JPS61272208A - Fluorine-contained polymer and production thereof - Google Patents

Abstract

PURPOSE:To obtain a novel polymer useful as a coating compound, adhesive, drug, agricultural chemical, etc., by polymerizing a specific fluorine-containing polymer so that a specific amount of a fluorine-containing functional group is bonded to a main chain consisting of C-C bond. CONSTITUTION:A fluorine-containing monomer compound shown by the formula I (R is H or lower alkyl; Rf is residue obtained by removing H participating in addition reaction from fluorine-containing hydrogen compound such as 2- amino-5-bromobenzotrifluoride, etc.) is polymerized alone or with a monomer (e.g., styrene, etc.) containing no active hydrogen, to give a novel polymer having 1,000-100,000 molecular weight and 0.1-99.9wt% fluorine-containing group shown by the formula II bonded to a main chain consisting of C-C bond. EFFECT:Since this polymer has a fluorine-containing group containing an acylurethane (or urea) bond, it shows both characteristics of the acylurethane (or urea) bond and the fluorine-containing group.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention provides a novel polymer, in particular, a main chain consisting of carbon-carbon bonds having the formula: % formula % [wherein Rf is added from a fluorine-containing active hydrogen compound] The present invention relates to a fluorine-containing polymer having molecules mtoooo to 100,000 to which fluorine-containing functional groups represented by [representing residues excluding hydrogen atoms involved in the reaction] are bonded at a ratio of 01 to 99.9% by weight, and a method for producing the same.

(Background of the Invention) Compounds having isocyanate groups are widely used in the field of polymer chemistry because of their excellent reactivity. In particular, compounds that have both a polymerizable carbon-carbon unsaturated group and an isocyanate group in the same molecule, because both of these functional groups participate in various reactions with different reaction mechanisms,
It can be used in a wide range of industrial technology fields. Focusing on such usefulness, the present inventors previously provided an isocyanate compound represented by the following formula [Japanese Patent Application No. 58-225]
No. 226]: CH,=C(I[) \, C-N=C=0 [wherein, R represents a lower alkyl group. ]. The method of the invention can also be used when R is hydrogen.

Furthermore, the present inventors have discovered that the above isocyanate compound (II)
The present invention provides a polymer having a monomer of

The acyl isocyanate group (-C-N=C=O) introduced into these polymers has a carbonyl group adjacent to the isocyanate group 1ε, and this carbonyl group increases the activity of the isocyanate group, allowing for a wide variety of addition reactions. etc. is in a state where it can operate. Therefore, acylisocyanate group-containing polymers have found wide range of uses and usefulness.

(Objective of the Invention) As described above, the present invention introduces a fluorine-containing functional group into a polymer chain by reacting a highly reactive acylisocyanate group with a fluorine-containing active hydrogen compound, and The purpose is to impart this performance to polymers.

(Structure of the Invention) That is, the present invention provides a main chain -C-N consisting of carbon-carbon bonds.
The fluorine-containing functional group represented by H-C-Rr [wherein Rf represents a residue obtained by excluding the hydrogen atom involved in the addition reaction from the fluorine-containing active hydrogen compound] is 0.1 to 99.9% by weight The present invention provides a fluorine-containing polymer having 1 to 100,000 molecules bonded at a ratio of 1 to 100,000%, and a method for producing the same.

The first method for obtaining the fluorine-containing polymer of the present invention is as follows: %Formula%() [In the formula, R represents hydrogen or a lower alkyl group, and Rf represents the hydrogen involved in the addition reaction from the fluorine-containing active hydrogen compound. Residues with atoms excluded are shown. ] It can be obtained by polymerizing a fluorine-containing monomer compound (III) represented by:

The fluorine-containing monomer compound (III) is a fluorine-containing active hydrogen compound (formula:
It is obtained by reacting with Rf-1((II+')).

Isocyanate compound (I [)
It may be obtained by the method of No. 225226, but it may be obtained by the method of D ie Makromol Chemie.
131 (1970)
247-257 (No. 3199). Isocyanate compound (II), which is a raw material, can usually be produced by a reaction between α-alkylacrylamide and oxalyl halide.

