JPS58105943A - Fluoride-containing unsaturated carboxylic acid ester and its preparation - Google Patents

Abstract

NEW MATERIAL:The compound of formulaI[R1 is H or CH3; R2 is CH2, benzene, etc.,; R2' is CH2, benzene, etc.; R3 is group of formula II (n is O or 1); Y is group of formula III; l is same as n]. USE:A raw material for crosslinking agent of polymer. The polymer derived from the compound is coloreless transparent liquid at normal temperature and pressure having water repellency, and is soluble in organic solvents such as benzene, ether, chloroform, etc., and insoluble in water. It has high boiling point, i.e. it is necessary to heat at >=100 deg.C under the vacuum 2-3mm.Hg for the evaporation of the compound. The compound is useful as a dental filler. PROCESS:The compund of formulaIcan be prepared by reacting the perfluorocarboxylic acid halide of formula CF3CF2COX (X is halogen) or formula IV with the unsaturated carboxylic acid ester of formula V preferably in an organic solvent at -78-+100 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a parent compound, a fluorine-containing unsaturated cardanic acid ester, and a method for producing the same. The present invention also provides a dental filler composition containing at least one component of the fluorine-containing unsaturated cardanic acid ester.

Currently, in addition to amalgam and cement, composite materials (hereinafter referred to as composite resins) whose main components are polyfunctional acrylic (or methacrylic) derivatives and inorganic fillers are used as filling materials for restorations after treating cavities. In addition, similar polyfunctional acrylic (
or methacrylic) derivatives as the main component (
(hereinafter referred to as sealant) is used.

Filling materials such as composite resins and sealants have many advantages over conventional restorative materials and filling materials, but due to their high water absorption, water easily enters the gap between the filling material and the tooth structure, and is mixed with water. It has the disadvantage that Streptococcus minitans, which causes cavities, invades the teeth and causes secondary caries. This is due to the fact that the polyfunctional acrylic (or methacrylic) derivative, which is the main component of the filler, is hydrophilic.

In the present invention, we have continued research for many years to develop a water-repellent dental upper for the purpose of preventing secondary caries.

As a result, they discovered that a new substance represented by the following formula exhibits remarkable water repellency and is also useful as a dental filling composition, leading to the completion of the present invention.

Namely, 1. The present invention relates to a new substance, which has the general formula (However, R1 is H or CHI, and R2 is -OH.

It is. ) is a fluorine-containing unsaturated cardanic acid ester. This compound is a colorless and transparent liquid at room temperature and pressure. It is soluble in common organic solvents such as Jl/, chloroform, ethyl acetate, and alcohol, but insoluble in water. In addition, its boiling point is extremely high, 2 to 3
Even under the reduced pressure of Hy, heating to temperatures above 'too much Celsius' is required.

Mae The fluorine-containing unsaturated carboxylic acid ester of the present invention is as follows (
It can be confirmed by analysis using methods such as a) to 61).

(&) Infrared absorption spectrum (R0) In general, in methacrylic esters (or acrylic esters), absorption by carbonyl group is observed at 1720 aw-' and absorption due to double bond is observed at 1640 m+-'. On the other hand, absorption of the carbonyl group adjacent to the fluoroalkyl group is observed around 178051-'. It is also known that absorption due to expansion and contraction of C-1 appears in the range 1400 to 110051.

When the fluorine-containing unsaturated carmenic acid ester represented by the above general formula of the present invention is subjected to R1 analysis, the absorption of the carbonyl group of the methacrylic ester or acrylic ester is 172
0ak, the absorption of the carbonyl group adjacent to the fluoroalkyl group appears at 1780ak-', and the absorption based on the double bond appears at 1640at-'. Also c-y
Absorption due to expansion and contraction appears between 1400 and 11003-1. Furthermore, in the case of a fluorine-containing unsaturated cardanic acid ester having a benzene ring bonded thereto, absorption based on the cough benzene ring appears at 1495aw*-'.

Therefore, the presence or absence of a carmenyl group based on a cardanic acid ester, a fluoroalkyl group, a carbonyl group based on a fluoroalkyl group, a double bond, and a benzene ring can be confirmed by engineering and R0 analysis.

(b) Carbon-13 nuclear magnetic resonance spectra H and 1? In a decoupled 1!0 nuclear magnetic resonance spectrum, each carbon in a different environment shows one peak. The product can be identified by examining this chemical shift. The specific identification of the compound of the present invention will be described in the Examples below, but the identity of the compound of the present invention can be completely confirmed by Cardan 13 nuclear magnetic resonance spectrum.

(C) Mass spectrum In normal mass spectrometry, ions are created by bombarding the sample with electrons, but in the case of fluorine-containing compounds, branching and rearrangement reactions occur using this method, and molecular ion C is not observed. There are many things. Therefore, in this study, field ion-mass spectrometry was used as a method for ionization under relatively mild conditions.

By this method, the molecular ion beak C can be confirmed.
can. The molecular weight can be confirmed by combining this data with the results of Carmen 13 nuclear magnetic resonance spectrum, infrared absorption spectrum, elemental analysis, etc.

