NZ737511B2 - Biodegradable super-spreading, organomodified trisiloxane - Google Patents
Biodegradable super-spreading, organomodified trisiloxane Download PDFInfo
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- NZ737511B2 NZ737511B2 NZ737511A NZ73751116A NZ737511B2 NZ 737511 B2 NZ737511 B2 NZ 737511B2 NZ 737511 A NZ737511 A NZ 737511A NZ 73751116 A NZ73751116 A NZ 73751116A NZ 737511 B2 NZ737511 B2 NZ 737511B2
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- New Zealand
- Prior art keywords
- formula
- sample
- polyether
- mol
- siloxanes
- Prior art date
Links
- 238000003892 spreading Methods 0.000 title description 8
- ZQTYRTSKQFQYPQ-UHFFFAOYSA-N trisiloxane Chemical class [SiH3]O[SiH2]O[SiH3] ZQTYRTSKQFQYPQ-UHFFFAOYSA-N 0.000 title description 5
- 239000000203 mixture Substances 0.000 abstract description 43
- -1 siloxanes Chemical class 0.000 abstract description 37
- 229920000570 polyether Polymers 0.000 abstract description 34
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 21
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 12
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 23
- 239000002671 adjuvant Substances 0.000 description 20
- 229910052739 hydrogen Inorganic materials 0.000 description 19
- 239000001257 hydrogen Substances 0.000 description 19
- 241000196324 Embryophyta Species 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000000575 pesticide Substances 0.000 description 15
- 239000007921 spray Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 239000004094 surface-active agent Substances 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 239000004009 herbicide Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- LINPVWIEWJTEEJ-UHFFFAOYSA-N methyl 2-chloro-9-hydroxyfluorene-9-carboxylate Chemical compound C1=C(Cl)C=C2C(C(=O)OC)(O)C3=CC=CC=C3C2=C1 LINPVWIEWJTEEJ-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 239000004480 active ingredient Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 230000002363 herbicidal effect Effects 0.000 description 6
- 230000007480 spreading Effects 0.000 description 6
- 239000013543 active substance Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000003337 fertilizer Substances 0.000 description 5
- 239000000417 fungicide Substances 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000006459 hydrosilylation reaction Methods 0.000 description 5
- 239000002917 insecticide Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 4
- 101150065749 Churc1 gene Proteins 0.000 description 4
- 102100038239 Protein Churchill Human genes 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000003630 growth substance Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000006353 oxyethylene group Chemical group 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011785 micronutrient Substances 0.000 description 2
- 235000013369 micronutrients Nutrition 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- HBEMYXWYRXKRQI-UHFFFAOYSA-N 3-(8-methoxyoctoxy)propyl-methyl-bis(trimethylsilyloxy)silane Chemical compound COCCCCCCCCOCCC[Si](C)(O[Si](C)(C)C)O[Si](C)(C)C HBEMYXWYRXKRQI-UHFFFAOYSA-N 0.000 description 1
- 239000005660 Abamectin Substances 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 241000209048 Poa Species 0.000 description 1
- 241000209049 Poa pratensis Species 0.000 description 1
- 239000005616 Rimsulfuron Substances 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 241001148683 Zostera marina Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 239000012681 biocontrol agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- SWGZAKPJNWCPRY-UHFFFAOYSA-N methyl-bis(trimethylsilyloxy)silicon Chemical compound C[Si](C)(C)O[Si](C)O[Si](C)(C)C SWGZAKPJNWCPRY-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003750 molluscacide Substances 0.000 description 1
- 230000002013 molluscicidal effect Effects 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- MEFOUWRMVYJCQC-UHFFFAOYSA-N rimsulfuron Chemical compound CCS(=O)(=O)C1=CC=CN=C1S(=O)(=O)NC(=O)NC1=NC(OC)=CC(OC)=N1 MEFOUWRMVYJCQC-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012873 virucide Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
- A01N25/06—Aerosols
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0876—Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage
- C07F7/0878—Si-C bond
- C07F7/0879—Hydrosilylation reactions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2230/00—Compositions for preparing biodegradable polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
Abstract
The invention relates to polyether-modified siloxanes which are both superspreading and biodegradable. In particular, the invention is directed to a composition including polyether-modified siloxanes of Formula (I) MaDbD?c where M=R13SiO1/2, D=R12SiO2/2, D?=R1R2SiO2/2, where a is 2, b is between 0 and 0.1, c is between 1.0 and 1.15, 0 and 1.05, R1 are independently hydrocarbyl having 1 to 8 carbon atoms, preferably methyl, ethyl, propyl or phenyl radicals, especially preferably methyl radicals, R2 are independently a polyether radical. nd 0.1, c is between 1.0 and 1.15, 0 and 1.05, R1 are independently hydrocarbyl having 1 to 8 carbon atoms, preferably methyl, ethyl, propyl or phenyl radicals, especially preferably methyl radicals, R2 are independently a polyether radical.
Description
Biodegradable super-spreading, organomodified trisiloxane
Abstract:
her-modified siloxanes which are both preading and readily biodegradable.