The reaction is usually carried out at a temperature of 0 to 80°C in the presence of an inert solvent such as a halogenated hydrocarbon.

As mentioned above, the isocyanate compound (II) has the potential to carry out various reactions, so when the fluorine-containing active hydrogen compound (IV) is reacted with it, the desired isocyanate compound (n) is formed. In addition to and/or instead of the addition reaction between the fluorine-containing active hydrogen compounds (IV), trimerization, trimerization, multimerization (polymerization), etc. of the isocyanate compound (II) itself, and the produced fluorine-containing monomer compounds ( Polymerization of I), resulting fluorine-containing monomer compound (
III) amide NH group and isocyanate compound (n
Although it was predicted that various side reactions would proceed, such as the reaction of (), it was actually confirmed that the desired reaction proceeds preferentially in a temperature range that does not exceed at least 100°C. In particular, at relatively low temperatures not exceeding room temperature (0 to 30°C), only the desired reaction proceeds quantitatively, and various predicted side reactions can be virtually completely avoided.

The fluorine-containing active hydrogen compound (IV) used in the present invention is an active hydrogen-containing compound with fluorine introduced, for example,
o-, m-, p-aminobenzotrifluoride, 2-amino-5-promobenzotrifluoride, 3-amino-
4-promobenzotrifluoride, 5-amino-2-promobenzotrifluoride, 2-amino-5-chloropenzotrifluoride, 3-amino-4-chloropenzotrifluoride, 5-amino-2-chloropene zotrifluoride, 2-amino-5-fluorobenzotrifluoride, 3-amino-4-fluorobenzotrifluoride,
5-amino-2-fluorobenzotrifluoride, 3-
Amino-5-methoxybenzotrifluoride, 2-amino-5-nitropenzotrifluoride, 4-amino-3
-Nitropenzotrifluoride, 5-amino-2-nitropenzotrifluoride, 4-amino-2,3,5,6
-titrafluorohenzamide, 4-amino-2,3,
5゜6-tetrafluorobenzoic acid, 4-amino-2゜3
．． 5.6-titrafluoropenzonitrile, bis(trifluoromethylacetamide), chlorodifluoroacetamide, chlorodifluoroacetic acid, 3-chloro-4-fluoroaniline, 2-chloro-6-fluorobenzoic acid,
3-chloro-4-fluorobenzoic acid, 2-chloro-6-
Fluorobenzyl alcohol, 2-chloro-4-fluorophenol, 2-chloro-6-fluorophenylic acid L
l-chloro-3-fluoro-2-propatol, 4
-Chloro-3-hydroxybenzotrifluoride, decafluorobenzhydrol, 3,4-diaminobenzotrifluoride, 3,5-diaminobenzotrifluoride, 4,4'-diaminooctafluorobiphenyl, 1
．． 3-dichlorotetrafluoroisopropanol, difluoroacetic acid, 2.4-difluoroaniline, 2.5-difluoroaniline, 2.6-difluoroaniline, 2.
4-difluorobenzamide, 2,5-difluorobenzamide, 2,6-difluorobenzamide, 3゜4-
Examples include difluorobenzamide, 2,4-difluorobenzoic acid, 2,5-difluorobenzoic acid, 2,6-difluorobenzoic acid, 3,4-difluorobenzoic acid, IH, IH-pentadecafluorooctatatool, and the like.

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

It is generally preferred to carry out the reaction at a temperature of -20 to 100°C, but it is advantageous to carry out the reaction near room temperature (0 to 30°C).

At high temperatures of 100℃ or higher, side reactions may occur.
On the other hand, if the temperature is too low, the reaction rate will be low, which is disadvantageous. Although the use of a catalyst may be considered during the reaction, the necessity of using a catalyst is usually not recognized.

The polymerization may be carried out with the fluorine-containing monomer compound (1) alone to obtain a homopolymer, or it may be polymerized with another ethylenically unsaturated monomer having no active hydrogen to obtain a copolymer. Monomers having active hydrogen cannot be used because they react with isocyanate groups.

