U.S. patent application number 12/948888 was filed with the patent office on 2011-04-21 for surfactant composition for agricultural chemicals.
Invention is credited to Hiroyuki Izumoto, Akinori Kanetani, Takaaki Kano, Shiro Sato.
Application Number | 20110092370 12/948888 |
Document ID | / |
Family ID | 41340230 |
Filed Date | 2011-04-21 |
United States Patent
Application |
20110092370 |
Kind Code |
A1 |
Kanetani; Akinori ; et
al. |
April 21, 2011 |
Surfactant Composition for Agricultural Chemicals
Abstract
A surfactant composition for agricultural chemicals, containing
fatty acid polyoxyalkylene alkyl ether expressed by the following
general formula (I), R.sup.1CO(EO).sub.m(PO).sub.nOR.sup.2 (I)
wherein the fatty acid polyoxyalkylene alkyl ether has a narrow
ratio of 55% by mass or more, where the narrow ratio is expressed
by the following formula (A): Narrow ratio = i = n MAX - 2 i = n
MAX + 2 Y i ( A ) ##EQU00001##
Inventors: |
Kanetani; Akinori; (Tokyo,
JP) ; Izumoto; Hiroyuki; (Tokyo, JP) ; Sato;
Shiro; (Tokyo, JP) ; Kano; Takaaki; (Tokyo,
JP) |
Family ID: |
41340230 |
Appl. No.: |
12/948888 |
Filed: |
November 18, 2010 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
PCT/JP2009/059459 |
May 22, 2009 |
|
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12948888 |
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Current U.S.
Class: |
504/358 ;
514/785; 554/223; 554/227 |
Current CPC
Class: |
A01N 25/30 20130101;
C07C 67/24 20130101; C07C 67/08 20130101 |
Class at
Publication: |
504/358 ;
554/227; 554/223; 514/785 |
International
Class: |
A01N 25/00 20060101
A01N025/00; C07C 53/126 20060101 C07C053/126; C07C 57/03 20060101
C07C057/03; A01P 7/04 20060101 A01P007/04; A01P 7/02 20060101
A01P007/02; A01P 1/00 20060101 A01P001/00; A01P 13/00 20060101
A01P013/00; A01P 21/00 20060101 A01P021/00 |
Foreign Application Data
Date |
Code |
Application Number |
May 23, 2008 |
JP |
2008-135337 |
Claims
1. A surfactant composition for agricultural chemicals, comprising:
fatty acid polyoxyalkylene alkyl ether expressed by the following
general formula (I), R.sup.1CO(EO).sub.m(PO).sub.nOR.sup.2 (I)
where R.sup.1CO is a C14-22 saturated or unsaturated fatty acid
residue; R.sup.2 is a C1-3 alkyl group; m and n each express an
average number of moles added, where m is an integer of 2 to 10,
and n is an integer of 1 to 4; and EO expresses a structural unit
of ethylene oxide, and PO expresses a structural unit of propylene
oxide, where a form of additions of EO and PO is a block polymer,
wherein the fatty acid polyoxyalkylene alkyl ether has a narrow
ratio of 55% by mass or more, where the narrow ratio is expressed
by the following formula (A): Narrow ratio = i = n MAX - 2 i = n
MAX + 2 Y i ( A ) ##EQU00005## where i is the number of moles of
alkylene oxide added (the total number of moles of EO and PO which
are added), n.sub.MAX is the value of i of the fatty acid
polyoxyalkylene alkyl ether whose number of moles of alkylene oxide
added presents in the largest amount on mass basis among all the
fatty acid polyoxyalkylene alkyl ether expressed by the general
formula (I), and Yi is a proportion (% by mass) of the fatty acid
polyoxyalkylene alkyl ether whose number of moles of alkylene oxide
added is i in the entire fatty acid polyoxyalkylene alkyl
ether.
2. A surfactant composition for agricultural chemicals, comprising:
the fatty acid polyoxyalkylene alkyl ether as defined in claim 1;
water; and C1-4 lower alcohol, wherein a composition ratio of the
surfactant composition expressed by the fatty acid polyoxyalkylene
alkyl ether/the water/the C1-4 lower alcohol is 10% by mass to 60%
by mass/10% by mass to 70% by mass/10% by mass to 70% by mass.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This is a continuation application of PCT/JP2009/059459,
filed on May 22, 2009.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a surfactant composition
for agricultural chemicals, which is suitably used as an
emulsifier, dispersing agent, spreading agent, functional spreading
agent (adjuvant), and water dispersible agent for agricultural
chemicals.
[0004] 2. Description of the Related Art
[0005] In order to allow agricultural chemicals to sufficiently
exhibit their effects, formulations of agricultural chemicals, such
as bactericides, insecticides, acaricides, weed-killers, and plant
growth regulators, are suitably selected considering efficiency for
spraying an agricultural chemical for use, safety thereof, or the
like. Among such formulations, an emulsified dispersion liquid of
an agricultural chemical is expected to be entirely and uniformly
deposit on the target for spraying, and has been used in the art.
In order to disperse an agricultural chemical, which is generally
an oily substance, in water, various surfactants have been used in
the emulsified dispersion liquid of the agricultural chemical.
[0006] Surfaces of leaves or stems of plants and surfaces of
insects have a substance or structure which repels of liquids, or
prevents from being wet by liquids. For example, on surfaces of
plants, wax-lipoids are secreted, or feathery fibers are closely
grown. In another case, fine irregularities are present on surfaces
of plants. Moreover, a layer similar to a keratin is present on
surfaces of pest insects. All of these materials have such
qualities as to repel an aqueous dispersion liquid of agricultural
chemicals. Due to this, there are cases where the sprayed
agricultural chemical may not provide a sufficient effect thereof.
Therefore, spreading agents and functional spreading agents
(adjuvants) are used in agricultural chemicals for providing
agricultural chemicals with enhanced qualities such as wetting
ability, permeability, spreading, and fixing, to thereby increase
chemical effects of the agricultural chemicals.
[0007] Conventionally, as these surfactants for agricultural
chemicals, nonionic surfactants of various alkyl oxide adducts have
been known. For example, a spreading agent for agricultural
chemicals, which contains a nonionic ester surfactant formed of
specific fatty acid polyoxyalkylene alkyl ether, is disclosed in
Japanese Patent Application Laid-Open (JP-A) No. 06-329503. An
agrochemical spreader composition, which is a surfactant
composition excellent in low-temperature stability is disclosed in
JP-A No. 2001-288006.
[0008] A surfactant for agricultural chemicals formed of a nonionic
surfactant is generally used for formulating a fluid agricultural
chemical, or is commonly added to a fluid preparation of an
agricultural chemical as a fluid spreading agent for an
agricultural chemical. Therefore, in actual practices, such
surfactant is required to have basic performances such as
solubility for dissolving an oil-soluble agricultural chemical
component; low foamability and defoamability for improving handling
at the time of preformulation in a tank and at the time of
spraying, and preventing foaming (polluting) in rivers or the like;
and permeability to surfaces of plants and the like, as well as
stability which prevents precipitation or separation of substances
at the time of use, during storage at low temperature, or when the
temperature is changed from low temperature to normal
temperature.