Description of the invention:
In crop protection, in pesticides and also in the industrial non-crop sector, the biological efficacy of
such pesticides or pesticide mixtures is frequently improved by using what are called adjuvants or else
aries or additives. Efficacy is frequently also referred to as effectiveness. The Pesticides Safety
orate (PSD, the executive branch of the Health and Safety Executive (HSE), a non-governmental
public organization in Great Britain) defines an adjuvant as a substance other than water which is not
itself pesticidally active but increases the effectiveness of a pesticide.
(http://www.pesticides.gov.uk/guidance/industries/pesticides/topics/pesticideapprovals
/legislation/adjuvants-an-introduction). These are either added to the aqueous spray liquor
shortly before deployment and spray application (as tankmix additive) or incorporated directly into crop
protection composition formulations. With regard to the use of the word adjuvant, patents or the
literature often use the terms surfactant or g agent mously, but these are much too nging
and can therefore be interpreted as more of an umbrella term. Because of the use envisaged
here, the term "adjuvant" is employed.
In practice, there are numerous crop protection active ingredients which achieve acceptable
effectiveness, i.e. practically relevant efficacy, only with the aid of adjuvants. The adjuvants help here
to compensate for the weaknesses of the active ingredient, for example the UV sensitivity of
avermectins (destroyed by ultraviolet ion) or the water instability of sulphonylureas. More recent
active ingredients are generally water-insoluble and, in order ore to be able to spread ively
over a target = target organism = plant, adjuvants are indispensable for the aqueous spray liquor, in
order to compensate for the poor wetting of surfaces by way of a physical influence on the aqueous
solutions. In addition, adjuvants help to overcome cal application problems, such as low water
ation rates, different water ies and the trend to increased application rates. The increase in
pesticide efficacy and the sation for weaknesses in the crop protection compositions by
adjuvants are generally referred to as increasing the activity or enhancing the effect of the crop
protection composition application.
In crop protection, in pest l and in the industrial sector, chemical or biological crop protection
compositions (also called pesticides hereinafter) or pesticide mixtures are employed. These may be,
for example, herbicides, fungicides, insecticides, growth regulators, molluscicides, bactericides,
virucides, micronutrients and biological crop protection compositions based on natural products or
living or sed microorganisms. Active pesticidal ingredients are listed in connection with their
fields of use, for example, in ‘The Pesticide Manual', 14th edition, 2006, The British Crop Protection
2 2016/062134
Council; biological active ingredients are ied in ‘The Manual of Biocontrol Agents', 2001, The
British Crop Protection l. "Pesticide" is always used as a collective term hereinafter.
In order to be able to assess the agricultural potential and the activities of substances, it is necessary
to carry out not only the laboratory and greenhouse experiments, but also realistic applications in
agriculture, for example field trials.
In practice, crop tion compositions of this kind are often added to a tank with water as an
ingredient and distributed in what is called the spray liquor with gentle stirring, in order to dilute the
concentrated ation of the active ingredient prior to ng and to make it tolerable for the
plants. Adjuvants are either incorporated into the crop protection formulation here prior to the
tankmixing operation or added to the spray liquor as separate tankmix additives.
Adjuvants used are frequently synthetic surfactants, for example ethoxylated alcohols or alkyl
polyglycosides. The use of water-soluble hydrophilic polyglyceryl esters as nts in crop protection
formulations is likewise known (, US 2006/0264330A1). In general, a feature
common to these nts is that they are water-soluble hydrophilic substances. Further adjuvants
frequently used are additionally lated trisiloxane surfactants which lower the static surface
tension of spray liquors or water to a greater degree than the organic surfactants used in the past, for
example nonylphenol ethoxylates. Trisiloxane surfactants have the general structure Me3SiO-SiMeROSiMe3
where the R radical is a polyether radical. The use of superspreading oxane surfactants,
for example, BREAK-THRU® S-240, Evonik Industries AG, in combination with a pesticide, leads to an
improvement in pesticide uptake by the plant and generally to a rise in the efficacy or iveness
thereof. US 6,734,141 states that this increase in effectiveness is occasioned specifically by a low
surface tension and not necessarily by the spreading. The term "surface tension" is understood in the
prior art to mean static surface tension. In the case of trisiloxanes, for example, static surface tension is
about 20 to 25 mN/m.
WO1994022311 discloses superspreading compositions sing her-modified siloxanes
which may have two groups of polyethers: firstly polyethers having exclusively oxyethylene groups,
and secondly polyethers which, in addition to oxyethylene groups, may also have pylene
groups. Experimental data are disclosed for modified siloxanes n the polyether residue contains
exclusively ylene groups. These are known, for example, as SILWET L-77.
A disadvantage of the prior art is that none of the superspreading trisiloxanes are biodegradable. For
environmental reasons in particular, ever greater value is being placed on environmentally friendly
products, particularly in order to gain popular acceptance with t to chemical products in
agriculture.
