Heterocyclic amine modified siloxanes

Details Heterocyclic amine modified siloxanes Heterocyclic amine modified siloxanes

1999-02-24

2001-03-06

Dawson, Robert (Department: 1712)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

At least one aryl ring which is part of a fused or bridged...

C524S189000, C524S190000, C524S211000, C524S214000, C524S261000, C524S285000, C524S287000, C524S612000, C528S027000, C528S028000, C528S033000, C528S038000, C504S104000, C504S209000, C252S391000, C071SDIG004

Reexamination Certificate

active

06197876

ABSTRACT:

BACKGROUND OF THE INVENTION
Many herbicides require the addition of an adjuvant to the spray mixture to provide wetting and spreading on foliar surfaces. Often that adjuvant is a surfactant, which can perform a variety of functions, such as increasing spray droplet retention on difficult to wet leaf surfaces, or to provide penetration of the herbicide into the plant cuticle. These adjuvants are provided either as a tankside additive or used as a component in herbicide formulations.
Gaskin, et al., (
Pestic. Sci.
1993, 38, 185-192) demonstrated that some trisiloxane ethoxylates (TSE), such as Silwet L-776® surfactant (available from Witco Corp. of Greenwich, Conn.), can antagonize cuticular penetration of a herbicide into grasses, when compared to the herbicide alone. The term antagonism is used to indicate that the treatment of herbicide plus adjuvant is less effective than the comparative herbicide treatment.
Sandbrink, et al., (
Pest. Sci.
1993, 38, 272-273) published that a TSE antagonized glyphosate performance relative to glyphosate alone in the control of
Panicum maximum.
Jacq. Snow, et. al., Langmuir, 1993, 9, 424-30, discusses the physical properties and synthesis of novel cationic siloxane surfactants. These siloxanes are based on the reaction of a chloropropyl modified trisiloxane with an alkanolamine, such as N-methylehanolamine, which was further reacted with a halide to make a quaternary surfactant.
Petroff, et al., (EP 92116658) describes the use of cationic, quaternary trisiloxanes to enhance the efficacy of glyphosate on velvetleaf, a broadleaf weed. Henning, et al., (DE4318537) describes cationic siloxanyl modified polyhydroxy hydrocarbon or carbohydrate for use with plant protection agents. These compounds are derived from a saccharide containing 1 to 10 pentose and/or hexose units, modified with a quaternary ammonium group, and a siloxane moiety. Reid, et al., (U.S. Pat. No. 3,389,160) describes amino modified siloxane alkoxylates where the amino functionality appears as the terminal group on the alkyleneoxide moiety, opposite the siloxane group. Policello in PCT WO 97/32475 discloses amino modified siloxanes wherein the amine is bound by an ether bond to the siloxane backbone wherein the amine may be terminal or pendant to the backbone.
Kilgour and Petty in U.S. Pat. No. 4,526,996 disclose the manufacture of heterocyclic modified monomeric silanes, but the utility of such silanes is as cross linkers, not as intermediates for any further silicone compounds. Czech in U.S. Pat. No. 5,8087,956 discloses the use of amino/epoxide/siloxane polymers, referred to as amino [AB]n polymers, but the amines therein are generally linear in nature, not cyclic.
SUMMARY OF THE INVENTION
The present invention teaches heterocyclic amine substituted siloxanes, known henceforth as heterocyclic amino modified siloxanes, and their use, a preferred of which is as adjuvants for pesticides. The heterocyclic amine modified siloxanes have siloxane backbones with pendant, terminal or intermediate heterocyclic amine groups, which may contain one or more heteroatoms.
Optionally, the heterocyclic amine modified siloxanes of this invention may be blended with conventional trisiloxane alkoxylates (TSAs). Blends of these amino containing siloxanes with TSAs provide superspreading properties on difficult to wet surfaces. Moreover, these amine modified siloxanes may be blended with organic surfactants, as emulsifiers, dispersants or cosurfactants.
HETEROCYCLIC AMINE MODIFIED SILOXANES
