JPS59184222A - Polymerization - Google Patents

Abstract

PURPOSE:To obtain a nonshrinkable polymer which can be used in the mouth, has a short gelation time and, accordingly good workability and operability and is useful as a dental resin, by polymerizing an unsaturated bicyclo compound in the presence of a specified catalyst. CONSTITUTION:An unsaturated bicyclo compound having at least one polymerizable vinyl group in the molecule and having a 2,6,7-trioxabicyclo[2.2.2]octane ring, e.g., 4-alkyl-1-hydroxyalkyl-2,6,7-trioxabicyclo[2.2.2]octane unsaturated carboxylic acid ester, is polymerized by using a tert. amine compound (e.g., triethylamine) and an acid anhydride (e.g., acetic anhydride) as a catalyst. It is possible to obtain a nonshrinkable polymer which has a very short gelation time and accordingly good workability and operability. Polymers of this kind have heretofore been inapplicable to dental resins because they were produced by using strongly acidic compounds such as BF3, but the use of the above catalyst makes their dental application possible.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polymerization method for polymerizing an unsaturated bicyclo compound using a tertiary amine and an acid anhydride as a catalyst.

Some of the unsaturated bicyclo compounds represented by the specific general formula that are the object of the present invention are known, for example, to be polymerized using BF3 as a catalyst.

The resulting polymer has been found to be a non-shrinkable polymer, but no industrially useful use has yet been found.

The present inventors have repeatedly conducted research into applications in which the above-mentioned non-shrinkable polymer can be advantageously used. As a result, it was found to be useful as a dental resin. However, in the case of dental resins, known strong acidic compounds such as BF3 cannot be used. As a result of further research, it was discovered that when a tertiary amine compound and an acid anhydride, which can be used in the mouth, are used as catalysts, extremely good polymerizability is exhibited, leading to the completion of the present invention.

The present invention has at least one polymerizable vinyl group in the molecule, and 2,6,7-trioxabicyclo[2,2,
2] This is a polymerization method characterized by polymerizing an unsaturated bicyclo compound having an octane ring using a tertiary amine compound and an acid anhydride as a catalyst.

The unsaturated bicyclo compound of the present invention can be any compound as long as it has at least one polymerizable vinyl group in the molecule and a 2,6,7-trioxabicyclo[2,2,2]octane ring. May be used without restriction. Typical examples of the above-mentioned unsaturated bicyclo compounds that are generally preferably used include the following compounds.

For example, 4-alkyl-1-hydroxyalkyl-2 represented by the general formula
, 6,7-trioxabicyclo[2,2,2]octane unsaturated carboxylic acid ester, or 1-alkyl-4-hydroxyalkyl-2 represented by the general formula
, 6,7-trioxabicyclo[2,2,2]octane unsaturated carboxylic acid ester. However, the above general formula [
I] and [II], R1 is hydrogen or a monovalent organic group. The monovalent organic group is not particularly limited, and any monovalent organic group, either saturated or unsaturated, can be used. Specific examples of generally suitably used monovalent organic groups include CH3-, C2H5-, n-C3H7-, is
o-C3H7-, n-C4H9-, iso-C5H11
-, C10-H21- and other saturated hydrocarbon residues; H2C=
Unsaturated hydrocarbon residues having CH- group, CH3-CH=CH- group, etc.; NH2-, CH3NH-, CH3CO
Organic group containing NH-; CH3NHCO-, CH3CO
Organic group containing an amide group such as NH-, CH3NHCOOCH2-, CH3CH2NHCOOC
Urethane groups such as H2-; CH2=CHCOO-, CH2
=C(CH3)COO-, CH2=CHCOOCH2-
residues of acrylic acid, methacrylic acid, etc.; and organic groups in which some or all of the hydrogen atoms have been replaced with halogen atoms, hydroxyl, etc.

Further, in the above general formula, R2 is hydrogen or a methyl group.

Furthermore, in the general formula, R3 is Or (CR4HCH2)m.

Here, R4 is hydrogen or an alkyl group, and n is 0 to 10
m is an integer from 1 to 500. The above R3 is (
The value of m when OCR2CH2)m differs depending on the raw materials ethylene glycol, propylene glycol, these oligomers, and the type of these polymers. Generally, the smaller the value of m, the easier it is to use.
The most suitable value is about 50, more preferably about 1 to 20.

Although some of the unsaturated bicyclo compounds represented by the above general formula include new compounds, it is known that they can be polymerized using, for example, BF3 as a catalyst, as described above. However, the above BF3
When used as a catalyst, there are defects that prevent it from being used in applications that come into contact with the human body, such as dental resins.