"Superspreading" in the context of the present invention is understood to mean that a 0.1 per cent by
weight solution in water, after examination in accordance with ASTM E2044 – 99 (2012), has a
diameter of spread of at least 35 mm. Preferably, a droplet of a 0.1 per cent by weight solution in water
having a volume of 50 µm on a polypropylene film spreads to an area of at least 10 cm2. Preferably,
the spread is ed at 25°C; preferably, the spread is determined at a relative air humidity of 60%
and a pressure of 1013 mbar.
"Readily biodegradable" within the scope of the present invention describes degradability according to
OECD Method 301F CD, preferably as described in the examples.
It was an object of the present invention to overcome at least one disadvantage of the state of the art.
It has been found that, surprisingly, compositions comprising her-modified siloxanes as
described in the claims are both preading and readily biodegradable.
The present invention provides itions comprising polyether-modified siloxanes of formula (I)
MaDbD' c Formula (I)
with M = R13SiO 1/2 , D = R12SiO 2/2 , D‘ = R1R2SiO 2/2 ,
where
a is 2
b is between 0 and 0.1, preferably 0,
c is between 1.0 and 1.15,
preferably between 1.0 and 1.10, especially preferably between 1.00 and 1.05,
R1 are ndently hydrocarbyl having 1 to 8 carbon atoms, preferably methyl, ethyl, propyl or
phenyl radicals, especially preferably methyl radicals,
R2 are independently a polyether l of the formula (II)
-R3O[CH 2CH 2O] m[CH 2CH(CH 3)O] n R5 Formula (II)
where
m = 3.4 to 11.0, preferably 3.6 to 9.9, more ably 4.5 to 8.5,
n = 2.5 to 8.0, preferably 2.7 to 7.5, more preferably 3.0 to 6.0,
but with the provisos that:
m/n = 1.9 to 2.8,
R3 are independently divalent arbyl radicals having 2 to 8 carbon atoms, preferably
ethylene, propylene, 1-methylpropylene, 1,1-dimethylpropylene radical, especially preferably
-CH 2CH 2CH 2-,
R5 is hydrogen,
the polyether-modified siloxanes of formula (I) having a biodegradability of greater than 60%, more
preferably of greater than or equal to 63% and especially preferably of greater than or equal to 65%, the
maximum value being 100%.
In a particular aspect, the t invention provides compositions comprising polyether-modified
siloxanes of formula (I)
MaDbD' c Formula (I)
with M = R13SiO 1/2 , D = R12SiO 2/2 , D‘ = R1R2SiO 2/2 ,
where
a is 2
b is between 0 and 0.1,
c is between 1.0 and 1.15,
R1 are independently hydrocarbyl having 1 to 8 carbon atoms,
R2 are independently a polyether radical of the a (II)
-R3O[CH 2CH 2O] m[CH 2CH(CH 3)O] n R5 Formula (II)
where
the molar mass of the polyether radical M(PE) is greater than 520 g/mol and less than 660 g/mol,
m = 3.4 to 11.0,
n = 2.5 to 8.0,
but with the provisos that:
m/n = 1.9 to 2.8,
R3 are independently divalent hydrocarbyl radicals having 2 to 8 carbon atoms, R5 is hydrogen,
the polyether-modified siloxanes of formula (I) having a biodegradability of r than 60%, the
maximum value being 100%.
Preferably, the polyether radical, calculated without R3O and calculated without R5, has a molar mass M
(PE) calculated by 44 g/mol * m + 58 g/mol * n where the indices m and n relate to formula (II).
The red values of M (PE) are: lower limits M (PE) greater than 520 g/mol, ably greater than
530 g/mol, more preferably r than 535 g/mol; upper limit M (PE) less than 660 g/mol, preferably
less than 630 g/mol, more preferably less than 600 g/mol.
[FOLLOWED BY PAGE 4a]
Preferably, the value of M (PE) is greater than 520 g/mol and less than 660 g/mol, especially greater
than 535 g/mol and less than 600 g/mol.
Preferably, the sum total of m + n is greater than 9 up to 19, more preferably greater than 9.5 up to 15
and especially preferably greater than 10 up to 12.
More preferably, the inventive compositions include the her-modified siloxanes of the formula (I)
with an index c between 1 and 1.05, where the indices of the polyether radical of formula (II) are m from
3.4 to 11.0 and n from 2.5 to 8.0.
More preferably, the inventive compositions include the polyether-modified siloxanes of the formula (I)
with an index c between 1 and 1.05, where the ratio m/n is 1.9 to 2.8.
ally preferably, the inventive compositions include the polyether-modified siloxanes of the formula
(I) with an index c n 1 and 1.05, where the molar mass of the polyether residue M(PE) is greater
than 520 g/mol and less than 660 g/mol.
Especially preferably, the inventive compositions include the polyether-modified siloxanes of the a
(I) with an index c between 1 and 1.05, where the R5 radical is hydrogen.
Especially preferably, the inventive compositions include the polyether-modified nes of the formula
(I) with an index c between 1 and 1.05, where the molar mass of the her residue M(PE) is greater
than 520 g/mol and less than 660 g/mol and the R5 radical is hydrogen.
Preferably, the inventive compositions do not include any further polyether-modified siloxanes apart from
those of formula (I).