(d) Elemental analysis The reliable identification of fluorine-containing unsaturated carmenic acid esters is
As revealed by the Cardan 13 nuclear magnetic resonance spectrum,
H in the compound.

By comparing the theoretically calculated values of each C1v element with the results of decomposition of each element with the actually obtained compound, clear identification becomes possible.

The fluorine-containing unsaturated cardanic acid/ester of the present invention can be identified by the analytical means described in (a) to (d) above.

As mentioned above, the fluorine-containing unsaturated cardanic acid ester of the present invention is a new substance and can be widely used as a general raw material for polymers. Furthermore, since it has two methacrylic groups (or acrylic groups) in its molecule, it can also be used as a crosslinking agent.

Furthermore, since the polymer obtained by polymerizing the above monomer has a perfluoroalkyl group exhibiting water repellency in the side chain, the polymer exhibits higher water repellency than conventional hydrocarbon polymers. Furthermore, since this new substance exhibits an extremely low refractive index as shown in the Examples described later, the refractive index can be adjusted by adding it to other monomers and copolymerizing it.

The method for producing the fluorine-containing unsaturated carmenic acid ester of the present invention is not particularly limited and may be produced by any method. Typical manufacturing methods that can be generally suitably employed include the following methods.

(I) (1) General formula (However, R1 is H or OH5, "2 is CH2e Oa is 1." However, X is halogen, or fluorine or chlorine, n
is 0 or 1. ) The fluorine-containing unsaturated ester represented by the above general formula can be produced by reacting the compound represented by the following.

In the above reaction, the raw material compounds may be mixed in any order to carry out the reaction. Further, the reaction can be carried out by mixing all of these raw material component compounds in one step, or the reaction can be carried out by mixing these raw material component compounds in several stages.

Although the reaction conditions in the above production method are not particularly limited, it is generally carried out in the presence of a solvent. As the solvent, an anhydrous polar non-aqueous solvent that does not react with the raw materials can be used without particular limitation. Representative examples of the polar nonaqueous solvent include ether, tetrahydrofuran, dioxane, monoglyme, and diglyme.

Ether solvents such as tridatum and tetoglyme; oxosulfur solvents such as dimethyl sulfoxide and sulfolane; acetonitrile.

Nitrile solvents such as propionitrile and benzonitrile, amide solvents such as dimethylformamide, diethylformamide, dimethylacetamide, M-methylpyrrolidone, and hexamethylphosphoramide are preferably used. Furthermore, when producing a fluorine-containing unsaturated cardanic acid ester having a benzene ring in the molecule, a benzene solvent can be used. However, there are no particular restrictions on the method and order of mixing the raw material component compounds and the solvent used.

The reaction temperature in the above production method is not particularly limited or defined, but it is usually preferably selected from a temperature range of -78°C or higher and 100°C or lower. #Although the reaction proceeds even at high temperatures exceeding 100° C., it is usually not recommended to use this method because it tends to cause polymerization of raw materials or products or side reactions. Therefore, in view of the yield of the target product, the reaction temperature is preferably selected from a temperature range of -78 to 100°C, more preferably from a temperature range of -78 to 50°C.

The reaction in the above production method is usually conveniently carried out under natural pressure at the reaction temperature with the raw material components and solvent charged, but if necessary, it can be carried out under further pressure or reduced pressure to avoid backfilling. . The atmosphere for the reaction is not particularly limited, but in general, replacing the atmosphere with an inert gas often gives preferable results. -Reaction time in the above production method: The reaction time varies depending on the type of raw material component metal solvent used, the reaction temperature, etc., but it is generally preferable to select a range from several minutes to several days, and as necessary. Depending on the reaction, it is preferable to select other conditions so that the reaction time ranges from several minutes to several hours.

The material of the reaction vessel in the above manufacturing method is not particularly limited as long as it is a material that is resistant to corrosion and does not participate in the reaction, but metals such as glass and stainless steel can be used.

Teflon and the like are generally preferred. Ceramic, cylcy
Since 2cox is a gas at room temperature, it is preferable to use a pressure-resistant container when reacting.

When carrying out the above production method, a means of stirring the reaction system can often be employed as a suitable means in order to uniformly disperse the reaction heat and the raw material components.

The method for separating the nine-containing fluorine-unsaturated carboxylic acid ester produced by the above production method from the mixture in the reaction vessel is not particularly limited, and any known method can be used, but the boiling point is high in normal operations such as distillation. Moreover, at temperatures above 100C, polymerization partially begins, which is often very difficult.

Therefore, in such a case, you can separate it by the following operation. For example, once you have a large amount of water, carbon tetrachloride, chloroform, methylene chloride.

A preferred method is to add a mixture with a halogen-containing solvent such as 1.1.2-)lichloro-1,2,2-)lifluoroethane to extract the fluorine-containing unsaturated carboxylic acid ester with a solvent. Furthermore, the hydrogen halide produced in the above reaction, perfluorocarbon II, and the unreacted raw material perfluoro acid halide are soluble in water, so a weak alkaline aqueous solution (for example, Ma
HOOj, M&2CO5, etc.) can be neutralized and separated from the monomer. After separating these, the solvent was removed under reduced pressure at 106
The fluorine-containing unsaturated carboxylic acid ester is preferably obtained by distillation using the following aim.