BRIEF SUMMARY OF THE INVENTION
[0009] The present invention aims at solving various problems in
the art, and achieving the following object. Specifically, the
object of the present invention is to provide a surfactant
composition for agricultural chemicals, which has excellent surface
activity (e.g. solubilization ability, dispersibility,
permeability, low foamability, and defoaming ability), excellent
stability at low temperature, desirable biodegradability, and
excellent safety in the environment (e.g. no phytotoxicity and fish
toxicity).
[0010] Means for solving the aforementioned problems are as
follows:
<1> A surfactant composition for agricultural chemicals,
containing:
[0011] fatty acid polyoxyalkylene alkyl ether expressed by the
following general formula (I),
[0012] wherein the fatty acid polyoxyalkylene alkyl ether has a
narrow ratio of 55% by mass or more, where the narrow ratio is
expressed by the following formula (A).
R.sup.1CO(EO).sub.m(PO).sub.nOR.sup.2 (I)
[0013] In the general formula (I), R.sup.1CO is a C14-22 saturated
or unsaturated fatty acid residue; R.sup.2 is a C1-3 alkyl group; m
and n each express an average number of moles added, where m is an
integer of 2 to 10, and n is an integer of 1 to 4; and EO expresses
a structural unit of ethylene oxide, and PO expresses a structural
unit of propylene oxide, where a form of additions of EO and PO is
a block polymer.
Narrow ratio = i = n MAX - 2 i = n MAX + 2 Y i ( A )
##EQU00002##
[0014] In the formula (A), i is the number of moles of alkylene
oxide added (the total number of moles of EO and PO which are
added), n.sub.MAX is the value of i of the fatty acid
polyoxyalkylene alkyl ether whose number of moles of alkylene oxide
added presents in the largest amount on mass basis among all the
fatty acid polyoxyalkylene alkyl ether expressed by the general
formula (I), and Yi is a proportion (% by mass) of the fatty acid
polyoxyalkylene alkyl ether whose number of moles of alkylene oxide
added is i in the entire fatty acid polyoxyalkylene alkyl
ether.
<2> A surfactant composition for agricultural chemicals,
containing:
[0015] the fatty acid polyoxyalkylene alkyl ether as defined in
<1>;
[0016] water; and
[0017] C1-4 lower alcohol,
[0018] wherein a composition ratio expressed by the fatty acid
polyoxyalkylene alkyl ether/the water/the C1-4 lower alcohol is 10%
by mass to 60% by mass/10% by mass to 70% by mass/10% by mass to
70% by mass.
[0019] According to the present invention, various problems in the
art can be solved, the aforementioned object can be achieved, and a
surfactant composition for agricultural chemicals, which has an
excellent surface activity (solubilization ability, dispersibility,
permeability, low foamability, and defoamability), excellent
stability at low temperature, and excellent safety in the
environment (e.g. no phytotoxicity and fish toxicity) can be
provided.
DETAILED DESCRIPTION OF THE INVENTION
[0020] The nonionic ester surfactant formed of fatty acid
polyoxyalkylene alkyl ether for use in the present invention is
fatty acid polyoxyalkylene alkyl ether, which is expressed by the
general formula (I) below, and has a narrow ratio of 55% by mass or
more, where the narrow ratio is expressed by the formula (A)
below.
R.sup.1CO(EO).sub.m(PO).sub.nOR.sup.2 (I)
[0021] In the general formula (I), R.sup.1CO is a C14-22 saturated
or unsaturated fatty acid residue, R.sup.2 is a C1-3 alkyl group, m
and n respectively express average numbers of moles of EO and PO
added, where m is an integer of 2 to 10, and n is an integer of 1
to 4, EO expresses a structural unit of ethylene oxide, PO
expresses a structural unit of propylene oxide, and EO and PO are
added in the form of a block polymer.
Narrow ratio = i = n MAX - 2 i = n MAX + 2 Y i ( A )
##EQU00003##
[0022] In the formula (A), i is the number of moles of alkylene
oxide added (the total number of moles of EO and PO added),
n.sub.MAX is the value of i of the fatty acid polyoxyalkylene alkyl
ether whose number of moles of alkylene oxide added is present in
the largest amount on mass basis among all of the fatty acid
polyoxyalkylene alkyl ether expressed by the general formula (I),
and Yi is a proportion (% by mass) of the fatty acid
polyoxyalkylene alkyl ether whose number of moles of alkylene oxide
is i in the entire fatty acid polyoxyalkylene alkyl ether.
[0023] When the number of carbon atoms in the fatty acid residue
R.sup.1CO is 14 to 22, the excellent surface activity such as
surface tension, permeability, and low foamability, and excellent
safety in the environment such as no phytotoxicity and no fish
toxicity are attained. When the number of carbon atoms in R.sup.1CO
is in the range of 16 to 18, the surface activity and safety in the
environment are improved further.
[0024] The fatty acid residue R.sup.1CO can be derived from
myristic acid, 5-methyltetradecanoic acid,
2,2-dimethyltetradecanoic acid, pentadecanoic acid, palmitic acid,
zoomaric acid (9-hexadecenoic acid), margaric acid, stearic acid,
oleic acid, vaccenic acid (11-octadecenoic acid), linoleic acid,
linolenic acid, ricinoleic acid (caster oil),
9,10-dihydroxyoctadecanoic acid (caster oil), elaidic acid,
isostearic acid, or the like. As seen from the listed examples
above, the fatty acid residue R.sup.1CO may have a substituent such
as a hydroxyl group.
[0025] Also, the fatty acid residue R.sup.1CO may be derived from a
mixture of compounds having the substituents, or derived from fatty
acid having a composition distribution originated from vegetable
oils such as soya bean oil, rape seed oil, and palm oil.
Especially, the production quantity of the palm oil is largest
among the vegetable oils, and thus there are stable supplies of the
palm oil. In addition, the fatty acid derived from the palm oil is
preferable, as it has excellent oxidation resistance compared to
soya bean oil or rape seed oil.
[0026] The fatty acid residue R.sup.1CO is suitably selected
depending on the intended purpose without any restriction. For
example, in view of low temperature stability, a fatty acid residue
having an unsaturated bond, such as oleic acid, linoleic acid, and
linolenic acid, is preferable, especially those fatty acid methyl
esters, which are in the equivalent form of the fatty acid residue
R.sup.1CO, having an iodine value of 60 to 150 are preferable, and
those having the iodine value of 70 to 130 are more preferable.
Moreover, in view of oxidation stability, the iodine value of the
fatty acid residue is particularly preferably 70 to 110. Specific
examples thereof include M 181 and M182, both manufactured by Lion
Corporation, which are fatty acid methyl esters derived from palm
oil.
[0027] The number of carbon atoms contained in the lower alkyl
group R.sup.2 is suitably selected depending on the intended
purpose without any restriction, but is 1 to 3, preferably 1 to 2,
and more preferably 1, i.e. the lower alkyl group being a methyl
group, because it can be easily produced.
[0028] When the number of carbon atoms in the lower alkyl group
R.sup.2 is 4 or more, the resulting surfactant composition may have
higher fish toxicity and higher phytotoxicity. When the number
thereof is 5 or more, in addition to the above, the permeability of
the resulting surfactant composition may be decreased. When R.sup.2
is a hydrogen atom, the permeability of the resulting surfactant
composition may be significantly decreased, and hence the
functionality thereof as a spreading agent may be reduced.