One advantage of the inventive compositions is that they have preading ties in water in the
sense defined above. For this purpose, the area of a droplet on a polypropylene film is determined as
described in detail in the examples.
Preferably, the ive compositions have, as a 0.1 per cent by weight solution in water, a spreading
area of 10 to 60 cm2, preferably of 15 to 50 cm2 and more ably of 20 to 40 cm2. More preferably,
the inventive compositions have the aforementioned spreads at a temperature of 25°C.
[FOLLOWED BY PAGE 5]
Polyether-modified siloxanes of formula (I) in which index c is at least 1.2 are known according to US
6,734,141 as non-spreading compounds and are excluded from the present invention.
Preferably, the inventive compositions include the polyether-modified siloxanes of the formula (I) where
the index d is 1.0 to 1.05 and a 0.1 per cent by weight solution of these siloxanes in water has a
ing area of 15 to 60 cm2.
More preferably, the inventive compositions include the polyether-modified siloxanes of the formula (I)
having an index c between 1 and 1.05, where the m/n ratio is 0.8 to 2.8 and a 0.1% by weight solution
of these siloxanes in water has a ing area of 15 to 60 cm2.
A further advantage of the inventive compositions is their biodegradability.
Biodegradability is preferably determined by the OECD 301 F . More preferably,
biodegradability is determined in accordance with OECD 301 F after 28 d at 22°C. Especially
preferably, biodegradability is determined as bed in the examples.
Preferably, the her-modified siloxanes of formula (I) in the inventive compositions have a
biodegradability of greater than 60%, further more preferably of greater than or equal to 63% and
especially preferably of r than or equal to 65%, the maximum value being 100%.
Preferably, the inventive itions include the polyether-modified siloxanes of the formula (I) where
the index d is 1.0 to 1.05 and biodegradability of the siloxanes is greater than 60%.
More preferably, the inventive compositions include the her-modified siloxanes of the formula (I)
a biodegradability of greater than 60%, and the index c is additionally between 1 and 1.05, where the
molar mass of the polyether radical M(PE) is greater than 520 g/mol and less than 660 g/mol and the
R5 radical is hydrogen.
More preferably, the inventive itions include the polyether-modified nes of the formula (I)
a biodegradability of greater than 60%, and the index c is additionally between 1 and 1.05, where the
molar mass of the polyether radical M(PE) is greater than 520 g/mol and less than 660 g/mol, the R5
radical is hydrogen and a 0.1% by weight solution of these siloxanes in water has a spreading area of
to 60 cm2.
Preferably, the ive compositions do not include any odegradable polyether-modified
siloxanes.
The present invention further provides a process for producing polyether-modified siloxanes, in which,
in a first step, an H-siloxane of the a (V)
MaDbD' d (V)
with M = R13SiO 1
1/2; D = R 2SiO 2/2 , D‘ = R1R2SiO 2/2 ,
where
a is 2,
b is between 0 and 0.1,
d is n 1.16 and 3,
R1 are independently hydrocarbyl having 1 to 8 carbon atoms, preferably methyl, ethyl, propyl or
phenyl radicals, especially preferably methyl radicals,
R2 is en
is purified and, in a second step, is reacted in the manner of a hydrosilylation with a terminally
unsaturated polyether of the formula (VI)
R4O[CH 2CH 2O] m[CH 2CH(CH 3)O] nR5 (VI)
where
m = 3.4 to 11.0, preferably 3.6 to 9.9, more preferably 4.5 to 8.5,
n = 2.5 to 8.0, preferably 2.7 to 7.5, more preferably 3.0 to 6.0,
but with the provisos that:
m/n = 0.44 to 3.08, preferably 0.55 to 3.00, more preferably 0.8 to 2.8, especially preferably 1.9 to
2.8,
R5 are each independently hydrocarbyl radicals having 1 to 16 carbon atoms or hydrogen,
preferably hydrogen or methyl, ally hydrogen,
R4 are independently monovalent terminally rated hydrocarbyl having 2 to 8 carbon atoms,
ably CH2=CH 2-, CH2=CHCH 2-, CH2=CHCH(CH 3)-, CH2=CHC(CH 3)2, ally preferably
CH 2=CHCH 2-.
In another particular aspect, the present invention provides a process for preparing polyether-modified
siloxanes, in which, in a first step, an H-siloxane of the formula (V)
MaDbD' d (V)
with M = R13SiO 1
1/2; D = R 2SiO 2/2 , D‘ = R1R2SiO 2/2 ,
where
a is 2,
b is between 0 and 0.1,
d is between 1.16 and 3,
R1 are independently hydrocarbyl having 1 to 8 carbon atoms,
[FOLLOWED BY PAGE 6a]
R2 is hydrogen
is purified and, in a second step, is d in the manner of a hydrosilylation with a terminally
unsaturated polyether of the formula (VI)
R4O[CH 5
2CH 2O] m[CH 2CH (CH 3)O] nR (VI)
where
m = 3.4 to 11.0,
n = 2.5 to 8.0,
but with the provisos that:
m/n = 1.9 to 2.8,
R5 are each independently hydrocarbyl radicals having 1 to 16 carbon atoms or hydrogen,
R4 are independently monovalent terminally unsaturated hydrocarbyl having 2 to 8 carbon atoms.