(1) (1) General formula % Formula %) A method is adopted for producing a fluorine-containing unsaturated carmenic acid ester by reacting it in an anhydrous polar nonaqueous solvent in which a tertiary amine is present.

In the reaction of the production method described in (1) above, the raw materials are mixed in what order and the reaction is carried out. The reaction temperature is not particularly limited, but is usually -78°C
It is desirable to select from a temperature range of 100° C. or above and 100° C. or below. Although the reaction proceeds even at high temperatures exceeding 100° C., polymerization of raw materials or products or side reactions tends to occur, so it is preferable not to use this method except in special cases. Therefore, from the viewpoint of yield of the target product, the reaction temperature is preferably selected between -78 and 100°C,
More preferably, the temperature is selected from a temperature range of -78 to SOC.

The reaction in the above production method (Otori) is usually conveniently carried out under natural pressure at the reaction temperature with the raw material components and solvent charged, but if necessary, the pressure may be further increased or reduced. It can also be done in the state. The reaction atmosphere is not particularly limited, but in general, replacing the atmosphere with an inert gas often gives preferable results.

The reaction time in the production method described above (...) varies depending on the raw material component compound used, the type of solvent, the reaction temperature, etc., and cannot be limited to a certain part, but is generally preferably selected within the range of several minutes to several days. It is preferable to select other conditions such that the reaction time ranges from several minutes to several hours, as necessary.

The material of the reaction vessel in the production method (1) is not particularly limited as long as it is resistant to corrosion and is not involved in the reaction, but glass, metals such as stainless steel, Teflon, etc. are generally suitably used and are more preferred. It is preferable to use a pressure-resistant container.

When carrying out the production method of (1) above, means for stirring the reaction system for uniform dispersion of reaction heat and uniform dispersion of raw material component compounds can often be employed as a suitable means.

To separate the fluorine-containing unsaturated carmenic acid ester produced by the production method described in (1) above from the mixture in the reaction vessel, operate in the same manner as the separation method in the production method described above (I). Bye.

Next, a method for utilizing the fluorine-containing unsaturated carboxylic acid ester, which is a novel substance of the present invention, will be explained below.

The fluorine-containing unsaturated carboxylic ester of the present invention has an unsaturated bond as described above, and therefore is widely used as a monomer, a crosslinking agent, etc. for polymers or copolymers. For example, it is suitably used in dental filler compositions. When the fluorine-containing unsaturated carboxylic acid ester is used in a dental filler composition, it will be de-energized below. Dental filler compositions are generally called co-reposit resins, such as paste-like mixtures of polymerizable monomers and inorganic fillers, or cured materials, or polymerizable monomers. This liquid or polymeric state is used as a polymerizable monomer in what is commonly referred to as a sealant.

Currently, among compartment materials, especially dental materials, materials whose main components are bisphenolglycidyl methacrylate (hereinafter referred to as Big-GM) and inorganic fillers (hereinafter referred to as Big-GMA composite resin) are used as filling materials for restorations. In addition, an organic material containing Big-GM as a main component (hereinafter referred to as "Big-GM-based sheets") has also been used as a filling material for small bud fissures, etc.

However, because these Big-GMA-based filling materials have a high water absorption rate, water tends to enter between the leprosy and the filling material, and as a result, Streptococcus minitans, which causes tooth decay, can enter along with the water. This can cause secondary caries.

In addition, since the refractive index of B15-GIJ is as high as 1.55, inorganic substances with a low refractive index (such as amorphous silica) may have a transparent appearance when mixed with the inorganic filler used as a raw material for composite resin. It has the disadvantage that it cannot be used as a filler because it does not release. However, the above-mentioned defects can be solved by the Big-GMA composite resin and by using the fluorine-containing unsaturated carboxylic acid ester of the present invention in place of the Big-GM resin.

The new material of the present invention has excellent characteristics of low viscosity, low refraction, and water repellency. In addition, in practical use, when used in composite resins, it is generally mixed with an inorganic filler, a catalyst for polymerizing the composite resin, a promoter that reacts with the scissors catalyst to generate free radicals, etc. . In addition, the inorganic filler includes quartz powder,
Glass powder, glass beads, aluminum oxide, amorphous silica, etc. may be used. Furthermore, it is preferred that the inorganic filler accounts for 50 to 90 weight X of the composite resin weight. In addition, the inorganic filler is pre-coupled with a coupling agent,
For example, treatment with r-methacryloxypropyltrimethoxysilane or vinyltriethoxysilane is preferable because it strengthens the bond between the inorganic filler and the resin composition and further improves the physical properties of the material for partitioning. Further, as typical catalysts, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 4-chlorobenzoyl peroxide, lauroyl peroxide, etc. are preferably used. These catalysts are generally used in resin compositions 10
It is used in a proportion of 0.1 to 2.0 parts by weight to 0 parts by weight. Further, typical examples of the t9 accelerator include y2M-dimethyl-P-toluidine, N,N-bis-(2-hydroxyethyl)-4-methylaniline, N,M-bis-(
2-hydroxyethyl)-3,5-dimethylaniline,
N,N-bis-(2-hydroxyethyl)-4,4-dimethyaniline and the like are preferably used.