[0029] The average number "m" of moles of ethylene oxide (EO) that
have been added is the range of 2 to 10, preferably 3 to 7. When
the average number of moles thereof is smaller than 2, the
permeability of the resulting surfactant composition decreases.
When the average number of moles thereof is larger than 10,
foamability of the resulting surfactant composition is excessively
high, as well as having low permeability. In view of desirable
permeability and foaming ability of the resulting surfactant
composition, the average number of moles of EO that have been added
is preferably in the range of 3 to 7.
[0030] The average number "n" of moles of propylene oxide (PO) that
have been added is in the range of 1 to 4, preferably 2 to 4. When
the average number "n" of moles added is 5 or more, the fluid
stability of the resulting surfactant composition may be low. When
the average number thereof is 0, the permeability of the resulting
surfactant composition may be decreased.
[0031] The combination of the number of moles of EO added and the
number of moles of PO added is preferably such combination that 3
to 7 moles of EO and 2 to 4 moles of PO, because with such
combination, the resulting surfactant composition has preferable
permeability, low foamability, fluid stability, and safety (without
giving any fish toxicity).
[0032] The form of addition of EO and PO is a block addition, and
the order of the addition needs to be, as presented in the general
formula (I), such that PO is added at the terminal (the side of
--OR.sup.2).
[0033] By adding EO and PO in the form of the block addition where
PO is added at the terminal, the resulting surfactant composition
attains low foamability, excellent permeability, and excellent low
temperature stability. Moreover, such surfactant composition has an
excellent safety in the environment in view of fish toxicity and
the like. On the other hand, when the form of the addition of EO
and PO is a random addition, the resulting surfactant composition
has poor permeability, and poor stability at low temperature. In
addition, those having PO added, not at the terminal, but at the
side of the fatty acid residue R.sup.1CO, have high foamability,
i.e. poor in low foamability.
[0034] The fatty acid polyoxyalkylene alkyl ether is suitably
selected depending on the intended purpose without any restriction.
The fatty acid polyoxyalkylene alkyl ether may be a mixture of
alkylene oxide adducts having various numbers of moles of alkylene
oxide added. In this case, such fatty acid polyoxyalkylene alkyl
ether needs to have a certain distribution of added mole numbers
specified by the narrow ratio expressed by the formula (A).
[0035] The narrow ratio expressed by the formula (A) means a sum of
alkylene oxide adducts having n.sub.MAX and alkylene oxide adducts
having the number of moles of alkylene oxide added which is in the
range of .+-.2 moles from the n.sub.MAX, where n.sub.MAX is the
number of moles of alkylene oxide added, which presents in the
largest amount based on "% by mass" in the entire alkylene oxide
adducts.
[0036] Here, the number of moles of alkylene oxide added is the
total number of moles of EO and PO added. The adducts having the
same number of moles of alkylene oxide added includes a plurality
of alkylene oxide adducts having mutually different numbers of
moles of EO added and different numbers of moles of PO added, but
the same number of moles of alkylene oxide added on the whole.
[0037] The narrow ratio expressed by Formula (A) is 55% by mass or
more, preferably 60% by mass or more, and more preferably 65% by
mass or more. The higher narrow ratio is more preferable. However,
in the case where a solid catalyst is used in the production, the
production time is extended due to low filtration speed of the
catalyst after the completion of the reaction, which increases a
production cost. In the case where an alkali catalyst is used in
the production, moreover, the production efficiency is lowered due
to low yield resulted from the distillation, which increases a
production cost. For these reasons, the upper limit of the narrow
ratio is practically 95% by mass or less. When the narrow ratio is
55% by mass or more, the resulting surfactant composition has low
foamability, and excellent defoamability and fluid stability.
[0038] The narrow ratio can be controlled by a production method of
the fatty acid polyoxyalkylene alkyl ether expressed by the general
formula (I).
[0039] The production method of the fatty acid polyoxyalkylene
alkyl ether is suitably selected depending on the intended purpose
without any restriction. Examples thereof include: a method in
which a block addition polymerization of PO and EO are performed to
fatty acid alkyl ester using a complex metal oxide catalyst (see
JP-A No. 2000-144179); a method in which a block addition
polymerization is performed on a lower alcohol, which is an
equivalent of R.sup.2O using the aforementioned complex metal oxide
catalyst (see JP-A 09-262456), and then the resultant is subjected
to transesterification with suitable fatty acid ester, or the
resultant is subjected to esterification with suitable fatty acid;
and a method in which PO and EO added to the lower alcohol by a
block addition polymerization using an alkali catalyst, followed by
appropriately evaporating and removing unreacted lower alcohol or
substances having low numbers of moles added to control the
distribution of the numbers of moles added to have a desired narrow
ratio, and then the resultant is subjected to transesterification
with suitable fatty acid ester, or the resultant is subjected to
esterification with suitable fatty acid.
[0040] When the block addition polymerization of PO and EO is
performed to the fatty acid alkyl ester in the production of the
fatty acid polyoxyalkylene alkyl ether, a catalyst for use is
suitably selected without any restriction. For obtaining the fatty
acid polyoxyalkylene alkyl ether having the desired narrow ratio
without using other purification member such as evaporator, the
catalyst for use is preferably a complex metal oxide catalyst, such
as baked catalysts of hydrotalcite a surface of which is modified
with metal hydroxide and/or metal alkoxide, and a complex metal
oxide catalyst such as magnesium oxide to which metal ions (e.g.
Al.sup.3+, Ga.sup.3+, In.sup.3+, Tl.sup.3+, Co.sup.3+, Sc.sup.3+,
La.sup.3+, and Mn.sup.2+) whose surface is modification with alkali
are added.
[0041] Specific examples of such catalyst include a catalyst which
is obtained by surface modifying alumina-magnesia complex oxide
with metal hydroxide or metal alkoxide, where the alumina-magnesia
complex oxide is obtained by baking a coprecipitate of aluminum
hydroxide and magnesium hydroxide, which is expressed by the
general formula (2) below.
nMgO.Al.sub.2O.sub.3.mH.sub.2O (2)
[0042] In the general formula (2), n is not particularly limited,
but preferably around 2.5, and m is not particularly limited.
[0043] The baking temperature of the coprecipitate is preferably
400.degree. C. to 950.degree. C., more preferably 500.degree. C. to
750.degree. C.
[0044] The metal hydroxide used for the modification is suitably
selected depending on the intended purpose without any restriction,
but it is preferably selected from hydroxides of alkali metals or
alkali earth metals, more preferably selected from sodium hydroxide
and potassium hydroxide.
[0045] The metal alkoxide is suitably selected depending on the
intended purpose without any restriction, but is preferably
selected from alkali metals, and alkali earth metals, more
preferably selected from sodium alkoxide, and potassium
alkoxide.
[0046] The production method of the modified catalyst is suitably
selected depending on the intended purpose without any restriction.