Preferably, the H-siloxane of formula (V) is purified in the first step of the process according to the
invention by subjecting the xane to a suitable thermal separation process. Thermal separation
processes are known by this term to those skilled in the art and include all processes based on the
establishment of a thermodynamic phase equilibrium. Preferred thermal separation processes are
selected from the list comprising distillation, ication, adsorption, crystallization, tion,
absorption, drying and freezing-out, particular preference being given to methods of distillation and
rectification. Particular preference is given to distillation and rectification under standard pressure.
Especially preferred is distillation and rectification at standard re for the compounds of the formula
(V) with R2 = hydrogen and the s a and b = zero and d = 1.16 to 1.22 at a top temperature of 142°C
under standard pressure for purification of the product.
ably, in the process according to the invention, no H-siloxanes of the a (V) which have been
subjected to any separation process other than a thermal separation process are employed.
[FOLLOWED BY PAGE 7]
The index d of the nds of the formula (V) can be determined by prior art methods, preferably
with the aid of 1H NMR oscopy, more preferably by the method as described in the examples.
The hydrosilylation reaction in the process ing to the invention is preferably catalysed with the
aid of the platinum group catalysts familiar to those skilled in the art, more preferably with the aid of
Karstedt catalysts.
The hydrosilylation on in the process according to the invention is preferably t to a full
conversion in relation to the hydrogen content of the H-siloxane of the formula (V). In the context of the
present invention, full conversion is understood to mean that the conversion of SiH functions is > 99%.
This is detected in a manner familiar to those skilled in the art, preferably by gas-volumetric means
after alkaline breakdown. This can be done, for example, by reacting a sample of the reaction mixture
with a butanolic sodium butoxide solution (w (sodium butoxide) = 5%) and concluding the amount of
SiH functions still present from the amount of hydrogen formed.
The polyethers of the formula (VI) and the polyethers of the formula (II) may have a statistical
construction. Statistical distributions are of blockwise construction with any desired number of blocks
and with any desired sequence or are subject to a randomized distribution; they may also have an
alternating construction or else form a gradient over the chain; more particularly they can also form any
mixed forms in which groups with different distributions may optionally follow one another. Specific
executions may result in restriction of the tical distributions by virtue of the ion. For all
ranges which are not affected by the restriction, there is no change in the statistical distribution.
Further preferably, it is also true of the polyethers of the formula (VI) in the process ing to the
invention that the polyether radical of formula (VI), ated t R4O and calculated without R5,
has a molar mass M (PE) calculated by 44 g/mol * m + 58 g/mol * n where the s m and n are as
defined for formula (II).
The preferred values for M (PE) are: lower limits for M (PE) greater than 520 g/mol, preferably greater
than 530 g/mol, more preferably greater than 535 g/mol; upper limits for M (PE) less than 660 g/mol,
preferably less than 630 g/mol. More preferably less than 600 g/mol.
Preferably, the value of M (PE) is greater than 520 g/mol and less than 660 g/mol, especially greater
than 535 g/mol and less than 600 g/mol.
Preferably, the sum total of m + n is r than 9 up to 19, more preferably greater than 9.5 up to 15
and especially preferably greater than 10 up to 12.
More preferably, R5 is hydrogen and the value of M (PE) is r than 520 g/mol and less than 660
g/mol; especially preferably, R5 is hydrogen and the value of M (PE) is greater than 535 g/mol and less
than 600 g/mol.
More preferably, the inventive H-siloxanes of the a (V) have an index d between 1 and 1.05 and
are reacted with terminally unsaturated polyethers of the formula (VI), where the indices m are from 3.4
to 11.0 and n from 2.5 to 8.0.
More preferably, the inventive H-siloxanes of the formula (V) have an index d between 1 and 1.05 and
are reacted with terminally unsaturated polyethers of the formula (VI), where the m/n ratio is 0.8 to 2.8.
More preferably, the inventive H-siloxanes of the a (V) have an index d between 1 and 1.05 and
are reacted with terminally unsaturated polyethers of the formula (VI), where the m/n ratio is 1.9 to 2.8.
Especially preferably, the inventive H-siloxanes of the formula (V) have an index d between 1 and 1.05
and are reacted with ally unsaturated polyethers of the formula (VI), where the molar mass of the
polyether radical M(PE) is greater than 520 g/mol and less than 660 g/mol.
Especially preferably, the inventive H-siloxanes of the formula (V) have an index d between 1 and 1.05
and are d with terminally unsaturated polyethers of the formula (VI), where the R5 radical is
hydrogen.
Especially preferably, the inventive H-siloxanes of the formula (V) have an index d between 1 and 1.05
and are reacted with terminally unsaturated polyethers of the formula (VI), where the molar mass of the
polyether l M(PE) is greater than 520 g/mol and less than 660 g/mol and the R5 radical is
hydrogen.
