U.S. patent application number 09/793700 was filed with the patent office on 2001-09-13 for method for producing a cement admixture, concrete and fluorine-containing oxyalkylene compounds.
This patent application is currently assigned to ASAHI GLASS COMPANY LTD.. Invention is credited to Enna, Genichirou, Fukuda, Hiroki, Ohtsuka, Yoshihiro.
Application Number | 20010021738 09/793700 |
Document ID | / |
Family ID | 18096477 |
Filed Date | 2001-09-13 |
United States Patent
Application |
20010021738 |
Kind Code |
A1 |
Enna, Genichirou ; et
al. |
September 13, 2001 |
Method for producing a cement admixture, concrete and
fluorine-containing oxyalkylene compounds
Abstract
The present invention is the following invention which provides
a cement admixture which satisfies fluidity of fresh concrete and
high strength of the hardened product of concrete simultaneously.
Namely, the present invention resides in a cement admixture which
is a mixture of fluorine-containing compounds represented by the
formula (1): R.sup.f-Q.sup.1-O-(A.sup.1-O).sub.k-R.sup.1 (1)
wherein R.sup.f is a C.sub.1-22 polyfluoroaliphatic hydrocarbon
group which may contain ethereal oxygen atoms or thioethereal
sulfur atoms, Q.sup.1 is a C.sub.1-5 linear or branched alkylene
group, k is an integer of from 1 to 100, A.sup.1 is a C.sub.2-4
linear alkylene group or a group having at least one hydrogen atom
of said alkylene group substituted by a hydrocarbon group which may
contain ethereal oxygen atoms, provided that when k is from 2 to
100, the plurality of A.sup.1 may be the same or different, and
R.sup.1 is a hydrogen atom, a C.sub.1-18 hydrocarbon group or a
C.sub.1-18 acyl group, said mixture having a ratio of the weight
average molecular weight (M.sub.w) to the number average molecular
weight (M.sub.n) (i.e. M.sub.w/M.sub.n) of at least 1.1, and
concrete which contains said cement admixture.
Inventors: |
Enna, Genichirou;
(Kawasaki-shi, JP) ; Fukuda, Hiroki;
(Kawasaki-shi, JP) ; Ohtsuka, Yoshihiro;
(Kawasaki-shi, JP) |
Correspondence
Address: |
OBLON SPIVAK MCCLELLAND MAIER & NEUSTADT PC
FOURTH FLOOR
1755 JEFFERSON DAVIS HIGHWAY
ARLINGTON
VA
22202
US
|
Assignee: |
ASAHI GLASS COMPANY LTD.
1-2, Marunouchi 2-chome
Tokyo
JP
100-8305
|
Family ID: |
18096477 |
Appl. No.: |
09/793700 |
Filed: |
February 27, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09793700 |
Feb 27, 2001 |
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09308640 |
May 28, 1999 |
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09308640 |
May 28, 1999 |
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PCT/JP97/04335 |
Nov 27, 1997 |
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Current U.S.
Class: |
524/366 ;
528/405 |
Current CPC
Class: |
C04B 2103/34 20130101;
C04B 24/005 20130101; C04B 24/32 20130101; C08G 65/007 20130101;
C08G 65/2639 20130101 |
Class at
Publication: |
524/366 ;
528/405 |
International
Class: |
C09J 163/00 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 28, 1996 |
JP |
8-318192 |
Claims
1. A cement admixture which is a mixture of fluorine-containing
compounds represented by the formula (1):
R.sup.f-Q.sup.1-O-(A.sup.1-O).sub.k-R.sup- .1 (1) wherein R.sup.f
is a C.sub.1-22 polyfluoroaliphatic hydrocarbon group which may
contain ethereal oxygen atoms or thioethereal sulfur atoms, Q.sup.1
is a C.sub.1-5 linear or branched alkylene group, k is an integer
of from 1 to 100, A.sup.1 is a C.sub.2-4 linear alkylene group or a
group having at least one hydrogen atom of said alkylene group
substituted by a hydrocarbon group which may contain ethereal
oxygen atoms, provided that when k is from 2 to 100, the plurality
of A.sup.1 may be the same or different, and R.sup.1 is a hydrogen
atom, a C.sub.1-18 hydrocarbon group or a C.sub.1-18 acyl group,
said mixture having a ratio of the weight average molecular weight
(M.sub.w) to the number average molecular weight (M.sub.n) (i.e.
M.sub.w/M.sub.n) of at least 1.1.
2. The cement admixture according to claim 1, wherein R.sup.1 is a
hydrogen atom.
3. The cement admixture according to claim 1 or 2, wherein A.sup.1
is an ethylene group and/or a propylene group.
4. The cement admixture according to claim 1, 2 or 3, wherein
R.sup.f is a C.sub.4-22 perfluoroalkyl group.
5. Concrete which contains the cement admixture as defined in claim
1, 2, 3 or 4.
6. A method for producing fluorine-containing oxyalkylene compounds
represented by the formula (4), which comprises ring opening
polymerization of at least one cyclic ether represented by the
formula (3) in the presence of an acid catalyst and a
fluorine-containing hydroxyl compound represented by the formula
(2): R.sup.f-Q.sup.2-OH (2) 2R.sup.f-Q.sup.2-O-(A.sup.2-O).sub.k--H
(4) wherein R.sup.f is a C.sub.1-22 polyfluoroaliphatic hydrocarbon
group which may contain ethereal oxygen atoms or thioethereal
sulfur atoms, Q.sup.2 is a C.sub.3-5 linear or branched alkylene
group, k is an integer of from 1 to 100, and A.sup.2 is a C.sub.2-4
linear alkylene group or a group having at least one hydrogen atom
of said alkylene group substituted by a hydrocarbon group which may
contain ethereal oxygen atoms.
7. A method for producing compounds represented by the formula (5),
which comprises further converting the terminal hydroxyl group of
the fluorine-containing oxyalkylene compounds represented by the
formula (4) obtained by the method of claim 6, to a R.sup.3O--
group: R.sup.f-Q.sup.2-O-(A.sup.2-O).sub.k-R.sup.3 (5) wherein
R.sup.f, Q.sup.2 and k are as defined for the formula (4), and
R.sup.3 is a C.sub.1-18 hydrocarbon group or a C.sub.1-18 acyl
group.
8. The method according to claim 6, wherein the ring opening
polymerization is conducted in the presence of at least one solvent
selected from glyme, diglyme, triglyme and methyl tert-butyl
ether.
9. A method for producing a mixture of fluorine-containing
oxyalkylene compounds represented by the formula (4), which
comprises ring opening polymerization of at least one cyclic ether
represented by the formula (3) in the presence of an acid catalyst
and a fluorine-containing hydroxyl compound represented by the
formula (2), said mixture having a ratio of the weight average
molecular weight (M.sub.w) to the number average molecular weight
(M.sub.n) (i.e. M.sub.w/M.sub.n) of at least 1.1:
R.sup.f-Q.sup.2-OH (2) 3R.sup.f-Q.sup.2-O-(A.sup.2-O).sub.k--H (4)
wherein R.sup.f is a C.sub.1-22 polyfluoroaliphatic hydrocarbon
group which may contain ethereal oxygen atoms or thioethereal
sulfur atoms, Q.sub.2is a C.sub.3-5 linear or branched alkylene
group, k is an integer of from 1 to 100, and A.sup.2 is a C.sub.2-4
linear alkylene group or a group having at least one hydrogen atom
of said alkylene group substituted by a hydrocarbon group which may
contain ethereal oxygen atoms.
10. A surface active agent which comprises fluorine-containing
compounds represented by the formula (6):
R.sup.f--CH.sub.2CH.sub.2CH(CH.sub.3)--O--
-(A.sup.1-O).sub.k-R.sup.1 (6) wherein R.sup.f is a C.sub.1-22
polyfluoroaliphatic hydrocarbon group which may contain ethereal
oxygen atoms or thioethereal sulfur atoms, k is an integer of from
1 to 100, A.sup.1 is a C.sub.2-4 linear alkylene group or a group
having at least one hydrogen atom of said alkylene group
substituted by a hydrocarbon group which may contain ethereal
oxygen atoms, provided that when k is from 2 to 100, plurality of
A.sup.1 may be the same or different, and R.sup.1 is a hydrogen
atom, a C.sub.1-18 hydrocarbon group or a C.sub.1-18 acyl group.
Description
TECHNICAL FIELD
[0001] The present invention relates to a cement admixture which
comprises specific fluorine-containing compounds and concrete
containing said cement admixture. The present invention further
relates to a method for producing specific fluorine-containing
compounds. The present invention still further relates to a novel
surface active agent.
BACKGROUND ART
[0002] In order to improve the strength of the hardened product of
concrete, it is most effective to reduce the water content of
concrete. However, there are drawbacks that if the water content is
reduced, fluidity of fresh concrete may decrease, whereby
workability at the work site may significantly deteriorate.
[0003] In recent years, along with the increase in high-rise
buildings, labor-saving is required, and fluidity of fresh concrete
is thereby required. Simultaneously, the hardened product of
concrete is required to have high strength including
anti-earthquake property. Accordingly, concrete is required to
satisfy both of the two performances which are in an antinomic
relation to each other.
[0004] The following methods have been proposed for such
requirements.
[0005] (1) A method to add, as an air-entraining agent (AE agent),
a compound having terminal hydroxyl groups of (polyoxyethylene)aryl
ether substituted by alkoxy groups to concrete to improve
workability and freezing damage property, and to add an emulsion
stabilizer for latex to prevent cracks.
[0006] (2) A method to use a block copolymer of oxyethylene and
oxypropylene as a water reducing agent and a dispersing agent for
concrete.
[0007] (3) A method to use an addition product of higher alcohol
alkylene oxide, as an air-entraining agent and an emulsion
stabilizer for latex.
[0008] (4) A method to use polyoxyalkylene glycol as a dispersing
agent for e.g. asbestos or glass wool, which are fibers to be
incorporated in concrete, and a method to use polyoxyalkylene
glycol together with a cement dispersing agent such as lignin
sulfonic acid, to further raise dispersibility of the fibers.
[0009] Further, the following methods have been proposed to reduce
the shrink of the hardened product of concrete.
[0010] (5) A method to add an alkylene oxide compound to concrete
(JP-A-2-1789).
[0011] (6) A method to add a compound having a higher carboxylic
acid and alkylene oxide added thereto, to concrete (JP-A-5-70196,
JP-A-3-290342).
[0012] Further, the following method has been proposed to obtain
high hardness.
[0013] (7) A method to add a surface active agent containing an
anionic surface active agent which comprises a hydrocarbon compound
as a main component, to concrete.
[0014] Further, the following methods have been proposed to prevent
reduction in fluidity of concrete when the water content is
reduced.
[0015] (8) A method to add a surface active agent of fluorine type
which comprises a compound having e.g. a sulfonyl bond, an ester
bond or an amide bond, inserted between a perfluoroalkyl group and
an oxyalkylene group (JP-A-7-17752).
[0016] (9) A method to use a surface active agent of hydrocarbon
type together with the surface active agent of fluorine type as
mentioned in (8) (JP-A-2-1789, JP-A-1-53215).
[0017] On the other hand, as the method for producing a compound
containing a perfluoroalkyl group and an oxyalkylene group, the
following methods have been proposed.
[0018] (10) A method in which a compound having a perfluoroalkyl
group and a hydroxyl group connected therewith by means of an
ethylene group (hereinafter referred to as perfluoroalkyl ethanol)
is used as an initiator, and when ring opening polymerization of
the alkylene oxide therewith is conducted, a three way catalyst
made of NaI/I.sub.2/NaBH.sub.4 is used (WO95-35272).
[0019] (11) A method to react a tosylate of polyalkylene glycol
with a perfluoroalkyl ethanol (JP-B-7-103059).
[0020] (12) A method in which perfluoroalkyl ethanol is used as an
initiator, and when ring opening polymerization of the alkylene
oxide compound therewith is conducted, a double metal cyanide
complex is used as a catalyst (JP-A-3-290430).
[0021] However, there are following drawbacks in the
above-mentioned proposals.
[0022] In the methods (1) to (4), both performances of strength
after concrete is hardened and fluidity of fresh concrete are
inadequate.
[0023] In proposals (5) and (6), in the case where the water
content is reduced, a drawback is confirmed such that fluidity of
fresh concrete decreases.
[0024] In the method (7), in order to obtain performance, it is
required to add a large amount of surface active agent, and even if
a large amount of surface active agent is added, strength and
fluidity are inadequate.