For example, there are methods such as a method in which baked
alumina-magnesia complex oxide is modified with hydroxide or
alkoxide of alkali metal or alkali earth metal in advance, and is
used as a catalyst for a reaction, and a method in which a baked
alumina-magnesia complex oxide is mixed with metal hydroxide or
metal alkoxide in fatty acid alkyl ester, which is a raw material,
in a reactor for alkoxylation to modify the catalyst in the fatty
acid alkyl ester, and then a reaction with alkylene oxide is
performed.
[0047] The former method is not particularly limited, but is
preferably a method in which an aqueous solution or alcohol
solution of metal hydroxide or metal alkoxide is sprayed onto the
baked alumina-magnesia complex oxide, followed by drying or
baking.
[0048] The latter method is not particularly limited, and the order
for adding the baked alumina-magnesia complex oxide and the metal
hydroxide or metal alkoxide to the raw material fatty acid alkyl
ester is not particularly limited. For addition, it is preferred
that the metal hydroxide or metal alkoxide is added in the form of
a lower alcohol solution or aqueous solution for uniformly and more
selectively partly modify the acid centers of the surface of the
catalyst.
[0049] The amount of the metal hydroxide or metal alkoxide used for
the modification of the baked alumina-magnesia complex oxide is not
particularly limited, but is preferably 1% by mass to 20% by mass
relative to the amount of the baked alumina-magnesia complex
oxide.
[0050] In the case where the surface modification is not performed,
the block addition reaction product having a desired narrow ratio
may not be obtained. In such case, the desired narrow ratio of
thereof may be obtained by the operation such as by evaporating
substances having small numbers of moles of EO and PO added. Note
that, in order to introduce PO at the terminal, it is necessary to
perform a block addition polymerization in the order of PO and
EO.
[0051] In the case the fatty acid polyoxyalkylene alkyl ether is
produced by the method in which a block addition polymerization is
performed on a lower alcohol, which is an equivalent of R.sup.2O
using the aforementioned complex metal oxide catalyst, and then the
resultant is subjected to transesterification with suitable fatty
acid ester, or the resultant is subjected to esterification with
suitable fatty acid, the complex metal oxide catalyst for use is
not particularly limited, but can be selected from those listed
above. Moreover, the complex metal oxide catalyst may be subjected
to a surface modification, but in the case of the addition reaction
to the lower alcohol, the desirable narrow ratio can be attained
without performing the surface modification.
[0052] The addition reaction of ethylene oxide and propylene oxide
using the solid catalyst can be performed in accordance with the
common method. For example, the reaction temperature is not
specifically limited, but generally is 80.degree. C. to 230.degree.
C., preferably 120.degree. C. to 190.degree. C. The reaction
pressure is, though it may be set depending on the reaction
temperature, generally 0 MPa to 0.8 MPa, preferably 0.2 MPa to 0.5
MPa (gauge pressure).
[0053] The amount of the catalyst for use is changed depending on
the molar ratio of alkylene oxide and fatty acid alkyl ester used
in the reaction, but is generally 0.1% by mass to 20% by mass
relative to the amount of the fatty acid alkyl ester.
[0054] In the case the fatty acid polyoxyalkylene alkyl ether is
produced by the method in which a block addition polymerization is
performed on a lower alcohol, which is an equivalent of R.sup.2O
using the aforementioned complex metal oxide catalyst, and then the
resultant is subjected to transesterification with suitable fatty
acid ester, or the resultant is subjected to esterification with
suitable fatty acid, a desirable narrow ratio cannot be obtained
only by the addition reaction.
[0055] In order to obtain a block adduct having PO unit at the
terminal as a final product in the present method, it is necessary
to perform an addition reaction of PO first, followed by performing
an addition reaction of EO.
[0056] In this case, as a method for obtaining a desirable narrow
ratio, there is a method in which the unreacted raw material,
adducts of low moles, and the like are removed from an intermediate
product obtained from the addition reactions of PO and EO, by
distillation. In the case where the unreacted raw material and the
like are removed by distillation, the distillation is performed in
the common method such as a vacuum distillation. It is preferred
that the amount of the unreacted raw material be 2.5% by mass or
less in the fatty acid polyoxyalkylene alkyl ether in view of
permeability and fluid stability.
[0057] Moreover, the following methods are also preferable because
the distribution of the number of moles of PO added and the
distribution of the number of moles of EO added can be separately
controlled, and a block adduct having a narrower distribution of
the number of moles added can be easily obtained. Namely, they are
a method in which unreacted substances and/or adducts of low moles
are removed from an intermediate product 1 obtained from the
addition reaction of PO, by distillation, and a method in which
after the procedure of the former method, an addition reaction of
EO is performed to attain a block adduct (an intermediate product
2), and adducts of low moles are again removed from the
intermediate product 2 by distillation.
[0058] In this case, the narrow ratio of the intermediate product 1
calculated by Formula (A) is preferably 40% by mass or more in view
of permeability and fluid stability, more preferably 50% by mass or
more, and even more preferably 55% by mass or more. Moreover, the
residual amount of the unreacted raw material alcohol is preferably
2.5% by mass or less in view of permeability and fluid stability,
and more preferably 1.0% by mass or less in the total amount of the
fatty acid polyoxyalkylene alkyl ether.
[0059] Such PO adduct having a high narrow ratio is not
particularly limited. As such PO adduct, a commercially available
raw material, which is obtained by performing an addition reaction
of PO to a lower alcohol such as tripropylene glycol monomethyl
ether (e.g. product name: methyl propylene triglycol (MFTG),
manufactured by Nippon Nyukazai Co., Ltd.), followed by
superfractionation. Use of the PO adduct of a single number of
moles added, which does not substantially have a distribution, by
superfractionation or the like is preferable, because the resulting
surfactant composition has particularly excellent permeability.
[0060] When the block adduct (the intermediate product 2) is
obtained by performing an addition polymerization of EO to the
intermediate product 1 having a narrow distribution of the numbers
of moles added, the residual intermediate product 1 to which EO has
not been added or adducts of low moles of EO added are removed from
the intermediate product 2 by distillation or the like so that the
resultant has a sharp distribution of numbers of moles of EO added.
As a result, the resulting surface composition has excellent
foamability and defoamability. Moreover, when the resulting surface
composition is formulated by mixing with a solvent such as water or
lower alcohol, such formulation has excellent low temperature
stability, preventing uniformity, precipitation, or solidification.
The removal of the adduct of low moles from the intermediate
product 2 by distillation can be performed by a common method such
as a vacuum distillation. Moreover, those obtained by the
aforementioned production method may be produced and used singly or
in an appropriate combination.
[0061] Examples of the production method of the fatty acid
polyoxyalkylene alkyl ether include a method in which a block
addition polymerization is performed with lower alcohol, which is
an equivalence of R.sup.2O using the complex metal oxide catalyst
in the same manner (see JP-A No. 09-262456) followed by
transesterification with suitable fatty acid ester or
exterification with suitable fatty acid, and a method in which PO
and EO are added and polymerized to the lower alcohol in the form
of a block polymer using an, alkali catalyst, and then unreacted
lower alcohol or adduct components of low moles are removed by
distillation to control a distribution of numbers of moles added to
thereby have a desirable narrow ratio, followed by
transesterification with suitable fatty acid ester or
exterification with suitable fatty acid. Here, the catalyst for
used in the transesterification with suitable fatty acid ester or
exterification with suitable fatty acid is suitably selected
depending on the intended purpose without any restriction. Examples
thereof include basic catalysts such as lithium hydroxide, cesium
hydroxide, sodium hydroxide, potassium hydroxide, magnesium
hydroxide, barium hydroxide, calcium hydroxide, sodium carbonate,
potassium carbonate, sodium hydrogen carbonate, lithium chloride,
sodium formate, and sodium methoxide. Examples of acid catalysts
include sulfuric acid, zirconium sulfonate, p-toluene sulfonic acid
(p-TS), benzene sulfonic acid (BS), and 2,4-dimethylbenzene
sulfonic acid (2,4-DMBS). Examples of inorganic oxide catalysts
include ZrO.sub.2, TiO.sub.2, SiO.sub.2, PO.sub.4, Al.sub.2O.sub.3,
and ZnO.