Especially preferably, the inventive H-siloxanes of the formula (V) have an index d between 1 and 1.05
and are reacted with terminally unsaturated polyethers of the formula (VI), where the R5 radical is
hydrogen and where the m/n ratio is 1.9 to 2.8.
Preferably, the products of the process according to the ion do not include any further polyethermodified
siloxanes that do not correspond to the products of the process according to the ion.
The inventive itions can be ed by the prior art methods, but preferably by the process
according to the ion.
The present invention further provides for the use of the inventive compositions and/or of the inventive
process products as adjuvant in crop protection.
The inventive adjuvant is suitable with all crop tion compositions for all plants. Advantageously,
the adjuvant is used together with herbicides, fungicides, insecticides, growth regulators and macro-
and utrients (fertilizers), preferably with herbicides. The crop protection compositions and
fertilizers may be either of synthetic origin or of biological and natural .
The inventive itions may include further ents. These further components may be
selected from herbicides, fungicides, insecticides, growth regulators and fertilizers, preferably
herbicides. Preferred fertilizers are macro- and micronutrients.
9 2016/062134
Preferably, the inventive compositions are used as a tankmix additive for spray s. red use
concentrations here are between 0.001% and 1% by volume, preferably between 0.01% and 0.5% by
volume and more ably between 0.02% and 0.15% by volume (also corresponding to about 0.1%
by weight) of the spray liquor. This is equivalent to 10 to 3000 ml/ha when typically 100 to 1000 l of
spray liquor per ha are deployed, and preferably an amount of nt of 50 to 700 ml/ha, which are
also added by the respective amounts of spray liquor irrespective of the total water application rate per
Active substances are those which are approved and/or registered and/or listed in the individual
countries for use on plants and crops in order to protect plants against damage, or to prevent yield loss
as the result of pests or the like in a crop, or to ate undesirable accompanying flora, such as
broad-leaved weeds and/or grass weeds, or to supply the plants with nutrients (also termed fertilizers).
Active substances may be synthetic substances or else ical substances. Active substances may
also be extracts, or natural substances, or nistically active sms. They are usually also
referred to as pesticides or plant protection agents. In general, active substances are incorporated into
formulations for handling and efficiency purposes.
For use on plants or plant parts, crop protection composition ations are usually diluted with water
before the standard spraying through nozzles, and contain not only the active component but also
other adjuvants such as emulsifiers, dispersing aids, antifrost agents, antifoams, biocides and surfaceactive
substances such as surfactants. Active substances, especially fungicides, insecticides and
nutrients, alone or in ation and having been provided with the other auxiliaries ied above,
can also be applied to seeds (seed) of plants by various methods. Such methods are also referred to
as seed treatment methods. The treatment of seed with fungicides and insecticides can protect plants
in the early stage of growth from diseases and attack by insects.
The inventive compositions comprising the polyether-substituted siloxanes of the a (I), the
process according to the invention and the inventive use of the compositions and/or process products
are described by way of example hereinafter, without any intention that the invention be restricted to
these illustrative embodiments. If ranges, general formulae or compound classes are specified
hereinafter, this shall encompass not only the corresponding ranges or groups of compounds that are
explicitly ned, but also all sub-ranges and oups of compounds which can be obtained by
extracting individual values (ranges) or compounds. Where documents are cited in the context of the
present description, it is intended that their content shall form a full part of the disclosure content of the
present invention. Where percentages are given below, they are percentages in % by weight unless
stated otherwise. In the case of compositions, the % figures, unless otherwise indicated, are based on
the overall composition. Where e values are reported below, the averages in question are mass
averages (weight averages), unless ise indicated. Where measurement values are reported
above and below, these measurement values, unless stated otherwise, have been determined under a
pressure of 101 325 Pa (standard pressure) and at a temperature at 25°C.
General methods and materials:
Trade name
Silwet L-77 Product and trademark of Momentive
Silwet 806 Product and trademark of Momentive
THRU S 240 Product and ark of Evonik Degussa GmbH, Germany
BREAK-THRU S 278 Product and trademark of Evonik Degussa GmbH, Germany
BREAK-THRU S 233 Product and trademark of Evonik Degussa GmbH, Germany
Sylgard 309 Product and trademark of Dow Corning, USA
Synthesis
Preparation of Me3SiO[SiMeHO] cSiMe 3
An SiH-functional siloxane of the general formula Me 3SiO[SiMeHO] 1.2 SiMe 3 was subjected to a
fractional distillation under standard pressure. The fraction at a top temperature of 142°C was
determined with the aid of a gas chromatograph to be the product having a purity of 99% by weight of
1,1,1,3,5,5,5-heptamethyltrisiloxane. Thus, the product of the formula (V) has an index d of 1.01.
Subsequently, the distillate and the starting siloxane were mixed in such a way as to obtain the
ing siloxanes: Me3SiO[SiMeHO] 1.2 SiMe 3, Me3SiO[SiMeHO] 1.15 SiMe 3, Me3SiO[SiMeHO] 1.10 SiMe 3,
Me 3SiO[SiMeHO] 1.05 SiMe 3 and Me3SiO[SiMeHO] 1.01 SiMe 3.