The heterocyclic amine modified siloxanes of the present invention are siloxanes, i.e., compounds with at least one Si-PSi bond, which have at least one heterocyclic amine attached to the silicon through an Si-C bond. A heterocyclic amine is a cyclic group of at least four carbon atoms and containing at least one nitrogen atom. The ring may contain one oxygen or sulfur atom or up to two additional nitrogen atoms and said heterocyclic group may have further substituents thereon, such as alkyls, hydroxyl and polyethers. In one preferred embodiment these substituents are on the additional nitrogen(s) in the ring. The heterocyclic ring should be fully saturated, though external substituents thereon may have unsaturated functionalities.
Preferably, the heterocyclic amine modified siloxanes of the present invention have the average general formula:
[SiO
4/2
]
d
[MeSiO
3/2
]
e
[O
1/2
MeSi(Q)O
1/2
]
f
[O
1/2
SiMe
2
Q]
g
wherein f is between 0 to 50, preferably 1 to 5, more preferably 1 to 2, most preferably 1, d=0 to 2, most preferably 0, e=0 to 3, most preferably 0, g is, if the siloxane is not cyclic, 2+e+2d, or zero if the siloxane is cyclic, d+e+f+g=2 to 50, Q is either B(O)
j
(C
a
H
2a
O)
b
RV or R
1
, each a is 2 to 4, preferably 2 to 3, each b is 0 to 15, preferably 0 to 8, B is a divalent bridging group of C1 to C6, preferably C3 to C4, R is a divalent organic group containing 2 to 8 carbons, preferably 3 to 4 carbons, each optionally OH substituted, R
1
is either a polyether or an alkyl radical containing 1 to 18 carbons, preferably methyl, j=0 or 1, preferably 1, at least one Q is not R
1
, and V is a heterocyclic amine monovalent radical of the formula, —NC
p
H
p
R
2
p
(NR
2
)
x
, or —NC
p
H
p
R
2
M
r
, where p=4 to 8, preferably 4 to 5, z=0 to 3, preferably 1, r=0 to 3, preferably 1, R
2
is hydrogen, a univalent organic group containing 1 to 4 carbons, or —(C
a
H
2a
O)
h
R
3
, where h=1 to 8, preferably 1 to 3, R
3
is hydrogen, an alkyl group of 1 to 4 carbons, or acetyl, and M=oxygen or sulfur.
Additionally the heterocyclic amine modified siloxane compositions of the present invention may have intermediate units of the heterocyclic amine, i.e., alternating units of polysiloxane [XSiO(R
1
)
2
X]
c
and a heterocyclic diamine of the general structure [—NC
p
H
p
R
2
p
N—] wherein c=1 to 30, more preferably c=1 to 15, X is —B(O)
j
(C
a
H
2a
O)
b
R— as defined above. Preferably such structures are of 1 to 100 repeating units, more preferably 1 to 30. It is noted that the ends of these polymers would be dependent on the chain terminator used in the reaction. These copolymers may be referred to as amino [AB]
n
copolymers.
Exemplary such structures are
Preferably a is such that there is a mixture of ethylene oxide (EO), propylene oxide (PO) units or butylene oxide (BO), where a=2 to 4. Preferably, for aqueous applications, there is a preponderance of EO units, most preferably every a=2. For non-aqueous applications, such as crop oil concentrates, there may be more PO and BO units. When Q contains a mixture of oxyalkylenes, it may be blocked or random. One skilled in the art will understand the advantages in the position of the oxyethylene relative to the oxypropylene, when the alkyleneoxide group is blocked.
Preferably most R
1
groups are methyl, but some may be polyethers of the structure —(C
a
H
2a
O)
h
R
3
as defined above. Exemplary B are —(CH
2
)
2
—, —(CH
2
)
3
—, and —CH
2
CH(OH)CH
2
—. Exemplary R groups are —(CH
2
)
2
—, —(CH
2
)
3
—, —CH
2
CH(OH)CH
2
— and —CH
2
C
6
H
9
(OH)CH
2
—. Examples of R
2
are —CH
3
, —C
2
H
5
, —C
2
H
2
OH, (C
2
H
4
O)
3
(C
3
H
6
O)
2
H; —(C
2
H
4
O)
2
CH
3
; and —(C
3
H
6
O)
3
OH.
Some examples of V are —NC
4
H
8
, —NC
4
H
8
O, —NC
4
H
8
S, —NC
5
H
10
, —NC
4
H
8
NH, —NC
4
H
7
(CH
3
); —NC
4
H
8
NC
3
H
6
OH; and —NC
4
H
8
N(C
2
H
4
O)
2
OH.
The Q groups may include protonated amines, i.e, where there is a hydrogen ion attached to the nitrogen in the Q group, which can occur to the heterocyclic amine modified siloxanes under acidic conditions. Also contemplated herein are quaternary versions of Q, i.e., where there is a fourth group on the nitrogen in Q consisting essentially of an alkyl group containing 1 to 4 carbons, but said quaternary compounds are not preferred for use since they would tend to be phytotoxic.
Preferred Q structures are wherein B is a 3 carbon, alkylene gr

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