JPH0639503B2 - Fluorine-containing polymer and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel polymers, in particular of the formula: [Wherein R represents hydrogen or a lower alkyl group, and Rf is composed of aminoaminobenzene, fluorinated acetamide, fluoroacetic acid, fluorinated benzoic acid, fluorinated alcohol, fluorinated phenol, fluorinated biphenol, and fluorinated benzamide. A residue obtained by removing hydrogen from the active hydrogen group of the fluorine-containing active hydrogen compound selected from the group is shown. ] and [Wherein P, Q, Y and Z are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an aralkyl group having 10 or less carbon atoms, halogen,
Cyano group, -O-COR '(R' is an alkyl group having 1 to 6 carbon atoms, an aryl group having 8 or less carbon atoms, an alkylaryl group, a haloaryl group, an alkoxyaryl group, a carbon number of 4
The following haloalkyl group or hydroxylalkyl group is shown. ), A cyanomethyl group —CH ₂ OCOR ″ (R ″)
Represents an alkyl group having 9 or less carbon atoms, a haloalkyl group, or a phenyl group. ) And COORa (Ra represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 10 or less carbon atoms, or an aralkyl group having 10 or less carbon atoms)].
M repeating units of formula (I) (where m is a positive integer) and n repeating units of formula (V) (n is 0 or a positive integer)
Exists and the fluorine-containing functional group in the formula (I) is 0.1 to 9
Molecular weight of 1,000 to 10 bound at a ratio of 9.9% by weight
10,000 fluoropolymers and processes for their preparation.

BACKGROUND OF THE INVENTION Compounds having an isocyanate group are widely used in the field of polymer chemistry because of their excellent reactivity. Particularly, a compound having both a polymerizable carbon-carbon unsaturated group and an isocyanate group in the same molecule is used in a wide range of industrial technical fields because both functional groups participate in various reactions with different reaction mechanisms. You can do it. Focusing on such usefulness, the present inventors previously provided an isocyanate compound represented by the following formula [Japanese Patent Application No. 58-2522].
No. 6]: [In the formula, R represents a lower alkyl group. ]. The method of the present invention is also used when R is hydrogen.

Further, the present inventors have provided a polymer having the above-mentioned isocyanate compound (II) as a monomer.

Acyl isocyanate groups introduced into these polymers Has a carbonyl group adjacent to the isocyanate group,
The carbonyl group enhances the activity of the isocyanate group, and is in a state where it can carry out various addition reactions and the like. Therefore, the polymer containing an acylisocyanate group has a wide range of applications and usefulness.

(Object of the Invention) The present invention, as described above, reacts a highly reactive acylisocyanate group with a fluorine-containing active hydrogen compound to introduce a fluorine-containing functional group into a polymer chain, thereby providing a unique performance of the fluorine-containing functional group. It is intended to be applied to a polymer.

(Constitution of Invention) That is, the present invention has the formula: [Wherein R represents hydrogen or a lower alkyl group, and Rf is composed of aminoaminobenzene, fluorinated acetamide, fluoroacetic acid, fluorinated benzoic acid, fluorinated alcohol, fluorinated phenol, fluorinated biphenyl, and fluorinated benzamide. A residue obtained by removing hydrogen from the active hydrogen group of the fluorine-containing active hydrogen compound selected from the group is shown. ] and [Wherein P, Q, Y and Z are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an aralkyl group having 10 or less carbon atoms, halogen,
Cyano group, -O-COR '(R' is an alkyl group having 1 to 6 carbon atoms, an aryl group having 8 or less carbon atoms, an alkylaryl group, a haloaryl group, an alkoxyaryl group, a carbon number of 4
The following haloalkyl group or hydroxylalkyl group is shown. ), A cyanomethyl group —CH ₂ OCOR ″ (R ″)
Represents an alkyl group having 9 or less carbon atoms, a haloalkyl group, or a phenyl group. ) And COORa (Ra represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 10 or less carbon atoms, or an aralkyl group having 10 or less carbon atoms)].
M repeating units of formula (I) (where m is a positive integer) and n repeating units of formula (V) (n is 0 or a positive integer)
Exists and the fluorine-containing functional group in the formula (I) is 0.1 to 9
Molecular weight of 1,000 to 10 bound at a ratio of 9.9% by weight
Provided are 10,000 fluoropolymers and a method for producing the same.