The present invention solves the conventional technical problems by using a tertiary amine compound and an acid anhydride as a catalyst. That is, the unsaturated bicyclo compound represented by the above general formula has radical polymerizability based on unsaturated bonds and polymerizability due to ring opening of the bicyclo ring.

In the present invention, by using a tertiary amine compound and an acid anhydride as a catalyst, both ring-opening polymerization of bicyclo rings and radical polymerization of unsaturated bonds are induced, and the resulting polymer becomes a crosslinked polymer. Therefore, it becomes a non-shrinkable polymer.

The above-mentioned tertiary amine compound is not particularly limited, and known ones can be used. Specific examples of tertiary amine compounds that are preferably used include triethylamine, tributylamine, pyridine, N,N-dimethylaniline, N,N-dimethyl-P-toluidine, and N,N-dimethyl-P-xylidine. , N,N-dihydroxyethyl-P-toluidine, and the like.

Further, the acid anhydride mentioned above is not particularly limited, and any known acid anhydride can be used. Typical examples that are generally suitably used are as follows. Examples include acetic anhydride, propionic anhydride, acrylic anhydride, methacrylic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, maleic anhydride-styrene copolymer, and the like.

In the present invention, the amounts of the tertiary amine compound and acid anhydride to be used vary depending on various reaction conditions and may be appropriately determined in advance. Generally, the tertiary amine compound is 0.01 to 20 mol%, preferably 0.01 to 20% by mole based on the unsaturated bicyclo compound.
．． It may be selected from the range of 1 to 10 mol%. Further, the acid anhydride may be selected from the range of 0.01 to 50 mol%, preferably 0.1 to 20 mol%, based on the unsaturated bicyclo compound.

Further, in the present invention, when a commonly known radical initiator is used together with the catalyst component consisting of the tertiary amine compound and acid anhydride, favorable results can often be expected. The above-mentioned radical initiator is not particularly limited, and known ones can be used. Examples of radical initiators that are generally preferably used include 2,2'-azobisisobutyronitrile, di-ter
t-Butyl peroxide, 2,5-dimethyl-2,5
-di(tert-butylperoxy)hexane, ter
These include t-butyl hydroperoxide, tert-butyl peroxybenzoate, benzoyl peroxide, and the like. Further, it is generally sufficient to use these radical initiators in an amount of 0.01 to 10 mol %, preferably 0.1 to 5 mol %, based on the unsaturated bicyclo compound.

In carrying out the present invention, conventionally known polymerizable monomers may be mixed with the vinyl compound. Examples of polymerizable monomers particularly suitable for mixing include styrene,
Diacrylic acids such as vinyl acetate, methyl acrylate, methyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, N,N-dimethylaminoethyl methacrylate, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, butylene glycol, etc. Esters and dimethacrylic esters; triacrylic esters and trimethacrylic esters such as trimethylolpropane and trimethylolethane;
Tetraacrylic acid and tetramethacrylic acid esters of tetramethylolethane; bisphenol-A-dimethacrylate, bisphenol-A-diglycidyl methacrylate, 2,2-bis(4-methacryloxyethoxyphenyl)propane, and the like. In addition, P-
Polymerization accelerators such as sodium toluenesulfinate and sodium benzenesulfinate; Polymerization inhibitors such as hydroquinone and plasticized hydroxytoluene; 2-hydroxy-4-methoxybenzophenone, 2(2'-hydroxy-5' - Ultraviolet absorbers such as -methylphenyl)benzotriazole; polymeric compounds such as polymethyl methacrylate, unsaturated polyester resins, and epoxy resins; addition of spiroornoesters, bicycloorthoesters, etc. is also effective.

The manner in which the unsaturated bicyclo compound of the present invention is polymerized is not particularly limited, and may be carried out by selecting from known methods as necessary. The commonly practiced method is casting correct. For example, the polymerization may be carried out by melting the unsaturated bicyclo compound with the catalyst in a mold or on a plate. Generally from 0°C to 200°C, preferably from 60°C
A wide range of polymerization temperatures of 130°C can be selected. Furthermore, when the unsaturated bicyclo compound is liquid, polymerization can be started by directly adding and mixing the catalyst, but when the unsaturated bicyclo compound is solid, the unsaturated bicyclo compound is usually added. It is preferable to dissolve the saturated bicyclo compound in a soluble monomer, for example, a polymerizable monomer such as methyl methacrylate or methyl acrylate, and subject it to polymerization. Further, the polymerization time may be controlled depending on the manner in which the obtained polymer is used.

