Patent Application
20250236579
The present invention relates to a method for extracting a fluorinated ether compound.
Fluorinated ether compounds having a perfluoropolyether chain, which have high lubricity etc., are used for various applications. Methods for extracting such a fluorinated ether compound from a composition containing the fluorinated ether compound and other components, have been studied.
For example, Patent Document 1 discloses a method of extracting a perfluoropolyether oil (a fluorinated ether compound) contained in grease, with use of liquid or supercritical carbon dioxide.
Patent Document 1: JP-A-2017-503651
Technique to extract a fluorinated ether compound with use of liquid or supercritical carbon dioxide has been known as disclosed in Patent Document 1. However, methods for efficiently extracting a desired fluorinated ether compound by means of another method have been required.
Under these circumstances, the object of the present invention is to provide a method for extracting a fluorinated ether compound by which a desired fluorinated ether compound can efficiently be extracted.
The present inventors have conducted extensive studies on the above object and as a result found that when extracting a desired fluorinated ether compound from a plurality of fluorinated ether compounds, the desired fluorinated ether compound can efficiently be extracted with use of an organic solvent containing no fluorine atom, and accomplished the present invention.
That is, the present inventors have found that the above object can be achieved by the following construction.
According to the present invention, provided is a method for extracting a fluorinated ether compound by which the desired fluorinated ether compound can efficiently be extracted.
In this specification, a compound represented by the formula (A1) may sometimes be referred to as Compound (A1). The same applies to compounds etc. represented by other formulae.
A fluoroalkyl group generically means a perfluoroalkyl group and a partial fluoroalkyl group. The perfluoroalkyl group means an alkyl group in which all hydrogen atoms are replaced with fluorine atoms. The partial fluoroalkyl group means an alkyl group in which 1 or more hydrogen atoms are replaced with fluorine atoms and which has 1 or more hydrogen atoms. That is, the fluoroalkyl group is an alkyl group having 1 or more fluorine atoms.
A “reactive silyl group” generically means a hydrolysable silyl group and a silanol group (Si—OH), and the “hydrolysable silyl group” means a group capable of forming a silanol group when hydrolyzed.
An “organic group” manes a hydrocarbon group which may have a substituent and which may have a hetero atom or another bond in a carbon chain.
A “hydrocarbon group” is a group composed of carbon atoms and hydrogen atoms and is an aliphatic hydrocarbon group (for example, a bivalent aliphatic hydrocarbon group may be a linear alkylene group, an alkylene group having a branch or a cycloalkylene group), an aromatic hydrocarbon group (for example, a bivalent aromatic hydrocarbon group may be a phenylene group) or a combination thereof.
A “surface layer” means a layer to be formed on the surface of a substrate.
A “molecular weight” of a fluoropolyether chain is a number average molecular weight calculated from the number (average) of oxyfluoroalkylene units based on the terminal groups by means of 1H-NMR and 19F-NMR.
A “molecular weight” of another partial structure of the fluorinated ether compound other than the fluoropolyether chain may be calculated by conducting structural analysis of the fluorinated ether compound by means of 1H-NMR and 19F-NMR.
A range of numerical values represented by “to” means a range including numerical values before and after it as the lower limit value and the upper limit value. In the numerical ranges described stepwise in this specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with an upper limit value or a lower limit value of another numerical range described stepwise. In the numerical ranges described in this specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with a value indicated in Examples.
In this specification, each component may be used singly or in combination of 2 or more types of substances corresponding to the component. In a case where 2 or more types of substances are used in combination for a component, the content of the component means the total content of the substances used in combination, unless otherwise specified.
In this specification, a combination of 2 or more preferred embodiments corresponds to a more preferred embodiment.
The method for extracting a fluorinated ether compound of the present invention (hereinafter sometimes referred to as “present extraction method”) is a method of extracting a first component from a composition (hereinafter sometimes referred to as “present composition”) containing the first component composed of at least one fluorinated ether compound selected from the group consisting of a compound represented by the formula (A1) described later, a compound represented by the formula (A2) described later and a compound represented by the formula (A3) described later, and
According to the present extraction method, the first component can efficiently be extracted from the present composition. The detailed mechanism for this reason is unclear, but is estimated as follows. That is, compatibility of the first component and the non-fluorinated organic solvent is improved by the number of linked carbon atoms at the R11-T11 moiety in the formula (A1), the number of linked carbon atoms at the R21-T21 moiety and the T31-R31 moiety in the formula (A2), and the number of linked carbon atoms at the R41-T41 moiety in the formula (A3) being predetermined values.
The present composition contains the first component and the second component and may contain another component. In the following, the components contained in the present composition will be described.
The first component is at least one fluorinated ether compound selected from the group consisting of a compound represented by the following formula (A1), a compound represented by the following formula (A2) and a compound represented by the following formula (A3), and is a compound to be extracted in the present extraction method.
In the formula (A1),
In the formula (A2),
In the formula (A3),
Since the first component has the fluoropolyether chain, a surface layer formed by using the first component is excellent in water/oil repellency and fingerprint stain removability.
A first component having —CH═CH2 at its terminal is suitably used as a material of a compound having a reactive silyl group at its terminal.
Since a reactive silyl group is firmly chemically bonded to a substrate, a surface layer formed by using a first component having a reactive silyl group at its terminal is excellent in durability such as abrasion resistance.
Now, structures of the respective compounds will be described. Reference symbols representing the same structures are indicated as such and may properly be read for reference.
The first component has a fluoropolyether chain, which is a group having 2 or more oxyfluoroalkylene units.
Such a fluoropolyether chain may have a hydrogen atom. In order that an obtainable surface layer will be more excellent in abrasion resistance and fingerprint removability, the proportion of fluorine atoms represented by the following formula (I) in the fluoropolyether chain is preferably 60% or more, more preferably 80% or more, further preferably substantially 100%, that is the fluoropolyether chain is a perfluoropolyether chain. When the proportion of fluorine atom is 60% or more, the fluorine amount in the fluoropolyether chain is large, and lubricity and fingerprint stain removability will more improve.
Formula (I): proportion of fluorine atoms (%)=(number of fluorine atoms)/{(number of fluorine atoms)+(number of hydrogen atoms)}×100
The molecular weight of one of the above fluoropolyether chains (that is, the molecular weight of the group represented by (ORf11)y1, the molecular weight of the group represented by (ORf12)y2, and the molecular weight of the group represented by (ORf13)y3) is, in order that the obtainable surface layer has both fingerprint stain removability and lubricity, preferably 2,000 to 20,000, more preferably 2,500 to 15,000, further preferably 3,000 to 10,000. When the molecular weight of the fluoropolyether chain is 2,000 or more, the fluoropolyether chain has improved flexibility and in addition, the fluorine amount in the molecule is large, whereby lubricity and fingerprint removability will further improve. On the other hand, when the molecular weight of the fluoropolyether chain is 20,000 or less, the obtainable surface layer will be more excellent in abrasion resistance.
The Compound (A1) has a structure represented by the following formula (A1).
[Rf1—(ORf11)y1—O—R1]j-L1-(R11-T11)x1 (A1)
Rf1 is a C1-20 fluoroalkyl group. The fluoroalkyl group may be linear, or may have a branch and/or a cyclic structure. In view of abrasion resistance, it is preferably a linear fluoroalkyl group, and in view of easiness in synthesis, etc., the number of carbon atoms in the fluoroalkyl group is preferably 1 to 6.
Rf11 is a C1-6 fluoroalkylene group, and when there is a plurality of Rf11, the plurality of Rf11 may be the same or different from each other. (ORf11)y1 represents a fluoropolyether chain, y1 is an integer of 1 or more and is preferably 1 to 200.
(ORf11)y1 preferably has a structure represented by the following formula (G11).
In the formula (G11), the order of binding of (OGf1) to (OGf6) is optional. m1 to m6 in the formula (G11) respectively means the numbers of (OGf1) to (OGf6), not the arrangement. For example, (OGf5)m5 means that the number of (OGf5) is m5, not a block arranged structure of (OGf5)m5. Likewise, the order of description of (OGf1) to (OGf6) does not represent the order of binding of the respective units.
The fluoroalkylene group having 3 to 6 carbon atoms may be a linear fluoroalkylene group, or may be a fluoroalkylene group having a branch or a cyclic structure.
Specific examples of Gf1 include —CF2—, and —CHF—.
Specific examples of Gf2 include —CF2CF2—, —CHFCF2—, —CHFCHF—, —CH2CF2—, and 13 CH2CHF—.