The first method of obtaining the fluoropolymer of the present invention is of the formula: [In the formula, R and Rf have the same meanings as described above. ] It is obtained by polymerizing the fluorine-containing monomer compound (III) represented by

The fluorine-containing monomer compound (III) is obtained by converting the isocyanate compound (II) into a fluorine-containing active hydrogen compound (formula: Rf-H (I
V)).

The isocyanate compound (II) is the same as the above-mentioned Japanese Patent Application No. 58-22.
It may be obtained by the method of 5226, but Die Makromoleklare Chemie 1
31 (1970) 247 to 257 (No. 3199). Generally, the isocyanate compound (II), which is a raw material, can be produced by reacting an α-alkylacrylamide with an oxalyl halide. The reaction is usually performed in the presence of an inert solvent such as a halogenated hydrocarbon at a temperature of 0 to 80 ° C.

As described above, since the isocyanate compound (II) has a possibility of carrying out various reactions, when the fluorine-containing active hydrogen compound (IV) is allowed to act on the isocyanate compound (II), the isocyanate compound (II) and the desired isocyanate compound (II) are contained. In addition to and / or in addition to the addition reaction between the fluorine active hydrogen compound (IV), the isocyanate compound (II) itself is dimerized, trimerized or polymerized (polymerized), or the generated fluorine-containing monomer compound (III) polymerization,
Amide NH of the fluorinated monomer compound (III) thus formed
The progress of various side reactions such as the reaction of the group with the isocyanate compound (II) was predicted, but in reality, at least 1
It was confirmed that the above-mentioned desired reaction preferentially proceeded in the temperature range not exceeding 00 ° C. Especially room temperature (0-30
At relatively low temperatures not exceeding (° C.), only the desired reaction proceeds quantitatively, and various predicted side reactions can be substantially completely avoided.

The fluorine-containing active hydrogen compound (IV) used in the present invention is one in which fluorine is introduced into the active hydrogen-containing compound, and specifically,
Fluorinated aminobenzenes such as o-, m-, p-aminobenzotrifluoride, 2-amino-5-bromobenzotrifluoride, 3-amino-4-bromobenzotrifluoride, 5-amino-2-bromobenzo Trifluoride, 2-amino-5-chlorobenzotrifluoride, 3-amino-4-chlorobenzotrifluoride, 5
-Amino-2-chlorobenzotrifluoride, 2-amino-5-fluorobenzotrifluoride, 3-amino-
4-fluorobenzotrifluoride, 5-amino-2-
Fluorobenzotrifluoride, 3-amino-5-methoxybenzotrifluoride, 2-amino-5-nitrobenzotrifluoride, 4-amino-3-nitrobenzotrifluoride, 5-amino-2-nitrobenzotrifluoride, 2 , 4-difluoroaniline, 2,5-difluoroaniline, 2,6-difluoroaniline, 4-amino-2,3,5,6-tetrafluorobenzoic acid, 4-amino-2,3,5,6 -Tetrafluorobenzonitrile, 3-chloro-4-fluoroaniline, 3,4-diaminobenzotrifluoride and 3,5-diaminobenzotrifluoride; fluorinated benzamides such as 4
-Amino-2,3,5,6-tetrafluorobenzamide, 2,4-difluorobenzamide, 2,5-difluorobenzamide, 2,6-difluorobenzamide and 3,4-difluorobenzamide; fluorinated benzoic acids such as 2 -Chloro-6-fluorobenzoic acid, 3-
Chloro-4-fluorobenzoic acid, 2,4-difluorobenzoic acid, 2,5-difluorobenzoic acid, 2,6-difluorobenzoic acid and 3,4-difluorobenzoic acid; fluorinated phenols such as 4-chloro- 3-hydroxybenzotrifluoride, decafluorobenzhydrol and 2-chloro-4-fluorophenol; fluorinated alcohols such as 1-chloro-3-fluoro-2-
Propanol, 2-chloro-6-fluorobenzyl alcohol, 1,3-dichlorotetrafluoroisopropanol and 1H, 1H-pentadecafluorooctanol; fluoroacetic acids such as difluoroacetic acid, chlorodifluoroacetic acid and 2-chloro-6-fluorophenyl. Acetic acid; Fluorinated biphenyls such as 4,4'-diaminooctafluorobiphenyl; Fluorinated acetamides such as bis (trifluoromethylacetamide)
And chlorodifluoroacetamide; and the like.

