JPS60170606A - Preparation of fluorine-containing polymer - Google Patents

Abstract

PURPOSE:To prepare a polymer important for water and oil repellents, resist materials, optical fibers, molded materials, e.g. sheets, and medical materials, etc., by anion polymerizing a fluorine-containing unsaturated ester monomer in the presence of an organomagnesium catalyst. CONSTITUTION:A fluorine-containing unsaturated ester monomer of formula I [R1 is H or CH3; R2 is group of formula II (n is an integer 0-5; Rf is 1- 20C polyfluoroalkyl; R' is lower alkyl; H or Rf)], e.g. 2,2,2-trifluoroethyl acylate or 1H,1H-heptafluorobutyl methacrylate, is reacted preferably in the presence of 2-0.05mol%, based on the monomer of formula I , organomagnesium catalyst. A compound of the formula R3MgX [R3 is phenyl, benzyl or group of the formula CmH2m+1 (m is an integer); X is Cl, Br or I] or (R3)2Mg, e.g. ethylmagnesium chloride, is preferred for the organomagnesium catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the production of a fluorine-containing polymer by polymerizing a fluorine-containing unsaturated ester monomer such as a fluorine-containing acrylate or a fluorine-containing methacrylate in the presence of an organomagnesium catalyst. It is related to.

Fluorine-containing acrylates or fluorine-containing methacrylates provide industrially important polymers. Fields where the functionality of fluorine-based compounds is particularly useful.

For example, fiber treatment agents that take advantage of the water and oil repellent properties of fluorine.
Applications are being considered for fluorine rubber rubber and plastics that take advantage of their chemical resistance, paints that take advantage of their weather resistance, plastic optical fibers that take advantage of their low refractive properties, other anti-fog materials, contact lenses, and medical materials such as dental materials. Many of them have been developed and put into practical use.

The main monomers currently in practical use have a general formula where n is an integer from 0 to 5 from the viewpoint of manufacturing methods and economy. Rf is a polyfluoroalkyl group having 1 to 20 carbon atoms. R' is a lower alkyl group, H or Rf group. ]There are many compounds shown by. A method for producing polymers from these monomers is a method using radical polymerization. For example, at a polymerization temperature of 0 to 90°C, an oil-soluble peroxide such as benzoyl peroxide, an azo compound such as azobisinbutyronitrile, an inorganic peroxide such as potassium persulfate hydrogen peroxide, etc. are used. This method involves solution polymerization in an organic medium, suspension polymerization or emulsion polymerization in an aqueous system. The stereoregularity of the polymer produced by such a radical polymerization method is generally said to be atactic.

On the other hand, it is known that hydrocarbon-based acrylates or methacrylates undergo cyanion polymerization using organometallic catalysts such as n-butyllithium. For example, methyl methacrylate is anionically polymerized in citoluene with an n-butyllithium catalyst to give an isotactic polymer.

However, there have been only a few attempts to anionically polymerize fluorine-based acrylates or methacrylates.

Based on the above facts, we applied various anionic polymerization catalysts to the fluorine-containing acrylate and fluorine-containing methacrylate monomers and found that organomagnesium catalysts have polymerization activity. The present invention has now been completed.

The fluorine-containing acrylate and fluorine-containing methacrylate monomers used in the present invention have a polyfluoroalkyl group having the general formula. R1 is a lower alkyl group, H or Rf group. ]
A compound represented by 2,2.2-trifluoroethyl acrylate%2,2.2-)trifluoroethyl methacrylate.

IH, IH, 3H-tetrafluoroglobyl acrylate, IH, IH, 3H-tetrafluoropropyl methacrylate.

Hexafluoroisoglobyl acrylate, hexafluoroisopropyl methacrylate, IH, IH-hebutafluorobutyl acrylate, IH, IH-hebutafluorobutyl methacrylate, IH, IH, 5H-octafluoropentyl acrylate, IH, IH, 5H-octa Fluoropentyl methacrylate, IH, IH, 7
H-dodecafluorohebutyl acrylate, IH, IH
,7H-dodecafluorohebutyl methacrylate), I
H, JH-pentadecafluorooctyl acrylate)
, IH, IH-pentadecafluorooctyl methacrylate.