Specific examples of Gf3 include —CF2CF2CF2—, —CF2CHFCF2—, —CF2CH2CF2—, —CHFCF2CF2—, —CHFCHFCF2—, —CHFCHFCHF—, —CHFCH2CF2—, —CH2CF2CF2—, —CH2CHFCF2—, —CH2CH2CF2—, —CH2CF2CHF—, —CH2CHFCHF—, —CH2CH2CHF—, —CF(CF3)—CF2—, —CF(CHF2)—CF2—, —CF(CH2F)—CF2—, —CF(CH3)—CF2—, —CF(CF3)—CHF—, —CF(CHF2)—CHF—, —CF(CH2F)—CHF—, —CF(CH3)—CHF—, —CF(CF3)—CH2—, —CF(CHF2)—CH2—, —CF(CH2F)—CH2—, —CF(CH3)—CH2—, —CH(CF3)—CF2—, —CH(CHF2)—CF2—, —CH(CH2F)—CF2—, —CH(CH3)—CF2—, —CH(CF3)—CHF—, —CH(CHF2)—CHF—, —CH(CH2F)—CHF—, —CH(CH3)—CHF—, —CH(CF3)—CH2—, —CH(CHF2)—CH2—, and —CH(CH2F)—CH2—.
Specific examples of Gf4 include —CF2CF2CF2CF2—, —CHFCF2CF2CF2—, —CH2CF2CF2CF2—, —CF2CHFCF2CF2—, —CHFCHFCF2CF2—, —CH2CHFCF2CF2—, —CF2CH2CF2CF2—, —CHFCH2CF2CF2—, —CH2CH2CF2CF2—, —CHFCF2CHFCF2—, —CH2CF2CHFCF2—, —CF2CHFCHFCF2—, —CHFCHFCHFCF2—, —CH2CHFCHFCF2—, —CF2CH2CHFCF2—, —CHFCH2CHFCF2—, —CH2CH2CHFCF2—, —CF2CH2CH2CF2—, —CHFCH2CH2CF2—, —CH2CH2CH2CF2—, —CHFCH2CH2CHF—, —CH2CH2CH2CHF—, and —cycloC4F6—.
Specific examples of Gf5 include —CF2CF2CF2CF2CF2—, —CHFCF2CF2CF2CF2—, —CH2CHFCF2CF2CF2—, —CF2CHFCF2CF2CF2—, —CHFCHFCF2CF2CF2—, —CF2CH2CF2CF2CF2—, —CHFCHECF2CF2CF2—, —CHECH2CF2CF2CF2—, —CF2CF2CHFCF2CF2—, —CHFCF2CHFCF2CF2—, —CH2CF2CHFCF2CF2—, —CH2CF2CF2CF2CH2—, and —cycloC5F8—.
Specific examples of Gf6 include —CF2CF2CF2CF2CF2CF2—, —CF2CF2CHFCHFCF2CF2—, —CHFCF2CF2CF2CF2CF2—, —CHFCHFCHFCHFCHFCHF—, —CHFCF2CF2CF2CF2CH2—, —CH2CF2CF2CF2CF2CH2—, and -cycloC6F10—.
-cycloC4F6— means a perfluorocyclobutanediyl group, and its specific examples include a perfluorocyclobutene-1,2-diyl group. cycloC5F8— means a perfluorocyclopentanediyl group and its specific examples include a perfluorocyclopentan-1,3-diyl group. -cycloC6F10— means a perfluorocyclohexanediyl group and its specific examples include a perfluorocyclohexan-1,4-diyl group.
(ORf11)y1 particularly preferably has a structure represented by any one of the following formulae (G2) to (G4), in view of more excellent water/oil repellency, abrasion resistance and fingerprint stain removability.
Symbols in the formulae (G2) to (G4) are as defined for the above formula (G11).
In the formulae (G2) and (G3), the orders of binding of (OGf1) and (OGf2), and (OGf2) and (OGf4), are respectively optional. For example, in the formula (G2), (OGf1) and (OGf2) may alternately be arranged, (OGf1) and (OGf2) may be arranged respectively in blocks, or may be randomly arranged.
In the formula (G2), m1 is preferably 1 to 30, more preferably 1 to 20. m2 is preferably 1 to 30, more preferably 1 to 20.
In the formula (G3), m2 is preferably 1 to 30, more preferably 1 to 20. m4 is preferably 1 to 30, more preferably 1 to 20.
In the formula (G4), m3 is preferably 1 to 30, more preferably 1 to 20.
In the fluoropolyether chain (ORf11)y1, the proportion of fluorine atoms [{number of fluorine atoms/(number of fluorine atoms+number of hydrogen atoms)}×100 (%)] is, in view of excellent water/oil repellency and fingerprint removability, preferably 60% or more, more preferably 70% or more, further preferably 80% or more. The upper limit is for example 100%.
The molecular weight of the fluoropolyether chain (ORf11)y1 moiety is, in view of abrasion resistance, preferably 2,000 to 20,000, more preferably 2,500 to 15,000, further preferably 3,000 to 10,000.
R1 is an alkylene group or a fluoroalkylene group. The alkylene group and fluoroalkylene group as R1 may be linear or may have a branch and/or a cyclic structure. In view of easiness in synthesis, etc., preferred is an alkylene group or a fluoroalkylene group that is linear or that has a branch, more preferred is an alkylene group or a fluoroalkylene group that is linear or that has a methyl group or a fluoromethyl group as a branch. The number of carbon atoms in R1 is preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 10, particularly preferably 1 to 6. In a case where j is 1 and L1 is a single bond, R1 is bonded to R11. In such a case, the carbon atom in R1, bonded to R11, is bonded to at least one fluorine atom or fluoroalkyl group.
j represents the number of [Rf1—(ORf11)y1—O—R1] in one molecule and is an integer of 1 or more, preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 4.
R11 is an alkylene group in which the atom bonded to L1 may be an etheric oxygen atom, and which may have an etheric oxygen atom between carbon atoms.
The alkylene group as R11 may be linear, or may have a branch and/or a cyclic structure. It is preferably an alkylene group that is linear or that has a branch, more preferably a linear alkylene group, whereby the Compound (A1) will densely be arranged when forming a surface layer.
In a case where T11 is —CH═CH2, at least one R11 has a carbon chain having 2 or more carbon atoms linked to each other, and in order that the first component will more efficiently be extracted, at least one R11 preferably has a carbon chain having 4 or more carbon atoms linked to one another, more preferably has a carbon chain having 7 or more carbon atoms linked to one another, further preferably has a carbon chain having 10 or more carbon atoms linked to one another. The number of the linked carbon atoms in the carbon chain is, in view of easiness of production, preferably 28 or less, more preferably 18 or less. In a case where T11 is —CH═CH2, the carbon chain is linked to T11.
On the other hand, in a case where T11 is —SiRa11z11Ra123-z11, at least one R11 has a carbon chain having 4 or more carbon atoms linked to one another, and in order that the first component will more efficiently be extracted, at least one R11 preferably has a carbon chain having 6 or more carbon atoms linked to one another, more preferably has a carbon chain having 9 or more carbon atoms linked to one another, further preferably has a carbon chain having 12 or more carbon atoms linked to one another. The number of the linked carbon atoms in carbon chain is, in view of easiness of production, preferably 30 or less, more preferably 20 or less.
“Having a carbon chain having X or more carbon atoms linked to one another” means that R11 has an alkylene group having X or more carbon atoms. In the case of an alkylene group having a branch and/or a cyclic structure, carbon atoms in the branch and the cyclic structure are included. Specifically, for example, —CH2CH2CH(—CH2CH3)—CH2CH2CH2CH2— has a carbon chain having 9 carbon atoms linked including carbon atoms in the branch.
R11 is specifically represented by the following formula (g2).
*—(O)a1—(Rg2O)a2—Rg2—** (g2)
When a1 is 0, the atom having the binding site * is a carbon atom, and when a1 is 1, the atom having the binding site * is an oxygen atom. In the Compound (A1), a1 may be either 0 or 1 and is properly selected depending upon e.g. the synthesis.
a2 represents the number of repetition of Rg2O and in view of durability of the obtainable surface layer, is preferably 0 to 6, more preferably 0 to 3, further preferably 0 to 1.
The alkylene group as Rg2 is the same as the alkylene group as R11, and its preferred embodiment is also the same.
R11 is further preferably a group represented by the following formula (g3), whereby the obtainable surface layer is more excellent in water/oil repellency and fingerprint stain removability and is also excellent in durability such as abrasion resistance.
*—(O)a1—Rg3—** (g3)
The alkylene group as Rg3 is the same as the alkylene group as R11, and its preferred embodiment is also the same.
T11 is —CH═CH2, or a group represented by —SiRa11z11Ra123-z11,
In a case where Ra11 is a hydroxy group, it constitutes a silanol (Si—OH) group with the Si atom. The hydrolysable group is a group to be a hydroxy group (that is a silanol group) when hydrolyzed. The silanol group further undergoes intermolecular reaction to form a Si—O—Si bond. The silanol group undergoes a dehydration condensation reaction with a hydroxy group on the surface of a substrate (substrate-OH) to form a chemical bond (substrate-O—Si). The Compound (A1), which has 1 or more Ta11, impart excellent abrasion resistance to the formed surface layer.