In carrying out the reaction, it is usual to use an inert solvent. For example, aliphatic hydrocarbons such as pentane, hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decalin, petroleum ether,
Hydrocarbon solvent such as petroleum benzine, carbon tetrachloride, chloroform, halogenated hydrocarbon solvent such as 1,2-dichloroethane, ether solvent such as ethyl ether, isopropyl ether, anisole, dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone, acetophenone, ketones such as isophorone, ethyl acetate, esters such as butyl acetate, acetonitrile, dimethylformamide, appropriately selected from dimethyl sulfoxide,
Can be used.

The reaction is generally preferably carried out at -20 to 100 ° C, but it is advantageous to carry out the reaction near room temperature (0 to 30 ° C).
There is a possibility of causing side reactions at high temperatures of 100 ° C or higher,
On the other hand, if the temperature becomes too low, the reaction rate becomes slow, which is disadvantageous. The use of a catalyst may be considered in the reaction, but the necessity of using a catalyst is not generally recognized.

The polymerization may be carried out by using the fluorine-containing monomer compound III) alone to obtain a homopyrimer, or by copolymerizing with another ethylenically unsaturated monomer having no active hydrogen to obtain a copolymer. Monomers with active hydrogen cannot be used as they react with isocyanate groups.

Monoolefins without active hydrogen have the formula: [In the formula, P, Q, Y and Z are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 10 or less carbon atoms, an aralkyl group having 10 or less carbon atoms. , Halogen, cyano group, -O-COR '
(R'represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 8 or less carbon atoms, an alkylaryl group, a haloaryl group, an alkoxyaryl group, a haloalkyl group having 4 or less carbon atoms, or a hydroxyalkyl group), cyanomethyl group _-CH 2 OCOR "(R" represents an alkyl group, a haloalkyl group or a phenyl group, a 9 or less carbon atoms.) and COORa (Ra represents an alkyl group having 1 to 20 carbon atoms, or an aryl group having 10 or less carbon atoms An aralkyl group having 10 or less carbon atoms is shown. ], And specific examples thereof include monoolephene hydrocarbons, that is, monomers having only hydrogen atoms and carbon atoms, for example, styrene, α-methylstyrene, α-ethylstyrene, isobutylene. (2-methyl-propane-1), 2-methyl-butene-1, 2-methyl-pentene-1,2,3-dimethyl-butene-1,2,3-dimethyl-pentene-1,
2,4-Dimethyl-pentene-1,2,3,3-trimethyl-heptene-1,2,3-dimethyl-hexene-
1,2,4-dimethyl-hexene-1,2,5-dimethyl-hexene-1,2-methyl-3-ethyl-pentene-1,2,3,3-trimethyl-pentene-1,2
3,4-Trimethyl-pentene-1,2-methyl-octene-1,2,6-dimethyl-heptene-1,2,6-
Dimethyl-octene-1,2,3-dimethyl-decene-
1,2-methyl-nonadecene-1, ethylene, propylene, butylene, amylene, hexylene, butadiene-
1,3, isoprene and the like; halogenated mono-olefins and di-olefin hydrocarbons, that is, monomers having carbon atoms, hydrogen atoms and one or more halogen atoms, for example α-chlorostyrene,
α-bromostyrene, 2,5-dichlorostyrene, 2,