[0062] The catalyst used for room temperature transesterification
is suitably elected depending on the intended purpose without any
restriction. Examples of such catalyst include a tin compound, such
as dialkyl tin chloride, dialkyl tin oxide, fluoroalkyl tin, and
aminopropyl tin.
[0063] Other examples thereof include titanium compounds such as
tetraisopropyl titanate, tetra-n-butyl titanate, tetraethanol amine
titanate, and tetrastearyl titanate. In addition, examples thereof
include, other than those listed above, samarium iodide, and
N-heterocyclic carbine. Further examples thereof include
lanthanum(III)triisopropoxide ([La(Oi-Pr).sub.3]),
lanthanum(III)tristrifluoromethylsulfonate ([La(OTf).sub.3]),
lanthanumtrisacetylacetonate, lead compounds such as lead acetate
and lead naphthenate, litharge, calcium naphthenate, and
enzyme.
[0064] The surfactant composition for agricultural chemicals is
used as a raw material of an agricultural pesticide, and thus it is
not desirable that titanium or tin is left therein. Therefore, it
is preferred that the surfactant composition be subjected to an
adsorption treatment or filtration purification. Particularly
preferable embodiment in view of the environment is such that
sodium hydroxide, sodium hydrogen carbonate, or sodium methoxide is
used as a catalyst for transesterification or esterification, and
then an adsorption treatment or filtration purification is
performed.
[0065] When the transesterification is performed with fatty acid
ester such as fatty acid methyl ester in the course of the
production of the fatty acid polyoxyalkylene alkyl ether, the
residual amount of the fatty acid ester in the resulting fatty acid
polyoxyalkylene alkyl ether is preferably 3.0% by mass or less,
more preferably 2.0% by mass or less in view of the fluid stability
and permeability.
[0066] The surfactant composition of the agricultural pesticide is
suitably used as a spreading agent of an agricultural pesticide
containing an agricultural pesticide active ingredient, is suitably
formulated and used in a fluid agricultural pesticide formulation
as a dispersing agent, or solubilizing agent of an agricultural
pesticide active ingredient and the like, or is suitably used
together with a fluid agricultural pesticide as a spreading agent
for agricultural chemicals.
[0067] In the case where the surfactant composition for
agricultural chemicals of the present invention is used as a
spreading agent for agricultural chemicals, for example, it is
generally mixed in a chemical solution of an agricultural pesticide
and is used at the time when the agricultural pesticide is sprayed.
The concentration thereof for use is generally about 30 ppm to
about 5,000 ppm in water, and is suitably adjusted depending on an
agricultural pesticide for use, or whether or not a targeted plant
is easily wet.
[0068] In the case where the surfactant composition for
agricultural chemicals is used as a spreading agent for
agricultural chemicals, it is preferred that the surfactant be
mixed with water and a solvent, and used as a mixed solution,
because the fatty acid polyoxyalkylene alkyl ether is not easily
dissolved in water.
[0069] Examples of the solvent include lower alcohol and glycols,
since these can be easily dissolve the fatty acid polyoxyalkylene
alkyl ether therein, and are easily mixed with water.
[0070] In the present specification, the term "lower alcohol" means
C1-4 alcohol.
[0071] The lower alcohol is suitably selected depending on the
intended purpose without any restriction, and examples thereof
include methanol, ethanol, isopropyl alcohol, n-propyl alcohol,
isobutyl alcohol, and n-butyl alcohol.
[0072] The glycols are suitably selected depending on the intended
purpose without any restriction, and examples thereof include
ethylene glycol, and propylene glycol. Moreover, acetone, propylene
carbonate, N-methylpyrrolidone, .gamma.-butyrolactone, or the like
may also be used as the solvent. Concerning that it is released to
the environment as a spreading agent for agricultural chemicals,
ethanol, isopropyl alcohol, and isobutyl alcohol are preferable. In
view of a high flash point for increasing safety, isopropyl alcohol
and isobutyl alcohol are suitable.
[0073] In the case where the surfactant composition for
agricultural chemicals is used as a spreading agent for
agricultural chemicals, a proportion of the fatty acid
polyoxyalkylene alkyl ether serving as a surfactant in the
surfactant composition for agricultural chemicals is 10% by mass to
60% by mass, preferably 20% by mass to 40% by mass, a proportion of
water therein is 10% by mass to 70% by mass, preferably 20% by mass
to 60% by mass, and a proportion of the lower alcohol therein is
10% by mass to 70% by mass, preferably 20% by mass to 50% by mass.
Instead of the lower alcohol, a solvent formed of the glycols or a
mixed solution of the lower alcohol and the glycols can be used at
the same proportion.
[0074] In the case where the surfactant composition for
agricultural chemicals is used as a spreading agent for
agricultural chemicals, a specific example of a formulation of the
surfactant composition for agricultural chemicals is consisted of
30% by mass of a surfactant of the fatty acid polyoxyalkylene alkyl
ether; 30% by mass of water; and 40% by mass of isopropyl alcohol
(i.e. a surfactant of the fatty acid polyoxyalkylene alkyl
ether/water/isopropyl alcohol=30% by mass/30% by mass/40% by mass),
which is preferable in view of its excellent low temperature
stability.
[0075] In addition to the above, the surfactant composition for
agricultural chemicals serving as a spreading agent for
agricultural chemicals can contain a sticking agent such as
carboxymethylcellulose, Arabian gum, and casein, and a dispersing
agent such as a naphthalenesulfonic acid-formaldehyde condensate,
and lignin sulfonate, if necessary.
[0076] The surfactant composition for agricultural chemicals can be
used, as an activator for agricultural chemicals, for a functional
spreading agent (adjuvant), water dispersible agent, emulsifier,
and dispersing and dissolving agent. Moreover, it can be used as a
surfactant for agricultural chemicals such as a bactericide,
insecticide, acaricide, weedkiller, and plant growth regulator.
[0077] In the case where the surfactant composition for
agricultural chemicals is used as the dispersing and dissolving
agent for a preparation of an agricultural pesticide, an amount of
the surfactant composition for agricultural chemicals for use as a
surfactant is about 5% by mass to about 50% by mass.
[0078] The present invention can provide a surfactant composition,
which has low foamability, excellent defoamability, and excellent
low temperature stability, prevents separation (heterogeneity),
precipitation, and solidification, when it is formulated as a
preparation where the surfactant composition is mixed with a
solvent such as water, lower alcohol, and the like as mentioned
above, and which is suitably applied and easily handled as a
spreading agent for agricultural chemicals, or a dispersing and
dissolving agent for a preparation of an agricultural
pesticide.
