AU705120B2 - New emulsifying system for the preparation of emulsifiable concentrates of vegetable oils - Google Patents

Description

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AUSTRALIA

PATENTS ACT 1990 CO0M P LET E S PEC IF TI CAT I 0 M FOR A STANDARD PATENT

ORIGINAL

4* *S49 4* 004 *4*ROS 0 0 949 0 0* Name of Applicantt Actual Inventors: Address for Service: Invention Title: RHONE -POULENC CHIMIE Valeria BRAMVATI, Isabelle GUBELMAN, Antonio MARCHETTO and Marie-Luce PREVOTAT SHELSTON WATERS 60 Margaret Street SYDNEY NSW 2000 "NEW EMULSIFYING SYSTEM FOR THE PREPARATION OF EMULSIFIABLE CONCENTRATES OF VEGETABLE OILS" 0* 40 4 0 *49.4.

4 The following statement is a full description of this invention,

I,

including the best method of performing it known to us: b I §4A"u la The subject of the present invention is a new emulsifying system for the preparation of emulsifiable concentrates of vegetable oil and the use of the said concentrate as plant-protective additive, as adjuvant for plant-protection formulations or as formulation base for active materials which are soluble or insoluble in vegetable oils.

Pesticides formulated in the form of emulsifiable concentrates are most often formulated in 1C organic solvent medium; the solvents are generally of the type comprising petroleum aromatic fractions, xylene, alone or mixed with polar solvents such as cyclohexanone, dimethylformamide, isophorone, isobutyl phthalate and the like. Current trend is towards the S" 15 protection of the environment and the replacement of these solvents by mineral or vegetable oils.

Currently, vegetable oils are used as adjuvant to be diluted at the same time as the pesticide formulation, at the time -f application 20 (GAUVRIT. C. "Les huiles en phytosanitaire: le cas des herbicides" [Oils in plant protection: the case of herbicides] -Phytoma No. 458, page 37-41, 1994).

These vegetable oils are formulated with the S" aid of at least one surfactant of the type comprising ethoxylated derivatives ofovegetable oils, triglyceride ester, ethoxylatedc fatty acids or ethoxylated fatty alcohols. Large quantities of surfactant (15 by weight minimum) are necessary to obtain emulsifiable r- sD rrPI*swauw~-- 2 concentrates of vegetable oil capable, on dilution, of giving fine emulsions (mean size from 1 to 2 pm); in addition, at such a concentration, these surfactants are insufficiently soluble and lead to a separation of the constituents of the emulsifiable concentrate during storage at room temperature.

The applicant has found an emulsifying system which makes it possible to obtain emulsifiable concentrates of vegetable oils with enhanced appearance and stability.

The new emulsifying system which is the subject of the invention is characterized in that it consists -of at least one surfactant chosen from 15 ethoxylated C 8

-C

2 2 preferably C 2 z-C8, triglycerides containing about 1 to 60 oxyethylene units, preferably .9.

of the order of 2 to 60 oxyethylene units, optionally ethoxylated C 8

-C

22 preferably C 12

-C

18 S. fatty acids containing about 0 to 60 oxyethylene units, 20' preferably of the order of 2 to 60 oxyethylene units, Sand optionally ethoxylated C 8

-C

22 preferably C 12 -C18, fatty alcohols containing about 0 to 60 oxyethylene units, preferably of the order of 2 to 60 oxyethylene units, and, a cosurfactant consisting of an alkali or alkaline-earth metal dialkylsulphosuccinate (DSS), whose linear or branched alkyl radical is a

CS-C

1 preferably a C.-C12; Q T 7 ^*a -3in a surfactant (S)/cosurfactant (CS) weight ratio of the order of 90-80/10-20.

Unless the context clearly requires otherwise, throughout the description and the claims, the words 'comprise', 'comprising', and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of "including, but not limited to".

The ethoxylated triglycerides are the ethoxylation derivatives of vegetable oils; these oils may be previously hydrogenated before ethoxylation so as to remove the unsaturations; among the ethoxylated triglycerides, there may be mentioned most particularly optionally hydrogenated ethoxylated castor oil containing 10 oxyethylene units.

Among the optionally oxyethylenated fatty acids, there may be mentioned oleic acids optionally containing 2 to 4 oxyethylene units, erucic acid and the like.

Among the optionally oxyethylenated fatty alcohols, there may be mentioned tridecyl alcohol containing 10 oxyethylene units, C 12

-C

14 aliphatic alcohols containing 3 oxyethylene units and the like.