The hydrolysable group as Ra11 may, for example, be an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group or an isocyanate group (—NCO). The alkoxy group is preferably a C1-4 alkoxy group. The acyl group is preferably a C1-6 acyl group. The acyloxy group is preferably a C1-6 acyloxy group.
Ra11 is, in view of easiness of production of the Compound (A1), preferably a C1-4 alkoxy group or a halogen atom. The alkoxy group as Ra11 is preferably a C1-4 alkoxy group, whereby the Compound (A1) will be excellent in storage stability and outgassing at the time of reaction is suppressed, particularly preferably an ethoxy group in view of long-term storage stability, and particularly preferably a methoxy group in view of a short hydrolysis time. The halogen atom is preferably a chlorine atom.
The non-hydrolysable group as Ra12 may, for example, be a hydrogen atom or a monovalent hydrocarbon group.
The hydrocarbon group may, for example, be an alkyl group, a cycloalkyl group, an alkenyl group or an allyl group, and the hydrocarbon group may be substituted by fluorine. In view of easiness of production, the hydrocarbon group is preferably an alkyl group. In view of easiness of production, the number of carbon atoms in the hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, further preferably 1 to 2.
z11 is an integer of 1 to 3, and in view of adhesion to a substrate, preferably 2 or 3, more preferably 3.
In a case where T11 is —SiRa11z11Ra123-z11, specific examples include —Si(OCH3)3, —SiCH3(OCH3)2, —Si(OCH2CH3)3, —SiCl3, —Si(OCOCH3)3, —Si(NCO)3, and —Si(OCH2CF3)3. In view of handling efficiency in production, preferred is —Si(OCH3)3.
When there is a plurality of T11 in one molecule, the plurality of T11 may be the same or different from each other.
x1 represents the number of (R11-T11) in one molecule and is an integer of 1 or more, preferably 1 to 32, more preferably 1 to 18, further preferably 2 to 12.
L1 is a single bond or a (j+x1)-valent group which may have N, O, S or Si and may have a branch point, and in which the atoms bonded to R1 and R11 are each independently N, O, S, Si, a carbon atom constituting the branch point, or a carbon atom having a hydroxy group or an oxo group (═O). The atom bonded to R1 and the atom bonded to R11 may be the same atom or may be different atoms.
In a case where L1 is a single bond, R1 and R11 in the formula (A1) are directly bonded, and the Compound (A1) is represented by the following formula (A1′).
Rf1—(ORf11)y1—O—R1—R11-T11 (A1′)
Symbols in the formula (A1′) are as defined for the formula (A1).
In a case where L1 is a trivalent or higher valent group, L1 has at least one type of branch point (hereinafter referred to as “branch point P1”) selected from the group consisting of C, N, Si, a cyclic structure and a (j+x1)-valent organopolysiloxane residue.
In a case where the branch point P1 is N, the branch point P1 is represented, for example, by *—N(—**)2 or (*—)2N—** . *is a binding site on the R1 side, and ** is a binding site on the R11 side.
In a case where the branch point P1 is C, the branch point P1 is represented, for example, by *—C(—*)3, (*—)2C(—**)2, (*—)3C—**, *—CR29(—**)2, or (*—)2CR29—**. * is a binding site on the R1 side, ** is a binding site on the R11 side, and R29 is a monovalent group and may, for example, be a hydrogen atom, a hydroxy group, a hydrocarbon group, or an alkoxy group. The hydrocarbon group may be an aliphatic hydrocarbon group such as a linear alkyl group, an alkyl group having a branch or a cycloalkyl group, an aromatic hydrocarbon group such as a phenyl group, or a combination thereof.
In a case where the branch point P1 is Si, the branch point P1 is represented, for example, by *—Si(—**)3, (*—)2Si(—**)2, (*—)3Si—**, *—SiR29(—**)2, or (*—)2SiR29—**. * is a binding site on the R1 side, ** is a binding site on the R11 side, and R29 is a monovalent group and may, for example, be a hydrogen atom, a hydroxy group, a hydrocarbon group, or an alkoxy group. The hydrocarbon group may be an aliphatic hydrocarbon group such as a linear alkyl group, an alkyl group having a branch or a cycloalkyl group, an aromatic hydrocarbon group such as a phenyl group, or a combination thereof.
The cyclic structure constituting the branch point P1 is preferably at least one member selected from the group consisting of a 3- to 8-membered aliphatic ring, a 3- to 8-membered aromatic ring, a 3- to 8-membered heterocyclic ring and a condensed ring of 2 or more of such rings, more preferably a cyclic structure of any of the following formulae, in view of easy production of the Compound (A1) and whereby the obtainable surface layer will be more excellent in abrasion resistance, light resistance and chemical resistance. The cyclic structure may have a substituent such as a halogen atom, an alkyl group (which may have an etheric oxygen atom between carbon atoms), a cycloalkyl group, an alkenyl group, an allyl group, an alkoxy group or an oxo group (═O).
As the organopolysiloxane residue constituting the branch point P1, the following groups may, for example, be mentioned. In the following formulae, R25 is a hydrogen atom, an alkyl group, an alkoxy group or a phenyl group. The number of carbon atoms in the alkyl group or the alkoxy group as R25 is preferably 1 to 10, more preferably 1. The plurality of R25 may be the same or different from each other.
Bivalent or higher valent L1 may have at least one bond selected from the group consisting of —C(O)N(R26)—, —N(R26)C(O)—, —C(O)O—, —OC(O)—, —C(O)—, —C(OH)—, —O—, —N(R26)—, —S—, —OC(O)O—, —NHC(O)O—, —OC(O)NH—, —NHC(O)N(R26)—, —SO2N(R26)—, —N(R26)SO2—, —Si(R26)2—, —OSi(R26)2—, —Si(CH3)2-Ph-Si(CH3)2— and a bivalent organopolysiloxane residue (hereinafter referred to as “bond B1”).
In the above formulae, R26 is a hydrogen atom, a C1-6 alkyl group or a phenyl group, and Ph is a phenylene group. The number of carbon atoms in the alkyl group as R26 is, in view of easy production of the Compound (A1), preferably 1 to 6, more preferably 1 to 3, further preferably 1 to 2.
As the bivalent organopolysiloxane residue, the following groups may, for example, be mentioned. In the following formulae, R27 is a hydrogen atom, an alkyl group, an alkoxy group or a phenyl group. The number of carbon atoms in the alkyl group or the alkoxy group as R27 is preferably 1 to 10, more preferably 1. The plurality of R27 may be the same or different from each other.
The bond B1 is, in view of easy production of the Compound (A1), preferably at least one bond selected from the group consisting of —C(O)NR26—, —N(R26)C(O)—, —C(O)—, and —NR26—, more preferably —C(O)NR26—, —N(R26)C(O)— or —C(O)—, whereby the obtainable surface layer will be more excellent in light resistance and chemical resistance.
In bivalent L1, the atoms bonded to R1 and R11 are each independently N, O, S, Si, or a carbon atom having a hydroxy group or an oxo group (═O). That is, the atoms adjacent to R1 and R11 are respectively elements constituting the bond B1. Specific examples of the bivalent L1 include 1 or more of the bonds B1 (for example *—B1—**, *—B1—R28—B1—**). R28 is a single bond or a bivalent organic group, * is a binding site on the R1 side, and ** is a binding site on the R11 side.
In trivalent or higher valent L1, the atoms bonded to R1 and R11 are each independently N, O, S, Si, a carbon atom constituting the branch point, or a carbon atom having a hydroxy group or an oxo group (═O). That is, the atoms adjacent to R1 and R11 are respectively elements constituting the bond B1 or the branch point P1. Specific examples of the trivalent or higher valent L1 include 1 or more of the branch points P1 (for example {(*—)jP1(—**)x1}, {(*—)jP1—R28—P1(—**)x1}), a combination of 1 or more of the branch points P1 and 1 or more of the bonds B1 (for example {*—B1—R28—P1(—**)x1}, {*—B1—R28—P1(—R28—B1—**)x1}). R26 is a single bond or a bivalent organic group, * is a binding site on the R1 side, and ** is a binding site on the R11 side.
The bivalent organic group as R28 may, for example, be a hydrocarbon group such as a bivalent aliphatic hydrocarbon group (e.g. an alkylene group or a cycloalkylene group), a bivalent aromatic hydrocarbon group (e.g. a phenylene group), and may have the bond B1 between carbon atoms in the hydrocarbon group. The number of carbon atoms in the bivalent organic group is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4.