5-dibromostyrene, 3,4-dichlorostyrene, ortho, meta and para-fluorostyrene, 2,6-dichlorostyrene, 2,6-difluorostyrene, 3-fluoro-4-chlorostyrene, 3-chloro-4-. Fluorostyrene, 2,4,5-trichlorostyrene, dichloromonofluorostyrene, 2-chloropropene, 2-chlorobutene, 2-chloropentene, 2-chlorohexene, 2-chloroheptene, 2-bromobutene, 2-bromoheptene, 2- Fluorohexene, 2-fluorobutene, 2-iodopropene, 2-iodopentene, 4-bromoheptene, 4-chloroheptene, 4-fluoroheptene, cis and trans-1,2-dichloroethylene, 1,2-dibromoethylene, 1, , 2-difluoroethylene, 1,2-diyo Doechiren, chloroethylene (vinyl chloride), 1,1-dichloroethylene (vinylidene chloride), Promo ethylene, fluoroethylene, iodo ethylene, 1,1-dibromo-ethylene,
1,1-difluoroethylene, 1,1-diiodoethylene, 1,1,2-trifluoroethylene, chlorobutadiene and other halogenated diolefin compounds; esters of organic and inorganic acids such as vinyl acetate, Vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl caproate, vinyl enanthate, vinyl benzoate, vinyl toluate, vinyl-p-chlorobenzoate, vinyl-o-chlorobenzoate and similar. Vinyl halobenzoates, vinyl-p-methoxybenzoate, vinyl-p-ethoxybenzoate, methyl methacrylate, ethyl methacrylate, propyl methacrylate,
Butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, decyl methacrylate, methyl crotonate and ethyl tiglate; methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, heptyl acrylate, octyl acrylate, 3,5,5-trimethylhexyl acrylate, decyl acrylate and dodecyl acrylate; isopropenyl acetate, isopropenyl propionate, isopropenyl butyrate, isopropenyl isobutyrate, isopropenyl Valerate, Aesop Penyl caproate, isopropenyl enanthate, isopropenyl benzoate, isopropenyl-p-chlorobenzoate, isopropenyl-o-chlorobenzoate, isopropenyl-o-bromobenzoate, isopropenyl-m-chlorobenzoate, isopropenyl toluate , Isopropenyl-α-chloroacetate and isopropenyl-α-bromopropionate; vinyl-α-chloroacetate, vinyl-α-bromoacetate, vinyl-α-chloropropionate, vinyl-α-bromopropionate , Vinyl-α-iodopropionate, vinyl-α-chlorobutyrate, vinyl-
α-chlorovalerate and vinyl-α-bromovalerate; allyl chloride, allyl cyanide, allyl bromide, allyl fluoride, allyl iodide, allyl chloride carbonate, allyl nitrate, allyl thiocyanate, allyl formate, allyl acetate, acetate pro Pionate, allyl butyrate, allyl valerate, allyl caproate, allyl-3,5,5-trimethylhexoate, allyl benzoate, allyl acrylate, allyl crotonate, allyl oleate,
Allyl chloroacetate, allyl trichloroacetate, allyl chloropropionate, allyl chlorovalerate, allyl lactate, allyl pyruvate, allyl aminoacetate, allyl acetoacetate, allyl thioacetate, methallyl esters corresponding to these allyl esters, and β- Ethyl allyl alcohol, β-propyl allyl alcohol, 1-buten-4-ol, 2-
Esters derived from alkenyl alcohols such as methyl-buten-4-ol, 2- (2,2-dimethylpropyl) -1-buten-4-ol and 1-penten-4-ol; methyl-α-chloro Acrylate, methyl-α-bromoacrylate, methyl-α-fluoroacrylate, methyl-α-iodoacrylate, ethyl-α-chloroacrylate, propyl-α-chloroacrylate, isopropyl-α-bromoacrylate, amyl-α-chloroacrylate. , Decyl-α-chloroacrylate, methyl-α-cyanoacrylate, ethyl-α-cyanoacrylate, amyl-α-cyanoacrylate and decyl-α-cyanoacrylate; dimethyl maleate, diethyl maleate, diallyl maleate, dimethyl fuma rate , Diethyl fumarate,
Dimethallyl fumarate and diethyl glutaconate; organic nitriles such as acrylonitrile, methacrylonitrile, ethacrylonitrile, 3-octene nitrile, crotonitrile, oleonitrile and the like.