Examples of monomers without active hydrogen are: monoolefin and diolefin hydrocarbons, i.e. monomers with only hydrogen and carbon atoms, such as 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-hebutene-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-L 2.3.4-)dimethyl-pentene-112-methyl-octene-1,2
,6-cystylene-hebutene-1,2,6-cystylene-octene-112゜3-dimethyl-decene-1,2-methyl-nonadecene-1, ethylene, propylene, butylene, amidino, hexylene, butadiene-1,3 , isoprene, etc.; halogenated monoolebuin and diolefin hydrocarbons, i.e. monomers having carbon atoms, hydrogen atoms and one or more halogen atoms, such as α-chlorostyrene,
α-bromostyrene, 2゜5-dichlorostyrene, 2,
5-dipromostyrene, 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,
(2) 2-dibromoethylene, 1,2-difluoroethylene, l, 2-short ethylene, chloroethylene (vinyl chloride), 1,1-dichloroethylene (vinylidene chloride), bromoethylene, fluoroethylene, iodoethylene, l.

! -dibromoethylene, 1,1-difluoroethylene,
1,1-short ethylene, 1,1,2-trifluoroethylene, chlorobutadiene and other halogenated diolefin compounds; esters of organic and inorganic acids, such as vinyl acetate, vinyl propionate, vinyl butylene; vinyl isobutyrate, vinyl brate, vinyl caproate, vinyl acetate, vinyl benzoate, vinyl toluate, vinyl-p-chlorobenzoate, vinyl-
〇-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-) dimethylhexyl acrylate, decyl acrylate and dodecyl acrylate; isopropenyl acetate, isopropenyl propionate, isopropenyl butyrate, isopropenyl isobutyrate, isopropenyl valerate, isopropenyl capro ate, isopropenyl acetate, isopropenyl benzoate, isopropenyl-p-chlorobenzoate, isopropenyl-〇-chlorobenzoate, isopropenyl-0-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 iosito, allyl chloride carbonate, allyl nitrate, allyl thiocyanate, allyl pormate, allyl acetate, acetate pro pionate, allyl butyrate, allyl valerate, allyl caprotate, 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, β-ethyl allyl alcohol, β-
Allyl alcohol, l-buten-4-ol,
Esters derived from alkenyl alcohols such as 2-methyl-buten-4-ol, 2-(2,2-dimethylpropyl)-1-buten-4-ol and l-penten-4-ol; methyl-α -chloroacrylate, methyl-α-bromoacrylate, methyl-α-fluoroacrylate, methyl-α-iodoacrylate, ethyl-α-chloroacrylate, propyl-α-chloroacrylate, isopropyl-α-bromoacrylate, amyl-α- Chloroacrylate, decyl-α-chloroacrylate, medyl-α-cyanoacrylate, ethyl-α-cyanoacrylate, amyl-α-cyanoacrylate and decyl-α-cyanoacrylate; dimethyl maleate,
Diethyl maleate, diallyl maleate, dimethyl fumarate, diethyl fumarate, diallyl maleate and diethyl geltaconate; organic nitriles such as acrylonitrile, methacrylonitrile, ethacrylonitrile, 3-octenenitrile, crotonitrile, oleonitrile, etc. .

Polymerization is carried out by radical reaction in the presence of the inert solvent. As the polymerization catalyst, a common radical catalyst is preferably used. For example, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, tetramethylthiuram disulfide, 2,2゛-azobis(4-
Metquin-2,4-dimethylvaleronitrile), acetylcyclohexylsulfonyl peroxide, 2,2'-
Examples include azobis(2,4-dimethylvaleronitrile). The amount of catalyst blended is usually 0.0% relative to the amount of monomer.
1-10% by weight.

Polymerization temperature is usually 20-200°C, preferably 80-15°C.
It is 0°C.

During polymerization, other additives such as polymerization regulators may be added as desired.

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, conditions, etc. used for the reaction are as described above.