The above L1 is, in view of easy production of the Compound (A1), preferably a group represented by any one of the following formulae (L1) to (L7).
The group of each of the formulae (L1) to (L7) is linked to R1 of the formula (A1) on the A1, A2 or A3 side, and is linked to R11 on the Q22, Q23, Q24, Q25 or Q26 side.
A1 is a single bond, —B3—, —B3—R30—, or, —B3—R30—B2—, wherein R30 is an alkylene group or a group having —C(O)NRe6—, —C(O)—, —CO(O)—, —NRe6— or —O— between carbon atoms of an alkylene group having 2 or more carbon atoms, B2 is —C(O)NRe6—, —C(O)—, —NRe6— or —O—, and B3 is —C(O)NRe6—, —C(O)—, or —NRe6—,
The directions of B2 and B3 are not limited. When there is a plurality of A1, the plurality of A1 may be the same or different from each other. The same applies to A2, A3, Q22, Q23, Q24, Q25, Re1, Re2, and Re3.
Further, d1+d3, d5, d7, d8, d10 are j, and d2+d4, d6, 3−d7, d9, d11, and 1+d12 are x1.
The number of carbon atoms in the alkylene group as R30 is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, in view of easiness of production of the Compound (A1), and whereby the obtainable surface layer will be more excellent in abrasion resistance, light resistance and chemical resistance. In a case where the alkylene group has a specific bond between carbon atoms, the lower limit of the number of carbon atoms in such an alkylene group is 2.
The cyclic structure in Z1 may be the above described cyclic structure, and its preferred embodiment is also the same.
The number of carbon atoms in the alkyl group as Re1, Re2 or Re3 is, in view of easy production of the Compound (A1), preferably 1 to 6, more preferably 1 to 3, further preferably 1 to 2.
The number of carbon atoms in the alkyl group moiety of the acyloxy group as Re2 is, in view of easiness of production of the Compound (A1), preferably 1 to 6, more preferably 1 to 3, further preferably 1 to 2.
d9 is preferably 2 to 6, more preferably 2 to 4, further preferably 2 or 3, in view of easiness of production of the Compound (A1), and whereby the obtainable surface layer will be more excellent in abrasion resistance and fingerprint stain removability.
As other embodiments of L1, groups represented by the following formulae (L11) to (L17) may be mentioned.
The group of each of the formulae (L11) to (L17) is linked to R1 of the formula (A1) on the A1, A2 or A3 side, and is linked to R11 on the Q22, Q23, Q24, Q25 or Q26 side. G is the following group (G21), and 2 or more G which L1 has may be the same or different from each other. Symbols other than G are the same as the symbols in the formulae (L1) to (L7).
In a case where Q3 is —R52—B3—, the number of carbon atoms in the alkylene group as R52 is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, in view of easy production of the Compound (A1), and whereby the obtainable surface layer will be more excellent abrasion resistance, light resistance and chemical resistance. In a case where the alkylene group has a specific bond between carbon atoms, the lower limit of the number of carbon atoms in such an alkylene group is 2.
The number of carbon atoms in the alkyl group as R51 is, in view of easy production of the Compound (A1), preferably 1 to 6, more preferably 1 to 3, further preferably 1 to 2.
The number of carbon atoms in the alkyl group as R22 is, in view of easy production of the Compound (A1), preferably 1 to 6, more preferably 1 to 3, further preferably 1 to 2.
The number of carbon atoms in the alkoxy group as R22 is, in view of excellent storage stability of the Compound (A1), preferably 1 to 6, more preferably 1 to 3, further preferably 1 to 2.
p11 is preferably 0 or 1.
The molecular weight of the group represented by L1-(R11-T11)x1 is preferably 300 or more, more preferably 450 or more, further preferably 600 or more, whereby the obtainable surface layer will have more improved abrasion resistance.
On the other hand, the molecular weight is preferably 2,000 or less, more preferably 1,500 or less, further preferably 1,000 or less, in view of more excellent antifouling property.
The ratio of the molecular weight of the fluoropolyether chain represented by [Rf1—(ORf11)y1—O—R1]j to the molecular weight of the group represented by L1-(R11-T11)x1, is preferably 10% or more, more preferably 12% or more, further preferably 13% or more, whereby the obtainable surface layer will have more improved abrasion resistance.
The upper limit of the above ratio is preferably 40% or less, more preferably 25% or less, in view of more excellent antifouling property.
As the Compound (A1), the following may, for example, be mentioned.
Rf2 is each independently the same as [Rf1—(ORf11)y1—O—R1] or [Rf1—(ORf11)y1—O—], T is the same as T11, and Me represents a methyl group.
The Compound (A2) has a structure represented by the following formula (A2).
(T31-R31)x3-L3-R3—(ORf12)y2—O—R2-L2-(R21-T21)x2 (A2)
Symbols in the formula (A2) are as defined above.
Rf12 and (ORf12)y2 are the same as the above Rf11 and (ORf11)y1, and their preferred embodiments are also the same.
R2 and R3 are each independently the same as R1, and their preferred embodiments are also the same.
R21 and R31 are the same as R11, and their preferred embodiments are also the same.
“Bonded to L1” is read as “bonded to L2” in the case of R21, and is read as “bonded to L3” in the case of R31.
“Bonded to T11” is read as “bonded to T21” in the case of R21, and is read as “bonded to T31” in the case of R31.
“Linked to T11” is read as “linked to T21” in the case of R21, and is read as “linked to T31” in the case of R31.
“In the case of —SiRa12z11Ra123-z11” is read as “in the case of —SiRa21z21Ra223-z21”
In a case where L2 is a single bond, R21 is directly bonded to R2. In a case where L3 is a single bond, R31 is directly bonded to R3.
T21 and T31 are each independently —CH═CH2, or —SiRa21z21Ra223-z21, Ra21, Ra22 and z21 are each independently the same as Ra1, Ra2 and z1 constituting T11, and their preferred embodiments are also the same.
x2 and x3 are each independently the same as x1, and their preferred embodiments are also the same.
L2 and L3 are each independently the same as L1 wherein j is 1.
For example in a case where L2 and L3 are a single bond, the Compound (A2) is represented by the following formula (A2′).
T31-R31—R3—(ORf12)y2—O—R2—R21-T21 (A2′)
Symbols in the formula (A2′) are as defined for the formula (A2).
In a case where L2 or L3 is a trivalent or higher valent group, the trivalent or higher valent L2 or L3 has at least one type of branch point (hereinafter referred to as “branch point P2”) selected from the group consisting of C, N, Si, a cyclic structure and a (1+x2)-valent or (1+x3)-valent organopolysiloxane residue.
In a case where the branch point P2 is N, the branch point P2 is represented, for example, by *—N(—**)2. * is a binding site on the R2 or R3 side, and ** is a binding site on the R21 or R31 side.
In a case where the branch point P2 is C, the branch point P2 is represented, for example, by *—C(—**)3, or *—CR29(—**)2. * is a binding site on the R2 or R3 side, ** is a binding site on the R21 or R31 side, and R29 is a monovalent group. R29 may, for example, be a hydrogen atom, a hydroxy group, an alkyl group, or an alkoxy group.
In a case where the branch point P2 is Si, the branch point P2 is represented, for example, by *—Si(—**)3, or *—SiR29(—**)2.
* is a binding site on the R2 or R3 side, ** is a binding site on the R21 or R31 side, and R29 is a monovalent group. R29 may, for example, be a hydrogen atom, a hydroxy group, an alkyl group, or an alkoxy group.
The cyclic structure and the organopolysiloxane residue constituting the branch point P2 are the same as for the branch point P1, and their preferred embodiments are also the same.
The bivalent or higher valent L2 and L3 may each independently have the bond B1. The embodiment of the bond B1 is as defined above, and its preferred embodiment is also the same.
In the bivalent L2 or L3, the atoms bonded to R2 and R21, or R3 and R31, are each independently N, O, S, Si, or a carbon atom having a hydroxy group or an oxo group (═O). That is, the atoms adjacent to R2 and R21, or R3 and R31, are respectively elements constituting the bond B1. Specific examples of the bivalent L2 or L3 include 1 or more of the bonds B1 (for example *—B1—**, *—B1—R28—B1—**). R28 is a single bond or a bivalent organic group, * is a binding site on the R2 or R3 side, and ** is a binding site on the R21 or R31 side.
In the trivalent or higher L2 or L3, the atoms bonded to R2 and R21, or R3 and R31, are each independently N, O, S, Si, a carbon atom constituting the branch point, or a carbon atom having a hydroxy group or an oxo group (═O). That is, the atoms adjacent to R2 and R21, or R3 and R31, are respectively elements constituting the bond B1 or the branch point P2. Specific examples of the trivalent or higher valent L2 or L3 include 1 or more of the branch points P2 (for example {*—p2(—**)x}, {*—P2—R28—P2(—**)x1}), and a combination of 1 or more of the branch points P2 and 1 or more of the bonds B1 (for example {*—B1—R28—P2(—**)x}, {*—B1—R28—P2(—R28—B1—**)x}). x is x2 in the case of L2, and is x3 in the case of L3. R28 is a single bond or a bivalent organic group, * is a binding site on the R2 or R3 side, and ** is a binding site on the R21 or R31 side.
