JPS6236512B2 - - Google Patents
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- Publication number
- JPS6236512B2 JPS6236512B2 JP11360980A JP11360980A JPS6236512B2 JP S6236512 B2 JPS6236512 B2 JP S6236512B2 JP 11360980 A JP11360980 A JP 11360980A JP 11360980 A JP11360980 A JP 11360980A JP S6236512 B2 JPS6236512 B2 JP S6236512B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- dimethacrylate
- glycerin
- absorption
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】
本発明は２−（３・４−ジカルボキシベンゾイ
ルオキシ）−１・３−ジメタクリロイルオキシプ
ロパンおよびその製造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to 2-(3,4-dicarboxybenzoyloxy)-1,3-dimethacryloyloxypropane and a method for producing the same.
従来、金属、人体硬質組織（歯、骨）に接着性
を有する接着性モノマーとして種々のものが知ら
れているが、金属と人体硬質組織の両者によく接
着し、しかも高い機械的強度を与えるものはまだ
知られていない。かかる接着性モノマーが得られ
れば、とくに人体硬質組織の修復用接着剤の接着
性成分として非常に有用なものになると考えられ
る。 Various adhesive monomers have been known to have adhesion properties to metals and hard tissues of the human body (teeth, bones). things are still unknown. If such an adhesive monomer can be obtained, it is thought that it will be extremely useful, especially as an adhesive component of an adhesive for repairing hard tissues of the human body.
本発明者らは、かかる点に鑑み鋭意検討を行な
い、次の化学構造式で表わされるベンゼン環に結
合した２個のカルボキシル基を有するジビニル化
合物〔２−（３・４−ジカルボキシベンゾイルオ
キシ）−１・３−ジメタクリロイルオキシプロパ
ン〕を合成し、その接着性を調べたところ、金
属・人体硬質組織によく接着することを認め、本
発明に到達した。 The present inventors conducted intensive studies in view of the above points and developed a divinyl compound [2-(3,4-dicarboxybenzoyloxy)] having two carboxyl groups bonded to a benzene ring represented by the following chemical structural formula. -1,3-dimethacryloyloxypropane] was synthesized and its adhesive properties were investigated, and it was found that it adhered well to metals and hard tissue of the human body, leading to the present invention.
本発明の化合物(A)は新規化合物であり、その構
造は核磁気共鳴吸収スペクトル、赤外スペクト
ル、元素分析により次のようにして決定された。
後述の実施例記載の方法により合成された化合物
を５％CDCl3溶液にして、核磁気共鳴吸収装置で
分析したところ次の結果が得られた。すなわち、
メチル基の存在を示す吸収がδ1.83に積分強度比
６で、エステル結合に隣接したメチレン基の存在
を示す吸収がδ4.40に積分強度比４で、エステル
結合に隣接したメチン基の存在を示す吸収がδ
5.59に積分強度比１で、メタクリル酸残基のH2C
＝の存在を示す吸収がδ5.50とδ6.04に積分強度
比４で、ベンゼン環に結合した３種の水素の存在
を示す吸収がδ7.76、δ8.22、δ8.50に積分強度
比３で、カルボン酸の存在を示す吸収がδ9.70に
積分強度比２で観測された。また、赤外吸収スペ
クトルでは、1850、1780cm-1の酸無水物のＣ＝Ｏ
伸縮振動に由来する吸収は認められず、1700〜
1750cm-1にエステル及びカルボン酸のＣ＝Ｏ伸縮
振動に由来する吸収、2200〜3700cm-1にカルボン
酸のOH伸縮振動に由来する幅広い吸収が認めら
れた。また、元素分析結果はＣ：Ｈ：Ｏ＝
57.31：4.88：37.81（計算値、Ｃ：Ｈ：Ｏ＝
57.14：4.80：38.06）であつた。 Compound (A) of the present invention is a new compound, and its structure was determined by nuclear magnetic resonance absorption spectrum, infrared spectrum, and elemental analysis as follows.
A compound synthesized by the method described in the Examples below was made into a 5% CDCl 3 solution and analyzed using a nuclear magnetic resonance absorption apparatus, and the following results were obtained. That is,
The absorption indicating the presence of a methyl group has an integrated intensity ratio of 6 at δ1.83, and the absorption indicating the presence of a methylene group adjacent to the ester bond has an integrated intensity ratio of 4 at δ4.40, indicating the presence of a methine group adjacent to the ester bond. The absorption that shows δ
H 2 C of methacrylic acid residue with an integrated intensity ratio of 1 to 5.59
The absorption indicating the presence of = has an integrated intensity ratio of 4 at δ5.50 and δ6.04, and the absorption indicating the presence of three types of hydrogen bonded to the benzene ring has an integrated intensity at δ7.76, δ8.22, and δ8.50. At a ratio of 3, an absorption indicating the presence of carboxylic acid was observed at δ9.70 with an integrated intensity ratio of 2. In addition, in the infrared absorption spectrum, C=O of acid anhydride at 1850 and 1780 cm -1
Absorption due to stretching vibration was not observed, and 1700~
Absorption originating from the C=O stretching vibration of the ester and carboxylic acid was observed at 1750 cm -1 , and a wide range of absorption originating from the OH stretching vibration of the carboxylic acid was observed from 2200 to 3700 cm -1 . In addition, the elemental analysis results are C:H:O=
57.31:4.88:37.81 (calculated value, C:H:O=
57.14:4.80:38.06).