Generally, these accelerators may be used in an amount of 0.1 to 2.0 parts by weight per 100 parts by weight of the resin composition. Furthermore, in order to improve the storage stability of the resin composition, it is necessary to add a UV absorber such as a benzophenone compound or f41+-12-hydroxy-4-methylbenzophenone to the resin composition.
0 parts by weight, 0.5 to 2.0 parts by weight is generally a stabilizer called a free radical chain reaction terminator, such as P-methoxyphenol, 2,5-di-tart-butyl-4-methylphenol, etc. A paste-like material (pasteum) consisting of a gin-compound accelerator and a paste-like material (paste B) consisting of an inorganic filler resin composition catalyst are prepared in advance, and when used by a doctor, these two pastes are combined. The resin composition starts polymerization simply by mixing, which is very convenient.

When the novel substance of the present invention is used as a sealant, an inorganic filler may be used in combination, but other materials such as catalysts, accelerated steel,
Regarding ultraviolet absorbers, etc., it is the same as for composite resin.

゛ When used by a doctor, a similar method is used in which the two liquids are mixed and the resin composition starts polymerizing.

The resin composition of the present invention can be used as a bone cement artificial bone in the field of orthopedics and plastic surgery, or as a crown restoration material or abutment tooth material 1 in the prosthetics field. It can be used as filling material, lining agent, root canal filling agent, etc.

The present invention will be specifically explained below using Examples. In the Examples, the preparation and curing method of the composite resin and sealant, and the measurement of the physical properties of the sample after curing (water absorption, toothbrush wear depth, compressive strength, viscosity refractive index) are as follows:
The following method was followed.

(Support) Sample preparation and curing method (a) Amorphous silica surface-treated with f,r-methacryloxypropyltrimethoxysilane and a vinyl monomer containing the novel substance of the present invention as one component in a predetermined ratio. Place in an agate mortar and mix thoroughly until it becomes a uniform paste.

The paste was then divided into two equal parts, and a polymerization accelerator was further added to one of the pastes and thoroughly mixed.

(This is called Pastem). Further, an organic peroxide catalyst was added to the other paste and thoroughly mixed. (Let this be Pace B). Next, equal amounts of pastem and paste) B were kneaded for about 50 seconds, filled into a mold, and hardened.

(b) A vinyl monomer containing the novel substance of the present invention as one component was divided into two equal parts, and a heavy accelerator was added to one of the liquids and thoroughly mixed. (This is called liquid A).

Further, an organic peroxide catalyst was added to the other monomer liquid and thoroughly mixed. (This is called liquid B).

Next, equal amounts of Liquid Sum and Liquid B were kneaded for about 30 seconds, filled into a mold, and hardened.

(→ Water absorption) Paste and paste B (or liquid and liquid B) were mixed and polymerized at room temperature for 30 minutes, followed by vacuum drying at 57° C. for 45 hours.

Next, after measuring the dry weight, the sample was immersed in warm water at 37° C., and the change in weight was measured every few days. The shape of the sample is 10
It is a cube of snow x 10 x 1.5 -.

(Compressive strength) Paste A and paste B (or liquid A and liquid B) were mixed and polymerized for 30 minutes at room temperature, and then immersed in water at 37°C for 24 hours to prepare a test piece.The size The shape is cylindrical with a diameter of 6 cm and a height of 12 cm.The test piece was attached to a testing machine (Toyo Baudouin UτM-5?) and the compressive strength was measured at a crosshead speed of 10 points/min. did.

(c) Toothbrush abrasion depth Paste and paste B (or liquid and liquid B) were mixed and polymerized at room temperature for 30 minutes, and then immersed in water at 37°C for 24 hours. Its size and shape are 1
．． It has a plate shape of 5 x 10 x 10 cm. The test piece was abraded for 1500 wa with a toothbrush under a load of 400 f, and the abrasion depth was determined. Ceramic, abrasion depth is determined by abrasion polymerization with composite resin (
Or polymer) was calculated by dividing by the degree of writing.

(e) Viscosity measurement The viscosity of the fluoro-containing bulk unsaturated carboxylic acid ester was determined using a type I viscosity needle manufactured by Tokyo Keiki.

The measurements were performed in a constant temperature room at 2.1C.

(f) Refractive index of the refractive index of the fluorine-containing unsaturated carboxylic acid ester and the refractive index of the polymer obtained by heating and polymerizing the fluorine-containing unsaturated carboxylic acid ester with an organic peroxide catalyst added at 100C. It was measured with

In addition, the abbreviations of good raw materials used in the examples are shown in Table 1. Example 1 In a 100-mm stainless steel autoclave, bisGM 1.84 F and benzene 30-
The mixture was thoroughly stirred and mixed, and the mixture was cooled with a dry ice-methanol solution on the back wall.

Next, store it in a 100-℃ pressure-resistant glass container that has been cooled to -78℃ in advance. %/-h of perfluoropropionic acid fluoride (boiling point -28 DEG C.) was introduced into the autoclave through a copper pipe. Then, while stirring, transfer the autoclave container to a separatory funnel and add a large amount of water to cool the aqueous layer from the strong acidity. After neutralizing the aqueous layer with an aqueous sodium bicarbonate solution, the benzene layer was removed, and the benzene was evaporated to give the desired product. Yield is 7
It was 9%.