The embodiment of the above R28 is as described above, and its preferred embodiment is also the same.
L2 or L3 are, in view of easy production of the Compound (A2), each independently preferably any one of groups represented by the following formulae (L21) to (L27).
The group of each of the formulae (L21) to (L27) is linked to R2 or R3 on the A1, A2 or A3 side, and is linked to R21 or R31 on the Q22, Q23, Q24, Q25 or Q26 side.
A1, A2, A3, Q11, Q22, Q23, Q24, Q25, Q26, Re1, Re2Re3 and Re6 are as defined for L1, and their preferred embodiments are also the same.
Z1 is a (1+d9)-valent group having a cyclic structure, having a carbon atom or a nitrogen atom to which A3 is directly bonded and having a carbon atom or a nitrogen atom to which Q24 is directly bonded,
d9 is preferably 2 to 6, more preferably 2 to 4, further preferably 2 or 3, in view of easy production of the Compound (A2) and whereby the obtainable surface layer will be more excellent in abrasion resistance and fingerprint stain removability.
As other embodiments of L2 and L3, groups represented by the following formulae (L31) to (L37) may be mentioned.
The group of each of the formulae (L31) to (L37) is bonded to R2 or R3 on the A1, A2 or A3 side, and is bonded to R21 or R31 on the Q22, Q23, Q24, Q25 or Q26 side. G is the above group (G21), and its preferred embodiment is also the same. Symbols other than G are the same as the symbols in the formulae (L21) to (L27), and their preferred embodiments are also the same.
In the Compound (A2), the molecular weight of at least one of the group represented by L2-(R21-T21)x2 and the group represented by (T31-R31)x3-L3 is preferably 300 or more, more preferably 450 or more, further preferably 600 or more, whereby the obtainable surface layer will have more improved abrasion resistance.
On the other hand, the above molecular weight is preferably 2,000 or less, more preferably 1,500 or less, further preferably 1,000 or less, in view of more excellent antifouling property.
It is preferred that both the molecular weight of the group represented by L2-(R21-T21)x2 and the molecular weight of the group represented by (T31-R31)x3-L3 are within the above range.
The ratio of the molecular weight of the group represented by R3—(ORf12)y2—O—R2 to the sum of the molecular weight of the group represented by L2-(R21-T21)x2 and the molecular weight of the group represented by (T31-R31)x3-L3, is preferably 10% or more, more preferably 12% or more, further preferably 13% or more, whereby the obtainable surface layer will have more improved abrasion resistance.
The upper limit of the above ratio is, in view of more excellent antifouling property, preferably 40% or less, more preferably 25% or less.
As the Compound (A2), the following may, for example, be mentioned.
Rf3 is each independently the same as [R3—(ORf12)y2—O—R2] or [(ORf12)y2—O], and T is the same as T21 or T31.
The Compound (A3) has a structure represented by the following formula (A3).
Q1[-(ORf13)y3—O—R4-L4-(R41-T41)x4]r1 (A3)
Symbols in the formula (A3) are as defined above.
Rf13 and (ORf13)y3 are the same as Rf11 and (ORf11)y1, and their preferred embodiments are also the same.
R4 is the same as R1, and its preferred embodiment is also the same.
R41 is the same as R11, and its preferred embodiment is also the same.
“Bonded to L1” is read as “bonded to L4”.
“Bonded to T11” is read as “bonded to T41”.
“Linked to T11” is read as “linked to T41”.
“In the case of —SiRa11z11Ra123-z11” is read as “in the case of —SiRa41z41Ra423-z41”.
In a case where L4 is a single bond, R41 is directly bonded to R4.
T41 is —CH═CH2 or —SiRa41z41Ra423-z41, Ra41, Ra42 and z41 are each independently the same as Ra1, Ra2 and z1 constituting T11, and their preferred embodiments are also the same.
Q1 is a r1-valent group having a branch point, and r1 is 3 or 4.
The branch point constituting Q1 (hereinafter referred to as “branch point P3”) may be N, C, Si or a cyclic structure. Q1 may have one branch point P3, or may have 2 or more branch points P3.
In a case where the branch point P3 is N, the branch point P3 is represented for example by N(—*)3, or NR29(—*)2.
In a case where the branch point P3 is C, the branch point P3 may, for example, be C(—*)4, CR29(—*)3, or C(R29)2(—*)2.
In a case where the branch point P3 is Si, the branch point P3 may, for example, be Si(—*)4, SiR29(—*)3, or Si(R29)2(—*)2.
* is a binding site on the ORf13 side, and R29 is a monovalent group. R29 may, for example, be a hydrogen atom, a fluorine atom, a hydroxy group, an alkyl group, a fluoroalkyl group, or a fluoropolyether chain having no R41-T41.
The cyclic structure constituting the branch point P3 may be the same cyclic structure constituting the branch point P1, and the cyclic structure may further have, as a substituent, in addition to the above substituent, at least one group selected from the group consisting of a fluorine atom, a fluoroalkyl group and a fluoropolyether chain having no R41-T41.
As Q1, in view of easy production of the Compound (A3), preferred are groups represented by the following formulae (Q1) to (Q6).
In the formulae (Q1) to (Q6), A11, A12 or A13 is linked to (ORf13).
A11 is a single bond, —R40—, or —B13—R40—, R40 is an alkylene group, a fluoroalkylene group or a group having —C(O)NRe16—, —C(O)—, —CO(O)—, —NRe16— or —O— between carbon atoms of an alkylene group or fluoroalkylene group having 2 or more carbon atoms, B13 is —C(O)NRe16—, —C(O)—, —NRe16— or —O—,
The direction of B13 is not limited. When there is a plurality of A11, the plurality of A11 may be the same or different from each other. The same applies to A12, A13, Re11, Re12 and Re13.
The number of carbon atoms in the alkylene group or the fluoroalkylene group as R40 is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, in view of easy production of the Compound (A3), and whereby the obtainable surface layer will be more excellent in abrasion resistance, light resistance and chemical resistance. In a case where the alkylene group has a specific bond between carbon atoms, the lower limit of the number of carbon atoms in such an alkylene group is 2.
The cyclic structure in Z1 may be the cyclic structure constituting the branch point P3, and its preferred embodiment is also the same.
The number of carbon atoms in the alkylene group or the fluoroalkylene group as Re11, Re12 or Re13 is, in view of easy production of the Compound (A3), preferably 1 to 6, more preferably 1 to 3, further preferably 1 to 2.
In the Compound (A3), the molecular weight of at least one of the groups represented by L4-(R41-T4)x4 is preferably 300 or more, more preferably 450 or more, further preferably 600 or more, whereby the obtainable surface layer will have more improved abrasion resistance.
On the other hand, the molecular weight is, in view of more excellent antifouling property, preferably 2,000 or less, more preferably 1,500 or less, further preferably 1,000 or less.
It is preferred that the molecular weights of all the groups represented by L4-(R41-T41)x4 are within the above range.
The ratio of the sum of the sum of the molecular weights of r1 groups represented by (ORf13)y3—O—R4 and the molecular weight of the group represented by Q1, to the sum of the molecular weights of r1 groups represented by L4-(R41-T41)x4, is preferably 10% or more, more preferably 12% or more, further preferably 13% or more, whereby the obtainable surface layer will have more improved abrasion resistance.
The upper limit of the above ratio is, in view of more excellent antifouling property, preferably 40% or less, more preferably 25% or less.
As the Compound (A3), the following may, for example, be mentioned.
In the above compounds, {—O—Rf4—} is each independently the same as [—(ORf13)y3—O—R4—], or [—(ORf13)y3—O—], and T is the same as T41.
The present composition may contain a single type of the first component or may contain 2 or more types of the first components.
The content of the first component is, to the total mass of the present composition, preferably 1 to 99 mass %, more preferably 5 to 95 mass %, further preferably 10 to 90 mass %.
The concentration of the first component to the total molar amount of the first component and the second component contained in the present composition is preferably 5 to 95 mol %, more preferably 10 to 90 mol %.
The second component is at least one fluorinated ether compound selected from the group consisting of a compound represented by the following formula (B1) and a compound represented by the following formula (B2) and is a compound to be extracted in the present extraction method.
In the formula (B1),
Rf17 and Rf19 are each independently a C1-20 fluoroalkyl group,
The Compound (B1) has a structure represented by the following formula (B1).