The determination of purity was conducted with the aid of 1H NMR and 29 Si spectroscopy. These
methods, ally taking t of the multiplicity of the couplings, are familiar to those skilled in the
art.
With the aid of these siloxanes, 21 s were produced analogously to the general preparation
method which follows.
General synthesis method for hydrosilylation:
A 1000 ml three-neck flask equipped with r and reflux condenser was initially charged with 0.5 mol
of a polyether of the general formula CH2=CHCH 5
2O[CH 2CH 2O] m[CH 2CH(CH 3)O] nR and heated to
90°C. Subsequently, 10 ppm of Pt were added in the form of a toluenic solution of the Karstedt catalyst
(Pt content 2 mol%). The mixture was stirred for 10 min and then 0.38 mol of SiH groups in the form of
the nctional siloxane Me3SiO[SiMeHO] cSiMe 3 was added dropwise within 15 min. An exothermic
reaction was observed; the reaction mixture was stirred at 90°C for a further 4 h. In all cases, it was no
longer possible to detect any SiH functions by gas-volumetric means.
? 12
Table 1: Samples prepared; the R5, c, m, n, M (PE) and m/n data relate to formula (I) and, respectively,
to a (II); in the cases when n = 0, m/n is undefined and consequently not stated:
Sample R5 c m n M (PE) m/n
Tego XP 11022 H 1.00 8.0 3.3 543 2.45
Sample 1 H 1.01 7.8 0.0 343 ---
Sample 2 H 1.20 6.0 3.0 438 1.98
Sample 3 H 1.01 10.0 0.0 440 --
Sample 4 Me 1.01 7.8 0.0 343 --
Sample 5 H 1.20 9.9 1.9 545 5.27
Sample 6 H 1.01 14.6 0.0 642 --
Sample 7 Me 1.01 12.3 0.0 541 --
Sample 8 H 1.01 12.3 0.0 541 --
Sample 9 H 1.01 9.9 1.9 546 5.27
Sample 10 H 1.01 8.0 3.3 543 2.45
Sample 11 H 1.01 6.2 4.7 545 1.32
Sample 12 H 1.01 4.9 5.6 540 0.88
Sample 13 H 1.01 3.4 10.2 741 0.33
Sample 14’ H 1.01 10.7 8.1 941 1.32
Sample 15’ H 1.01 14.4 7.0 1040 2.06
Sample 16’ H 1.05 8.0 3.3 543 2.45
Sample 17’ H 1.10 8.0 3.3 543 2.45
Sample 18 H 1.15 8.0 3.3 543 2.45
Sample 19 H 1.20 9.2 4.1 643 2.24
Sample 20 H 1.20 3.4 10.2 741 0.33
Sample 21 H 1.20 10.7 8.1 941 1.32
WO 02564 13
Samples 2, 5, 19, 20 and 21 are entive polyether siloxanes since the index c is too high.
Samples 1, 3, 4, 6, 7 and 8 are noninventive since the index n is zero. Samples 5 and 9 are
noninventive e the content of oxyethylene groups is too low.
Test solutions:
0.1% by weight ons of the test substances in distilled water were made up.
Spreading test
Spreading was examined by applying a 50 µl droplet of the test solutions to a standard polypropylene
film (of the Forco-OPPB type, from Van Leer). The droplet was applied with a micropipette. The area of
spread was measured 90 seconds after the application. The experiments were conducted at 23°C and
a relative air humidity of 60%.
Surface tensions
Surface tensions were measured by the Wilhelmy plate method with a Kruss K 12 tensiometer at 25°C.
OECD biodegradability
Biodegradability was determined in accordance with OECD Method 301F by manometric respirometry
at a temperature of 22°C ± 1°C. The degradation rate was determined within 28 days. The samples
had been analysed in a concentration of 100 mg/l and 28 mg/l both against a zero sample al
) and against a sodium benzoate solution of equal concentration. The values were recorded
both after 14 days and after 28 days. After 14 days, no plateau phase had been reached yet. The
sewage sludge samples used came from the sewage treatment plant belonging to the Ruhrverband
water company, Sunthelle 6, 57392 Schmallenberg on 16 September 2014. The concentration used
was 29.6 mg of dry matter per litre of mineral ; the pH was determined before the start of the
experiments to be 7.4 ± 0.2.
Results of the interfacial activity study:
ative substances used for some commercial products, and substances according to US
6,734,141.