According to the infrared absorption spectrum of the obtained reaction product, 5
50 The absorption due to the OH group near Gam-' disappears, and the i yield due to the cardanate ester bonded to the perfluoroalkyl group at 1780 am-', 1400-11005
Absorption due to 0-IP binding appeared at 11.

In addition, the yield of carmenic acid ester of methacrylic group is 1
72051-' e Absorption due to double bond flE 16
Absorption by 40a+-'s benzene is 149 Scl
m-' was observed.

Next, product 13 (3) was identified using nuclear magnetic resonance spectroscopy.The results are as follows.

(a) 12&6ppm (b) 15&6ppm (c)
17:7ppmK) IS7.8ppm (a) 4
47ppm (7 & 9pI) m(g) 69 S
PI)m (b)157. OpPm (i)
144.7 ppm (j) 1244 ppm axis) 114.
9p4 (442, to 2ppm) 3α9 ppm (a
)11 &8 ppm 01107.0 ppm(0
) 15a, ltPm m/ese by mass spectrometry spectrum of the purified product
A molecular ion peak of 804 was observed.

The results of elemental analysis of the product again in the summer are shown below.

From these analysis results, the reaction product was heated at 100°C for 1 hour using Lafroyl peroxide as an initiator.
The refractive index values of the polymers obtained by heating polymerization for 0 hours were 1.480 and 1.499, respectively.

Example 2 BisGM (16.7 F) ethylamine 1f was placed in a 100-mm stainless steel autoclave.

After adding 50% of acetonitrile and stirring thoroughly, the mixture was cooled with a dry ice-methanol solution. Next, I stored it in a 100-grade pressure-resistant glass container that had been cooled to -78℃ beforehand. Fluoropropylene oxide (hereinafter referred to as HFPO) 35 was then introduced into the autoclave through a copper pipe while being returned to room temperature. After the introduction, the autoclave was gradually returned to room temperature and left stirring overnight. The pressure once rose to 5-/-, but then gradually decreased and finally stabilized at 2.7147-/-. The gas component is considered to be propionic acid fluoride produced by the isomerization reaction of HFPO, since the infrared absorption spectrum shows an absorption of acid fluoride at 1890 m-'. Next, after removing the reaction gas, the reaction product was transferred to a separatory funnel, and a large amount of water and 1,1.2-)lichloro-1,2,2-)lifluoroethane solvent (aatv, cct, y) were added. Ta. Here, unreacted bisGM and solvent a7tonitrile are transferred to the aqueous layer. The aqueous layer is strongly acidic, so hydrogen carbonate is used)
The firefly, 1,1,2-)lichloro-1,2,2-trifluoroethane layer neutralized with an aqueous solution of IJ was taken out, and the solvent was evaporated to obtain the desired product. The yield was 75%. The obtained product showed an infrared absorption spectrum completely similar to that of Example 1. In addition, %II! is included in the 1Na nuclear magnetic resonance spectrum and mass spectrometry spectrum. The results were similar to those of Koji Example 1. The result of elemental analysis is 0:52.15. H:4.39. F: It became 11.7+6. These analysis results revealed that the reaction product was the same compound as in Example 1.

In addition, this product and this product were polymerized in the same manner as in Example 1, and the refractive index of each of the nine polymers was 1.480.
and 1.499.

Example 3 MsGM 11.9 F and benzene 25- were placed in a 100-3-necked flask, and while stirring thoroughly, a dimer of HFPO (cyscy2cy2ocy(07m)00IP) was added.
20.79 was added dropwise. After the dropwise addition, stirring was performed for about 5 hours.

Next, the raw acid fluoride and benzene were removed from the reaction solution at 50° C. under reduced pressure for two tries. Transfer the remaining product to a separating funnel and add water and 1,1,2-tritalol 1 $292-
)! J fluoroethane solvent was added. Unreacted bis G M A *produced hydrogen fluoride and perfluorocardic acid move to the aqueous layer. Since the aqueous layer was strongly acidic, it was neutralized with an aqueous NILHOO3 solution. then 1,1
．． The 2-trichloro-1,2,2-)realoloethane layer was removed and the solvent was evaporated to obtain a viscous liquid. The yield of this reaction is 9B! Met.

The infrared absorption spectrum of this product showed the same absorption as in Example 1. Next, the product was identified using 11C nuclear magnetic resonance spectrum.

The results were as follows.

(0) (B) (4) (a) to (III): (a) to (Illi) of Example 1
) Same as (A) 117.9 ppm (B) 107.4
1) pm ((') 116 Jppm (D) 1014 p
pm (E9118.9 pI)m (F)1590p
pm and mass spectrometry spectra of the product to determine m/e engineering 1
69 (City) and 1156 (molecular ion peak) were observed.

Furthermore, the results of elemental analysis of the product were as shown below.

From these analysis results, the reaction products are It was confirmed that

Further, the refractive index of this product and the polymer obtained by polymerizing this product in the same manner as in Example 1 are each 1.45?
, 1.478.

