strength solution in relation to the air-dried kaolinite. It was mixed well and at 50 ⁰ O dried. From these dried samples, grains with a diameter of 10 to 7 mm were prepared, which were immersed in ordinary water for more than 10 hours. Water-resistant grains of various diameters were separated by sieving in water with sieves of various sizes. The results are shown in Table 2. The fact that the diameter and amount of the water stable aggregates are large means that the bonding forces between the soil particles are excellent. For comparison, the same test was performed on one acetalized with HBA

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PVA with a degree of etalization of 9 »3 Mo 1- $ and a degree of polymerization made by 170Q, the results of which can also be found in Table 2.

The table shows that by adding mixed acetalized PVA the binding forces of the water-stable aggregates increase considerably. In particular, the presence of one increases n-decyl acetal group surprisingly the binding forces of the soil particles stronger than a single amino acetal group.

Table 2

Added - amount of water-resistant grains mean (in jo based on the amount of dried soil)

> 4 mm> 2 mm> 1 mm> 0.5 mm > 0.25 mm

Without addition

PYA with a. HBA degree of 9.3 mole #

Mixed "acetalized PYA with a degree of formalization of 10 mol $ and an HBA grade of 8.7

Mixed acetalized PYA with a degree of n ~ decylaeetalization of 5 mol% and an HBA degree of 9.5 mol%

11.2

18.8

58.1

31.4 66 _t 7 83.2

43.3 75.6 88.7

78.1 90.4 94.1

89.8

92.1

95.7

-11-

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Example 6

A mixed acetalized PVA having a degree of n-deeylaeetalization of 5 mol%, an HBA degree of 14 mol% and a degree of polymerization of 1700 was added to kaolinite in the same manner as in Example 5. The water-stable aggregates were sieved out in water. The result is shown in Table 3. For comparison, a PVJfc acetalized with HBA with a degree of acetalization of 13.8 mol? » and a degree of polymerization of 1700} the results are also shown in Table 3 ©

The table clearly shows that the binding forces of the water-stable aggregates of mixed acetalized PVA are considerable are bigger.

Table 3

Added means

Amount of water-resistant grains (in $ based on the amount of dried soil) 4 mm ^ 2 mm j> 1 mm j> 0.5 mm _> 0.25 mm

Without addition

PVA with an HBA grade of 13.8

9.1

Mixed acetalized PViL with a degree of n-decyl acetalization from 5 Μο1-? έ and an HBA grade of 14 mole-96 24.7

22.7 56.7

50.7 78.9

75.9

85.7

87.9

91.1

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Example 7

Air-dried "Kuroboku" soil, manufactured by Kagoshisia Prefecture, with a grain size of less than 0.25 ma was used as volcanic soil and mixed with the aqueous granulation of acetalized PYA with an n-Deoylaeetalisigrungggrad of 5 mol-j6 | a HBA ßrad of 9 »5 mol ~ $ and $ a Eolymerlsationsgrad of 1700 Ir an amount of from 0.2> (based on the air-dried soil) was added to the & anae mixed well and" dried at 5O ⁰ C. The water stable aggregates were measured in the same way as in Example 5. The results are shown in the table below For comparison, a partially saponified PIA with an acetyl group content of 10 mol $ and a degree of polymerization of 1700, an n-decylaoetalized PYA with a! polymer ionsgr ad γόη 1700 and a aeetalisierter with HBA PVA having a degree of polymerization of 1700 and a degree of acetalization of 13j, # 8.Mol- tested for 'the same way and the amount of water "measured stable aggregates" If bentonite along with ΈΎΑ, is used in volcanic soil, it turns out, & a & this mixture is very effective, however, was auc & this tibet checks © mixture in this test series, όΰα ₀ partially hydrolyzed PYA with a @ a acetyl of 10 lol "^ and a pole yagrisationsgrad of 1700 * was added in an amount of 0 2 is a soil sample, whereupon he also $ 2 "bentonite (manufactured by Ho.3ua Yoko-factory under the Handeienaaen" silicalite · A *) were sugeftigt. The amount of wassergtabilen aggregates was measured in the usual way · The Srgetaiieee are shown in Table 4 to '.

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[Table 4

Added
middle lot
(in 9 of the water-resistant grains
5 based on the amount of dried soil} > ¹ mm > 0.5 mm> 0.25 mm 1.1 p4 ^mm > 2 mm O 0 19.6 - Without addition O 0 O 2.8 41.0 Partially saponified
PVA O 0 0 8.4 58.2 n ~ decylaeetali-
sated PVA 0 0 5, , 5 35.7 75.8 With HBA acetali-
sated PVA 0 0 41, Λ 66.2 76.2 Partially saponified
PVA bentonite O 2.2 61, , 2 72.2 With n-decylaldehyde
and HBA mixed
acetalized PVA 5.6 31.7

With partially saponified PVA, the achievable formation of water-stable aggregates is very low, while with non-deoylacetalized PVA and with HBA acetalized PVA a weak, but nevertheless inadequate, effect can be achieved. On the other hand, the effect that can be achieved with an acetalized PVA mixed with HBA and n-decylaldehyde is surprisingly great, even greater than with PVA and bentonite used together.

The relationship between the relative turbidity and the amount of polymer added is shown in the accompanying drawings.

Fig. 1 shows the change in the cloudiness due to the addition of a polymer, curve A showing the change when adding n-decylaeetaiisiertia PVA and curve B the change when adding it

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of mixed acetalized PVA according to the invention illustrated _f

Fig. 2 is a similar Beziehung'wie J Ig ¹ * 1, where the curves A and B the addition of heptylacetalisiertem PTA or 2-ätiiyl'hexylacetalisiertem PYA illustrate _y while curve C mixed with the addition of HBA and n-Decylaidehyd acetalized PYA showed

From these curves it can be seen that the turbidity increased with. Addition of coagulants and soil conditioning agents according to the invention increases almost linearly from 0.1 to < >

Patent claims:

BATH ORIGINAL

Ha - * 15,518

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Claims (4)

PATENTANWÄLTL · <£ Qtiy H 4 2 4 3 PATENTANWALT MÜLLER-BÖRNER PATENTANWALT DIPL.-INQ. WEV BERLIN-DAHLEM -POOBIELSKIALLEES ^ fr MUNICH ZZ ' WIDENMAYERSTRASSE A-0 TELEPHONE 762007 ■ TELEGRAMS: PROPINOUS f ij TELEPHONE: 22SS85 TELEGRAMS: PROPINOUS 15 518 Berlin, October 19th, 1962 Dr. Expl. KURASHIKI RAYON COMPAlTY HMITED, Kurashiki City (Japan) Claims 1 · Coagulant, characterized in that it has a Aldehyde and aminoaldehyde mixed acetalized pelyvinyl än contains water alcohol for coagulation and sedimentation / suspended or dissolved particles consisting of inorganic or organic substances » 2. Soil conditioning agent, characterized in that it contains an acetalized polyvinyl alcohol mixed with aldehyde and aminoaldehyde. 3t coagulant according to claim 1, characterized in that it contains a polyvinyl alcohol that is mixed with aeetaliaiert aldehyde and amino aldehyde with more than seven carbon atoms _# 4. Soil conditioning agent according to claim 2, characterized in that it contains thin polyvinyl alcohol which is mixed with aldehyde * and aminoaldehyde with more than seven carbon atoms • is aoetallßiert. T-Tr- 809812/0703 ■ Λ · B & - 15 518 TELEPHONE: 018 4007