[0025] In the methods (8) and (9), when the surface active agent is
added to concrete, a problem of foaming phenomenon (a phenomenon
such that foams are likely to foam, and formed foams hardly
disappear) is confirmed. Further, concrete is likely to involve air
during mixing, whereby apparent density after hardened decreases,
and as a result, a problem such that the strength of the hardened
product of concrete decreases is confirmed. Particularly in the
case of employing a conventional fluorine-containing surface active
agent having an amide bond or an ester bond between a
perfluoroalkyl group and an oxyalkylene group, foaming phenomenon
is significant, and depending upon the conditions of use of
concrete, a problem such that the fluorine-containing surface
active agent is hydrolyzed is confirmed. Further, among
fluorine-containing surface active agents as described in the above
references, some are hardly available practically, and some are
extremely expensive even if they are available, whereby some of the
fluorine-containing surface active agents can not be used
practically.
[0026] Further, there are following problems in the above-mentioned
method.
[0027] In the method (10), a special catalyst is used, and the
control of the reaction is difficult. Further, it is
disadvantageous in view of cost, and the method can not be
industrially used practically. Further, the foaming phenomenon is
confirmed.
[0028] In the method (11), the side reaction occurs, whereby the
yield of the desired compound will be extremely low.
[0029] In the method (12), purification after the reaction takes a
lot of time and labor. Further, in the case where the metal complex
remains in the compound obtained by said method, performance as a
cement admixture tends to decrease.
[0030] In each method (10) to (12), if it is attempted to change
the structure of the initiator or to change the kind of the
oxyalkylene group, the reaction is less likely to proceed, and such
methods can not be used widely.
DISCLOSURE OF THE INVENTION
[0031] The present inventors have studied on a cement admixture,
i.e. compounds having an excellent performance as an additive to be
added to concrete for the purpose of improving fluidity, and found
a mixture of the following fluorine-containing compounds. Further,
they have found a method for effectively producing specific
fluorine-containing compounds among said compounds, and a novel
surface active agent.
[0032] Namely, the present invention provides a cement admixture
which is a mixture of fluorine-containing compounds represented by
the formula (1), and which is fluorine-containing compounds having
a ratio of the weight average molecular weight (M.sub.w) to the
number average molecular weight (M.sub.n) (i.e. M.sub.w/M.sub.n) of
at least 1.1:
R.sup.f-Q.sup.1-O-(A.sup.1-O).sub.k-R.sup.1 (1)
[0033] wherein R.sup.f is a C.sub.1-22 polyfluoroaliphatic
hydrocarbon group which may contain ethereal oxygen atoms or
thioethereal sulfur atoms, Q.sup.1 is a C.sub.1-5 linear or
branched alkylene group, k is an integer of from 1 to 100, A.sup.1
is a C.sub.2-4 linear alkylene group or a group having at least one
hydrogen atom of said alkylene group substituted by a hydrocarbon
group which may contain ethereal oxygen atoms, provided that when k
is from 2 to 100, the plurality of A.sup.1 may be the same or
different, and R.sup.1 is a hydrogen atom, a C.sub.1-18 hydrocarbon
group or a C.sub.1-18 acyl group, concrete which contains the
cement admixture, a method for producing fluorine-containing
oxyalkylene compounds and a novel surface active agent.
[0034] The mixture having a ratio of the weight average molecular
weight (M.sub.w) to the number average molecular weight (M.sub.n)
(M.sub.w/M.sub.n) of at least 1.1 of the present invention, is a
mixture of fluorine-containing compounds represented by the formula
(1). Hereinafter "the fluorine-containing compound represented by
the formula (1)" is referred to as "fluorine-containing compound
(formula (1))", and "the mixture of the fluorine-containing
compounds (formula (1)) having a ratio of the weight average
molecular weight (M.sub.w) to the number average molecular weight
(M.sub.n) (M.sub.w/M.sub.n) of at least 1.1" is referred to as
"fluorine-containing compounds (mixture)".
[0035] "The hydrocarbon group" in the present specification
basically means a hydrocarbon group comprising only carbon atoms
and hydrogen atoms. Only when it is specified that ethereal oxygen
atoms may be contained or thioethereal sulfur atoms may be
contained, said hydrocarbon group may contain atoms besides carbons
atoms and hydrogen atoms.
[0036] "The hydrocarbon group" refers to both "aliphatic
hydrocarbon group" and "aromatic hydrocarbon group". As the
aliphatic hydrocarbon group, an alkyl group and an alkenyl group
are preferred. Further, at least one hydrogen atom of the aliphatic
hydrocarbon group may be substituted by an aromatic hydrocarbon
group. A benzyl group may, for example, be mentioned.
[0037] Further, as the aromatic hydrocarbon group, a phenyl group
is preferred.
[0038] R.sup.f in the compound represented by the formula (1) of
the present invention means a C.sub.1-22 polyfluoroaliphatic
hydrocarbon group which may contain ethereal oxygen atoms or
thioethereal sulfur atoms. "The polyfluoroaliphatic hydrocarbon
group which may contain ethereal oxygen atoms or thioethereal
sulfur atoms" is hereinafter referred to as "R.sup.f group". The
R.sup.f group means a group having at least two hydrogen atoms in
the aliphatic hydrocarbon group substituted by fluorine atoms.
[0039] Further, R.sup.f group in the formula (1) is preferably a
group having at least one fluorine atom bonded to the carbon atom
adjacent to Q.sup.1.
[0040] The number of carbons in R.sup.f group is from 1 to 22,
preferably from 4 to 16, particularly preferably from 6 to 14. The
higher the number of carbons in R.sup.f group, the lower surface
tension and the lower volatility, such being favorable. However,
too high number of carbons is unfavorable in view of cost.
[0041] R.sup.f group is preferably a polyfluoroalkyl group which
may contain ethereal oxygen atoms or thioethereal sulfur atoms.
Said polyfluoroalkyl group means a group having at least two
hydrogen atoms of an alkyl group which may contain ethereal oxygen
atoms or thioethereal sulfur atoms substituted by fluorine atoms.
"A polyfluoroalkyl group which may contain ethereal oxygen atoms or
thioethereal sulfur atoms" is hereinafter referred to as "R.sup.F
group".
[0042] Among such R.sup.F groups, a polyfluoroalkyl group which
does not contain ethereal oxygen atoms or thioethereal sulfur
atoms, is preferred.
[0043] The number of carbons in R.sup.F group is preferably from 4
to 16, particularly preferably from 6 to 14.
[0044] Further, in the case where the number of fluorine atoms in
R.sup.F group is represented by (number of fluorine atoms in
R.sup.F group)/(number of hydrogen atoms in an alkyl group
corresponding to R.sup.F group having the same number of
carbons).times.100 (%), it is preferably at least 60%, particularly
preferably at least 80%. R.sup.F group is preferably linear or
branched, and it is particularly preferably linear. In the case
where it is branched, it is preferred that the branched part is a
short chain having a number of carbons of from about 1 to about 3,
and exists at the terminal part of R.sup.F group. Further, in the
case where unsubstituted hydrogen atoms are contained in R.sup.F
group, said hydrogen atoms may be substituted by chlorine
atoms.
[0045] R.sup.f group is preferably a perfluoroalkyl group having
substantially all hydrogen atoms of the alkyl group which may
contain ethereal oxygen atoms or thioethereal sulfur atoms
substituted by fluorine atoms. Among such perfluoroalkyl groups, a
perfluoroalkyl group which does not contain ethereal oxygen atoms
or thioethereal sulfur atoms is preferred.
[0046] The perfluoroalkyl group is preferably linear. The number of
carbons of the perfluoroalkyl group is preferably from 1 to 18,
more preferably from 4 to 16, particularly preferably from 6 to 14.
Namely, the perfluoroalkyl group is preferably a linear group
represented by CF.sub.3(CF.sub.2).sub.m--, wherein m is an integer
of from 3 to 15.
[0047] As the specific example of the polyfluoroalkylene group,
following examples are mentioned. In the following examples, groups
corresponding to structural isomers of each group are included.
[0048] C.sub.4F.sub.9-- [structural isomers such as
CF.sub.3(CF.sub.2).sub.3--, (CF.sub.3).sub.2CFCF.sub.2--,
(CF.sub.3).sub.3C-- and CF.sub.3CF.sub.2CF(CF.sub.3)--],
C.sub.5F.sub.11-- [structural isomers such as
CF.sub.3(CF.sub.2).sub.4--, (CF.sub.3).sub.2CF(CF.sub.2).sub.2--,
(CF.sub.3).sub.3CCF.sub.2-- and
CF.sub.3(CF.sub.2).sub.2CF(CF.sub.3)--], C.sub.8F.sub.17--,
C.sub.10F.sub.21--, C.sub.12F.sub.25--, C.sub.14F.sub.29--,
C.sub.16F.sub.33--, C.sub.18F.sub.37--,
(CF.sub.3).sub.2CFC.sub.sF.sub.2s- --, wherein s is an integer of
from 1 to 22, and HC.sub.tF.sub.2t--, wherein t is an integer of
from 1 to 22.
[0049] Further, as the specific example of the polyfluoroalkyl
group which contains ethereal oxygen atoms or thioethereal sulfur
atoms, the following examples may be mentioned. Here, u means an
integer of from 1 to 6, v means an integer of from 1 to 6, w means
an integer of from 1 to 10, and m means an integer of from 1 to
6.
[0050] CF.sub.3(CF.sub.2).sub.4OCF(CF.sub.3)--,
F[CF(CF.sub.3)CF.sub.2O].s- ub.uCF(CF.sub.3)--,
F(CF.sub.2CF.sub.2CF.sub.2O).sub.vCF.sub.2CF.sub.2--,
F(CF.sub.2CF.sub.2O).sub.wCF.sub.2CF.sub.2-- and
F[CF(CF.sub.3)CF.sub.2O]- .sub.mCF(CF.sub.3)--.
[0051] CF.sub.3(CF.sub.2).sub.4SCF(CF.sub.3)--,
F[CF(CF.sub.3)CF.sub.2S].s- ub.uCF(CF.sub.3)--,
F(CF.sub.2CF.sub.2CF.sub.2S).sub.vCF.sub.2CF.sub.2--,
F(CF.sub.2CF.sub.2S).sub.wCF.sub.2CF.sub.2-- and
F[CF(CF.sub.3)CF.sub.2S]- .sub.mCF(CF.sub.3)--.
[0052] Further, the fluorine-containing compounds (mixture) of the
present invention may be a mixture of at least two compounds having
different numbers of carbons in R.sup.f group.
[0053] Q.sup.1 in the fluorine-containing compound (formula (1)) is
a C.sub.1-5 linear or branched alkylene group. Namely, the
fluorine-containing compound (formula (1)) is a compound having a
linear connecting group such as a methylene group (--CH.sub.2--), a
dimethylene group (--CH.sub.2CH.sub.2--), a trimethylene group
(--CH.sub.2CH.sub.2CH.sub.2--), a tetramethylene group
(--CH.sub.2CH.sub.2CH.sub.2CH.sub.2--) or a pentamethylene group
(--CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2--), inserted between
the above-mentioned R.sup.f group and the oxyalkylene group, or a
compound having a branched connecting group such as
--CH.sub.2CH(CH.sub.3 )-- (propylene group),
--CH.sub.2CH(CH.sub.3)CH.sub.2--, CH.sub.2CH.sub.2CH(CH.sub.3)--,
--CH.sub.2CH.sub.2CH(CH.sub.3)CH.sub.2-- or
--CH.sub.2CH.sub.2CH.sub.2CH(CH.sub.3)--, inserted
therebetween.
[0054] The connecting group is a connecting group which prevent
foaming and involving of air, and a connecting group which
contributes to imparting chemical stability to the compound, in the
case where the fluorine-containing compound is used as a cement
admixture.
[0055] Q.sup.1 in the fluorine-containing compound (formula (1)) is
preferably a C.sub.2-5 linear or branched alkylene group, more
preferably a C.sub.3-4 linear or branched alkylene group. A
compound having Q being a C.sub.3 linear or branched alkylene
group, is a compound which is excellent in chemical stability as
dispersed in water, and is excellent in heat resistance. A compound
having Q being a C.sub.4 linear or branched alkylene group, is a
compound which is excellent in chemical stability as dispersed in
water, which is excellent in chemical stability also as dispersed
in an alkaline aqueous solution, and which is excellent in heat
resistance, and it is thereby most excellent compound to be used
for a cement admixture.