Rf14—(ORf15)y4—O—R5—Rb1 (B1)
Symbols in the formula (B1) are as defined above.
Rf14 is a C1-20 fluoroalkyl group.
The number of carbon atoms in the fluoroalkyl group is preferably 1 to 10, more preferably 1 to 6, particularly preferably 1 to 3, whereby the obtainable surface layer will be more excellent in water repellency.
The fluoroalkyl group may be any of linear, branched or cyclic.
The fluoroalkyl group is preferably a group having all hydrogen atoms in a fluoroalkyl group replaced with fluorine atoms (perfluoroalkyl group).
Rf15 is a C1-6 fluoroalkylene group.
The preferred embodiment of Rf15 is the same as Rf11 in the formula (A1). The preferred embodiment of (ORf15) is the same as (ORf11) the above formula (A1).
The number y4 of repetition of (ORf15) is an integer of 1 or more. The preferred embodiment of y4 is the same as the number y1 of repetition of the above (ORf11).
R5 is an alkylene group which may have a substituent.
The number of carbon atoms in the alkylene group which may have a substituent is preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 10, particularly preferably 1 to 6. In a case where the substituent has a carbon atom, the number of the carbon atom in the substituent is not included in the number of carbon atoms in the alkylene group which may have a substituent.
The alkylene group which may have a substituent may be any of linear, branched and cyclic.
The substituent which the alkylene group may have may, for example, be a halogen atom, a hydroxy group or an amino group. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom and is preferably a fluorine atom. In a case where the alkylene group has a fluorine atom, the alkylene group, that is a fluoroalkylene group, may be a group having all hydrogen atoms in the fluoroalkylene group replaced with fluorine atoms (perfluoroalkylene group).
R5 is, in view of more excellent extraction efficiency of the first component, preferably a fluoroalkylene group, more preferably a fluoroalkylene group having a hydrogen atom (that is a fluoroalkylene group excluding a perfluoroalkylene group), further preferably —Rfb1—Rb11. Rfb1 is a C1-6 perfluoroalkylene group, Rb11 is a non-substituted C1-6 alkylene group, and Rb11 is bonded to Rb1. The sum of the number of carbons in Rfb1 and the number of carbon atoms in Rb11 is the same as the above number of carbon atoms in R5.
Rb1 is a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom.
Rb1 is preferably a hydrogen atom or an iodine atom, more preferably a hydrogen atom.
The Compound (B1) may be used in combination of 2 or more.
Specific examples of the Compound (B1) include the following. PFPE in the following compounds is the same as Rf14—(ORf15)y4— in the formula (B1), and its preferred embodiment is also the same. Rfb1 is a C1-6 perfluoroalkylene group, and represents the partial structure of R5 in the formula (B1). X in the following compounds is the same as Rb1 in the formula (B1), and its preferred embodiment is also the same. R in the following compound is the same as the substituent which the alkylene group which may have a substituent represented by R5 in the formula (B1) may have, and its preferred embodiment is also the same.
The method for producing the Compound (B1) is not particularly limited and description in WO2013/121984 may be mentioned.
The Compound (B2) has a structure represented by the following formula (B2).
Rf19—(ORf18)y6—O—R7-Lb1-R6—O—(Rf16O)y5—Rf17 (B2)
Symbols in the formula (B2) are as defined above.
Rf17 and Rf19 are each independently a C1-20 fluoroalkyl group. The preferred embodiments of Rf17 and Rf19 are the same as Rf14 in the above formula (B1).
Rf16 and Rf18 are each independently a C1-6 fluoroalkylene group. The preferred embodiments of Rf16 and Rf18 are the same as Rf15 in the above formula (B1).
The number y5 of repetition of (Rf16O) is an integer of 1 or more. The preferred embodiment of y5 is the same as the number y4 of repetition of the above (ORf15).
The number y6 of repetition of (ORf18) is an integer of 1 or more. The preferred embodiment of y6 is the same as the number y4 of repetition of the above (ORf15).
R6 and R7 are an alkylene group which may have a substituent. The preferred embodiments of R6 and R7 are the same as R5 in the above formula (B1).
The total number of carbon atoms in the alkylene group which may have a substituent as R6 and the alkylene group which may have a substituent as R7 is preferably 2 to 40, more preferably 2 to 20, further preferably 2 to 16. In a case where the substituent has a carbon atom, the number of the carbon atom in the substituent is not included in the number of carbon atoms in the alkylene group which may have a substituent.
R6 and R7 may be the same group or may be different groups, and are preferably the same group.
R6 is, in view of more excellent extraction efficiency of the first component, preferably a fluoroalkylene group, more preferably a fluoroalkylene group having a hydrogen atom (that is a fluoroalkylene group excluding a perfluoroalkylene group), further preferably —Rfb2—Rb12—. Rfb2 is a C1-6 perfluoroalkylene group, Rb12 is a non-substituted C1-6 alkylene group, and Rb12 is bonded to Lb1 (R6 in a case where Lb1 is a single bond). The sum of the number of carbon atoms in Rfb2 and the number of carbon atoms in Rb12 is the same as the number of carbon atoms in R6.
R7 is, in view of more excellent extraction efficiency of the first component, preferably a fluoroalkylene group, more preferably a fluoroalkylene group having a hydrogen atom (that is a fluoroalkylene group excluding a perfluoroalkylene group), further preferably —Rb13—Rfb3—. Rfb3 is a C1-6 perfluoroalkylene group, Rb13 is a non-substituted C1-6 alkylene group, and Rb13 is bonded to Lb1 (R7 in a case where Lb1 is a single bond). The sum of the number of carbon atoms in Rfb3 and the number of carbon atoms in Rb13 is the same as the number of carbon atoms in R7.
Lb1 is a single bond or a bivalent linking group (excluding (ORf18)y7 and (Rf16O)y8, and y7 and y8 are each independently an integer of 1 or more).
Specific examples of the bivalent linking group include an alkylene group, an etheric oxygen atom, an amide bond and a group having these combined with each other. Among the bivalent linking groups, preferred are an alkylene group, a group having an alkylene group and an etheric oxygen atom combined, and a group having an alkylene group and an amide bond combined.
The bivalent linking group as Lb1 does not include (ORf18)y7 and (Rf16O)y8. The definitions of (ORf18) and (Rf16O) are as defined above, and y7 and y8 are each independently an integer of 1 or more
Lb1 is, in view of more excellent extraction efficiency of the first component, preferably a single bond.
The Compound (B2) may be used in combination of 2 or more.
Specific examples of the Compound (B2) include the following. PFPE in the following compounds is the same as Rf19—(ORf18)y6— or —(Rf16O)y5—Rf17 in the formula (B2), and its preferred embodiment is also the same. Rfb2 is a C1-6 perfluoroalkylene group and represents the partial structure of R6 in the formula (B2). Rfb3 is a C1-6 perfluoroalkylene group and represents the partial structure of R7 in the formula (B2). R in the following compounds is the same as the substituent which the alkylene group which may have a substituent represented by R6 and R7 in the formula (B2) may have, and its preferred embodiment is also the same.
The method for producing the Compound (B2) is not particularly limited and may be a method of subjecting Compounds (B1) to a known coupling reaction.
The present composition may contain a single type of the second component or may contain 2 or more types of the second component.
The content of the second component is, to the total mass of the present composition, preferably 1 to 99 mass %, more preferably 5 to 95 mass %, further preferably 10 to 90 mass %.
The present composition may contain a component other than the first component and the second component (hereinafter sometimes referred to as “other component”).
Specific examples of such other component include an organic solvent containing a fluorine atom (hereinafter sometimes referred to as “fluorinated organic solvent”).
Specific examples of the fluorinated organic solvent include a fluorinated alkane, a fluorinated aromatic compound, a fluoroalkyl ether, a fluorinated alkylamine, a fluoroalcohol and a hydrofluoroolefin.
Specific examples of a preferred fluorinated alkane include C4-8 compounds. Commercial products include C6F13H (manufactured by AGC Inc., ASAHIKLIN (registered trademark) AC-2000), C6F13C2H5 (manufactured by AGC Inc., ASAHIKLIN (registered trademark) AC-6000), and C2F5CHFCHFCF3 (manufactured by Chemours, Vertrel (registered trademark) XF).
Specific examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfuorotoluene and bis(trifluoromethyl)benzene.
The fluoroalkyl ether is preferably a C4-12 compound. Commercial products include CF3CH2OCF2CF2H (manufactured by AGC Inc., ASAHIKLIN (registered trademark) AE-3000), C4F9OCH3 (manufactured by 3M, Novec (registered trademark) 7100), C4F9OC2H5 (manufactured by 3M, Novec (registered trademark) 7200), and C2F5CF(OCH3)C3F7 (manufactured by 3M, Novec (registered trademark) 7300).