Polymerization is carried out by a radical reaction in the presence of the inert solvent. A usual radical catalyst is preferably used as the polymerization catalyst. For example, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, tetramethylthiuram disulfide, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), acetylcyclohexylsulfonyl peroxide, 2, 2'-azobis (2,4-dimethylvaleronitrile) and the like can be mentioned. The amount of the catalyst compounded is usually 0.1 to the amount of the monomer.
It is 10% by weight.

The polymerization temperature is usually 20 to 200 ° C., preferably 80 to 15
It is 0 ° C.

During the polymerization, if desired, other additives such as a polymerization regulator may be added.

Another method for obtaining the polymer of the present invention is the reverse of the above method, in which the compound (II) is first polymerized to form a polymer and then reacted with the fluorine-containing active hydrogen compound (IV). The reagents and conditions used in the reaction are as described above.

[Action and Effect] Since the polymer of the present invention has a fluorine-containing functional group (I) having an acyl urethane (or urea) bond, the properties of both the acyl urethane (or urea) bond and the fluorine-containing group Exert. The acylurethane (or urea) bond has strong intermolecular cohesive force, high intermolecular hydrogen bond forming ability, and becomes a tough polymer. Also, it imparts high adhesiveness. Contrary to the acylurethane bond, the fluorine-containing group has a small intermolecular cohesive force, water- and oil-repellency, non-adhesiveness, a small surface friction coefficient, and the like, so that the surface characteristics can be modified. In addition, it has medicinal and agrochemical properties such as strong C—F bond and mimic effect.

Therefore, paints, plastics, elastomers, release agents,
It can also be used for applications such as medicines and agricultural chemicals, or for modification of polymers.

(Examples) The present invention will be described in detail with reference to Examples.

Example 1 Synthesis of Copolymer A copolymer was synthesized using the following formulation. Component parts by weight (g) Methyl methacrylate 8.0 n-Butyl acrylate 8.0 Styrene 4.0 MAF-1 ¹ 2.0 V-65 ² 0.5 Toluene 33.0 ² 2,2'-azobis (2,4-dimethylvaleronitrile) commercially available from Wako Pure Chemical Industries, Ltd.

Methyl methacrylate, n-butyl acrylate, styrene, MAF-1 and styrene mixture 105 to 11
Dropped into 0 ° C. triene over 1.5 hours. After dropping, the mixture was heated with stirring for 3 hours and then cooled with water to obtain a copolymer.
The molecular weight of the obtained copolymer was 14900 (by gel permeation chromatography (GPC)). The nonvolatile content was 33.8%.