[0056] k in the fluorine-containing compound (formula (1)) means an
integer of from 1 to 100. It is preferably from 1 to 50,
particularly preferably from 1 to 30. The fluorine-containing
compounds (mixture) of the present invention are mixtures having at
least two fluorine-containing compounds (formula (1)) having
different values of k. When the average of k in the
fluorine-containing compounds (mixture) is taken as k.sub.av,
k.sub.av is preferably within a range of from 3 to 50, more
preferably within a range of from 5 to 30, particularly preferably
within a range of from 5 to 15.
[0057] The fluorine-containing compounds (mixture) are required to
have a ratio of the weight average molecular weight (M.sub.w) and
the number average molecular weight (M.sub.n) (M.sub.w/M.sub.n)
being at least 1.1. Compounds having M.sub.w/M.sub.n of less than
1.1 do not have adequate effect to suppress foamability.
M.sub.w/M.sub.n is preferably at most 1.5, more preferably at most
1.3, most preferably at most 1.2.
[0058] As a factor to give the value of M.sub.w/M.sub.n being at
least 1.1 to the fluorine-containing compounds (mixture), it may be
mentioned that the molecular weight of each compound is different
with each other, since any of R.sup.f, Q.sup.1, A.sup.1, k and
R.sup.1 in the formula (1) is different. In the present invention,
preferred are fluorine-containing compounds (mixture) having
M.sub.w/M.sub.n of at least 1.1 due to difference in the value of
k, or the value of k and R.sup.f, among compounds.
[0059] Particularly fluorine-containing compounds (mixture) having
M.sub.w/M.sub.n of at last 1.1, due to broad distribution of the
values of k of each compound in the mixture, are preferred. When
the average value of k of said mixture is k.sub.av, it is preferred
that k of each compound in the mixture distributes to a wide range
of from 0 to about 3 k.sub.av. Although the mechanism is not clear,
it is considered that the broadness of the distribution has some
influences on suppression of foaming.
[0060] A.sup.1 in the fluorine-containing compound (formula (1)) is
a C.sub.2-4 linear alkylene group or a group having at least one
hydrogen atom of said alkylene group substituted by a hydrocarbon
group which may contain ethereal oxygen atoms.
[0061] As the C.sub.2-4 linear alkylene group, a dimethylene group,
a trimethylene group or a tetramethylene group may be
mentioned.
[0062] Further, A.sup.1 may be a group having at least one hydrogen
atom of the above-mentioned alkylene group substituted by a
hydrocarbon group which may contain ethereal oxygen atoms.
[0063] As the hydrocarbon group which may contain ethereal oxygen
atoms, a group such as an alkyl group, a phenyl group or a benzyl
group, or a group having ethereal oxygen atoms inserted between the
carbon-carbon linkage or at the terminals of such a group, may be
mentioned.
[0064] As specific examples of A.sup.1, the following examples may
be mentioned. Ph means a phenyl group.
[0065] --CH.sub.2CH(CH.sub.3)--(propylene group),
--CH.sub.2CH(CH.sub.2CH.- sub.3)--, --CH(CH.sub.3)CH(CH.sub.3)--,
--C(CH.sub.3).sub.2CH.sub.2--, --CH.sub.2CH.sub.2CH (CH.sub.3)--,
--CH.sub.2CH(CH.sub.3)CH.sub.2--,
--CH.sub.2CH[CH.sub.2OCH.sub.2CH(CH.sub.2CH.sub.3)(CH.sub.2).sub.3CH.sub.-
3]--, --CH.sub.2CH(CH.sub.2OPh)-- and --CH.sub.2CH(OPh)--.
[0066] Among these, A.sup.1 of the fluorine-containing compound
(formula (1)) is preferably --CH.sub.2CH.sub.2--,
--CH.sub.2CH(CH.sub.3)--, --CH.sub.2CH(CH.sub.2CH.sub.3)-- or
--CH.sub.2CH.sub.2CH.sub.2CH.sub.2--.
[0067] Further, in the case where k is an integer of from 2 to 100,
the plurality of A.sup.1 in the fluorine-containing compound
(formula (1)) may be the same or different. In the case where they
are different, the number of kinds of A.sup.1 is preferably 2 or 3,
particularly preferably 2. The number of kinds of A.sup.1 in the
fluorine-containing compound (formula (1)) is preferably 1 or 2,
and only one kind of ethylene groups or two kinds of ethylene
groups and propylene groups, are particularly preferred.
[0068] The fluorine-containing compounds (mixture) of the present
invention are preferably one having characteristic such that they
can be dissolved or dispersed in water. Accordingly, it is
preferred that an oxyethylene group which is a hydrophilic group is
essential as the oxyalkylene group. Namely, it is preferred that
the fluorine-containing compounds (mixture) contains the
fluorine-containing compound (formula (1)) containing an
oxyethylene group as (A.sup.1-O) in the fluorine-containing
compound (formula (1)).
[0069] In such a case, preferably at least 20%, particularly
preferably at least 50%, more preferably at least 70%, by number,
of the total oxyalkylene groups in the fluorine-containing
compounds (mixture) are oxyethylene groups.
[0070] R.sup.1 in the fluorine-containing compound (formula (1))
means a hydrogen atom, a C.sub.1-18 hydrocarbon group or a
C.sub.1-18 acyl group.
[0071] In the case where R.sup.1 is a C.sub.1-18 hydrocarbon group,
a C.sub.1-5 hydrocarbon group is preferred, and a C.sub.1-5 alkyl
group is more preferred. CH.sub.3--, C.sub.2H.sub.5--, linear or
branched C.sub.3H.sub.7--, linear or branched C.sub.4H.sub.9 --, or
linear or branched C.sub.5H.sub.11--, may be mentioned.
[0072] In the case where R.sup.1 is a C.sub.1-18 acyl group, as
said acyl group, a C.sub.1-10 acyl group is preferred, and a
C.sub.1-6 acyl group is particularly preferred. When R.sub.1 is an
acyl group, the fluorine-containing compound (formula (1)) has a
structure containing an ester linkage at the terminal of the
molecule, whereby the foamability is suppressed.
[0073] Further, when said acyl group is represented by
R.sup.10CO--, the R.sup.10 part is preferably a C.sub.1-17 alkyl
group or alkenyl group.
[0074] As specific examples of the acyl group (R.sup.10CO--), a
group such as CH.sub.3CO--, CH.sub.3CH.sub.2CO--,
CH.sub.3(CH.sub.2).sub.2CO--,
CH.sub.3(CH.sub.2).sub.3CH(CH.sub.2CH.sub.3)CO--,
CH.sub.3(CH.sub.2).sub.- 7CH.dbd.CH(CH.sub.2).sub.7CO-- or
CH.sub.3(CH.sub.2).sub.16CO--, may, for example, be mentioned.
[0075] Among these, a hydrogen atom or a methyl group is preferred
as R.sup.1, and hydrogen atom is particularly preferred.
[0076] As the fluorine-containing compound (formula (1)) of the
present invention, a compound represented by the formula (1A) or
the following formula (1B) is preferred. Here, the linkage of
oxyethylene groups and oxypropylene groups in the formula (1B) may
be block or random. In the case of the block chain, it is preferred
that the polyoxypropylene group links to
R.sup.f(CH.sub.2).sub.3O--, and the polyoxyethylene group links to
said polyoxypropylene group.
[0077] Here, R.sup.f and R.sup.1 in the formulae (1A) and (1B) are
as defined for the formula (1), and the preferred modes are also as
defined for the formula (1).
[0078] In the formula (1A), a is an integer of from 1 to 100,
preferably from 1 to 50, particularly preferably from 3 to 30.
[0079] In the formula (1B), b is an integer of from 1 to 100, c is
an integer of from 0 to 100, and 1.ltoreq.b+c.ltoreq.100. Further,
b is preferably an integer of from 1 to 30, c is preferably an
integer of from 0 to 20, and preferably 1.ltoreq.b+c.ltoreq.30.
Further, preferably 0.2.ltoreq.b/(b+c).ltoreq.1, more preferably
0.5.ltoreq.b/(b+c).ltoreq.1, and particularly preferably
0.7.ltoreq.b/(b+c).ltoreq.1:
R.sup.f(CH.sub.2).sub.3O(CH.sub.2CH.sub.2O).sub.aR.sup.1 (1A)
R.sup.f(CH.sub.2).sub.3O--[CH(CH.sub.3)CH.sub.2O].sub.c(CH.sub.2CH.sub.2O)-
.sub.bR.sup.1 (1B)
[0080] Specific examples of the fluorine-containing compound
(formula (1)) include the following compounds. However, it is not
restricted thereto. In the following formulae, the moiety
corresponding to the perfluoroalkyl group may be linear or
branched, and it is preferably linear. When at least two
oxyalkylene moieties exist, the linkage may be block or random. The
(C.sub.3H.sub.6O) moiety means an oxypropylene group, and is
[CH(CH.sub.3)CH.sub.2O] or [CH.sub.2CH(CH.sub.3)O]:
[0081]
C.sub.6F.sub.13(CH.sub.2).sub.3O(CH.sub.2CH.sub.2O).sub.5H,
[0082]
C.sub.6F.sub.13(CH.sub.2).sub.3O(CH.sub.2CH.sub.2O).sub.8H,
[0083]
C.sub.7F.sub.15(CH.sub.2).sub.3O(CH.sub.2CH.sub.2O).sub.5H,