By selecting the type of catalyst, polymerization conditions, etc., the polymers obtained in the present invention can range from those in which some of the bicyclo rings remain unopened to those in which all of the bicyclo rings have completely undergone ring-opening polymerization. I can do it.

Since both are obtained as crosslinked polymers, the shrinkage of the polymer is small, but the more completely the bicyclo ring is opened, the smaller the shrinkage is. The polymer obtained by the present invention is characterized by a very short gelation time, as shown in the Examples below. Therefore, the workability is good and the operability is also good. Because of the above-mentioned characteristics, the polymer of the present invention exhibits particularly excellent performance as dental resins, such as floor resins, composite resins, sealant adhesives, and the like.

EXAMPLES In order to explain the present invention more specifically, the present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.

Production example 1 22.82 g of glycolic acid was placed in a 500cc eggplant-shaped flask equipped with a water metering receiver, a cooling tube, and a calcium chloride tube.
(0.3 mol), trimethylolpropane 40.25
g (0.3 mol) and benzene 150 cc,
Stirring was performed at 95°C for 2 hours. Thereafter, 0.1 g of p-toluenesulfonic acid was added to the reaction solution, and benzene reflux was performed. 5.4 ml (about 0.3 mol) of water distilled out in about 2 hours.

Stirring of the reaction system was stopped, and the reaction system was air-cooled to room temperature, and then benzene was removed using an evaporator. Thereafter, vacuum distillation was performed using an oil refinery under conditions of 0.2 mmHg/170 to 180°C to obtain a fraction of 116°C/0.2 mmHg. This was recrystallized from methylene chloride to obtain the physical properties of a white solid. The yield was 65.5%.

The physical properties and various measured values of the white solid thus obtained were as follows.

1) Melting point 60-61℃ 2) Infrared absorption spectrum 3350cm-1 (νOH) 1100, 1090, 1050 and 1020 cm-1 3) 1H-nuclear magnetic resonance vector Measurement solvent: deuterated chloroform Standard: Tetramethylsilane 4) Mass spectrometry spectrum EI method m/e=175(M+1)+ 5) Elemental analysis From the above measurement results, it is confirmed that the white solid has a structural formula. I could recognize it.

Next, 4-ethyl-1-hydroxymethyl-2,6,7-trioxabicyclo[2,
2,2] Octane 32.74g (0.188mol),
50 g (0.50 mol) of triethylamine and 200 cc of benzene were charged.

While stirring this at 0°C, methacrylic acid chloride 2
6.13 g (0.25 mol) was added dropwise into the reaction solution from a dropping funnel. Added dropwise. After completion of the dropwise addition, the reaction solution was stirred at 0° C. for about 2 hours and further stirred at room temperature for 15 hours. Thereafter, the anti-core liquid was filtered to remove triethylamine hydrochloride generated during the reaction. After removing benzene and excess triethylamine in the filtrate using an evaporator, hexane was added, extraction was performed, and the hexane layer was made convex to obtain 13.61 g of a pale yellow liquid. The yield was 29.9%.

The physical properties and various measured values of the pale yellow liquid thus obtained were as follows.

1) Boiling point 95℃/0.07mmHg 2) Specific gravity 1.1519 (20℃) 3) Infrared absorption spectrum 1720cm-1 (νC=O) 1635cm-1 (νC=C) 1280cm-1 1116, 1105, 1060, 1020 and 1000
cm-1 4) 1H-Nuclear Magnetic Resonance Absorption Spectrum Measurement Solvent: Deuterium chloroform Standard: Tetramethylsilane 5) Mass spectrometry FD method m/e=242 (M+) 6) From the measurement results of elemental analysis and above, the light yellow liquid was confirmed to be the structural formula.

Production Example 2 31.9 g of lactic acid (0.35 g
mol) trimethylolpropane 40.86g (0.3
mol) and 150 cc of toluene, and
Stirring was performed at 0°C for 10 minutes. Thereafter, 0.1 g of p-toluenesulfonic acid was added to the reaction solution, and toluene was refluxed. 6.3ml (about 0.35mol) in about 2.5 hours
of water collected. Stirring of the reaction system was stopped, and after air cooling to room temperature, toluene was removed using an evaporator.

After that, using a purification device, 0.13 mmHg/170
Perform vacuum distillation under conditions of ~190°C to obtain 102-106
．． A fraction of 5° C./0.15 mmHg was obtained.