本発明の化合物(A)はグリセリン−１・３−ジメ
タクリレートと無水トリメリツト酸ハライドの脱
ハロゲン化反応によりグリセリン−１・３−ジメ
タクリレートのトリメリツト酸無水物を合成した
後、該化合物の酸無水物基を加水分解して製造さ
れる。例えば、約等モル量のグリセリン−１・３
−ジメタクリレートと無水トリメリツト酸クロリ
ドとをこれら化合物に対して不活性な有機溶剤
（たとえばベンゼン、トルエン、テトラヒドロフ
ラン、ジオキサン、酢酸エチル、酢酸メチル、ア
セトン、メチルエチルケトン、塩化メチレン、ク
ロロホルムなど）中で等モル量の第三級アミン存
在下20℃〜−100℃で反応させた後、生成したア
ミンの塩酸塩を別する。液中のグリセリン−
１・３−ジメタクリレートのトリメリツト酸無水
物は、一度単離してから加水分解を行うか、また
は単離せずに液に水を加えて加水分解を行うこ
とができる。前法では少量の重合禁止剤を液に
加えた後、溶媒を減圧溜去して得られる該酸無水
物を、エチルエーテル、酢酸エチル、ジクロルメ
タン等の水と混合した場合相分離し得る溶剤に溶
解または分散し、更に水を加えて室温で約１日、
激しく撹拌すれば酸無水物基は完全に加水分解さ
れて本発明の化合物(A)が得られる。水層を分離
し、溶媒を減圧溜去すると該化合物は白色固体状
で単離される。一方、後法では酢酸エチル、酢酸
メチル、塩化メチレン、クロロホルム等のグリセ
リン−１・３−ジメタクリレートのトリメリツト
酸無水物および本発明の化合物の両方を溶解し、
且つ水と混合した場合相分離し得る溶媒を脱塩化
水素及び加水分解反応に使用するのが好ましい。
脱塩化水素反応終了後、アミンの塩酸塩を別
し、液に水を加える。その後の加水分解法は前
法と同じである。 The compound (A) of the present invention is obtained by synthesizing trimellitic anhydride of glycerin-1,3-dimethacrylate through a dehalogenation reaction of glycerin-1,3-dimethacrylate and trimellitic anhydride halide, and then producing the acid anhydride of the compound. Manufactured by hydrolyzing a chemical group. For example, approximately equimolar amounts of glycerin-1.3
- dimethacrylate and trimellitic anhydride chloride in equimolar amounts in an organic solvent inert to these compounds (e.g. benzene, toluene, tetrahydrofuran, dioxane, ethyl acetate, methyl acetate, acetone, methyl ethyl ketone, methylene chloride, chloroform, etc.). After reacting at 20°C to -100°C in the presence of a certain amount of tertiary amine, the hydrochloride of the amine produced is separated. Glycerin in liquid
The trimellitic anhydride of 1,3-dimethacrylate can be isolated once and then hydrolyzed, or can be hydrolyzed by adding water to the solution without isolation. In the previous method, after adding a small amount of polymerization inhibitor to the liquid, the solvent is distilled off under reduced pressure, and the resulting acid anhydride is converted into a solvent that can undergo phase separation when mixed with water, such as ethyl ether, ethyl acetate, or dichloromethane. Dissolve or disperse, add water and leave at room temperature for about 1 day.
Vigorous stirring will completely hydrolyze the acid anhydride group to yield the compound (A) of the present invention. The aqueous layer is separated and the solvent is distilled off under reduced pressure to isolate the compound as a white solid. On the other hand, in the latter method, both the trimellitic anhydride of glycerin-1,3-dimethacrylate such as ethyl acetate, methyl acetate, methylene chloride, chloroform, etc. and the compound of the present invention are dissolved,
It is preferable to use a solvent for the dehydrochlorination and hydrolysis reactions that is also capable of phase separation when mixed with water.
After the dehydrochlorination reaction is completed, the amine hydrochloride is separated and water is added to the solution. The subsequent hydrolysis method is the same as the previous method.
本発明の化合物(A)は各種の重合開始剤（例え
ば、ベンゾイルパーオキサイド、αα′−アゾビ
スイソブチロニトリル、芳香族スルフイン酸塩／
アシルパーオキサイド／第三級アミン系、トリブ
チルボラン、ベンゾインアルキルエーテル、α−
ジケトン等）によりそれ単独で重合し、また他の
ビニル化合物（アクリル酸エステル系、メタクリ
ル酸エステル系、スチレン等）と共重合すること
ができる。 The compound (A) of the present invention can be used with various polymerization initiators (e.g., benzoyl peroxide, αα′-azobisisobutyronitrile, aromatic sulfinate/
Acyl peroxide/tertiary amine type, tributylborane, benzoin alkyl ether, α-
diketone, etc.), or can be copolymerized with other vinyl compounds (acrylic acid ester type, methacrylic acid ester type, styrene, etc.).