Specific examples of the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.
Specific examples of the fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol and hexafluoroisopropanol.
Specific examples of the hydrofluoroolefin include 1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd), a reaction product of methanol with 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-3-heptene, and a reaction product of methanol with 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-3-heptene. Commercial products include AMOLEA (registered trademark) AS-300 manufactured by AGC Inc., and Opteon (registered trademark) (SF01, SF05, SF10, SF30, SF33, SF70, SF79, SF80) manufactured by Chemours.
In a case where the present composition contains the fluorinated organic solvent, the content of the fluorinated organic solvent is, to the total mass of the present composition, preferably 67 mass % or less, more preferably 50 mass % or less, further preferably 33 mass % or less.
The non-fluorinated organic solvent is used for extraction of the first component in an extraction step described later. Since the first component and the non-fluorinated organic solvent are well compatible, the first component can efficiently be extracted by using the non-fluorinated organic solvent.
The non-fluorinated organic solvent may be any organic solvent containing no fluorine atom, and is preferably a non-halogenated solvent in view of more excellent extraction efficiency of the first component.
The non-halogenated solvent is an organic solvent containing no halogen atom and may, for example, be a hydrocarbon-based organic solvent, an alcohol-based organic solvent, a ketone-based organic solvent, an ether-based organic solvent, an ester-based organic solvent, an amide-based organic solvent, or a sulfoxide-based organic solvent.
The hydrocarbon-based organic solvent is a compound composed solely of hydrogen atoms and carbon atoms and may be any of an aromatic hydrocarbon, an aliphatic hydrocarbon and an unsaturated hydrocarbon.
The aromatic hydrocarbon may, for example, be benzene, toluene or xylene.
The aliphatic hydrocarbon may, for example, be n-hexane, n-heptane, n-octane or n-decane.
The unsaturated hydrocarbon may, for example, be cyclopentene, hexene, heptene or butene.
The ketone-based organic solvent may, for example, be acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methyl amino ketone, 2-heptanone, diisobutyl ketone or diacetone alcohol.
The alcohol-based organic solvent may, for example, be methanol, ethanol, propanol, isopropanol or butanol. A glycol-based solvent described later is not included in the alcohol-based solvent.
The ether-based organic solvent may, for example, be diethyl ether, diisopropyl ether, methyl t-butyl ether, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, cyclopentyl methyl ether, 4-methyltetrahydrofuran, 2-methyltetrahydrofuran, or a glycol-based solvent.
The glycol-based solvent may, for example, be a mono- or di-alkylene glycol mono- or di-alkyl ether, or a mono- or di-alkylene glycol mono- or di-alkyl ether acetate. The alkylene group is preferably an ethylene group or a propylene group. The alkyl group is preferably a C1-4 alkyl group, more preferably a methyl group or an ethyl group. The glycol-based solvent may be more specifically ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether or propylene glycol monobutyl ether.
The ester-based organic solvent may, for example, be ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate, methyl formate, methyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, or an esterified compound of the glycol-based solvent and a carboxylic acid such as acetic acid.
The amide-based organic solvent may, for example, be N,N-dimethylformamide.
The sulfoxide-based organic solvent may, for example, be dimethyl sulfoxide.
In view of more excellent extraction efficiency of the first component, the relative permittivity of the non-halogenated solvent is preferably 30 or less, more preferably 20 or less, further preferably 10 or less.
In this specification, the relative permittivity of the organic solvent means the relative permittivity at 25° C., and is measured with a known liquid dielectric constant meter.
The non-halogenated solvent is, in view of more excellent extraction efficiency of the first component, preferably a hydrocarbon-based solvent.
The non-fluorinated organic solvent may be used singly or in combination of 2 or more
In the extraction step, the amount of the non-fluorinated organic solvent used is, per 100 parts by mass of the present composition, preferably 50 to 3,000 parts by mass, more preferably 100 to 2,000 parts by mass, further preferably 300 to 1,500 parts by mass.
When the amount of the non-fluorinated organic solvent used is 50 parts by mass or more, the amount of the first component that elutes in the non-fluorinated organic solvent increases, and the first component will more efficiently be extracted.
When the amount of the non-fluorinated organic solvent used is 3,000 parts by mass or less, the second component can efficiently be removed.
The mass ratio of the amount of the non-fluorinated organic solvent used to the amount of the first component used is, in view of more excellent extraction efficiency of the first component, preferably 50 to 15,000, more preferably 100 to 10,000, further preferably 300 to 7,500.
In a case where the present composition contains the fluorinated organic solvent, the mass ratio of the amount of the non-fluorinated organic solvent used to the amount of the fluorinated organic solvent used is, in view of more excellent extraction efficiency of the first component, preferably 1 or more, more preferably 3 or more, further preferably 5 or more.
The present extraction method includes a step of extracting the first component from the present composition using the non-fluorinated organic solvent (hereinafter sometimes referred to as “extraction step”). By this step, an eluate in which the first component more selectively elutes in the non-fluorinated organic solvent than the second component can be obtained.
As an example of a preferred embodiment of the extraction step, such a method may be mentioned that a mixture of the present composition and the non-fluorinated organic solvent is stirred and then left at rest to separate into an eluate in which the first component more selectively elutes in the non-fluorinated organic solvent than the second component, and components that have not eluted in the non-fluorinated organic solvent, and the layer of the eluate is recovered.
The temperature in the extraction step (for example, the temperature of the above mixture) is preferably 0 to 50° C., more preferably 15 to 35° C.
The extraction step may include removal treatment of removing the non-fluorinated organic solvent from the eluate.
A specific example of the removal treatment includes distillation (for example vacuum distillation). Distillation may be conducted e.g. by a known distillation apparatus.
The extraction step may include filtration treatment of removing solids that may be included in the above mixture or eluate. The filtration treatment may be conducted e.g. by a filtration filter.
The extraction step may be conducted only once, or may be conducted twice or more. In a case where the extraction step is conducted twice or more, an eluate containing the first component with higher purity can be obtained.
In the second or subsequent extraction step, it is preferred to use a component obtained by removing the non-fluorinated organic solvent and solids from the eluate obtained in the previous extraction step.
Now, the present invention will be described in detail with reference to Examples. Examples 1 to 3 are Examples of the present invention, and Examples 4 to 6 are Comparative Examples. It should be understood that the present invention is by no means restricted to such specific Examples Amounts of the respective components in Tables described later are based on mass.
Into a reactor, 2.0 g of dimethyl malonate, 10.6 g of 11-bromo-1-undecene (CH2═CH(CH2)9—Br), 8.4 g of potassium carbonate and 50.0 g of dimethylformamide (DMF) were put and stirred in a nitrogen atmosphere at 85° C. After completion of the reaction, hydrochloric acid was added, an organic phase was recovered, and the recovered organic phase was concentrated by an evaporator to obtain 6.1 g of Compound X1.
wherein Me is a methyl group.
Into a reactor, 6.1 g of Compound X1, 24.4 g of dimethyl sulfoxide (DMSO), 2.4 g of lithium chloride and 3.27 g of water were put and stirred in a nitrogen atmosphere at 180° C. After completion of the reaction, hydrochloric acid was added, an organic phase was recovered, and the recovered organic phase was concentrated by an evaporator and subjected to silica gel column chromatography to obtain 4.0 g of Compound X2.
Into a reactor, 2.0 g of Compound X2, 20.0 g of dehydrated tetrahydrofuran (THF), 6.6 mL of 2.0M lithium diisopropylamide (THF solution) and 3.1 g of 11-bromo-1-undecene (CH2═CH(CH2)9—Br) were put and stirred in a nitrogen atmosphere at about −70° C. After completion of the reaction, hydrochloric acid was added, an organic phase was recovered, and the recovered organic phase was concentrated by an evaporator and subjected to silica gel column chromatography to obtain 2.1 g of Compound X3.
Into a reactor, 0.89 g of lithium aluminum hydride and 25 g of dehydrated THF were put and stirred in a nitrogen atmosphere at 0° C. Then, 2.5 g of Compound X3 was put and stirred in a nitrogen atmosphere at 0° C. After completion of the reaction, water and 1M sodium hydroxide were put, an organic phase was recovered, and the recovered organic phase was concentrated by an evaporator and subjected to silica gel column chromatography to obtain 2.0 g of Compound X4.
Using the above Compound X4, in accordance with the method in Examples 1 and 2 of WO2021/054413, the following Compound X5 was obtained.