Example 4 MsGMA 1αOt' in a 100-meter three-neck flask
e) ') Ethylamine 7.5 f Tobenene 25
- and stirring thoroughly, hexafluoropropylene oxide dimer acid chloride (C!7507
20720(!F(OFs)0004) 2 5.
Drop Of. After the addition, stirring was carried out overnight. Next, the raw material acid chloride and benzene were removed from the reaction solution at 50°C under a reduced pressure of 2wmHy. By adding a large amount of water and 1.1.2-)lichloro-1,2,2-)lifluoroethane to the remaining reaction solution, triethylamine hydrochloride is transferred to the aqueous layer, and only the desired product is produced. is dissolved in the 1.1.2-trichloro-1e2s2-)lifluoroethane layer. Therefore, the 1.1.2-) Refluoroethane layer was taken out using a separating funnel, and the solvent was evaporated to obtain the desired product. The yield of this reaction is 89
! Met. The obtained product showed an infrared absorption spectrum exactly the same as that of Example 3. Furthermore, the same results as in Example 3 were also shown in the l5(3 nuclear magnetic resonance spectrum and mass spectrum).

The results of elemental analysis are C: 43.50 H: 3.10 F: 18
．． It became 36. These analysis results revealed that the reaction product was the same compound as in Example 3.

Furthermore, the refractive index of this product and the polymer obtained by polymerizing this product in the same manner as in Example 1 are each 1.459.
, 1.478.

Example 5 The reaction between bisGM and aypo trimer was carried out in the same manner as in Example 5. Yield was 90X.

The infrared absorption spectrum of the raw acid product showed the same absorption as in Example 1. Next, the product was identified using 11c nuclear magnetic resonance spectrum.

The results were as shown below.

(&) to (→ were the same as in Example 1.

(A) 117.6ppm (B) 107.2ppm
(C') 1140ppm (D) 10AII)pm
Q! j) 11 lllppm CP) 1140ppm
(to) 10t 2ppm @119.0ppm
(1) 158.9 ppm Also, m/e-169 (OxF'y) e 146 B (molecular ion beak) was observed in the mass spectrometry spectrum.

Furthermore, the results of elemental analysis were as shown below.

From these analysis results, the reaction products are It was confirmed that

Furthermore, the refractive index of this product and the polymer obtained by polymerizing this product in the same manner as in Example 1 are each 1.428.
, 1.449.

Example 6 A methacrylic acid derivative (epoxy ester 3002M) having the structural formula shown in Table 1 was reacted with HIFPO. The same method as in Example 2 was carried out using triethylamine as a catalyst. The yield was 74%.

The infrared absorption spectrum of the product showed absorption similar to that of Example 1. Next, the product is identified using a magnetic resonance spectrum.

The result is as shown below.

(0) (a) 1244ppm (b) 136Jppm (
0) 18.2ppm (d) IS&7ppm (e
) 6 & Oppm (f) 6a9ppm (g) 6
9jppm (Re 711ppm (i) dl1
6ppm (j) 16.9 ppm (trans) 748
pPIm (4157,2ppia) 1158pp
m (→12 &4 ppm (01440m)P
m(p) 42.2ppm (q) 315pp
m (a) 11a8ppmCB) 107.0 pp
m (C) 15 &, 6 ppm In addition, a molecular ion peak of ym/.max 946 was observed in the mass spectrometry spectrum.

Furthermore, the results of elemental analysis were as shown below.

From these analysis results, the reaction products are It was confirmed that

Furthermore, the refractive index of this product and the polymer obtained by polymerizing the product in the same manner as in Example 1 are 1.467 and 1.467, respectively.
It was 1.484.

Example 7 A reaction between a methacrylic acid derivative (epoxy ester 3002M) having the structural formula shown in Table 1 and a dimer of HIFPO was carried out in the same manner as in Example 3. Yield was 54X. The infrared absorption spectrum of the product showed the same absorption as in Example 1. Next, the product was identified using a 130 magnetic resonance spectrum. The results were as shown below.

oclPjOF20Fl ←) to ■ were the same as in Example 6.

) 117.9ppm (B) 107.4ppm
(→1141)E)”E’(110tSppm cJ4
118.9ppm (F5159.Oppm Also, according to the mass spectrometry spectrum, m/・=169(C1Fy) 1
27B (molecule 4 on beak) was observed.

Furthermore, the results of elemental analysis were as shown below.

From these analysis results, the reaction products are \11 It was confirmed that

Furthermore, the refractive index of this product and the polymer obtained by polymerizing the product in the same manner as in Example 1 are 1.454 and 1.454, respectively.
It was 1.475.

Example 8 A reaction between a methacrylic acid derivative (epoxy ester 3002M) having the structural formula shown in Table 1 and a pentamer of 117PO was carried out in the same manner as in Example 3. Yield was 82X. The infrared absorption spectrum of the product showed the same absorption as in Example 1. Next, the product was identified using 130 nuclear magnetic resonance spectrum. The results are as shown below.9.

←) to (q) were the same as in Example 6.