[0084]
C.sub.8F.sub.17(CH.sub.2).sub.3O(CH.sub.2CH.sub.2O).sub.5H,
[0085]
C.sub.8F.sub.17(CH.sub.2).sub.3O(CH.sub.2CH.sub.2O).sub.10H,
[0086]
C.sub.6F.sub.13(CH.sub.2).sub.3O(C.sub.3H.sub.6O).sub.5(CH.sub.2CH.-
sub.2O).sub.10H,
[0087]
C.sub.7F.sub.15(CH.sub.2).sub.3O(C.sub.3H.sub.6O).sub.5(CH.sub.2CH.-
sub.2O).sub.10H,
[0088]
C.sub.8F.sub.17(CH.sub.2).sub.3O(C.sub.3H.sub.6O).sub.5(CH.sub.2CH.-
sub.2O).sub.10H,
[0089]
C.sub.6F.sub.13(CH.sub.2).sub.3O(C.sub.3H.sub.6O).sub.4(CH.sub.2CH.-
sub.2O).sub.15H,
[0090]
C.sub.7F.sub.15(CH.sub.2).sub.3O(C.sub.3H.sub.6O).sub.4(CH.sub.2CH.-
sub.2O).sub.15H,
[0091]
C.sub.8F.sub.17(CH.sub.2).sub.3O(C.sub.3H.sub.6O).sub.4(CH.sub.2CH.-
sub.2O).sub.15H,
[0092]
C.sub.6F.sub.13(CH.sub.2).sub.3O(CH.sub.2CH.sub.2CH.sub.2CH.sub.2O)-
.sub.5H,
[0093]
C.sub.6F.sub.13(CH.sub.2).sub.3O(CH.sub.2CH.sub.2CH.sub.2CH.sub.2O)-
.sub.8H,
[0094]
C.sub.7F.sub.15(CH.sub.2).sub.3O(CH.sub.2CH.sub.2CH.sub.2CH.sub.2O)-
.sub.5H,
[0095]
C.sub.8F.sub.17(CH.sub.2).sub.3O(CH.sub.2CH.sub.2CH.sub.2CH.sub.2O)-
.sub.5H,
[0096]
C.sub.8F.sub.17(CH.sub.2).sub.3O(CH.sub.2CH.sub.2CH.sub.2CH.sub.2O)-
.sub.10H,
[0097]
C.sub.8F.sub.17(CH.sub.2).sub.3O(CH.sub.2CH.sub.2CH.sub.2CH.sub.2O)-
.sub.20H,
[0098]
C.sub.6F.sub.13(CH.sub.2).sub.3O(CH.sub.2CH.sub.2O).sub.5CH.sub.3,
[0099]
C.sub.6F.sub.13(CH.sub.2).sub.3O(CH.sub.2CH.sub.2O).sub.8C.sub.2H.s-
ub.5,
[0100]
C.sub.7F.sub.15(CH.sub.2).sub.3O(CH.sub.2CH.sub.2O).sub.5COCH.sub.3-
,
[0101]
C.sub.8F.sub.17(CH.sub.2).sub.3O(CH.sub.2CH.sub.2O).sub.5COCH.sub.3-
,
[0102]
C.sub.8F.sub.17(CH.sub.2).sub.3O(CH.sub.2CH.sub.2O).sub.10COCH.sub.-
3,
[0103]
C.sub.6F.sub.13(CH.sub.2).sub.4O(CH.sub.2CH.sub.2O).sub.5H,
[0104]
C.sub.6F.sub.13(CH.sub.2).sub.4O(CH.sub.2CH.sub.2O).sub.8H,
[0105]
C.sub.7F.sub.15(CH.sub.2).sub.4O(CH.sub.2CH.sub.2O).sub.5H,
[0106]
C.sub.8F.sub.17(CH.sub.2).sub.4O(CH.sub.2CH.sub.2O).sub.5H,
[0107]
C.sub.8F.sub.17(CH.sub.2).sub.4O(CH.sub.2CH.sub.2O).sub.10H,
[0108]
C.sub.6F.sub.13(CH.sub.2).sub.4O(C.sub.3H.sub.6O).sub.5(CH.sub.2CH.-
sub.2O).sub.10H,
[0109]
C.sub.7F.sub.15(CH.sub.2).sub.4O(C.sub.3H.sub.6O).sub.5(CH.sub.2CH.-
sub.2O).sub.10H,
[0110]
C.sub.8F.sub.17(CH.sub.2).sub.4O(C.sub.3H.sub.6O).sub.5(CH.sub.2CH.-
sub.2O).sub.10H,
[0111]
C.sub.6F.sub.13(CH.sub.2).sub.4O(C.sub.3H.sub.6O).sub.4(CH.sub.2CH.-
sub.2O).sub.15H,
[0112]
C.sub.7F.sub.15(CH.sub.2).sub.4O(C.sub.3H.sub.6O).sub.4(CH.sub.2CH.-
sub.2O).sub.15H,
[0113]
C.sub.8F.sub.17(CH.sub.2).sub.4O(C.sub.3H.sub.6O).sub.4(CH.sub.2CH.-
sub.2O).sub.15H,
[0114]
C.sub.6F.sub.13(CH.sub.2).sub.4O(CH.sub.2CH.sub.2CH.sub.2CH.sub.2O)-
.sub.5H,
[0115]
C.sub.6F.sub.13(CH.sub.2).sub.4O(CH.sub.2CH.sub.2CH.sub.2CH.sub.2O)-
.sub.8H,
[0116]
C.sub.7F.sub.15(CH.sub.2).sub.4O(CH.sub.2CH.sub.2CH.sub.2CH.sub.2O)-
.sub.5H,
[0117]
C.sub.8F.sub.17(CH.sub.2).sub.4O(CH.sub.2CH.sub.2CH.sub.2CH.sub.2O)-
.sub.5H,
[0118]
C.sub.8F.sub.17(CH.sub.2).sub.4O(CH.sub.2CH.sub.2CH.sub.2CH.sub.2O)-
.sub.10H,
[0119]
C.sub.8F.sub.17(CH.sub.2).sub.4O(CH.sub.2CH.sub.2CH.sub.2CH.sub.2O)-
.sub.20H,
[0120]
C.sub.6F.sub.13(CH.sub.2).sub.4O(CH.sub.2CH.sub.2O).sub.5CH.sub.3,
[0121]
C.sub.6F.sub.13(CH.sub.2).sub.4O(CH.sub.2CH.sub.2O).sub.8C.sub.2H.s-
ub.5,
[0122]
C.sub.7F.sub.15(CH.sub.2).sub.4O(CH.sub.2CH.sub.2O).sub.5COCH.sub.3-
,
[0123]
C.sub.8F.sub.17(CH.sub.2).sub.4O(CH.sub.2CH.sub.2O).sub.5COCH.sub.3-
,
[0124]
C.sub.8F.sub.17(CH.sub.2).sub.4O(CH.sub.2CH.sub.2O).sub.10COCH.sub.-
3,
[0125]
C.sub.6F.sub.13(CH.sub.2).sub.5O(CH.sub.2CH.sub.2O).sub.5H,
[0126]
C.sub.6F.sub.13(CH.sub.2).sub.5O(CH.sub.2CH.sub.2O).sub.8H,
[0127]
C.sub.7F.sub.15(CH.sub.2).sub.5O(CH.sub.2CH.sub.2O).sub.5H,
[0128]
C.sub.8F.sub.17(CH.sub.2).sub.5O(CH.sub.2CH.sub.2O).sub.5H,
[0129]
C.sub.8F.sub.17(CH.sub.2).sub.5O(CH.sub.2CH.sub.2O).sub.10H,
[0130]
C.sub.6F.sub.13(CH.sub.2).sub.5O(C.sub.3H.sub.6O).sub.5(CH.sub.2CH.-
sub.2O).sub.10H,
[0131]
C.sub.7F.sub.15(CH.sub.2).sub.5O(C.sub.3H.sub.6O).sub.5(CH.sub.2CH.-
sub.2O).sub.10H,
[0132]
C.sub.8F.sub.17(CH.sub.2).sub.5O(C.sub.3H.sub.6O).sub.5(CH.sub.2CH.-
sub.2O).sub.10H,
[0133]
C.sub.6F.sub.13(CH.sub.2).sub.5O(C.sub.3H.sub.6O).sub.4(CH.sub.2CH.-
sub.2O).sub.15H,
[0134]
C.sub.7F.sub.15(CH.sub.2).sub.5O(C.sub.3H.sub.6O).sub.4(CH.sub.2CH.-
sub.2O).sub.15H,
[0135]
C.sub.8F.sub.17(CH.sub.2).sub.5O(C.sub.3H.sub.6O).sub.4(CH.sub.2CH.-
sub.2O).sub.15H,
[0136]
C.sub.6F.sub.13(CH.sub.2).sub.5O(CH.sub.2CH.sub.2CH.sub.2CH.sub.2O)-
.sub.5H,
[0137]
C.sub.6F.sub.13(CH.sub.2).sub.5O(CH.sub.2CH.sub.2CH.sub.2CH.sub.2O)-
.sub.8H,
[0138]
C.sub.7F.sub.15(CH.sub.2).sub.5O(CH.sub.2CH.sub.2CH.sub.2CH.sub.2O)-
.sub.5H,
[0139]
C.sub.8F.sub.17(CH.sub.2).sub.5O(CH.sub.2CH.sub.2CH.sub.2CH.sub.2O)-
.sub.5H,
[0140]
C.sub.8F.sub.17(CH.sub.2).sub.5O(CH.sub.2CH.sub.2CH.sub.2CH.sub.2O)-
.sub.10H,
[0141]
C.sub.8F.sub.17(CH.sub.2).sub.5O(CH.sub.2CH.sub.2CH.sub.2CH.sub.2O)-
.sub.20H,
[0142]
C.sub.6F.sub.13(CH.sub.2).sub.5O(CH.sub.2CH.sub.2O).sub.5CH.sub.3,
[0143]
C.sub.6F.sub.13(CH.sub.2).sub.5O(CH.sub.2CH.sub.2O).sub.8C.sub.2H.s-
ub.5,
[0144]
C.sub.7F.sub.15(CH.sub.2).sub.5O(CH.sub.2CH.sub.2O).sub.5COCH.sub.3-
,
[0145]
C.sub.8F.sub.17(CH.sub.2).sub.5O(CH.sub.2CH.sub.2O).sub.5COCH.sub.3-
,
[0146]
C.sub.8F.sub.17(CH.sub.2).sub.5O(CH.sub.2CH.sub.2O).sub.10COCH.sub.-
3,
[0147]
C.sub.6F.sub.13(CH.sub.2).sub.2CH(CH.sub.3)O(CH.sub.2CH.sub.2O).sub-
.5H,
[0148]
C.sub.6F.sub.13(CH.sub.2).sub.2CH(CH.sub.3)O(CH.sub.2CH.sub.2O).sub-
.8H,
[0149]
C.sub.7F.sub.15(CH.sub.2).sub.2CH(CH.sub.3)O(CH.sub.2CH.sub.2O).sub-
.5H,
[0150]
C.sub.8F.sub.17(CH.sub.2).sub.2CH(CH.sub.3)O(CH.sub.2CH.sub.2O).sub-
.5H,
[0151]
C.sub.8F.sub.17(CH.sub.2).sub.2CH(CH.sub.3)O(CH.sub.2CH.sub.2O).sub-
.10H,
[0152]
C.sub.6F.sub.13(CH.sub.2).sub.2CH(CH.sub.3)O(C.sub.3H.sub.6O).sub.5-
(CH.sub.2CH.sub.2O).sub.10H,
[0153]
C.sub.7F.sub.15(CH.sub.2).sub.2CH(CH.sub.3)O(C.sub.3H.sub.6O).sub.5-
(CH.sub.2CH.sub.2O).sub.10H,
[0154]
C.sub.8F.sub.17(CH.sub.2).sub.2CH(CH.sub.3)O(C.sub.3H.sub.6O).sub.5-
(CH.sub.2CH.sub.2O).sub.10H,
[0155]
C.sub.6F.sub.13(CH.sub.2).sub.2CH(CH.sub.3)O(C.sub.3H.sub.6O).sub.4-
(CH.sub.2CH.sub.2O).sub.15H,
[0156]
C.sub.7F.sub.15(CH.sub.2).sub.2CH(CH.sub.3)O(C.sub.3H.sub.6O).sub.4-
(CH.sub.2CH.sub.2O).sub.15H,
[0157]
C.sub.8F.sub.17(CH.sub.2).sub.2CH(CH.sub.3)O(C.sub.3H.sub.6O).sub.4-
(CH.sub.2CH.sub.2O).sub.15H,
[0158]
C.sub.6F.sub.13(CH.sub.2).sub.2CH(CH.sub.3)O(CH.sub.2CH.sub.2CH.sub-
.2CH.sub.2O).sub.5H,
[0159]
C.sub.6F.sub.13(CH.sub.2).sub.2CH(CH.sub.3)O(CH.sub.2CH.sub.2CH.sub-
.2CH.sub.2O).sub.8H,
[0160]
C.sub.7F.sub.15(CH.sub.2).sub.2CH(CH.sub.3)O(CH.sub.2CH.sub.2CH.sub-
.2CH.sub.2O).sub.5H,
[0161]
C.sub.8F.sub.17(CH.sub.2).sub.2CH(CH.sub.3)O(CH.sub.2CH.sub.2CH.sub-
.2CH.sub.2O).sub.5H,
[0162]
C.sub.8F.sub.17(CH.sub.2).sub.2CH(CH.sub.3)O(CH.sub.2CH.sub.2CH.sub-
.2CH.sub.2O).sub.10H,
[0163]
C.sub.8F.sub.17(CH.sub.2).sub.2CH(CH.sub.3)O(CH.sub.2CH.sub.2CH.sub-
.2CH.sub.2O).sub.20H ,
[0164]
C.sub.6F.sub.13(CH.sub.2).sub.2CH(CH.sub.3)O(CH.sub.2CH.sub.2O).sub-
.5CH.sub.3,
[0165]
C.sub.6F.sub.13(CH.sub.2).sub.2CH(CH.sub.3)O(CH.sub.2CH.sub.2O).sub-
.8C.sub.2H.sub.5,
[0166]
C.sub.7F.sub.15(CH.sub.2).sub.2CH(CH.sub.3)O(CH.sub.2CH.sub.2O).sub-
.5COCH.sub.3,
[0167]
C.sub.8F.sub.17(CH.sub.2).sub.2CH(CH.sub.3)O(CH.sub.2CH.sub.2O).sub-
.5COCH.sub.3 and
[0168]
C.sub.8F.sub.17(CH.sub.2).sub.2CH(CH.sub.3)O(CH.sub.2CH.sub.2O).sub-
.10COCH.sub.3.
[0169] Some of the fluorine-containing compounds (formula (1)) of
the present invention may be produced by the above-mentioned known
methods. However, the known production methods have drawbacks as
mentioned above. Accordingly, for effective production, it is
preferred to synthesize the fluorine-containing compound (formula
(1)) by the following method.
[0170] The method mentioned hereinafter is a method suitably
applied to the fluorine-containing compound (formula (1)) wherein
Q.sup.1 is a C.sub.3-5 linear or branched alkylene group. In view
of easiness to obtain materials, the method is particularly
preferred for compounds of C.sub.3-4 linear or branched alkylene
group. Further, it is a particularly preferred method as a method
for producing the fluorine-containing compounds for the cement
admixture of the present invention.
[0171] The present invention also provides the following method for
producing fluorine-containing compounds.