[0079] Since this surfactant composition is an excellently
environmentally safe surfactant composition, which can be used in
the field of agricultural pesticides, the surfactant can also be
used as a surfactant in the fields of engineering works, energy
industries, in which the surfactant will be released in the
environment.
EXAMPLES
[0080] The present invention will be more specifically explained
through Examples thereof, hereinafter. However, these Examples
shall not be construed as to limit a scope of the present
invention. The evaluation methods and analysis methods used in
Examples are shown below.
(1) Evaluation Method
(i) Foaming Power and Defoamability
[0081] To a 1,000-mL graduated cylinder, 100 mL of a test solution
having an active ingredient concentration of 1,000 ppm was added.
To this solution, nitrogen gas was introduced from the bottom of
the cylinder at the rate of 1,000 mL/min. for 3 minutes using a
glass ball filter (Filter Particle No. 4 (5 .mu.m to 10 .mu.m in
size), manufactured by Kinoshita Rika Kogyo Co., Ltd.). Just after
the completion of the introduction of the nitrogen gas, a foam
height was measured, and was determined as a foaming power. In
addition, the defoamability was determined based on the foam height
just after the completion of the introduction, and the height
thereof 5 minutes after the completion of the introduction, using
the following formula.
Defoamability(%)=(foam height just after the completion-foam height
5 minutes later)/foam height just after the
completion.times.100
[0082] The foaming power and defoamability were evaluated based on
the following criteria.
<Evaluation Criteria of Foaming Power (Foam Height)>
[0083] A: 0 mm or higher but lower than 90 mm
[0084] B: 90 mm or higher, but lower than 120 mm
[0085] C: 120 mm or higher
<Evaluation Criteria of Defoamability>
[0086] A: 70% or more
[0087] B: 40% or more but less than 70%
[0088] C: less than 40%
(ii) Permeability (Wettability)
[0089] A test was carried out in accordance with the Draves method.
A piece of wool knit cloth was cut out in the size of 20 cm in
length and 3 cm in width to prepare a sample cloth. A wire tool was
provided so that a wire anchor part of the tool would stay on the
bottom of a 1,000-mL graduated cylinder, and the wire anchor part
and a snake pin hook (about 0.1 g) were connected with a nylon
thread (about 3 cm). A test solution was prepared by diluting each
surfactant sample to 30 ppm with hard water having a hardness index
of 3, and was added to the 1,000-mL graduated cylinder. One side of
the test cloth was hanged on the snake pin hook, and the wire tool
was placed in the 1,000-mL graduated cylinder in which the test
solution was provided so that the wire anchor portion was sank and
located on the bottom of the cylinder and the test cloth was
floated in the test solution. The time from when the snake pin hook
was placed in the test solution to when the snake pin hook started
to sink (when the thread between the hook and the anchor lost
tension) was measured. The shorter the time is, more preferable the
permeability is. The time shorter than 30 second was determined as
acceptable, and the time equal to or longer than 30 seconds was
determined as unacceptable.
(iii) Fluid Stability Test
[0090] A solution was prepared with 30 parts by mass of a
surfactant sample, 30 parts by mass of ion-exchanged water, and 40
parts by mass of isopropyl alcohol, and the solution was stirred
until it became homogeneous. Then, the resulting solution was
placed in a sample bottle, and the sample bottle was sealed, and
placed in a constant temperature oven the temperature of which was
set to -5.degree. C. for 72 hours. After this storage period, the
solution which kept its homogeneous state at -5.degree. C. was
determined as A, the solution which had precipitates or caused
fluid separation, but recovered its homogeneous state when it was
heated to 20.degree. C. was determined B, and the solution which
did not recover the precipitation or fluid separation was
determined as C.
(iv) Solubility
[0091] An aqueous solution of each surfactant sample was prepared
at the concentration of 1,000 ppm as a sample solution. To 4 mL of
this sample solution, an oil soluble coloring agent Yellow OB was
added in an amount of 40 mg as an insoluble substance, and the
mixture was agitated at room temperature for 24 hours. Thereafter,
the resulting solution was filtered through a pretreatment filter
(Chromatodisk, manufactured by GL Sciences Inc., 13N, non-water
system, nonstelarized) having an opening size of 0.45 .mu.m,
followed by adding an equal amount of ethanol. An absorption of the
resulting solution was measured at 450 nm. As the dissolved amount,
the amount which was 30 ppm or more was determined as acceptable,
and the amount less than 30 ppm was determined as unacceptable.
(v) Biodegradability
[0092] A test was performed with reference to a degradation test of
a chemical substance by microbes or the like in accordance with Act
on the Evaluation of Chemical Substances and Regulation of their
manufacture, etc. (CSCL). Specifically, activated sludge was added
in an amount of 30 ppm (solid contents) was added as a seeding
source to a test solution having a sample concentration of 100 ppm,
and a biochemical oxygen demand (BOD) and the total oxygen demand
(TOD) where measured over time. The results of the biodegradation
degree, i.e. BOD/TOD (%), were evaluated based on the following
criteria.
[0093] A: The biodegradation degree reached 60% within 28 days.
[0094] B: It took 29 days or longer for the biodegration degree to
reach 60%, or the sample was only decomposed at a certain amount
but not more than that amount.
(vi) Fish Toxicity
[0095] A fish toxicity value, a median tolerance limit (TLm)(48
hours), was measured on Japanese variety of cyprinodonts with
reference to "71. Acute toxycity test for fish", defined in Testing
methos for industrial wastewater JIS K 0102, namely the median
lethal concentration (ppm) was measured after 48 hours. The result
which was 100 ppm or higher was defined as acceptable, and the
result which was lower than 100 ppm was defined as
unacceptable.
(vii) Phytotoxicity
[0096] The sample was sprayed to cabbage and garden pea as an
active ingredient (5,000 ppm) of a spreading agent, and a rate of
phytotoxicity occurred was determined 5 days later. The result of
the rate of the phytotoxicity which was less than 30% was
determined as acceptable, and the result of the rate thereof which
was 30% or more was determined as unacceptable.
(3) Analysis Method
[0097] The analysis method used is described hereinafter. The
average numbers of moles of EO, and PO added were calculated from
the balance of the masses of the charged raw materials and alkylene
oxide. Note that, in the case where the distillation was performed
after the addition reaction of EO and PO, the average number of
moles added was determined by .sup.1H-NMR described in (i)
below.
(i) Calculation Method of Average Number of Moles Added
[0098] The obtained compound (30 mg) was dissolved in 4 mL of
deuterochloroform, and the solution was then measured by
.sup.1H-NMR (300 MHz, FT NMR SYSTEM JNM-LA300, manufactured by JEOL
Ltd.). The chemical shift of the deuterochloroform was calculated,
using 7.30 ppm as a standard, from the integral value ratio of
chemical shift of each peak, 0.87 ppm (terminal methyl of fatty
acid), 1.13 ppm to 1.15 ppm (side chain methyl of PO), 3.32 ppm to
3.66 ppm (methine and methylene of PO), and 3.52 ppm to 3.71 ppm
(methylene of EO).