(A) 1174PPMl (n) 107.2ppm
(CO116,0ppm (I)1011Hpm Q
l') 11&1'Ppm (F) 116.0ppm (
G) 10t2ppm 0411? , OpPm CX)
m/・by 158.9 ppmti mass spectrometry spectrum
Tomi 169 (0sly) ISlo (molecular ion peak)
was observed.

Furthermore, the results of elemental analysis were as shown below.

From these analysis results, it was confirmed that the reaction product was . Further, the refractive index of this product and the polymer obtained by polymerizing the product in the same manner as in Example 1 were each 1.395.

It was 1.414.

Example 9 Metaku uJ kf & trout conductor (with the structural formula shown in Table 1)
Epoxy ester 401CM) was reacted with HFPO. At this time, the same method as in Example 2 was conducted using triethylamine as a catalyst. The yield was 68N, 9.

The infrared absorption spectrum of the product showed the same absorption as in Example 1 outside the point plate where there was no absorption (1495a+g-') due to acid and benzene S&=. Next, the product was identified using 1sC nuclear magnetic resonance spectrum. The results were as shown below.

(c) (G) (AR) (a) 126.5ppm (b) 1346ppm
(c) 18.1ppm (d) 167.2p'pm (
e) dLlppm (67L4ppmω 49.7p
pm (b) 7t8ppm ■118.811m1
m(B)107. OpPm (+1158.6ppm
Furthermore, m/e=638 (molecular ion beak) was observed in the mass spectrometry spectrum.

Furthermore, the results of elemental analysis were as shown below.

From these analysis results, it was confirmed that the reaction product was . Further, the refractive index of this product and the polymer obtained by polymerizing the product using the surface blade method in the same manner as in Example 1 were 1,415.

It was 1.457.

Example 10 A reaction between a methacrylic acid derivative (epoxy ester 401M) having the structural formula shown in Table 1 and a dimer of HFPO was carried out in the same manner as in Example 3. The yield was 76%.

The infrared absorption spectrum of the product showed absorption similar to that of Example 9. Next, the product was identified using C nuclear magnetic resonance spectrum. The results were as shown below.

(c) (-) to (b) were the same as in Example 9.

(A) 1179ppm (B) 107.4ppm
(0) 11LOppm (1otsppm (cocoon 11
&9 ppm (to) 159.0 ppH m/@x 169 (c5Fy) 970 by mass spectrum
(molecular ion beak) was detected. Furthermore, the results of elemental analysis were as shown below.

From these analysis results, it was confirmed that the reaction product was 2. Further, the refractive index of this product and a polymer obtained by polymerizing the product in the same manner as in Example 1 were each 1.377.

It was 1.404.

Example 11 A reaction between a methacrylic acid derivative (epoxy ester 401M) having the structural formula shown in Table 1 and a trimer of mFPO was carried out in the same manner as in Example 3. The yield was 65%.

The infrared absorption spectrum of the product showed absorption similar to that of Example 9. Next, the product was identified using 1sC nuclear magnetic resonance spectrum.

The results were as shown below.

(a) to (b) are the same as in Example 9;

(A) 1176ppm (B) 107.2ppm
((1')11LOppm(n)10&lppm @
118°1 ppm (F) 116. OpI)m(
G) 1012ppm (H) 119.0ppm (
1) 15 a, 9 ppm II Also, according to the mass spectrometry spectrum, m/・; 169 (0177), 13Q
2 (molecular ion peak) was observed. Furthermore, the results of elemental analysis were as shown below.

These analysis results confirmed that the reaction product was UFA UF5. Moreover, the refractive index of this product and the polymer that can be polymerized in the same manner as in Example 1 are 1. ! ! 65.

It was 1.381.

Example 12 Acrylic acid derivative (epoxy ester 70P) having the structural formula shown in Table 1! : HFPO reaction was performed. This was carried out in the same manner as in Example 2 using triethylamine as a catalyst. Yield: 68X.

The infrared absorption spectrum of the product showed absorption similar to that of Example 9. Next, the product was identified using 130 nuclear magnetic resonance spectrum.

The results were as shown below.

(a) 15tOppm (b) 127.9ppm
(e) 1155.911pm (a) 654ppm
(e) 6&4ppm (f) 69.9ppm (
y3 69.91)pm On) 67.9'pp
m (i) 17.0ppm (a) 118.8pp
m (B) 107.0 pI)! II (0)15&
4ppm Also, according to the mass spectrometry spectrum, m/・-62
A fourth molecular ion beak was detected. Furthermore, the results of elemental analysis were as shown below.

From these analysis results, the reaction products are It was confirmed that

Moreover, the refractive index of this product and the polymer obtained by polymerizing the product in the same manner as in Example 1 are 1,405 and 1,405, respectively.
It was 1.427.

Example 13 A dimer of acrylic acid derivative (epoxy ester 70P) and IIIFPO having the structural formula shown in Table 1 was reacted in the same manner as in Example 3. Collection rate was 96%.

The infrared absorption spectrum of the product showed absorption similar to that of Example 9. Next, the product was identified using 130 nuclear magnetic resonance spectrum.

The results were as shown below.

(a) to (1) were the same as in Example 12.