[0172] Namely, it is a method to obtain fluorine-containing
oxyalkylene compounds represented by the formula (4), which
comprises ring opening polymerization of at least one cyclic ether
represented by the formula (3) in the presence of an acid catalyst
and a fluorine-containing hydroxyl compound represented by the
formula (2):
R.sup.f-Q.sup.2-OH (2)
[0173] 1
R.sup.f-Q.sup.2-O-(A.sup.2-O).sub.k--H (4)
[0174] wherein R.sup.f is a C.sub.1-22 polyfluoroaliphatic
hydrocarbon group which may contain ethereal oxygen atoms or
thioethereal sulfur atoms, Q.sup.2 is a C.sub.3-5 linear or
branched alkylene group, k is an integer of from 1 to 100, and
A.sup.2 is a C.sub.2-4 linear alkylene group or a group having at
least one hydrogen atom of said alkylene group substituted by a
hydrocarbon group which may contain ethereal oxygen atoms.
[0175] Further, the fluorine-containing oxyalkylene compound
(formula (4)) can be induced to the formula (5), as the case
requires, by converting the terminal hydroxyl group to a R.sup.3O--
group, wherein R.sup.3 is a C.sub.1-18 hydrocarbon group or a
C.sub.1-18 acyl group:
R.sup.f-Q.sup.2-O-(A.sup.2-O).sub.k-R.sup.3 (5)
[0176] wherein R.sup.f, Q.sup.2 and k are as defined for the
formula (4), and R.sup.3 is as defined above.
[0177] The compound represented by the formula (4) corresponds to a
compound of the formula (1) wherein R.sup.1 is a hydrogen atom, and
Q.sup.1 is a C.sub.3-5 linear or branched alkylene group. The
compound represented by the formula (5) corresponds to a compound
of the formula (1) wherein R.sup.1 is a C.sub.1-18 hydrocarbon
group or a C.sub.1-18 acyl group, and Q.sup.1 is a C.sub.3-5 linear
or branched alkylene group.
[0178] The fluorine-containing hydroxyl compound (formula (2)) is a
known compound, and can be produced by known methods. It can be
synthesized, for example, by adding allylalcohol to a
perfluoroalkyl iodide, followed by substitution of the iodide atoms
by hydrogen atoms by a reducing agent.
[0179] Further, the cyclic ether (formula (3)) which undergoes the
ring opening polymerization in the presence of the
fluorine-containing hydroxyl compound (formula (2)) has, as the
A.sup.2 part, a C.sub.2-4 linear alkylene group or a group having
at least one hydrogen atom of said alkylene group substituted by a
hydrocarbon group which may contain ethereal oxygen atoms.
Preferred modes of A.sup.2 are as defined for A.sup.1 in the
formula (1).
[0180] The cyclic ether (formula (3)) may, for example, be ethylene
oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide,
isobutylene oxide, oxetane, methyloxetane, phenyl glycidyl ether,
tetrahydrofuran, styrene oxide or an alkyl glycidyl ether. The
alkyl glycidyl ether may, for example, be methyl glycidyl ether,
butyl glycidyl ether or 2-ethylhexyl glycidyl ether.
[0181] Among these, as the cyclic ether (formula (3)), ethylene
oxide, propylene oxide, 1,2-butylene oxide and tetrahydrofuran are
preferred.
[0182] At least one kind of the cyclic ether (formula (3)) may be
used, and it is preferred to use one or two kinds of them.
[0183] In the case where at least two kinds of the cyclic ethers
(formula (3)) undergo the ring opening polymerization, they may be
mixed to conduct the reaction, or they may be successively reacted.
Further, in either case of using one kind of the cyclic ether
(formula (3)), or in the case of using at least two kinds of them,
they may be charged at a stretch, or may be gradually added to the
reaction system.
[0184] The amount of the cyclic ether (formula (3)) to the
fluorine-containing hydroxyl compound (formula (2)) may be suitably
changed depending upon the value of the k of the desired compound
(in the case where a mixture is obtained, average k, i.e.
k.sub.av). Usually, it is preferred to use it from 1 to 1.5 molar
times the theoretical amount for the reaction.
[0185] The ring opening polymerization of the cyclic ether (formula
(3)) in the presence of the fluorine-containing hydroxyl compound
(formula (2)), is conducted in the presence of an acid
catalyst.
[0186] As the acid catalyst, boron trifluoride, an ether complex of
boron trifluoride, aluminum chloride, antimony pentachloride,
ferric chloride or a condensed inorganic acid is preferred, and an
ether complex of boron trifluoride is particularly preferred. As
the condensed inorganic acid, a heteropoly-acid constituted by at
least two metallic elements is preferred, and e.g. phosphomolybdic
acid, phosphowolframate, silicomolybdic acid or silicotungstic acid
is preferred.
[0187] The amount of the acid catalyst is preferably from 0.01 to 5
parts by weight, particularly preferably from 0.1 to 3 parts by
weight, based on 100 parts by weight of the theoretical amount of
the fluorine-containing oxyalkylene compound (formula (4))
produced.
[0188] The method of the present invention has an advantage that
the reaction proceeds with a particularly high yield, when
producing a compound of the formula (1) wherein Q.sup.1 is a
C.sub.3-5 linear or branched alkylene group. Namely, with regard to
a compound having a linear or branched alkylene group of a carbon
number of at least 3 inserted between the R.sup.f group and the
hydroxyl group, such as the compound of the formula (2), since the
electric absorptivity derived from the R.sup.f group can be made
adequately low, the reactivity of the terminal hydroxyl group will
be high under the acid catalyst conditions, whereby side reactions
such as production of an olefin due to separation of hydrogen are
less likely to take place, such being advantageous.
[0189] Further, as the catalyst can be removed only by conducting a
usual purification treatment after the reaction, it is not
necessary to worry about bad influences derived from the catalyst,
such being advantageous. Further, the kind of the alkylene oxide
unit can be freely changed, the method of the present invention is
thereby an excellent method to be used widely.
[0190] Usually, a compound obtainable by a method wherein a cyclic
ether undergoes ring opening polymerization, is in many cases a
mixture of compounds having different molecular weights. By the
above-mentioned method of the present invention,
fluorine-containing alkylene compounds represented by the formula
(4) can be obtained, as a mixture of compounds having different
molecular weights.
[0191] Namely, the present invention resides in a method for
producing a mixture of the fluorine-containing oxyalkylene
compounds represented by the formula (4), which comprises ring
opening polymerization of at least one cyclic ether represented by
the formula (3) in the presence of an acid catalyst and the
fluorine-containing hydroxyl compound represented by the formula
(2), said mixture having a ratio of the weight average molecular
weight (M.sub.w) to the number average molecular weight (M.sub.n)
(i.e. M.sub.w/M.sub.n) of at least 1.1.
[0192] By the method of the present invention, particularly a
mixture of fluorine-containing alkylene compounds (formula (4))
having M.sub.w/M.sub.n of at least 1.1 can be easily obtained. When
a single compound is selected as the fluorine-containing hydroxyl
compound (formula (2)), a mixture of the fluorine-containing
alkylene compounds (formula (4)) having M.sub.w/M.sub.n of at least
1.1 can be obtained by the method. Accordingly, it is evident that
the mixture of the fluorine-containing alkylene compounds (formula
(4)) having different values of k, can be produced by the
method.
[0193] To obtain a mixture of the fluorine-containing alkylene
compounds (formula (4)) having M.sub.w/M.sub.n of at least 1.1 by
the method, it is preferred to conduct the reaction by using a
three-membered cyclic ether (formula (3)) wherein A.sup.2 is a
C.sub.2 linear alkylene group or a group having at least one
hydrogen atom of said alkylene group substituted by a hydrocarbon
group which may contain ethereal oxygen atoms, as the essential
component.
[0194] Further, in such a case, the distribution of the values of k
of each compound in the mixture is considered to be broad. When the
average value of k in the mixture is taken as k.sub.av, values of k
of each compound distribute in a range of from 0 to 3 k.sub.av.
[0195] Further, it is particularly preferred to conduct the
above-mentioned ring opening polymerization in the presence of a
solvent, as a side reaction of separation of hydrogen atoms in the
--CH.sub.2-- group bonded to the terminal of the R.sup.f group, is
prevented.
[0196] As the solvent, an ether solvent having no active hydrogen
is preferred, and glyme (ethylene glycol dimethyl ether), diglyme
(diethylene glycol dimethyl ether), triglyme (triethylene glycol
dimethyl ether) or methyl tert-butyl ether is particularly
preferred. The solvent may be used alone or as a mixture of at
least two of them.
[0197] In the reaction wherein the cyclic ether (formula (3))
undergoes the ring opening polymerization in the presence of the
fluorine-containing hydroxyl compound (formula (2)), the reaction
temperature is preferably from -20.degree. C. to +180.degree. C.,
particularly preferably from 0.degree. C. to +130.degree. C.
However, in the case where a solvent having a low boiling point is
present in the reaction system, it is preferred to conduct reaction
at a temperature lower than (the boiling point of the solvent
+20).degree. C., considering the increase in the internal
pressure.
[0198] The amount of the fluorine-containing hydroxyl compound
(formula (2)) charged into a reactor may be suitably changed
depending upon the amount of the cyclic ether (formula (3)). In the
case where effective stirring is attempted, it is preferred to
charge it in an amount of at least one-tenth of the capacity of the
reactor. Considering the volumetric efficiency, the amount of the
product after the ring opening polymerization of the cyclic ether
(formula (3)) is preferably from 80 to 95% in volume fraction.
[0199] In the reaction wherein the fluorine-containing hydroxyl
compound (formula (3)) undergoes the ring opening polymerization in
the presence of the cyclic ether (formula (2)), the
fluorine-containing oxyalkylene compounds (formula (4)) are
produced.
[0200] The fluorine-containing oxyalkylene compounds (formula (4))
can be induced to a compounds represented by the formula (5), by
converting the terminal hydroxyl group to a R.sup.3O-- group,
wherein R.sup.3 is as defined above, as the case requires.
[0201] By converting the terminal hydroxyl group of the
fluorine-containing oxyalkylene compounds (formula (4)) to an
alkoxy group or an acyloxy group, various properties can be
controlled.
[0202] As a method to convert the terminal hydroxyl group of the
fluorine-containing oxyalkylene compound (formula (4)) to the
--OR.sup.3 group, wherein R.sup.3 is a C.sub.1-18 hydrocarbon
group, a known method for alkoxylation can be employed. It may, for
example, be a method to react the fluorine-containing oxyalkylene
compounds (formula(4)) with a C.sub.1-18 hydrocarbon monohalide
under strong alkali condition, a method to react the
fluorine-containing hydroxyalkylene compounds (formula(4)) with a
C.sub.1-18 alkyl sulfuric acid, or a method to convert the hydroxyl
group of the fluorine-containing hydroxyalkylene compounds
(formula(4)) to a tosyloxy group, which then undergoes C.sub.1-18
alkoxylation.
[0203] Among these, the method to react the fluorine-containing
hydroxyalkylene compounds (formula(4)) with an alkyl sulfuric acid,
or the method to conduct alkoxylation of the tosyloxy group, is
preferred, to suppress the reaction of fluorine-separation from the
fluorine-containing oxyalkylene compound (formula (4)).
[0204] The method for converting the terminal hydroxyl group of the
fluorine-containing oxyalkylene compounds (formula(4)) to
C.sub.1-18 acyloxy group (hereinafter referred to as
esterification), may be a method to react the fluorine-containing
oxyalkylene compounds (formula(4)) with a monocarboxylic acid, or
with an ester of monocarboxylic acid and an alcohol having a low
boiling point (hereinafter such compounds are referred to as
esterification agents).
[0205] The monocarboxylic acid may, for example, be acetic acid,
propionic acid, butanoic acid, 2-ethyl hexanoic acid, n-octanoic
acid, 3,5,5-trimethyl hexanoic acid (isononanoic acid), oleic acid
or stearic acid.
[0206] As the ester of the above-mentioned monocarboxylic acid and
an alcohol having a low boiling point, e.g. methyl acetate, ethyl
acetate, butyl acetate, isopropyl acetate and methyl propionate are
preferred.
[0207] The esterification can be conducted in such a manner that an
esterification agent is added to the fluorine-containing
hydroxyalkylene compounds (formula(4)), the mixture is heated and
stirred for the reaction, and dehydration or dealcohol is
conducted, or unreacted acids are distilled off.
[0208] The esterification can be conducted with or without a
catalyst. In the case where a catalyst is present, preferred is a
method wherein a trace amount of an acid catalyst such as p-toluene
sulfonic acid or sulfuric acid is present, or a method wherein an
alkali catalyst such as potassium hydroxide or sodium hydroxide is
present.