(ii) Measurement of Distribution of Numbers of Moles EO and PO
Added, and Calculation Method of Narrow Ratio
[0099] The distributions of numbers of moles of EO and PO added of
the final product and intermediate product were measured in the
following manner.
Condition of Device: gas chromatograph: HP-6890 Mass Selective
Detector (GC-MS),
Detector: FID
[0100] Column: UltraALLOYPY-1, 0.25 mm in diameter, 30 m in length,
film thickness of 0.25 .mu.m
Condition of Analysis Injection: 380.degree. C., Detector:
380.degree. C.
[0101] Initial: 50.degree. C..fwdarw.360.degree. C. (20 min),
temperature increasing rate: 10.degree. C./min, carrier gas: He
Split ratio: 50/1
[0102] The sample (0.5 g) was dissolved in 10 g of acetone, 1 .mu.L
of the obtained solution was introduced to the device, and a
concentration (%) per mole of EO (PO) added was measured. The total
proportion of the maximum peak of the obtained chromatogram and
adducts in the range of .+-.2 moles of the maximum peak (the total
of adducts in range of 5 moles) was determined as a narrow
ratio.
Narrow ratio = i = n MAX - 2 i = n MAX + 2 Y i ( A )
##EQU00004##
(iii) Determination of Amount of Unreacted Fatty Acid Methyl Ester
or Unreacted Methanol Contained in Intermediate Product 1 or 2
(1) For Unreacted Fatty Acid Methyl Ester
[0103] As internal standard, 0.06 g of methyl laurate and 2 g of a
sample were prepared and dissolved in 4 g of acetone, and the
obtained solution (2 .mu.L) was introduced to a device. An
analytical curve was formed from the peak area of the internal
standard, and the peak area obtained when the concentration of
methyl laurate was changed, and an amount of an unreacted component
contained the sample was determined.
(2) For Unreacted Methanol
[0104] A sample (1 .mu.L) was introduced to a device without
diluting with a solvent, and an amount of unreacted methanol was
calculated from the area % of the obtained chromatogram.
<Conditions for Device>
[0105] Gas chromatograph: Shimadzu GC-14A, detecting element: FID,
Column: made of glass 3 mm in diameter.times.1 m, fillers: 2%
silicon OV-1 (60/80 mesh)
--Universal Conditions--
[0106] Injection: 320.degree. C., Detecter: 320.degree. C.,
N.sub.2: 50 mL/min, H.sub.2: 0.75 kg/cm.sup.2, Air: 0.5
kg/cm.sup.2
--For Unreacted Methyl Ester--
[0107] Initial: 100.degree. C..fwdarw.+230.degree. C. (increasing
rate of temperature: 10.degree. C./min).fwdarw.320.degree. C.
(increasing rate of temperature: 30.degree. C./min), duration for
maintaining the temperature: 22 min
--For Unreacted Methanol--
[0108] Initial: 50.degree. C..fwdarw.320.degree. C. (maintaining
for 20 min), increasing rate of temperature: 10.degree. C./min
Example 1
[0109] An alumina-magnesia complex oxide (Kyowado 300, manufactured
by Kyowa Chemical Industry Co., Ltd.) expressed by the chemical
formula 2.5MgO.Al.sub.2O.sub.3.nH.sub.2O was baked at 750.degree.
C. for 3 hours under nitrogen gas streams to thereby obtain a baked
alumina-magnesia complex oxide (Al/Mg molar ratio=0.44/0.56)
catalyst. Into a 4-L autoclave, 1,073 g of methyl oleate (fatty
acid methyl ester derived from C18 fractions derived from palm oil,
product name: PASTELL M182, manufacturer: Lion Corporation, iodine
value: 91), 5 g of the obtained catalyst, and 0.58 g of 40% KOH as
a modifying agent for the catalyst were added, and the inner
atmosphere of the autoclave was replaced with nitrogen gas
twice.
[0110] Thereafter, the temperature was increased to 180.degree. C.,
the pressure inside the reaction vessel was returned to normal
pressure by nitrogen, and then 628 g of PO (3 moles relative to 1
mole of methyl oleate) was gradually introduced to the vessel. The
pressure just after the completion of the introduction of PO was
0.48 MPa, and was reduced as the reaction progressed. The PO
addition reaction was continued until the pressure became constant
at 0.22 MPa in 2 hours. A portion of the obtained intermediate
product 1A was sampled, and then analyzed by gas chromatography. As
a result, the sample contained 12.8% by mass of unreacted fatty
acid methyl ester.
[0111] Then, after the nitrogen purge was performed and the
temperature was increased in the aforementioned manners, 794 g of
EO (5 moles relative to 1 mole of methyl oleate) was gradually
introduced to the vessel. The pressure just after the completion of
the introduction of EO was 0.5 MPa, and was reduced as the reaction
progressed. The EO addition reaction was continued until the
pressure became constant at 0.24 MPa in 0.5 hours time. The
obtained reaction product was filtered using diatom earth to
thereby obtain a final product. The compound 1A obtained by a block
addition reaction of PO and EO contained 1.1% by mass of unreacted
fatty acid methyl ester. Results of measurements and evaluation
were shown in Tables 1 and 2.
Example 2
[0112] A compound 1B was obtained by a block addition reaction of
PO and EO in the same manner as in Example 1, provided that the
amount of PO added was changed to 565 g (2.7 moles relative to 1
mole of methyl oleate), and the obtained intermediate product 1B
was subjected to vacuum distillation by reducing the pressure to 10
Torr or lower, while increasing the temperature stepwise from
175.degree. C. to 200.degree. C. stepwise, so as to remove
unreacted methyl ester contained in the intermediate product 1B.
The intermediate product 1B contained 0.8% by mass of unreacted
fatty acid methyl ester. The compound 1B obtained by further
subjecting to an addition reaction of EO contained 0.3% by mass of
unreacted fatty acid methyl ester. The results of measurements and
evaluation are shown in Tables 1 and 2.
Example 3
[0113] A compound 1C was obtained by performed a block addition
reaction of PO and EO in the same manner as in Example 2, provided
that 40% KOH was not added as the modifying agent for the catalyst.
The intermediate product 1C after the vacuum distillation contained
1.8% by mass of fatty acid methyl ester. The compound 1C obtained
by further subjecting to an addition reaction of EO contained 1.6%
by mass of unreacted fatty acid methyl ester. The results of
measurements and evaluation are shown in Tables 1 and 2.
Comparative Example 1
[0114] A final product was obtained in the same manner as in
Example 1, provided that a mixture of 794 g of EO (5 moles relative
to 1 mole of methyl oleate) and 628 g of PO (3 moles relative to 1
mole of methyl oleate) was gradually introduced to the vessel, and
then a random addition reaction of EO and PO was performed. The
pressure in the vessel was 0.48 MPa just after the completion of
the mixture, but was reduced as the random addition reaction of EO
and PO progressed. The random addition reaction was continued until
the inner pressure became constant at 0.24 MPa in 2 hours time. The
compound 1D obtained by the random addition reaction of EO and PO
contained 1.2% by mass of unreacted fatty acid methyl ester. The
results of measurements and evaluation are shown in Tables 1 and
2.