This fraction turned into a white solid upon cooling to room temperature. The yield of this white solid was 44.25g,
The yield was 78.5%.

The physical properties and various measured values of the white solid thus obtained were as follows.

1) Melting point: 66-68℃ 2) Infrared absorption spectrum 3400cm-1 (νOH) 1125, 1070, 1015 and 990 cm-1 3) 1H-nuclear magnetic resonance absorption spectrum Measurement solvent: heavy dimethyl sulfoxide Standard: Tetramethylsilane 4) Mass spectrometry CI method m/e=189(M+1)+ 5) Elemental analysis From the above measurement results, the white solid has the structural formula: It was confirmed that this is the case.

Next, the 4-ethyl-1-(1-
hydroxyethyl)-2,6,7-trioxabicyclo[2,2,2]octane 41.05 g (0.218 mo
l) 50 g (0.50 mol) of triethylamine and 200 cc of benzene were charged. While stirring this at 0°C, 26.13g (0.25mol) of methacrylic acid chloride was added.
1) was added dropwise into the reaction solution from the dropping funnel. After the dropwise addition was completed, the reaction solution was stirred at 0° C. for about 2 hours and further stirred at room temperature for 20 hours. Thereafter, the reaction solution was filtered to remove triethylamine hydrochloride generated in the reaction solution.

After removing benzene and excess triethylamine from the filtrate using an evaporator, extraction was performed using hexane. By concentrating this hexane layer, 25.74 g of a pale yellow liquid was obtained. The yield was 46.1%.

The physical properties and various measured values of the pale yellow liquid thus obtained were as follows.

1) Boiling point 121°C/0.21 mmHg 2) Infrared absorption spectrum 1720 cm-1 (νC=O) 1640 cm-1 (νC=O) 1170, 1100, 1025 and 1000 cm-1 3) 1H-Nuclear magnetic resonance absorption spectrum measurement solvent : Deuterated chloroform ■ Quasi: Tetramethylsilane 4) Mass spectrometry CI method, m/e = 257 (M+1) + 5) From various measurement results including elemental analysis, it was confirmed that the structural formula of the pale yellow liquid is did it.

Production Examples 3 to 7 As a raw material, hydroxycarboxylic acid (HOR1COOH) in which R1 and R2 have alkyl groups as shown in Table 1
and trimethylolalkane [(HOCH2)3CR
2] and the corresponding bicyclo compounds were synthesized in the same manner as in Production Example 1.

The structures of the obtained compounds were confirmed according to the above-mentioned method for confirming bicyclo compounds.

Next, these bicyclo compounds and an unsaturated carboxylic acid halide in which R3 is hydrogen or an alkyl group shown in Table 1 (X is a halogen atom) are reacted in the same manner as in Production Example 1,
the corresponding 4-alkyl-1-hydroxyalkyl-2,6,7-trioxabicyclo-[2,2,2]
Octane unsaturated carboxylic acid ester was synthesized.

The results of elemental analysis and mass spectrometry of the compound thus obtained are as shown in Table 1, and each was in good agreement with the calculated values predicted from the above general formula (1).

Furthermore, the corresponding 4-alkyl-1 was determined by infrared absorption spectrum and 1H nuclear magnetic resonance spectrum.
-Hydroxyalkyl-2,6,7-trioxabicyclo[2,2,2]octane unsaturated carboxylic acid ester characteristic absorption band and hydrogen absorption peak were confirmed.

Production example 8 Pentaerythritol 68 in a 500cc eggplant flask
g (0.5 mol), ethyl orthopropionate 88 g
(0.5 mol) and p-toluenesulfonic acid about 0.5
I took g. Next, set up a distillation device and distill the water at 130 to 140 ml while stirring.
The deethanol reaction was carried out at ℃. 80cc in about 3 hours
After ethanol is distilled off, 0.1 mmHg/104~
Vacuum distillation was performed at 105°C to obtain 73.88 g of product. The yield was 84.9%.

Next, 32.74 g of the product obtained in the above reaction was placed in a 500 cc separable flask equipped with a stirrer and a dropping funnel.
(0.188 mol) triethylamine 50 g (0.5
0 mol) and 200 cc of benzene were added. While stirring this at 0℃, methacrylic acid chloride 26.13
g (0.25 mol) was added dropwise to react. reaction is 0
This was carried out by stirring at ℃ for 3 hours and at room temperature for 4 hours. After the reaction was completed, triethylamine hydrochloride was filtered off from the reaction mixture, and penzene and triethylamine were distilled off using an evaporator. Copper powder was added to the residue as a polymerization inhibitor, and vacuum distillation was performed at 100-104°C/0.1 mmHg to obtain 29.3 g of a transparent liquid. The yield was 64.5%.