1.03 g of the following Compound B1-1 was suspended in 5 ml of dehydrated THF, 0.0025 g of copper chloride was added and stirred at room temperature (25° C.). To the mixed solution, 1.15 g of the above Compound X5 adjusted to 17 mass % was slowly added dropwise, followed by stirring at 55° C. The mixed solution was cooled to room temperature (25° C.), water was added, extraction was conducted with 5 mL of -3000 (manufactured by AGC Inc., ASAHIKLIN (registered trademark) AE-3000), and sodium sulfate was added. After filtration, the solvent was distilled off. By conducting flash column chromatography with silica gel, a mixture containing Compound A1-1 was obtained. It was confirmed by NMR measurement that Compound A1-1 was obtained with a selectivity of 79%. In the formula, the average of the number n of repeating units is 13.
Compound B1-1 was obtained in accordance with the method described in Example 11 of WO2013/121984.
CF3—(OCF2CF2-OCF2CF2CF2CF2)n(OCF2CF2)—OCF2CF2CF2—CH2CH2I (B1-1)
The average of the number n of repeating units is 13.
Into a flask, 3.0 g of the above Compound B1-1, 22 mg of azobisisobutyronitrile, 6.0 g of 1,3-bis(trifluoromethyl)benzene and 574 mg of tributyltin hydride were put and stirred at 70° C. for 2 hours. After the mixture was cooled to room temperature (25° C.), the obtained reaction solution was purified by silica gel column chromatography to obtain 2.3 g of Compound B1-2.
NMR spectrum data of Compound B1-2;
CF3—(OCF2CF2—OCF2CF2CF2CF2)n(OCF2CF2)—OCF2CF2CF2—CH2CH3 (B1-2)
The average of the number n of repeating units is 13.
In an argon atmosphere, 3.0 g of the above Compound B1-1, 104 mg of metal copper and 3.0 mL of DMSO were put into a flask and stirred at 150° C. for 16 hours.
After the obtained reaction solution was cooled to room temperature (25° C.), it was purified by silica gel column chromatography to obtain 2.1 g of Compound B2-1. In the formula, the average of the number n of repeating units is 13.
NMR spectrum data of Compound B2-1;
60.0 g of diethyl diallyl malonate, 23.7g (559 mmol) of lithium chloride, 6.45 g (360 mmol) of water and 263 g of DMSO were added and stirred at 160° C. After the mixture was cooled to room temperature (25° C.), water was added and extraction with ethyl acetate was conducted. Hexane was added to an organic layer, and the organic layer was washed with saturated salt solution and dried over sodium sulfate. After filtration, the solvent was distilled off to obtain 39.5 g of the following Compound Y1.
wherein Et is an ethyl group.
NMR spectrum data of Compound Y1;
260 mL of THF and 29.8 mL of diisopropylamine were added, and the solution was cooled to −78° C. 96.6 mL of n-butyllithium hexane solution (2.76 M) was added and warmed to 0° C. After stirring, the mixture was cooled to −78° C. to prepare a THF solution of lithium diisopropylamide (LDA). 39.5 g of the above Compound Y1 was added to the THE solution and stirred, and 24.1 mL of allyl bromide was added. The mixture was warmed to 0° C., 100 mL of 1M hydrochloric acid was added, and THF was distilled off under reduced pressure. Extraction with dichloromethane was conducted, and sodium sulfate was added. After filtration, the solvent was distilled off, and flash column chromatography with silica gel was conducted to obtain 45.0 g of Compound Y2.
wherein Et is an ethyl group.
NMR spectrum data of Compound Y2;
45.0 g of the above Compound Y2 was dissolved in 620 mL of THF and cooled to 0° C. 104 mL of a THF solution of lithium aluminum hydride was added and stirred. Water and a 15% aqueous sodium hydroxide solution were added, and the mixture was stirred at room temperature (25° C.) and diluted with dichloromethane. After filtration, the solvent was distilled off, and flash column chromatography with silica gel was conducted to obtain 31.3 g of the following Compound Y3.
NMR spectrum data of Compound Y3;
380 mL of acetonitrile, 31.3 g of the above Compound Y3, 64.3 g of triphenylphosphine and 33.9 g of carbon tetrachloride were added and stirred at 90° C. After concentration, ethyl acetate and hexane were added and stirred. After filtration, the filtrate was concentrated and distilled to obtain 28.2 g of the following Compound Y4.
NMR spectrum data of Compound Y4;
35 mL of THF and 0.180 g of iodide were added to 2.36 g of magnesium and stirred at room temperature (25° C.). 14.0 g of the above Compound Y4 and 35 mL of THF were added and subjected to reflux with heating to obtain a solution (0.80M) of the following Compound Y5.
NMR spectrum data of Compound Y5;
1.03 g of the above Compound B1-1 was suspended in 5 mL of dehydrated THF, 0.0025 g of copper chloride was added and stirred at room temperature (25° C.). To the mixed solution, 0.31 g of the above Compound Y5 adjusted to 17 mass % was slowly added dropwise and stirred at 55° C. The mixed solution was cooled to room temperature (25° C.), water was added, extraction with AE-3000 was conducted, and sodium sulfate was added. After filtration, the solvent was distilled off. Flash column chromatography with silica gel was conducted to obtain a mixture containing Compound C1-1. It was confirmed by NMR measurement that Compound C1-1 was obtained with a selectivity of 84%. In the formula, the average of the number n of repeating units was 13.
NMR spectrum data of Compound C1-1;
1 g of a mixture containing Compound A1-1 (16 mol %), Compound B1-1 (10 mol %), Compound B1-2 (17 mol %) and Compound B2-1 (57 mol %) was prepared and dissolved in 1 g of AC-6000 to obtain reference composition X for extraction.
Hexane (10 g) as an extraction solvent was added to the reference composition X, and the obtained mixture was stirred at room temperature (23° C.) for 30 minutes. After stirring, the mixture was left at rest for 1 hour to separate into two layers, and the upper layer was recovered. Hexane and AC-6000 in the recovered upper layer were distilled off under reduced pressure to obtain sample 1 for purity measurement.
The concentrations (mol %) of the compounds contained in sample 1 were measured by 1H-NMR and 19F-NMR. The results are shown in Table 1.
The concentrations mean the concentrations (mol %) of the respective compounds to the total amount (100 mol %) of the fluorinated ether compounds contained in the sample. The same applies to the following Examples
In the same manner as in Example 1 except that the solvent as identified in Table 1 was used instead of hexane as the extraction solvent, the concentrations (mol %) of the respective compounds contained in each of samples in Examples 2 and 3 were measured. The results are shown in Table 1.
In the same manner as in Example 1 except that AE-3000 was used instead of hexane as the extraction solvent, the mixture after stirring was left at rest, however, the mixture was not separated into two layers.
The concentrations (mol %) of the respective components contained in the mixture were measured in the same manner as in Example 1 and found to be the same as the concentrations of the compounds contained in the reference composition X.
As shown in Table 1, it was confirmed that in extraction of the first component (Compound A1-1) from the composition containing the first component and the second component, by using the organic solvent containing no fluorine atom as the extraction solvent, the first component can efficiently be extracted (Examples 1 to 3).
1 g of a mixture containing Compound C1-1 (25 mol %), Compound B1-1 (7 mol %), Compound B1-2 (27 mol %) and Compound B2-1 (41 mol %) was prepared and dissolved in 1 g of AC-6000 to obtain reference composition Y for extraction.
10 g of hexane as an extraction solvent was added to the reference composition Y, and the obtained mixture was stirred at room temperature (23° C.) for 30 minutes. After stirring, the mixture was left at rest for 1 hour to separate into two layers, and the upper layer was recovered. Hexane and AC-6000 in the recovered upper layer were distilled off under reduced pressure to obtain sample 5 for purity measurement.
In the same manner as in Example 1 except that the sample 5 was used instead of the sample 1, the concentrations (mol %) of the respective compounds contained in the sample in Example 5 were measured. The results are shown in Table 2.
In the same manner as in Example 5 except that AE-3000 was used instead of hexane as the extraction solvent, the mixture after stirring was left at rest, however, the mixture was not separated into two layers.
The concentrations (mol %) of the respective components contained in the mixture were measured in the same manner as in Example 5 and found to be the same as the concentrations of the compounds contained in the reference composition Y.
As shown in Table 2, in a case where Compound C1-1 (compound other than the above described Compound A1, Compound A2 and Compound A3) was used as the fluorinated ether compound to be extracted, instead of Compound A1-1, Compound C1-1 to be extracted could not efficiently be extracted even by using hexane as the extraction solvent with which the fluorinated ether compound to be extracted could be extracted most efficiently among Examples 1 to 4 (Example 5).
This application is a continuation of PCT Application No. PCT/JP2023/036912, filed on Oct. 11, 2023, which is based upon and claims the benefit of priority from Japanese Patent Application No. 2022-164649 filed on Oct. 13, 2022. The contents of those applications are incorporated herein by reference in their entireties.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2022-164649 | Oct 2022 | JP | national |
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP2023/036912 | Oct 2023 | WO |
| Child | 19173893 | US |