Example 2 Synthesis from methacryloyl isocyanate copolymer A fluoropolymer of the present invention was obtained using the following formulation. Component parts by weight (g) methacryloyl isocyanate 1.1 1 methyl methacrylate 8.0 n-butyl acrylate 8.0 styrene 4.0 V-65 0.53 xylene 50.0 methacryloyl isocyanate, methyl methacrylate, n-butyl acrylate of the above formulation. , Styrene and V-65 mixture was added dropwise into xylene at 113 ° C. over 1.5 hours. After dripping, after heating and stirring for 3 hours,
1H, 1H-pentadecafluorooctanol 4.0g
A mixed solution of xylene / chloroform / ethyl acetate was added dropwise. After completion of the dropping, the mixture was cooled with water to obtain a copolymer. The obtained copolymer had a molecular weight of 7400 by GPC and a nonvolatile content of 18%.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C08F 220/44 MMY 7242-4J

Claims (5)

[Claims] 1. A formula: [Wherein R represents hydrogen or a lower alkyl group, and Rf is composed of aminoaminobenzene, fluorinated acetamide, fluoroacetic acid, fluorinated benzoic acid, fluorinated alcohol, fluorinated phenol, fluorinated biphenyl, and fluorinated benzamide. A residue obtained by removing hydrogen from the active hydrogen group of the fluorine-containing active hydrogen compound selected from the group is shown. ] and [Wherein P, Q, Y and Z are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an aralkyl group having 10 or less carbon atoms, halogen,
Cyano group, -O-COR '(R' is an alkyl group having 1 to 6 carbon atoms, an aryl group having 8 or less carbon atoms, an alkylaryl group, a haloaryl group, an alkoxyaryl group, a carbon number of 4
The following haloalkyl group or hydroxyalkyl group is shown. ), A cyanomethyl group —CH ₂ OCOR ″ (R ″ represents an alkyl group having 9 or less carbon atoms, a haloalkyl group, or a phenyl group) and COORa (Ra is a carbon number of 1).
Is an alkyl group having 20 to 20 carbon atoms, an aryl group having 10 or less carbon atoms, or an aralkyl group having 10 or less carbon atoms. )] Is a polymer having a repeating unit represented by
M repeating units of formula (I) (where m is a positive integer) and n repeating units of formula (V) (n is 0 or a positive integer)
Exists and the fluorine-containing functional group in the formula (I) is 0.1 to 9
Molecular weight of 1,000 to 10 bound at a ratio of 9.9% by weight
50,000 fluoropolymers. 2. The formula: [In the formula, R and Rf have the same meanings as described above. ] The compound and formula represented by: [Wherein P, Q, Y and Z have the same meanings as described above. ] Polymerizing an ethylenically unsaturated monomer having no active hydrogen represented by the formula: and A polymer having a repeating unit represented by:
M repeating units of formula (I) (where m is a positive integer) and n repeating units of formula (V) (n is 0 or a positive integer)
The fluorine-containing functional group present in the formula (I) is 0.1 to 9
Molecular weight of 1,000 to 10 bound at a ratio of 9.9% by weight
50,000 fluoropolymer production methods. 3. The method according to claim 2, wherein the polymerization is carried out in an inert solvent. 4. A formula, [In the formula, R has the same meaning as described above. ] and [Wherein P, Q, Y and Z have the same meanings as described above. ] An acylisocyanate group-containing polymer having a repeating unit represented by the formula: wherein the repeating unit of the formula (VII) is m (where m is a positive integer) and the repeating unit of the formula (V) is n (n Is 0 or a positive integer) and an acylisocyanate group-containing polymer having a molecular weight of 1,000 to 100,000 in which the acylisocyanate group in the formula (VII) is bound at a ratio of 0.1 to 72.2% by weight. And a formula: Rf-H [In formula, Rf is a same meaning as the above. ] A fluorine-containing active hydrogen compound represented by the formula: and A polymer having a repeating unit represented by:
There are m repeating units of formula (I) and n repeating units of formula (V).
And the fluorine-containing functional group in the formula (I) is 0.1 to 0.1.
Molecular weight of 1,000 to 1 combined at a proportion of 99.9% by weight
A method for producing a fluoropolymer having a viscosity of 0,000. 5. The process according to claim 4, wherein the polymerization is carried out in an inert solvent.