(A) 117.91) 1) m (B) 107.4pp
m ((91146ppm(41016ppm (
X) 118.91) pm (15159, Qppm Also, m/5 = 169 (Csl
'7) 956C molecular ion beak) was observed. Furthermore, the results of elemental analysis were as shown below.

From these analysis results, the reaction products are It was confirmed that

Furthermore, the refractive index of this product and the polymer obtained by polymerizing the product in the same manner as in Example 1 are 1.575 and 1.575, respectively.
1.394, which is nine.

Example 14 A reaction between an acrylic acid derivative (epoxy ester 70P) having the nine structures shown in Table 1 and RFPO trimer was carried out in the same manner as in Example 3. The yield was 80.0%.

Infrared absorption of the product -Similar absorption to Saktor's Example 9. Next, the product was identified using 11C nuclear magnetic resonance spectrum.

The results were as shown below.

(Respect (,) to (1) were the same as in Example 12.

(A)117. +6ppm (B) 1072ppm (
0) 11t [ppm (D) 10! i,lppm @11
8. lppm (ilioppm(G)10t2ppm
Q()119. OPpm (1) 15 & 9 ppm
Also, according to the mass spectrometry spectrum, m/e = 169
(0sFr)1288 (molecular ion peak) was observed. Furthermore, the results of elemental analysis were as shown below.

From these analysis results, the reaction products are It was confirmed that

Furthermore, the refractive index of this product and the polymer obtained by polymerizing the product in the same manner as in Example 1 are 1.351.1.
．． It was 369.

Example 15 0.3μ silica particles were surface-treated with r-methacryloxypropyltrimethoxysilane.
A product obtained by reacting a dimer of MA and HFPO (hereinafter referred to as F-b)
iaGM), and triethylene glycol dimethacrylate as the upper diluent (TKGDM).
A paste-like composite restorative material was obtained by blending the silica particles with the above silica particles and thoroughly kneading the mixture. On this occasion,
The filling amount of silica particles in the composite restorative material was 75.6 wtFX, and the viscosity of the paste was appropriate for operation. Next, divide the paste into three equal parts and add N to one part as a polymerization accelerator.

N-dimethyl-P-toluidine t-14-On the other hand, benzoyl peroxide was added as a polymerization initiator at 1 wt% of each vinyl monomer to prepare paste) A (former) and paste) B (latter). .

Equal amounts of the above paste and paste B were kneaded at room temperature for 30 seconds and cured, and the water absorption rate was measured. The ceramic, cured samples were vacuum dried at 37C for 45 hours. Next, after measuring the dry weight, the weight increase was measured one day and two days after immersing it in 37° C. warm water. Table 2 shows the results.
It was shown to.

Table 2 The numbers in parentheses indicate mol X.

Example 16 Ma GM, F-bisG as vinyl monomers
TICGDMA was used as MA k and a diluent monomer, and these were mixed to obtain a liquid repair material.

Next, divide the liquid into three equal parts, and use N and N as polymerization accelerators in one part.
-dimethyl-P-)luidine and benzoyl peroxide as a polymerization initiator were added to the vinyl monomer in an amount of 1 wtX, respectively, to prepare a solution A (former) and a solution B (latter). Equal amounts of the above liquids A and B were kneaded at room temperature for 30 seconds and cured, and the water absorption rate was measured. The measurement method is the same as in Example 15.

Table 5 shows the changes in water absorption of the above prototypes.

Table 3 Values in parentheses indicate mol%.

Example 17 A liquid restorative material was prepared in the same manner as in Example 16.

The mixing proportions of the vinyl monomer components are shown in Table 4 and are in good agreement. The liquid repair material was cured in the same manner as in Example 15, and the compressive strength was determined.

The results are shown in Table 4.

Table' 4 Example 18 A liquid restorative material was prepared in the same manner as in Example 15. The mixing proportions of the vinyl monomer components are shown in Table 5. Each liquid repair material was cured in the same manner as in Example 15.

...The depth of brush wear was investigated. The results are shown in Table 5.

Table 5 The numbers in parentheses indicate mol X.

Example 19 The fluorine-based monomer synthesized in Example 3, bisGMA, and TICGM, which is a diluting monomer, were mixed in the proportions shown in Table 6, and the viscosity of the mixture was measured. The results are shown in Table 6.

Table 6 Viscosity of vinyl monomer patent applicant Tokuyama Soda Co., Ltd.

Claims (1)

[Scope of Claims] 1) A fluorine-containing unsaturated carboxylic acid ester represented by the general formula (wherein R1 is H or OH3%, R2 is ca2, Q.). 2) General formula cy, cy, cox (however, X It 7%
A perfluorocarboxylic acid represented by the agen radical (where n is 0 or 1, and I is a halogen atom), -s ride, and the general formula (however, R1 is H or 0H1-1R1 is 间, 0゜t is O
or 1, n is 0 or 1). 3) In an organic solvent, in the presence of a tertiary amine, C1:y-
cip2 and general formula) (wherein R1 is ■ or Gls, and R2 is (!H2, Q. or 1). Manufacturing method 4) General formula % Formula % 1. ) A dental filler composition containing at least 41 components of fluorine-containing unsaturated carboxylic acid esters.