Among the alkali or alkaline-earth metal dialkylsulphosuccinates, there may be mentioned most particularly bis(2-ethylhexyl) sulphosuccinates of Na, K, Ca, Mg and the like.

S 5"'t According to a variant of the invention, of the order of 10 to 90%, preferably of the order of 50 to 90% by weight of the dialkylsulphosuccinate (DSS) can be replaced by S* ^"at least one other cosurfactant (ACS) chosen from: semisulphosuccinates of ammonium, of an alkali metal, of an alkaline-earth metal or of alkylammonium with a B 6 4 )t rr~ol~_l*~-la~L~yuu~,, Ilis~UY4iO~.~ ~XhpibIlLI~~~ 4

C

1

-C

6 alkyl radical, derived from CI-C 2 0 preferably

C

8

C

10 aliphatic alcohols optionally containing 1 to oxyethylene units, preferably 1 to 8 oxyethylene units, *optionally ethoxylated sucroglycerides containing about 0 to 40 oxyethylene units, preferably of the order of 2 to 30 oxyethylene units, sorbitan esters derived from C 8

-C

22 preferably Clo-C 20 fatty acids, which are optionally ethoxylated, containing about 0 to 30 oxyethylene units, preferably of the order of 2 to 20 oyethylene units.

Semisulphosuccinates such as those defined above are described in French Patent Application FR-A-2,690,812; sodium semisulphosuccinates derived from C 8

-C

10 aliphatic alcohols containing 2 oxyethylene units are particularly advantageous.

s ~Sucroglycerides are understood to mean the products obtained by transesterification of synthetic or preferably natural triglycerides with sucrose. Among the sucroglycerides, there may be mentioned especially oA a those obtained from palm oil, lard, copra oil, tallow, rapeseed oil or castor oil. A procedure for preparing sucroglycerides is described in French Patent Application FR-A-2,463,152.

S• Among the sorbitan esters, there may be mentioned sorbitan monolaurate, monooleate, trioleate and the like.

The naw emulsifying system described above can ht- used for the production of emulsifiable ~-~jlv Ldi -qu_-017 concentrates of vegetable oils, which crncentrates are stable during storage and are easily emulsifiable in water.

Another subject of the invention therefore consists in emulsifiable concentrates of vegetable oils, wherein they comprise: about 75 to 90% by weight, preferably about 80 to 87% by weight of a vegetable oil (0) and about 25 to 10% by weight, preferably about 20 to 13% by weight of an emulsifying system consisting: of at least one surfactant chosen from ethoxylated Cs-C 22 preferably C 12

-C

1 triglycerides containing about 1 to oxyethylene units, preferably of the order of 2 to 60 oxyethylene units, optionally ethoxylated C 8

-C

22 preferably C 12

-C

18 fatty acids containing about 0 to oxyethylene units, preferably of the order of 2 to 60 oxyethylene units, and optionally ethoxylated C 8

-C

22 preferably C 12

-C

1 8 fatty alcohols containing about 0 to 60 oxyethylene units, preferably of the order of 2 to 60 oxyethylene units, and, a cosurfactant consisting of an alkaline-earth metal dialkylsulphosuccinate (DSS), whose linear or branched alkyl radical is a C6-C18' preferably a C 8 -Ct 2 in a surfactant (S)/cosurfactant (CS) weight ratio of the order of 90-80/10-20.

According to a variant of the invention, about 10 to 90%, preferably about 50 to 90% by weight of the dialkylsulphosuccinate (DSS) can be replaced by at least one other cosurfactant (ACS) chosen from: semisulphosuccinates of ammonium, of an alkali metal, of an alkaline-earth metal or of alkylammonium with a CI-C alkyl radical, derived from Ci-C 20 preferably C 8 -CIo, S 25 aliphatic alcohols optionally containing 1 to 10 oxyethylene units, preferably 1 to 8 oxyethylene units, optionally ethoxylated sucroglycerides containing about 0 to 40 oxyethylene units, S*'o preferably of the order of 2 to 30 oxyethylene units, sorbitan esters derived from Cs-Czz, preferably Clo-C 2 o, fatty acids, which are 30 optionally ethoxylated, containing about 0 to 30 oxyethylene units, preferably of the order of 2 to 20 oxyethylene units.

1S%304O DOC I Ir 11-1 1 ~1b~r -6- As example of vegetable oil there may be mentioned castor, rapeseed, soya, palm, maize and sunflower oils and the like.

Vegetable oils possessing herbicidal properties, properties of a biological activator, such as rapeseed or soya oil and their methyl esters are preferably chosen.