[0209] A crude product obtained by the reaction to convert the
terminal hydroxyl group of the fluorine-containing oxyalkylene
compounds (formula (4)), is preferably purified by e.g. an acid
treatment using sulfuric acid, phosphoric acid or the like, or an
adsorption treatment using a synthetic magnesium, activated clay,
activated carbon or the like, as the case requires.
[0210] In the present invention, the above-mentioned
fluorine-containing compounds (mixture) are also used as a cement
admixture. By incorporating said cement admixture in concrete,
excellent fluidity can be imparted to concrete. This is considered
to be attributable to the fact that the fluorine-containing
compounds (mixture) have a chemical or physical action on cement
particles in concrete, whereby secondary agglomeration of cement
particles is prevented.
[0211] On the other hand, the fluorine-containing compounds
(mixture) have a low foamability, and have an effect to easily
eliminate foams once formed. Accordingly, concrete is less likely
to involve air during mixing, whereby the strength of the hardened
product of concrete will not be lowered, such being
advantageous.
[0212] As the concrete, cement mortar obtained by blending sand
into various cements, followed by kneading with water, or fresh
concrete obtained by blending e.g. sand, shingle or water in a
suitable ratio in said various cements, may be mentioned. As said
cement, plain Portland cement, high-early-strength Portland cement,
low heat Portland cement or Portland blast furnace cement may, for
example, be mentioned.
[0213] As the time to incorporate the fluorine-containing compounds
(mixture) in concrete, just like a conventional cement admixture,
it may be added to cement when water, or various aggregates such as
sand or shingle, as the case requires, are added to cement followed
by mixing; the fluorine-containing compounds may be preliminarily
dispersed or dissolved in water; or it may be added together with a
surface active agent such as an air-entraining agent or a water
reducing agent, or a dispersing agent.
[0214] The amount of the fluorine-containing compounds (mixture)
may be less than 10 parts by weight based on 100 parts by weight of
total concrete, and it may be from 300 to 1000 ppm.
[0215] The fluorine-containing compounds of the present invention
have an advantage that excellent effects can be obtained with a
significantly small amount of them, as compared with the amount of
conventional cement admixture added (from 1 to 3 wt %).
[0216] The fluorine-containing compounds (mixture) of the present
invention have effects that when they are dispersed in water, even
when the dispersant is shook strongly, the foamability is low, and
the foams once formed disappear quickly. Accordingly, they may be
used for a use of e.g. an aqueous cleaner for which chlorinated
fluorinated hydrocarbons are conventionally used, which requires a
low foamability, or for a resin additive for the purpose of
improving the resin, in addition for a use as a cement
admixture.
[0217] The present invention further provides a novel surface
active agent, i.e. a surface active agent which comprises
fluorine-containing compounds represented by the formula (6):
R.sup.f--CH.sub.2CH.sub.2CH(CH.sub.3)--O--(A.sup.1-O).sub.k-R.sup.1
(6)
[0218] wherein R.sup.f is a C.sub.1-22 polyfluoroaliphatic
hydrocarbon group which may contain ethereal oxygen atoms or
thioethereal sulfur atoms, k is an integer of from 1 to 100,
A.sup.1 is a C.sub.2-4 linear alkylene group or a group having at
least one hydrogen atom of said alkylene group substituted by a
hydrocarbon group which may contain ethereal oxygen atoms, provided
that when k is from 2 to 100, plurality of A.sup.1 may be the same
or different, and R.sup.1 is a hydrogen atom, a C.sub.1-18
hydrocarbon group or a C.sub.1-18 acyl group.
[0219] The fluorine-containing compound represented by the formula
(6) is a compound having a low surface tension. Said surface active
agent may be used alone, or in combination as a mixture with other
surface active agent.
[0220] The mixture of the fluorine-containing compounds represented
by the formula (6), having a ratio of the weight average molecular
weight (M.sub.w) to the number average molecular weight (M.sub.n)
(i.e. M.sub.w/M.sub.n) of at least 1.1, has effects that the
foamability is low, and the foams once formed are easily
eliminated, whereby it is more excellent as a surface active
agent.
[0221] The cement admixture of the present invention comprises
excellent compounds which impart excellent fluidity to fresh
concrete. With regard to concrete in which said cement admixture is
incorporated, workability is excellent, and the content of air can
be suppressed, whereby a hardened product of concrete having
suppressed foamability and high strength, can be obtained.
[0222] Further, by the method of the present invention,
fluorine-containing compounds useful as a cement admixture can be
effectively produced with a high yield.
[0223] The fluorine-containing compounds of the present invention
have a low surface tension and a low foamability, whereby it may be
used for an aqueous cleaner or for a resin additive for the purpose
of improving the resin.
[0224] The present invention further provides a novel surface
active agent.
EXAMPLES
[0225] Examples 1 to 12 are Examples for syntheses of
fluorine-containing compounds, Examples 13 to 21 are Comparative
Synthesis Examples, Examples 22 to 28 are Examples for evaluation
of fluorine-containing compounds, Examples 29 to 40 are Comparative
Evaluation Examples, and Examples 41 and 42 are Reference Examples.
The (C.sub.3H.sub.6O) moiety in compounds in Examples means an
oxypropylene group.
[0226] M.sub.w/M.sub.n was obtained by gel permeation
chromatography (GPC) using dichloropentafluoropropane as a solvent,
and gas chromatography-mass spectrometry analysis (GC-MAS).
Example 1
Example for Synthesis of Fluorine-Containing Compounds
[0227] 500 g of CF.sub.3(CF.sub.2).sub.7(CH.sub.2).sub.3OH as a
powder was added to a stainless pressure-resistant autoclave, and 5
g of BF.sub.3 etherate and 500 g of glyme were added thereto,
followed by stirring to dissolve them. The temperature was raised
to 60.degree. C., and while the temperature was kept at 60.degree.
C., 546 g of propylene oxide was continuously introduced thereto
over a period of 3 hours.
[0228] The aging reaction was conducted further for 5 hours, and
unreacted propylene oxide was distilled off under reduced pressure
to obtain a crude product. Then, KW-1000 and KW-600 (tradenames,
each manufactured by Kyowa Chemical Industry Co., Ltd.) as
adsorbents, were successively added thereto, each in an amount of 1
part by weight based on 100 parts by weight of the crude product,
followed by dehydration and filtration, to obtain
fluorine-containing compounds (1a). The hydroxyl number of the
fluorine-containing compounds (1a) was 57.4 mgKOH/g. By NMR
spectrum (.sup.1H-NMR, .sup.19F-NMR and .sup.13C-NMR) of the
product, the production of
CF.sub.3(CF.sub.2).sub.7(CH.sub.2).sub.3O(C.sub.3H.sub.6O).-
sub.nH, wherein the average of n obtained from the hydroxyl number
was 8.6, was confirmed. M.sub.w/M.sub.n was 1.16.
Example 2
Example for Synthesis of Fluorine-Containing Compounds
[0229] The reaction was conducted in the same manner as in Example
1, except that 546 g of a mixture comprising propylene oxide and
ethylene oxide with a weight ratio of 4 to 6, was used instead of
propylene oxide, to obtain fluorine-containing compounds (1b). The
hydroxyl number of the fluorine-containing compounds (1b) was 56.8
mgKOH/g. By NMR spectrum of the product, the production of
CF.sub.3(CF.sub.2).sub.7(CH.sub.2).sub.3O(-
C.sub.3H.sub.6O).sub.m(CH.sub.2CH.sub.2O).sub.nH, wherein the
linkage of oxyethylene and oxypropylene was random, the average of
m+n obtained from the hydroxyl number was 10, and the average of
m:n was 4:6, was confirmed. M.sub.w/M.sub.n was 1.14.
Example 3
Example for Synthesis of Fluorine-Containing Compounds
[0230] The reaction was conducted in the same manner as in Example
1, except that 546 g of a mixture comprising tetrahydrofuran and
propylene oxide with a weight ratio of 6 to 4, was used instead of
propylene oxide, to obtain fluorine-containing compounds (1c). The
hydroxyl number of the fluorine-containing compounds (1c) was 59.2
mgKOH/g. By NMR spectrum of the product, the production of
CF.sub.3(CF.sub.2).sub.7(CH.sub.2).sub.3O(-
C.sub.3H.sub.6O).sub.m[(CH.sub.2).sub.4O].sub.nH, wherein the
linkage of oxytetramethylene and oxypropylene was random, the
average of m+n obtained from the hydroxyl number was 7, and the
average of m:n was 6:4, was confirmed. M.sub.w/M.sub.n was
1.11.
Example 4
Example for Synthesis of Fluorine-Containing Compounds
[0231] 500 g of CF.sub.3(CF.sub.2).sub.7(CH.sub.2).sub.3OH as a
powder was added to a stainless pressure-resistant autoclave, and
0.5 g of BF.sub.3 etherate and 250 g of glyme were added thereto,
followed by stirring to dissolve them. Then, the temperature was
raised to 40.degree. C., and while the temperature was kept at
40.degree. C., 622 g of ethylene oxide was continuously introduced
thereto over a period of 3 hours.
[0232] The aging reaction was conducted further for 8 hours, and
unreacted ethylene oxide was distilled off under reduced pressure
to obtain a crude product. A 10% sodium hydroxide aqueous solution
was added thereto to neutralize acid contents, and KW-1000 and
KW-600 (tradenames, each manufactured by Kyowa Chemical Industry
Co., Ltd.) as adsorbents, were successively added thereto, each in
an amount of 1 part by weight based on 100 parts by weight of the
crude product, followed by dehydration and filtration, to obtain
fluorine-containing compounds (1d). The hydroxyl number of the
fluorine-containing compounds (1d) was 56.3 mgKOH/g. By NMR
spectrum of the product, the production of
CF.sub.3(CF.sub.2).sub.7(CH.su- b.2).sub.3O(CH.sub.2
CH.sub.2O).sub.nH, wherein the average of n obtained from the
hydroxyl number was 11.8, was confirmed. M.sub.w/M.sub.n was
1.12.
[0233] The surface tension of 0.01 wt % aqueous solution of the
fluorine-containing compounds (1d) was 17.6 dyn/cm.
Example 5
Example for Synthesis of Fluorine-Containing Compounds
[0234] The reaction was conducted in the same manner as in Example
4, except that 1456 g of ethylene oxide was used, to obtain
fluorine-containing compounds (1e). The hydroxyl number of the
fluorine-containing compounds (1e) was 36.8 mgKOH/g. By NMR
spectrum, the production of
CF.sub.3(CF.sub.2).sub.7(CH.sub.2).sub.3O(CH.sub.2CH.sub.2O-
).sub.nH, wherein the average of n obtained from the hydroxyl
number was 23.8, was confirmed. M.sub.w/M.sub.n was 1.18.
Example 6
Example for Synthesis of Fluorine-Containing Compounds
[0235] 200 g of the fluorine-containing compounds (1d) obtained in
Example 4 was charged into a reactor, 80 g of water and 15 g of KOH
were added thereto, and while the mixture was being stirred at a
temperature of 60.degree. C., 25 g of dimethylsulfuric acid was
dropwise added thereto over a period of 3 hours. Stirring was kept
further for 5 hours, to obtain a crude product. The stirring was
terminated, the mixture was left so that it was separated into two
layers, and the organic layer was recovered. Then, KW-1000 and
KW-600 as adsorbents, were successively added thereto, each in an
amount of 1 part by weight based on 100 parts by weight of the
crude product, followed by dehydration and filtration, to obtain
fluorine-containing compounds (1f). The terminal methylation ratio
obtained from the hydroxyl number was 95 mol %. By NMR spectrum,
the structure of the main product was confirmed to be
CF.sub.3(CF.sub.2).sub.7(CH.sub.2).sub.3O(CH.sub.2CH.sub.2O).sub.nCH.sub.-
3, wherein the average of n obtained from the hydroxyl number was
11.8.
Example 7
Example for Synthesis of Fluorine-Containing Compounds
[0236] Instead of ethylene oxide in Example 4, 300 g of
tetrahydrofuran, 243 g of propylene oxide and 92 g of ethylene
oxide were successively added to the mixture, to obtain
fluorine-containing compounds (1h). The hydroxyl number of the
fluorine-containing compounds (1h) was 52.6 mgKOH/g. By NMR
spectrum of the product, the production of
CF.sub.3(CF.sub.2).sub.7(CH.sub.2).sub.3O[(CH.sub.2).sub.4O].sub.m(C.sub.-
3H.sub.6O).sub.n(CH.sub.2CH.sub.2O).sub.pH, wherein the linkage of
the oxyalkylene groups was the block chain in order as shown in the
formula, the average of m:n:p was 2:2:1, and the average of (m+n+p)
obtained from the hydroxyl number was 10.0, was confirmed.