Surfactant B: Me3SiO-[MeR'SiO] 1.20 -OSiMe 3 , with R'= –(CH2)3-O-(CH 2CH 2O-)10 (CH 2CH(CH 3)O-)2-H
Surfactant C:Me3SiO-[MeR'SiO] 1.00 -OSiMe 3 , with R'= –(CH2)3-O-(CH 2CH 2O-)20 (CH 2CH(CH 3)O-)5-H
Surfactant D: Me3SiO-[MeR'SiO] 1.00 -OSiMe 3 , with R'= –(CH2)3-O-(CH 2CH 2O-)12.5 –H
THRU S 233: -[MeR'SiO] 1.20 -OSiMe 3, with R'= –(CH2)3-O-(CH 2CH 2O-)9.9
(CH 2CH(CH 3)O-)1.9-H
BREAK-THRU S 240: Me3SiO-[MeR'SiO] 1.20 -OSiMe 3 with R'= –(CH2)3-O-(CH 2CH 2O-)6 (CH 2CH(CH 3)O-
)3-H
BREAK-THRU S 278: Me3SiO-[MeR'SiO] 1.20 -OSiMe 3 with R'= –(CH2)3-O-(CH 2CH 2O-)7.8 -Me
SILWET L77: Me 3SiO-[MeR'SiO]-OSiMe 3 with R'= –(CH2)3-O-(CH 2CH 2O-)8 –Me
? 15
Adjuvant Static surface tension Spread Biodegradable
[mN/m] diameter [mm]
Tego XP 11022 22.9 70 yes
Sample 1 21.6 no
Sample 2 21.7 no
Sample 3 21.6 53 no
Sample 4 22.0 70 no
Sample 5 21.4 15
Sample 6 22.8 15
Sample 7 22.7 15 no
Sample 8 22.7 15 yes
Sample 9 21.9 30
Sample 10 21.4 70 yes
Sample 11 22.3 80
Sample 12 22.2 75
Sample 13 16
Sample 14’ 15
Sample 15’ 26.8 11
Sample 16’ 21.7 60 yes
Sample 17’ 21.7 60 yes
Sample 18 22.0 53 yes
Sample 19 23.5 16
Sample 20 34.8 12
Sample 21 25.3 12
Surfactant B 24.1 14
Surfactant C 28.2 10
Surfactant D 23.8 13
BREAK-THRU S 240 22.3 70
THRU S 278 22.0 70
BREAK-THRU S 233 21.4 15
Silwet 806 23.5 70
Silwet L77 23.8 80
Silguard 309 23.0 80
l superspreaders show a spread diameter in this test of 35 mm or more.
It is found that biodegradable superspreaders have a very defined structure.
WO 02564 16
The polyether has to have a n molar mass, but must not be too heavy either. In addition, the
polyether has to have a certain number of [CH2CH(CH 3)O] groups, but a n ratio between
[CH 2CH(CH 3)O] and [CH2CH 3O] groups still has to be maintained. Furthermore, the siloxane must may
not be too inhomogeneous.
The results show the advantageous use of the inventive substances.
Biodegradability s:
Adjuvant Biodegradability [%]
Sample 8 60%
Sample 10 66%
Sample 1 < 60%
Sample 2 < 60%
Sample 7 7%
Sample 3 < 60%
The results show the easy biodegradability of the inventive substances.
Greenhouse ments to determine the improvement in biological efficacy of a herbicide
In a greenhouse, common meadowgrass (Poa pratense) was grown in pots. As soon as the plants had
reached a height of about 5 to 7 cm, they were sprayed with spray liquor that contained the herbicide
Cato® (DuPont, Germany, active ingredient: rimsulfuron, concentration: 250 g of active ingredient/kg).
The amount of spray that contained the active ingredient corresponded to 200 l/ha. Various adjuvants
were added to the spray liquor. For each element of the experiment there were 3 pots that were treated
in the same way. The pesticide dosage was 10 g/ha. Commercial standard wetting agents added to the
tank were Break-Thru S240 and trisiloxane BREAK-THRU S233, each at 50 ml/ha. The dosage of
Tego XP 11022 was 100 ml/ha. The damage to the plants by the herbicide treatment is compared here
to ted plants and the efficacy of the sprayed treatment is expressed as a ratio to the untreated
plants. The efficacy was scored in each of the 3 pots per element of the experiment by methods known
to those skilled in the art 14 and 28 days after the treatment. The average was ated and reported
as results in the table as a percentage compared to the control without herbicide treatment.
WO 02564 17
Herbicide Adjuvant 14 d 28 d
Cato, 10 ml/ha none 50% 74%
Cato, 10 ml/ha Tego XP 11022, 100 ml/ha 70% 94%
Cato, 10 ml/ha BREAK-THRU S240, 50 g/ha 60% 84%
Cato, 10 ml/ha THRU S233, 50 g/ha 50% 83%
The results show that the inventive composition brought a distinct increase in action compared to
herbicide treatment without wetting agent. The advantageous use of the inventive compositions
compared to the prior art is shown by this experiment.
Claims (1)
1. itions sing polyether-modified nes of formula (I) MaDbD' c Formula (I) 5 with M = R13SiO
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP15172382.2 | 2015-06-16 | ||
EP15172382.2A EP3106033B1 (en) | 2015-06-16 | 2015-06-16 | Biodegradable super dispersing organomodified trisiloxane |
PCT/EP2016/062134 WO2016202564A1 (en) | 2015-06-16 | 2016-05-30 | Biodegradable super-spreading, organomodified trisiloxane |
Publications (2)
Publication Number | Publication Date |
---|---|
NZ737511A NZ737511A (en) | 2021-06-25 |
NZ737511B2 true NZ737511B2 (en) | 2021-09-28 |
Family
ID=
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