Various examples of surfactants or cosurfactants which may be present in the said emulsifiable concentrates have already been mentioned

X

i" BQ t S

S

'S 7 P above.

The said emulsifiable concentrates which are the subject of the invention can be obtained simply by dissolving, with stirring, the various surfactants or cosurfactants in the vegetable oil.

The emulsifiable concentrates which are the subject of the invention can be used as adjuvants by adding to a plant-protection formulation at the time the latter is used, so as to enhance its efficacy (better retention of the formulation on the surface of plants, better cuticular permeability and the like).

They can also be used as formulation base for active materials which are soluble or dispersible in vegetable oils.

15 The following examples are given by way of s* e example.

4*99 Example 1 *o Preparation of an emulsifiable concentrate of rapeseed oil An emulsifiable concentrate of the following composition is prepared by dissolv'.g, with stirring, the surfactant and cosurfactant in rapeseed oil: B rapeseed oil 80 parts by weigh calcium dioctylaulphosuccinate 3.5 parts by weight athoxylated hydrogenated castor oil 16.5 pars by weight (containing 10 oxyethylene units) Characteristics of the emulsifiable concentrate Appearance: clear.

1 10111 6- 8 Stability during storage: 15 days at 54WC and I month at 45 0

C.

Emulsification test carried out according to the CIPAC MT 36 standard, described in "ICIPAC Handbook" Vol. 1 Analysis of technical and formulated pesticides R. de B. ASHWORTH, J. HENRIET, J-F. LOVETT and A. MARTIJN.

The emulsifiable concentrate is diluted in a measuring cylinder, at 30 0 C, to 5 in standard water of different hardness. The measuring cylinder is turned upside down 10 times.

The 1ev!R.. of creaming or separation of the oil is measured after standing for 1 hour, 2 hours and 24 hours at 30 0

C.

15 The creaming levels measured are the following 9 0 99 9.

*99* 9. 9 0009 0990 94 94" 99S4U 9

L~

94 20 cramng water hardness Water hardness Water hardness level after 20 ppm 342 pps 500 pp= I h 0.5 Oi 0 IOMi 2 h 1 Ml Ml 1 MI ~24 h 3.5 ml 2J 1 2, =l Example 2 PrRaration of an emulsifiable concentrate oi An emulsifiable concentrate of soya oil of the f ollowing, composition is prepared according to the procedure of Example 1: I 11 1 I soya oil sodium dioctylsuiphosuccinate oleic acid ethoxylated hydrogenated castor oil (containing 10 oxyethylene units) 85 parts by weight 1.8 parts by weight 3 part. by weight 10.2 parts by weight Characteristics of the emulsifiable concentrate Appearance: clear Stability during storage: 15 days at 54 0 C and 1 month at E mulsifitcation test (according to the method described above) The creaming levels measured are the following Creaning water hAzdness Water hArdness Water hAzdnesa level after 20 prm 342 ppa 500 s 15 1lh 2.0 ml 1.5 ml 1.0 ml 2 h 2.0 ml 1.5 ml 1.5 ml Example 3 (comparative) Preparation of an emulsifiable concentrate of KRagseed 00 4 4 t~ 4 0* 0*44 *0 44 0 4 *0* 0*4* 0 44 44 4 0~, 00.04.

oil j 4.

An emulsifiable concentrate of the following composition is prepared as above: -rapeseed oil 80 parts $y weigI -ethoxylated castor oil 20 parts by weigI (containing 14 oxyethylene units) 0 Characteristics of the emulsifiable concentrate -,,Appearancez- two-phase (tt* surfactant separates Lt 2t 0 27, slowly) -,Unstable during storage even at room temperature E mulsification test (according to the method described above) The creaming levels measured are the following creaz;ing Water~ hardness Nate= hard-sss water hardness level after 20 ppa 342 ppa 500 pp.

min 2 ml 4 ml i 2 h 3ml. 4 ml 4 71 .0 24 h separation of separation of separation of Lconstituents constituents constituentsJ B. B

B.

0B .9.4' a. 4' B *9 Be C Beg 4 .4' cc e 47 C. B, B 9e4'4~* a U 0

C

2.

-Th

Claims (1)

1. 90-80/10-20. Emulsifiable concentrate of vegetable oils 15 comprising of the order of 75 to 90 %by weight of a vegetable oil and of the order of 25 to 10 by weight of the said emulsifying system. 41 4141 a 4141 .41.41 41 a 4141 41 41 .41.. 41 4141 4141 41 41414141 414141414141 41 4141 41 414141 41 .4141. 4141 41. 41 14 $3,