M.sub.w/M.sub.n was 1.11.
[0237] The surface tension of 0.01 wt % aqueous solution of the
fluorine-containing compounds (1h) was 18.4 dyn/cm.
Example 8
Example for Synthesis of Fluorine-Containing Compounds
[0238] 500 g of
CF.sub.3(CF.sub.2).sub.7CH.sub.2CH.sub.2CH(CH.sub.3)OH as a powder
was added to a stainless pressure-resistant autoclave, and 0.5 g of
BF.sub.3 etherate and 250 g of glyme were added thereto, followed
by stirring to dissolve them. Then, the temperature was raised to
30.degree. C., and while the temperature was kept at 30.degree. C.,
546 g of a mixture comprising tetrahydrofuran and ethylene oxide
with a weight ratio of 6 to 4, was continuously introduced thereto
over a period of 3 hours.
[0239] The aging reaction was conducted further for 5 hours, and
unreacted tetrahydrofuran and ethylene oxide were distilled off
under reduced pressure to obtain a crude product. A 10% sodium
hydroxide aqueous solution was added thereto to neutralize acid
contents, and KW-1000 and KW-600 were successively added thereto,
each in an amount of 1 part by weight based on 100 parts by weight
of the crude product, followed by dehydration and filtration, to
obtain fluorine-containing compounds (1i). The hydroxyl number of
the fluorine-containing compounds (1i) was 59.2 mgKOH/g. By NMR
spectrum of the product, the production of
CF.sub.3(CF.sub.2).sub.7CH.sub.2CH.sub.2CH(CH.sub.3)O[(CH.sub.2).sub.4O].-
sub.m(CH.sub.2CH.sub.2O).sub.nH, wherein the linkage of
tetrahydrofuran and ethylene oxide was random, the average of m+n
obtained from the hydroxyl number was 7, and the average of the m:n
was 5:5, was confirmed. M.sub.w/M.sub.n was 1.11.
Example 9
Synthesis of Fluorine-Containing Compounds
[0240] The reaction was conducted in the same manner as in Example
8, except that 546 g of a mixture comprising propylene oxide and
ethylene oxide in the weight ratio of 4 to 6 was used instead of
the mixture comprising tetrahydrofuran and ethylene oxide, to
obtain fluorine-containing compounds (1j). The hydroxyl number of
the fluorine-containing compounds (1j) was 56.5 mgKOH/g. By NMR
spectrum of the product, the production of
CF.sub.3(CF.sub.2).sub.7CH.sub.2CH.sub.2CH-
(CH.sub.3)O(C.sub.3H.sub.6O).sub.n(CH.sub.2CH.sub.2O).sub.mH,
wherein the linkage of propylene oxide and ethylene oxide was
random, the average of m+n obtained from the hydroxyl number was
10, and the average of m:n was 4:6, was confirmed. M.sub.w/M.sub.n
was 1.12.
Example 10
Synthesis of Fluorine-Containing Compounds
[0241] The reaction was conducted in the same manner as in Example
8, except that 546 g of ethylene oxide was used instead of the
mixture comprising tetrahydrofuran and ethylene oxide, to obtain
fluorine-containing compounds. (1k). The hydroxyl number of the
fluorine-containing compounds (1k) was 56.3 mgKOH/g. By NMR
spectrum of the product, the production of
CF.sub.3(CF.sub.2).sub.7CH.sub.2CH.sub.2CH-
(CH.sub.3)O(CH.sub.2CH.sub.2O).sub.nH, wherein the average of n
obtained from the hydroxyl number was 11, was confirmed.
M.sub.w/M.sub.n was 1.12.
Example 11
Synthesis of Fluorine-Containing Compounds
[0242] The reaction was conducted in the same manner as in Example
10, except that CF.sub.3(CF.sub.2).sub.7(CH.sub.2).sub.5OH was used
as an initiator, instead of
CF.sub.3(CF.sub.2).sub.7CH.sub.2CH.sub.2CH(CH.sub.3- )OH, to obtain
fluorine-containing compounds (1m). The hydroxyl number of the
fluorine-containing compounds (1m) was 56.3 mgKOH/g. By NMR
spectrum of the product, the production of
CF.sub.3(CF.sub.2).sub.7(CH.sub.2).sub.-
5O(CH.sub.2CH.sub.2O).sub.nH, wherein the average of n obtained
from the hydroxyl number was 11, was confirmed. M.sub.w/M.sub.n was
1.12.
Example 12
Synthesis of Fluorine-Containing Compounds
[0243] 500 g of a mixture of 3-perfluoroalkyl propanol comprising
CF.sub.3(CF.sub.2).sub.5(CH.sub.2).sub.3OH,
CF.sub.3(CF.sub.2).sub.7(CH.s- ub.2).sub.3OH,
CF.sub.3(CF.sub.2).sub.9(CH.sub.2).sub.3OH and
CF.sub.3(CF.sub.2).sub.11(CH.sub.2).sub.3OH with a molar ratio of
9:47:37:7 and the number average molecular weight of 520 as a
powder was added to a stainless pressure-resistant autoclave, and
0.5 g of BF.sub.3 etherate and 250 g of glyme were added thereto,
followed by stirring to dissolve them. Then, the temperature was
raised to 40.degree. C., and while the temperature was kept at
40.degree. C., 573 g of ethylene oxide was continuously introduced
thereto over a period of 3 hours.
[0244] The aging reaction was conducted further for 5 hours, and
unreacted ethylene oxide was distilled off under reduced pressure
to obtain a crude product. Then, KW-1000 and KW-600 were
successively added thereto, each in an amount of 0.5 part by weight
based on 100 parts by weight of the crude product, followed by
dehydration at a temperature of 120.degree. C. and filtration, to
obtain fluorine-containing compounds (1n) as liquid at normal
temperature. The hydroxyl number of the fluorine-containing
compounds (1f) was 56.2 mgKOH/g.
[0245] By NMR spectrum of the product, the production of
CF.sub.3(CF.sub.2).sub.q(CH.sub.2).sub.3O(CH.sub.2
CH.sub.2O).sub.nH was confirmed. M.sub.w/M.sub.n was 1.12.
Example 13
Comparative Synthesis Example
[0246] 500 g of CF.sub.3(CF.sub.2).sub.7CH.sub.2CH.sub.2OH as a
powder was added to a stainless pressure-resistant autoclave, 5.2 g
of a methanol solution having 28 wt % of sodium methoxide and 94.8
g of methanol were added thereto, and the temperature was raised to
50.degree. C. The mixture was stirred to dissolve them, and
methanol was distilled off under reduced pressure. Then, the
temperature was raised to 70.degree. C., and while the temperature
was kept at 70.degree. C., 578 g of propylene oxide was
continuously introduced thereto over a period of 3 hours.
[0247] After the completion of the reaction, unreacted propylene
oxide was distilled off under reduced pressure to obtain a crude
product. An aqueous phosphoric acid solution was added thereto for
neutralization, and KW-1000 and KW-600 were successively added
thereto, each in an amount of 1 part by weight based on 100 parts
by weight of the crude product, followed by dehydration and
filtration, to obtain a liquid material. As a result of analysis of
the liquid material by gas chromatography (GC), gel permeation
chromatography (GPC) and NMR spectrum, the main components were
C.sub.8F.sub.17CH.dbd.CH.sub.2 (boiling point: 149.degree. C.) and
C.sub.8F.sub.17CH.sub.2CH.sub.2OH, and the ratio of the desired
product C.sub.8F.sub.17CH.sub.2CH.sub.2O(C.sub.3H.sub.6O).sub.nH
wherein the average of n obtained from the hydroxyl number was 1.3
(hereinafter referred to as compounds (1p)) was 4.2% (area % in
GC). The hydroxyl number of the compounds (1p) was 103.6
mgKOH/g.
Example 14
Comparative Synthesis Example
[0248] 500 g of CF.sub.3(CF.sub.2).sub.7CH.sub.2CH.sub.2OH as a
powder was added to a stainless pressure-resistant autoclave, and
0.5 g of BF.sub.3 etherate and 250 g of glyme were added thereto,
followed by stirring to dissolve them. The temperature was raised
to 40.degree. C., and while the temperature was kept at 40.degree.
C., 578 g of propylene oxide was continuously introduced thereto
over a period of 3 hours.
[0249] After the completion of the reaction, unreacted propylene
oxide was distilled off under reduced pressure to obtain a crude
product. A 10% sodium hydroxide aqueous solution was added thereto
for neutralization, and KW-2000 and KW-500 were successively added
thereto, each in an amount of 1 part by weight based on 100 parts
by weight of the crude product, followed by dehydration and
filtration, to obtain a liquid material. As a result of analysis of
the liquid material by GC, GPC and NMR spectrum, the main component
was C.sub.8F.sub.17CH.sub.2CH.sub.2OH, and 17.5% (area % in GC) of
C.sub.8F.sub.17CH.dbd.CH.sub.2 (boiling point: 149.degree. C.) was
contained in the product.
[0250] Further,
CF.sub.3(CF.sub.2).sub.7CH.sub.2CH.sub.2O(C.sub.3H.sub.6O)-
.sub.nH, wherein the average of n obtained from the hydroxyl number
was 2.2 (hereinafter referred to as compounds (1q)), was contained
in an amount of 18% (area % in GC) in the product. The hydroxyl
number of the compounds (1q) was 94.8 mgKOH/g.
Example 15
Comparative Synthesis Example
[0251] 500 g of CF.sub.3(CF.sub.2).sub.7CH.sub.2CH.sub.2OH as a
powder was added to a stainless pressure-resistant autoclave, and
0.25 g of copper hexacyanocobaltate complex was added thereto. The
temperature was raised to 65.degree. C., and the mixture was
stirred for dissolution. Then, the temperature was raised to
80.degree. C., and while the temperature was kept at 80.degree. C.,
548 g of propylene oxide was continuously introduced thereto over a
period of 3 hours.
[0252] After the completion of the reaction, unreacted propylene
oxide was distilled off under reduced pressure, and a brown
high-viscous liquid was obtained. For the purpose of removing
copper hexacyanocobaltate complex, a chelating agent was added
thereto. However, copper hexacyanocobaltate complex was not
coordinated, whereby copper hexacyanocobaltate complex could not be
removed. KW-2000 and KW-500 were added thereto, each in an amount
of 1 part by weight based on 100 parts by weight of the brown
high-viscous liquid, followed by dehydration and filtration.
However, copper hexacyanocobaltate complex could not be recovered,
and the brown high-viscous liquid was obtained. Hereinafter the
brown high-viscous liquid will be referred to as compound (X1).
Example 16
Comparative Synthesis Example
[0253] 50 g of a hydroxyl compound
CH.sub.3(CH.sub.2).sub.3CH(CH.sub.2CH.s- ub.3)CH.sub.2OH and 2.6 g
of a methanol solution having 28% sodium methoxide were added to a
stainless pressure-resistant autoclave, followed by mixing by
stirring, and then methanol was distilled off under reduced
pressure. The temperature was raised to 70.degree. C., and while
the temperature was kept, propylene oxide was continuously
introduced thereto, and 1673 g of propylene oxide was introduced
thereto over a period of 3 hours.
[0254] After the completion of the reaction, unreacted propylene
oxide was distilled off under reduced pressure to obtain a crude
product. A phosphoric acid aqueous solution was added thereto to
neutralize alkali contents, KW-1000 and KW-600 were added thereto,
each in an amount of 1 part by weight based on 100 parts by weight
of the crude product to adsorb excessive inorganic compounds such
as phosphoric acid, potassium hydroxide and neutralized salt,
followed by dehydration, filtration and drying, to obtain compounds
(X2). The hydroxyl number was 58.3 mgKOH/g, and the production of
CH.sub.3(CH.sub.2).sub.3CH(CH.sub.2CH.sub.3)CH.sub.-
2O(C.sub.3H.sub.6O).sub.nH wherein the average of n obtained from
the hydroxyl number was 14.3 (hereinafter referred to as compounds
(X2)), was confirmed.