The organomagnesium compound that is a polymerization catalyst has the general formula R3M
gX or (Rs)2Mg + (However, R3 in one formula
7 AnyAy group, benzyl group, or OmH2m+1
: (m is an integer).

X = chlorine, bromine, iodine. ] Compounds represented by ash, specifically ethylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium iodide,
n-Butylmagnesium chloride, n-butylmagnesium bromide, n-butylmagnesium iodide, phenylmagnesium chloride, phenylmagnesium bromide, phenylmagnesium iodide, benzylmagnesium chloride, penzylmagnesicum promide, benzylmagnesium iodide, etc. and dialkyl and diarylmagnesium compounds such as diethylmagnesium, di-n-butylmagnesium, diphenylmagnesium, dibenzylmagnesium, and the like. These organomagnesium compounds are usually used as a dilute solution in n-hexane, n-heptane, xylene, benzene, toluene, tetrahydrofuran, dioxane, diethyl ether, or the like.

The manufacturing method of the present invention will be described in detail below.

Fluorine-containing acrylates and fluorine-containing methacrylates are purified by distillation under a stream of nitrogen or helium, and those having a purity of 99.5% or higher and completely deoxidized are used. Since trace amounts of water inhibit polymerization, it is preferable to dehydrate using a dehydrating agent such as molecular sieves.

Organomagnesium compounds are commercially available or available.

A compound synthesized from magnesium metal powder and an alkyl halide or an aryl halide is used. ``It is usually used as a solution of 0.5 mol/β to 5.0 mol/L, but because it reacts sensitively with air and moisture in the air, it must be stored in a sealed nitrogen-based container.

It is preferable to appropriately confirm the solution concentration by an organomagnesium compound quantitative method such as a titration method.

The amount of organomagnesium compound added to the polymerization system is 1 for fluorine-containing acrylate and fluorine-containing methacrylate.
0 to 0, O1 molt, preferably 2 to 0.05 molt.

The solvent is an inert aprotic organic solvent such as n-hexane, n-hebutane, toluene.

Xylene, benzene, tetrahydrofuran, dioxane, diethyl ether, etc. are used.

These are purified by conventional purification methods and used after being completely deoxidized and dehydrated.

In the laboratory, the polymerization equipment is in a glass ampoule.

It is carried out in a reactor equipped with a stirrer, but it is necessary to dry the inside of the reactor and replace it with nitrogen before charging the raw materials.

The polymerization temperature is 18℃~10G-'C1, preferably 140℃
℃~70℃ is suitable. The polymerization time is not limited and is determined by the type or combination of monomers and catalysts.

At the end of the polymerization, a small amount of a protic organic solvent such as methanol or ethanol is added to the polymerization system to stop the polymerization. The resulting polymer is washed with an organic solvent such as methanol, filtered repeatedly, and then dried.

The fluorine-containing acrylates and fluorine-containing methacrylates obtained by the above methods may be used alone or in combination of two or more, and from the viewpoint of modification or economic efficiency, hydrocarbon-based acrylates, methacrylates, and acrylonitriles.

Conventional anionically polymerizable monomers such as methacrylate tolyl and vinyl ketone can also be added as comonomers.

Examples of uses of the above-mentioned fluorine-containing copolymers include water and oil repellents, resist materials, optical fibers, sheets,
Examples include molding materials such as films and medical materials.

Hereinafter, the present invention will be explained in detail with reference to Examples.

Example 1 Purified hexafluoroisoglobil methacrylate
4.72 y% toluene 17.3 y, 3.5 mol/
J! Pour 0.1 lsd of diethyl ether solution of ethermagnesium bromide into 50 glass ampoules.