The physical properties and various measured values of the transparent liquid thus obtained were as follows.

1) Boiling point 100-104℃/0.1mmHg2) Infrared absorption spectrum 1720cm-1 (νC=O) 1640cm-1 (νC=C) 1160, 1105, 1060, 1040 and 100
0cm-1 3) 1H-Nuclear Magnetic Resonance Spectroscopy Measurement Solvent: Deuterium chloroform Standard: Tetramethylsilane 4) Mass spectrometry FD method m/e = 242 (M+) 5) From the measurement results of elemental analysis and above, the transparent liquid has a structure It was confirmed that the formula% is the formula%.

Production Examples 9-10 Tetrahydroxy compounds in which R1, R2 and R3 are hydrogen or alkyl groups as shown in Table 2 as raw materials [
(HOCH2)3CR1OH], orthoester (R2
The corresponding 1-alkyl4-hydroxyalkyl-
2,6,7-trioxabicyclo(2,2,2)octane unsaturated carboxylic acid ester was synthesized.

The results of elemental analysis and mass spectrometry of the compound thus obtained are as shown in Table 1, and each was in good agreement with the calculated values predicted from the general formula (II). Furthermore, the corresponding 1-alkyl-4-
The characteristic absorption band of hydroxyalkyl-2,6,7-trioxabicyclo[2,2,2]octane unsaturated carboxylic acid ester and the absorption peak of hydrogen were confirmed.

Example 1 0.55 g of the compound obtained in Production Example 1 was taken at an angle, and tertiary amine compounds and acid anhydrides of the types and amounts shown in Table (1) were added thereto.

The ampoule was then cooled and degassed in dry ice.
The tube was then sealed. After sealing, the ampoule was heated in an oil bath at 70°C to carry out a polymerization reaction.

During this polymerization reaction, the ampoules were taken out from time to time, and the fluidity of the contents was observed using a gradient method. The time when the contents lost fluidity due to polymerization and crosslinking and solidified into a gel was defined as the gelation time. The measurement results of gelation time are also listed in Table-(1).

* indicates a comparative example. RUN No. Polymers 3 to 13 are methylene chloride, benzene, acetone, dimethyl sulfoxide,
It was insoluble in dichloromethane and water at room temperature and 50°C.

Example 2 0.55 g of the compound obtained in Production Example 2 was placed in an ampoule, and the amount of N, N- as shown in Table (2) was added to it.
Dimethyl-P-toluidine and methacrylic anhydride were added. The subsequent operations were performed in the same manner as in Example 1, and the gelation time was measured.

The measurement results of gelation time are also listed in Table-(2).

* indicates a comparative example. RUN No. Polymers 4 to 11 and 13 to 18 were added to methylene chloride, benzene, acetone, dimethyl sulfoxide, dichloromethane, and water at room temperature and 50°C.
It was insoluble.

Example 3 0.50 g of the compound obtained in Production Example 8 was placed in an ampoule, and the amounts of N,N-dimethyl-P-toluidine and methacrylic anhydride as shown in Table (3) were added thereto. Ta. The subsequent operations were performed in the same manner as in Example 1, and the gelation time was measured. The measurement results of gelation time are shown in the table.
Also listed in (5).

* indicates a comparative example. RUN No. Polymers 2 to 4 were insoluble in methylene chloride, benzene, acetone, dimethyl sulfoxide, dichloromethane, and water at room temperature and 50°C.

Example 4 Among the compounds obtained in Production Examples 1 to 10, tertiary amines, acid anhydrides, and peroxides, as shown in Table (4),
The mixture was taken into an appropriate ampoule, and 0.5 g of methyl methacrylate was added thereto. The subsequent operations were performed in the same manner as in Example 1, and the gelation time was measured. The measurement results of gelation time are also listed in Table (4).

Furthermore, RUN No. The polymers obtained in Examples 1 to 5 were insoluble in methylene chloride, penzene, acetone, dimethyl sulfoxide, dichloromethane, and water at room temperature and 50°C.

Claims (1)

[Claims] (1) Has at least one polymerizable vinyl group in the molecule, and 2,6,7-trioxabicyclo[2,2,2]
A polymerization method comprising polymerizing an unsaturated bicyclo compound having an octane ring using a tertiary amine compound and an acid anhydride as a catalyst.