Example 17
Comparative Synthesis Example
[0255] 300 g of decanol and 1.0 g of 95% potassium hydroxide were
added to a stainless pressure-resistant autoclave, followed by
mixing by stirring at a temperature of 65.degree. C. The
temperature was raised to 130.degree. C., and water was removed
under reduced pressure. The temperature was lowered to 70.degree.
C., and while the temperature was kept at 70.degree. C., 1599 g of
ethylene oxide was continuously introduced thereto over a period of
3 hours.
[0256] After the completion of the reaction, unreacted ethylene
oxide was distilled off under reduced pressure, to obtain a crude
product. A phosphoric acid aqueous solution was added thereto for
neutralization, and KW-1000 and KW-600 were successively added
thereto, each in an amount of 1 part by weight based on 100 parts
by weight of the crude product, followed by dehydration and
filtration, to obtain compounds (X3). The hydroxyl number of the
compounds (X3) was 57.9 mgKOH/g, and by NMR spectrum, the
production of CH.sub.3(CH.sub.2).sub.9O(CH.sub.2CH.sub.2O).-
sub.nH, wherein the average of n obtained from the hydroxyl number
was 18, was confirmed.
[0257] The surface tension of 0.01 wt % aqueous solution of the
compounds was 34.2 dyn/cm.
Example 18
Comparative Synthesis Example
[0258] 500 g of CF.sub.3(CF.sub.2).sub.7(CH.sub.2).sub.3OH as a
powder was added to a stainless pressure-resistant autoclave, and
0.25 g of zinc hexacyanocobaltate complex was added thereto. The
temperature was raised to 65.degree. C., followed by stirring to
dissolve them. Then, the temperature was raised to 80.degree. C.,
and while keeping the temperature at 80.degree. C., 546 g of a
mixture comprising propylene oxide and ethylene oxide with a weight
ratio of 4 to 6 was continuously introduced thereto over a period
of 3 hours.
[0259] The aging reaction was conducted further for 5 hours, and
unreacted propylene oxide and ethylene oxide were distilled off
under reduced pressure to obtain a crude product. A chelating agent
was added thereto to remove heavy metal of the catalyst, and
KW-1000 and KW-600 were successively added thereto, each in an
amount of 1 part by weight based on 100 parts by weight of the
crude compound, followed by dehydration and filtration to obtain
fluorine-containing compounds (1r). The hydroxyl number of the
fluorine-containing compounds (1r) was 56.5 mgKOH/g. By NMR
spectrum of the product, the production of
CF.sub.3(CF.sub.2).sub.7(CH.su-
b.2).sub.3O(C.sub.3H.sub.6O).sub.m(CH.sub.2CH.sub.2O).sub.nH,
wherein the linkage of propylene oxide and ethylene oxide was
random, the average of m+n obtained from the hydroxyl number was
10, and the average of m:n was 4:6, was confirmed. M.sub.w/M.sub.n
was 1.04.
Example 19
Comparative Synthesis Example
[0260] 500 g of a mixture of 3-perfluoroalkyl-propanol comprising
(CF.sub.3(CF.sub.2).sub.5(CH.sub.2).sub.3OH,
CF.sub.3(CF.sub.2).sub.7(CH.- sub.2).sub.3OH,
CF.sub.3(CF.sub.2).sub.9(CH.sub.2).sub.3OH and
CF.sub.3(CF.sub.2).sub.11(CH.sub.2).sub.3OH with a molar ratio of
9:47:37:7 and having a number average molecular weight of 520, as a
powder, was added to a stainless pressure-resistant autoclave, and
0.5 g of zinc hexacyanocobaltate complex was added thereto, and the
temperature was raised to 65.degree. C. to dissolve them. Then, the
temperature was raised to 80.degree. C., and while the temperature
was kept at 80.degree. C., 500 g of a mixture comprising ethylene
oxide and propylene oxide with a weight ratio of 7 to 3 was
continuously introduced thereto over a period of 4 hours.
[0261] The aging reaction was conducted further for 5 hours, and
unreacted alkylene oxide was removed by deaeration under reduced
pressure. A chelating agent was added thereto to remove heavy metal
of the catalyst, KW-1000 and KW-600 were successively added
thereto, each in an amount of 0.5 part by weight based on 100 parts
by weight of the crude product, followed by dehydration and
filtration at a temperature of 120.degree. C., to obtain
fluorine-containing compounds (1s) as a liquid at normal
temperature. The hydroxyl number of the fluorine-containing
compounds (1s) was 56.2 mgKOH/g.
[0262] By NMR spectrum of the product, the production of
CF.sub.3(CF.sub.2).sub.q(CH.sub.2).sub.3O(CH.sub.2CH.sub.2O).sub.nH
was confirmed. M.sub.w/M.sub.n was 1.04.
Example 20
Comparative Synthesis Example
[0263] 500 g of CF.sub.3(CF.sub.2).sub.7(CH.sub.2).sub.2OH as a
powder was added to a stainless pressure-resistant autoclave, and
1.4 g of I.sub.2, 2.0 g of NaI and 1.7 g of NaBH.sub.4 were added
thereto, followed by stirring to dissolve them. The substitution by
nitrogen was conducted three times, the temperature was raised to
120.degree. C., and 560 g of ethylene oxide was continuously
introduced thereto over a period of 3 hours.
[0264] The aging reaction was conducted further for 5 hours,
unreacted ethylene oxide was removed by deaeration under reduced
pressure, and nitrogen bubbling was conducted for 30 minutes to
remove I.sub.2 from the system. KW-1000 and KW-600 were
successively added thereto, each in an amount of 0.5 part by weight
based on 100 parts by weight of the crude product, followed by
dehydration and filtration at a temperature of 120.degree. C., to
obtain fluorine-containing compounds (1t) as a solid at normal
temperature. The hydroxyl number of the fluorine-containing
compounds (1t) was 56.4 mgKOH/g.
[0265] By NMR spectrum of the product, the production of
CF.sub.3(CF.sub.2).sub.7(CH.sub.2).sub.2O(CH.sub.2CH.sub.2O).sub.nH,
wherein the average of n obtained from the hydroxyl number was 12,
was confirmed.
[0266] M.sub.w/M.sub.n was 1.03.
Example 21
Comparative Synthesis Example
[0267] 500 g of a mixture of 2-perfluoroalkyl-ethanol comprising
CF.sub.3(CF.sub.2).sub.5(CH.sub.2).sub.2OH,
CF.sub.3(CF.sub.2).sub.7(CH.s- ub.2).sub.2OH,
CF.sub.3(CF.sub.2).sub.9(CH.sub.2).sub.2OH and
CF.sub.3(CF.sub.2).sub.11(CH.sub.2).sub.2OH with a molar ratio of
9:47:37:7 and having a number average molecular weight of 506, as a
powder, was added to a stainless pressure-resistant autoclave, and
1.3 g of I.sub.2, 1.9 g of NaI and 1.5 g of NaBH.sub.4 were added
thereto, followed by stirring to dissolve them. The substitution by
nitrogen was conducted 3 times, the temperature was raised to
120.degree. C., and 498 g of ethylene oxide was continuously
introduced thereto over a period of 3 hours.
[0268] The aging reaction was conducted further for 5 hours, and
unreacted ethylene oxide was removed by deaeration under reduced
pressure, and nitrogen bubbling was conducted for 30 minutes to
remove I2 from the system. KW-1000 and KW-600 were successively
added thereto, each in an amount of 0.5 part by weight based on 100
parts by weight of the crude product, followed by dehydration and
filtration at a temperature of 120.degree. C., to obtain
fluorine-containing compounds (1u) as a solid at normal
temperature. The hydroxyl number of the fluorine-containing
compounds (1u) was 56.4 mgKOH/g.
[0269] By NMR spectrum of the product, the production of
CF.sub.3(CF.sub.2).sub.q(CH.sub.2).sub.2O(CH.sub.2CH.sub.2O).sub.nH
was confirmed. M.sub.w/M.sub.n was 1.03.
Examples 22 to 28
Examples in Evaluation of Fluorine-Containing Compounds
[0270] Using the fluorine-containing compounds (1b), (1e), (1i),
(1j), (1k), (1m) and (1n) synthesized in the above-mentioned
Synthesis Examples, evaluations of foamability, fluidity and air
content were conducted. The results of evaluation of foamability
are shown in Table 1, and the results of evaluations of fluidity
and air content are shown in Table 2.
[0271] The results of measurement in the surface tension of 0.01 wt
% aqueous solution of fluorine compounds are shown together in
Table 1. The unit is dyn/cm.
Evaluation in Foamability
[0272] With regard to a 1% aqueous dispersion of
fluorine-containing compounds as a test solution, loss miles value
and ampule value were measured. On the test solution, the same test
solution was dropped from a height of 120 cm, and the height of
foams formed was measured, which was taken as the loss miles value.
The unit is mm.
[0273] Further, 10 ml of the test solution was put in an ampule of
20 ml followed by shaking, and the height of the foams formed was
measured, which was taken as the ampule value. The unit is mm.
Method of Evaluation of Fluidity
[0274] Fluidity was evaluated by the following method, in
accordance with the method of JIS-R5201.
[0275] Water was put in a mixer, fluorine-containing compounds were
added thereto, and cement and sand were successively added thereto,
whereby flow value (mm) was evaluated. Commercially available
Portland cement manufactured by Mitsubishi Materials Corporation
and quartz sand No. 6 manufactured by Tokai Chemical Industry Co.,
Ltd. were used, as cement and sand, respectively.
[0276] Here, the water content was adjusted to be 55 wt % based on
the total amount of concrete having water added, whereas it is 60
wt % in the method described in JIS.
Method of Evaluation of Air Content
[0277] It was measured in accordance with a method of JIS-A1118.
The unit is vol %.
Examples 29 to 41
Examples in Evaluation of Comparative Compounds
[0278] Using, instead of the fluorine-containing compounds of
Example 22, the fluorine-containing compounds (1r), (1s), (1t) or
(1u) synthesized in the above-mentioned Comparative Synthesis
Examples, fluorine-containing compounds having a M.sub.w/M.sub.n
value of 1.04 manufactured by Du Pont Kabushiki Kaisha, tradename:
ZONYL FSN (hereinafter referred to as ZONYL), a fluorine type
surface active agent comprising compounds which contain amide bonds
manufactured by Asahi Glass Company Ltd., tradename: Surfluone
S-141 (hereinafter referred to as S141) or Surfluone S-145
(hereinafter referred to as S145), the compounds (X2) obtained in
Example 16, the compounds (X3) obtained in Example 17 or a water
reducing agent comprising compounds which do not contain fluorine,
manufactured by Kao Corporation, tradename: Mighty 150 (hereinafter
referred to as M150), foamability, fluidity and air content were
evaluated in the same manner as in Example 22
[0279] Fluidity and air content were evaluated by adding respective
compounds in an amount as shown in Table 2 to concrete.
[0280] The results are shown in Tables 1 and 2.
Examples 41 and 42
Reference Evaluation Examples
[0281] Fluidity and air content were evaluated without adding the
fluorine-containing compounds of Example 22 to concrete. The amount
of water was as shown in Table 2. The results are show in Table
2.
1TABLE 1 Surface Loss miles Ampule Example Compounds tension value
value 22 1b 21.2 12 1 23 1e 17.8 8 1 24 1i 22.4 12 1 25 1j 19.8 12
1 26 1k 17.6 10 1 27 1m 18.3 11 1 28 1n 18.0 8 1 29 1r 36.2 28 10
30 1s 35.9 27 9 31 1t 17.2 25 8 32 1u 17.0 24 8 33 ZONYL 16.8 25 8
34 S141 18.2 28 10 35 S145 17.6 187 20 36 X2 32.4 32 10 37 X3 34.2
36 13 38 M150 -- -- -- 39 M150 -- -- -- 40 M150 -- -- --
[0282]
2TABLE 2 Amount Amount Flow Air Example Compounds added of water
value content 22 1b 300 55 234 3% 23 1e 300 55 232 4% 24 1i 300 55
234 3% 25 1j 300 55 231 3% 26 1k 300 55 232 3% 27 1m 300 55 230 4%
28 1n 300 55 232 4% 29 1r 300 55 226 8% 30 1s 300 55 225 8% 31 1t
300 55 219 10% 32 1u 300 55 220 10% 33 ZONYL 300 55 220 10% 34 S141
300 55 249 21% 35 S145 300 55 224 17% 36 X2 300 55 192 3% 37 X3 300
55 188 7% 38 M150 300 55 192 2% 39 M150 3000 55 193 1% 40 M150
30000 55 230 3% 41 -- -- 55 192 3% 42 -- -- 65 242 2%
* * * * *