After sealing the tube, polymerization was carried out at -20°C for 48 hours. For polymerization, after opening the polymerization system to methanol, the resulting polymer was filtered and vacuum-dried. The polymer yield was 3.59 degrees and the yield was 74 inches. The intrinsic viscosity [η] of the polymer measured in an acetone solution at 30° C. was 0.089. The infrared absorption spectrum and torque of the polymer is O=0 at 1770 strokes, 1100~
O-F on 1400fi-1, 10H on 2960-1,
Absorption of -〇H2- was observed at 1, 2925 cm''.

The glass transition temperature of the polymer as measured by 'rG and D80 was 82°C, and the thermal decomposition onset temperature was 296°C. In addition,
No melting point was observed.

Example 2 Purified bexafluoroisopropyl methacrylate
4,721. ) Luene 17.551% 3.5 mol/
0.2 ethylmagnesium chloride solution in diethyl ether. Prepared in a glass ampoule of lttgi50-,
After sealing the tube, polymerization was carried out at -20°C for 48 hours. Polymerization was performed by opening the polymerization system to methanol, filtering the resulting polymer, and vacuum drying. The polymer yield was 3.5 mm, and the yield was 74%. The intrinsic viscosity [η] of the polymer measured in an acetone solution at 30° C. was Q, 119. The infrared absorption spectrum of the polymer was the same as in Example 1.

The glass transition temperature of the polymer as measured by TG and DSC was 83°C, and the thermal decomposition onset temperature was 286°C. Note that no melting point was observed.

Example 3 Same as Example 1, hexafluoroisopropyl methacrylate 4.72F,) Luene 17j f.

3.5 mol/! A diethyl ether solution of 0.11% of phenylmagnesium iodide was charged into a glass ampoule, and polymerization was carried out at 0°C for 48 hours.

The polymer yield was i4y, and the yield was 72cm.

Limiting viscosity of polymer measured in acetone solution at 50℃
4] is 0.102. The infrared absorption spectrum of the polymer was the same as in Example 1. The glass transition temperature of the polymer according to TG and DSO measurements is 82°C1 The thermal decomposition onset temperature is 280°C
It was ℃. Note that no melting point was observed.

Example 4 In the same manner as in Example 1, hexafluoroisopropyl methacrylate 4.72F and toluene 1"1.3F.

0.11111 of a 3.5 mol/L solution of benzylmagnesium chloride in diethyl ether was charged into a glass ampoule, and polymerization was carried out at -20°C for 7 days. The polymer yield was 1.65 f, and the yield was 35 g. The intrinsic viscosity [η] of the polymer measured in acetone solution at 50°C is 0.0
75, the infrared absorption spectrum of the polymer was similar to Example 1.

Example 5 In the same manner as in Example 1, trifluoroethyl methacrylate 33.6 f, ) toluene 200 @l, 1.8
4d of a 1 mol/λ diethyl ether solution of di-n-butylmagnesium was placed in a glass ampoule, and heated to -15°C.
Polymerization was carried out for 48 hours. The polymer yield was 13.8 mm, or 41%. The intrinsic viscosity [η] of the polymer measured in an acetone solution at 30° C. was found to be 0.123. Infrared absorption of polymer) y is "40 m-1 C=
0, t16 (1: m-', -0H3, 2925crnl, -OH, - absorption was observed.

Comparative Example Lithium ethoxide, lithium-1-butoxide, n-buterurium, and strontium were used in place of the organomagnesium compounds in Examples 1 and 2.

Polymerization was carried out using zinc tetraethyl or the like as a catalyst, but no polymer was produced in either case.

Patent applicant: Central Glass Co., Ltd.

Claims (1)

[Claims] General formula (1) [wherein R, =H or C3H5, R, =R2 is a polyfluoroalkyl group having 1 to 20 carbon atoms. R1
is a lower alkyl group, H or Rf group. ] A method for producing a fluorine-containing polymer, characterized by polymerizing a fluorine-containing unsaturated ester monomer represented by the following formula in the presence of an organomagnesium catalyst. 2) General formula % formula %) [However, in the formula, R3 = phenyl group, benzyl group or Om
H2m+ 1 (m is an integer). X = chlorine. Bromine, iodine. ] The method according to claim 1, characterized in that an organomagnesium catalyst represented by the following is used.