[Operations and Effects] Since the polymer of the present invention has a fluorine-containing functional group (1) having an acyl urethane (or urea) bond, it has both the characteristics of the acyl urethane (or urea) bond and the fluorine-containing functional group (1). Demonstrates the characteristics of Acyl urethane (or urea)
The bonds have strong intermolecular cohesive force and a high ability to form intermolecular hydrogen bonds, resulting in a tough polymer. It also provides high adhesion ability. Fluorine-containing groups have a small intermolecular cohesive force, contrary to annular urethane bonds, and have properties such as water and oil repellency, non-adhesiveness, and a small surface friction coefficient, making it possible to modify surface properties. It also has medicinal and agricultural properties such as strong C-F bond and m1m1c effect.

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

(Example) The present invention will be explained in detail by examples.

Example 1 Synthesis of copolymers A copolymer was synthesized using the following recipe.

Ingredients Part by weight (g) Methyl, methacrylate 8. O n-butyl acrylate 8.0 styrene
4・OMAP-1'
2.0V-65'
0.5 toluene 33.
0 Hs 0 0 CF s 2 2,2°-Azobis (commercially available from Wako Pure Chemical Industries, Ltd.)
2,4-dimethylvaleronitrile).

Methyl methacrylate, n-butyl acrylate, styrene, MAF-1 and styrene mixture at 105-1
It was added dropwise into toluene at 10°C over 1.5 hours.

After the dropwise addition, the mixture was heated and stirred for 3 hours and then cooled with water to obtain a copolymer. The molecular weight of the obtained copolymer was 14,900 (according to gel permeation chromatography (GPC))
Met.

The nonvolatile content was 33.8%.

Example 2 Synthesis from methacryloyl isocyanate copolymer A fluorine-containing polymer of the present invention was obtained using the following recipe.

Ingredients Part by weight (g) Methacryloyl isocyanate 1.11 Methyl methacrylate 8. On-butyl acrylate
8,0 styrene
4.0V-65o, 53 xylene 50.0 Methacryloyl isocyanate, methyl methacrylate, n-butyl acrylate, styrene and v-65 of the above formulation
The mixture was added dropwise into xylene at 113°C over 1.5 hours. After dropping, after heating and stirring for 3 hours, IH,
A mixed solution of 4.0 g of IH-pentadecafluorooctator in xylene/chloroform/ethyl acetate was added dropwise.

After the dropping was completed, the mixture was cooled with water to obtain a copolymer. The molecular weight of the obtained copolymer by GPC was 7400, and the nonvolatile content was 18.
%Met.

Claims (1)

[Claims] 1. Formula in the main chain consisting of carbon-carbon bonds: ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, Rf excludes the hydrogen atom involved in the addition reaction from the fluorine-containing active hydrogen compound A fluorine-containing polymer having a molecular weight of 1,000 to 100,000, in which fluorine-containing functional groups represented by the following formula are bonded in a proportion of 0.1 to 99.9% by weight. 2. Formulas: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R represents hydrogen or a lower alkyl group, and Rf represents a residue obtained by excluding the hydrogen atom involved in the addition reaction from the fluorine-containing active hydrogen compound. . ] The fluorine-containing monomer compound represented by is polymerized alone or with other monomers having no active hydrogen, and the main chain consisting of carbon-carbon bonds has the formula: -CONHCO
A method for producing a fluorine-containing polymer having a molecular weight of 1,000 to 100,000, in which fluorine-containing functional groups represented by Rf are bonded in a proportion of 0.1 to 99.9% by weight. 3. The main chain consisting of carbon-carbon bonds has an acylisocyanate group of 0.1 to 72.
Molecular weight 1000-10000 combined at a ratio of 2% by weight
An acylisocyanate group-containing polymer having 0 and a fluorine-containing active hydrogen compound represented by the formula: Rf-H [wherein Rf represents a residue obtained by removing a hydrogen atom involved in an addition reaction from a fluorine-containing active hydrogen compound]. to produce a fluorine-containing polymer having a molecular weight of 1,000 to 100,000, in which fluorine-containing functional groups represented by the formula: CONHCORf are bonded to the main chain consisting of carbon-carbon bonds at a ratio of 0.1 to 99.9% by weight. 1. A method for producing a fluoropolymer, the method comprising: obtaining a fluorine-containing polymer; 4. The method according to item 3, wherein the reaction is carried out in an inert solvent.