Comparative Example 2
[0115] A final product was obtained in the same manner as in
Example 1, provided that the order of the block addition was
changed from "PO first and then EO" to "EO first and then PO". The
compound 1E obtained by the block addition reaction of EO and PO
contained 1.1% by mass of unreacted fatty acid methyl ester. The
results of measurements and evaluation are shown in Tables 1 and
2.
Comparative Example 3
[0116] A final product was obtained in the same manner as in
Example 1, provided that 40% KOH was not added as the modifying
agent for the catalyst. The compound 1F obtained by the block
addition reaction of PO and EO contained 4.9% by mass of unreacted
fatty acid methyl ester. The results of measurements and evaluation
are shown in Tables 1 and 2.
Example 4
[0117] Into a 4-L autoclave, 387 g of methanol (manufactured by
Junsei Chemical Co., Ltd.), and 1 g of NaOH as a catalyst were
added, and the inner atmosphere of the autoclave was replaced with
nitrogen gas twice. Thereafter, the temperature was increased to
90.degree. C., and then 1,405 g of PO (2.0 moles relative to 1 mole
of methanol) was gradually introduced to the vessel to proceed an
addition reaction.
[0118] After the completion of the reaction, the temperature was
increased stepwise from 75.degree. C. to 100.degree. C. under
normal pressure, and distillation was performed until the methanol
residue became 1% or lower, to thereby obtain an intermediate
product 2A1. The average number of moles of PO added of the
intermediate product 2A1 was 2.4 moles. Thereafter, to 857 g of the
intermediate product 2A1, 881 g of EO (4 moles relative to 1 mole
of the intermediate product 2A1) was introduced, and an addition
reaction was performed. After the addition reaction was completed,
distillation was again performed by reducing the pressure to 10
Torr, while increasing the temperature stepwise from 175.degree. C.
to 220.degree. C. Into a reaction vessel fitted with a stirring
blade, 853 g of the obtained intermediate product 2A2, 614 g of
methyl oleate (PASTELL M182, iodine value: 91) (1.03 moles relative
to 1 mole of the intermediate product 2A2), and 7.3 g of sodium
hydrogen carbonate were added, and the temperature was increased
from 60.degree. C. to 210.degree. C. under stirring while reducing
the pressure stepwise from normal pressure to 10 Torr to thereby
perform transesterification. The compound 2A obtained by the
reaction contained 1.6% by mass of unreacted fatty acid methyl
ester. The results of measurements and evaluation are shown in
Tables 1 and 2.
Example 5
[0119] An addition reaction of PO was performed in the same manner
as in Example 4, provided that the amount of PO introduced was
changed to 2,108 g (3 moles relative to 1 mole of methanol). After
the completion of the reaction, distillation was performed under
normal pressure while increasing the temperature stepwise from
75.degree. C. to 130.degree. C., until the proportion of the
methanol residue and methanol-1PO product was 1% or less. Then,
vacuum distillation was further performed by increasing the
temperature stepwise from 175.degree. C. to 220.degree. C. while
reducing the pressure stepwise to 5 Torr, and then the distillate
was collected so as to give an intermediate product 2B1 from which
the portion of high boiling substances had been removed. The
average number of moles of PO added of the intermediate product 2B1
was 3 moles.
[0120] To the intermediate product 2B1, an addition reaction of EO
was performed in the same manner as in Example 4 to thereby obtain
an intermediate product 2B2. then, to the intermediate product 2B2,
transesterification was performed in the same manner as in Example
4, to thereby obtain a compound 2B. The obtained compound 2B
contained 1.6% by mass of unreacted fatty acid methyl ester. The
results of measurements and evaluation are shown in Tables 1 and
2.
Example 6
[0121] A block addition reaction of PO and EO was performed in the
same manner as in Example 4 to thereby obtain an intermediate
product 2C2, provided that an addition reaction of PO was performed
in the manner that the amount of PO introduced was changed to 1,686
g (2.4 moles related to 1 mole of methanol) and the distillation
was not performed after the addition reaction of PO, and to the
intermediate product 2C2 transesterification reaction was performed
in the same manner as in Example 4 to thereby obtain a compound
2C.
[0122] The intermediate product 2C1 contained 1.9% by mass of
unreacted methanol, and the obtained compound 2C contained 1.7% by
mass of unreacted fatty acid methyl ester. The results of
measurements and evaluation are shown in Tables 1 and 2.
Comparative Example 4
[0123] A compound 2D was obtained in the same manner as in Example
6, provided that the addition reaction of PO was performed in the
manner that the amount of PO introduced was changed to 2,108 g (3
moles relative to 1 mole of methanol), the addition reaction of EO
was performed in the manner that the amount of EO introduced was
changed to 1,289 g (5 moles relative to 1 mole of methanol), and
vacuum distillation was not performed after the addition reaction
of EO. The intermediate product 2D1 contained 10.3% by mass of
unreacted methanol, and the obtained compound 2D contained 1.6% by
mass of unreacted fatty acid methyl ester. The results of
measurements and evaluation are shown in Tables 1 and 2.
[0124] Note that, the sample used for each example was also
evaluated in terms of biodegradation ability, fish toxicity, and
phytotoxicity, and as a result, it was confirmed that all the
samples had excellent biodegradation ability (evaluation: A), and
were highly safe in the environment, which passed the acceptable
levels of the results of the tests for fish toxicity and
phytotoxicity.
TABLE-US-00001 TABLE 1 EO/PO Average number Narrow Sample Starting
addition of moles added Position ratio No. material Catalyst form
EO PO of PO (mass %) Ex. 1 1A Fatty acid Modified Block 5 3
Terminal 68 methyl ester solid Ex. 2 1B Fatty acid Modified Block 5
3 Terminal 76 methyl ester solid Ex. 3 1C Fatty acid Non-modified
Block 5 3 Terminal 60 methyl ester solid Comp. 1D Fatty acid
Modified Random 5 3 Inner 69 Ex. 1 methyl ester solid portion Comp.
1E Fatty acid Modified Block 5 3 Inner 66 Ex. 2 methyl ester solid
portion Comp. 1F Fatty acid Non-modified Block 5 3 Terminal 43 Ex.
3 methyl ester solid Ex. 4 2A Methanol NaOH Block 5 3 Terminal 65
Ex. 5 2B Methanol NaOH Block 5 3 Terminal 71 Ex. 6 2C Methanol NaOH
Block 5 3 Terminal 61 Comp. 2D Methanol NaOH Block 5 3 Terminal 48
Ex. 4
TABLE-US-00002 TABLE 2 Foaming power Defoamability Sample Foam
Value Permeability Fluid No. height (mm) Evaluation (%) Evaluation
(sec.) stability Ex. 1 1A 62 A 79 A 18 B Ex. 2 1B 49 A 85 A 14 A
Ex. 3 1C 85 A 71 A 28 B Comp. 1D 113 B 51 B 45 C Ex. 1 Comp. 1E 176
C 36 C 83 C Ex. 2 Comp. 1F 97 B 64 B 37 C Ex. 3 Ex. 4 2A 73 A 75 A
22 B Ex. 5 2B 55 A 82 A 16 A Ex. 6 2C 89 A 70 A 29 B Comp. 2D 143 C
45 C 57 C Ex. 4
* * * * *