本発明の化合物(A)と重合開始剤からなり、必要
に応じて他の共重合性単量体、充填剤を含む組成
物を金属、人体硬質組織（歯、骨）等に適用し、
硬化させると、金属、人体硬質組織に非常によく
接着することが認められた。したがつて、本発明
の化合物(A)を含む組成物は金属と金属の貼り合わ
せ、金属とプラスチツクスの貼り合わせ、塗装の
下塗り用の接着剤として、また歯科用接着剤（矯
正用、合着用セメント、シーラント、ボンデイン
グ剤）として好適に用いられるものである。とく
に、本発明の化合物(A)を含む接着剤は高い機械的
強度を有するため充填剤を用いて人体硬質組織を
修復する場合に好適である。例えば化合物(A)を構
成要素とする歯用コンポジツトレジンは歯質に対
して接着する為、従来法のように歯質と充填剤を
接着させる為にボンデイング剤を塗布する操作が
不要となる。このような効果は、本発明の化合物
(A)がカルボキシル基を有すると共に、架橋性を有
していることに起因するものと考えられる。従来
から知られている４−メタクリロキシエチルトリ
メリツト酸（特開昭54−12338号）は金属、歯牙
に対する接着性は有しているが、非架橋性である
ため、機械的強度は不十分であつた。 A composition consisting of the compound (A) of the present invention and a polymerization initiator, and optionally containing other copolymerizable monomers and fillers, is applied to metals, human hard tissues (teeth, bones), etc.,
When cured, it was found to adhere very well to metals and hard tissues of the human body. Therefore, the composition containing the compound (A) of the present invention can be used as an adhesive for bonding metals to metals, bonding metals to plastics, and as an undercoat for painting, as well as dental adhesives (for orthodontics, composites, etc.). It is suitably used as a wearable cement, sealant, bonding agent). In particular, since the adhesive containing the compound (A) of the present invention has high mechanical strength, it is suitable for repairing hard tissues of the human body using a filler. For example, a dental composite resin containing Compound (A) as a component adheres to the tooth structure, so there is no need for conventional methods to apply a bonding agent to bond the tooth structure and filling material. . Such effects are due to the compounds of the present invention.
This is thought to be due to the fact that (A) has a carboxyl group and has crosslinking properties. Conventionally known 4-methacryloxyethyl trimellitic acid (Japanese Patent Application Laid-open No. 12338/1983) has adhesive properties to metals and teeth, but is non-crosslinkable and therefore has insufficient mechanical strength. It was hot.
実施例 １
１の三つ口フラスコに無水トリメリツト酸ク
ロリド42.2ｇ（0.20モル）と試薬１級ベンゼン
260c.c.を入れて撹拌し、該酸クロリドを溶解した
後、氷で冷却した。グリセリン−１・３−ジメタ
クリレート45.7ｇ（0.20モル）と精製トリエチル
アミン20.3ｇ（0.20モル）を100c.c.のベンゼンに
溶解して側管付滴下ロートに入れ、フラスコ内温
を10℃以下に保つてフラスコ内へ滴下した。滴下
終了後１時間冷却下撹拌を続け、その後室温に戻
して４時間撹拌した。析出したトリエチルアミン
塩を別し、液に２・６−ジ−ｔ−ブチル−ｐ
−クレゾール20mgとハイドロキノンモノメチルエ
ーテル20mgを加え、室温でベンゼンを減圧溜去
し、80ｇの固形物を得た。該固形物を400c.c.の塩
化メチレンに溶解し、100c.c.の水を加えて、１昼
夜、35℃で激しく撹拌した。塩化メチレン層を水
層と分離し、100c.c.の水で４回水洗した後、無水
硫酸マグネシウムを入れて脱水した。一夜放置
後、硫酸マグネシウムを別し、液に２・６−
ジ−ｔ−ブチル−ｐ−クレゾール20mgとハイドロ
キノンモノメチルエーテル20mgを加え、室温で塩
化メチレンを減圧溜去し、73ｇの固体を取り出し
た。このものを前述のように構造決定したとこ
ろ、化合物(A)であることが確認された。Example 1 42.2 g (0.20 mol) of anhydrous trimellitic acid chloride and the reagent primary benzene were placed in a three-necked flask.
After adding 260 c.c. and stirring to dissolve the acid chloride, the mixture was cooled with ice. Dissolve 45.7 g (0.20 mol) of glycerin-1,3-dimethacrylate and 20.3 g (0.20 mol) of purified triethylamine in 100 c.c. of benzene and place in a dropping funnel with a side pipe, and lower the internal temperature of the flask to below 10°C. It was then dripped into the flask. After the dropwise addition was completed, stirring was continued under cooling for 1 hour, and then the mixture was returned to room temperature and stirred for 4 hours. Separate the precipitated triethylamine salt and add 2,6-di-t-butyl-p to the liquid.
- 20 mg of cresol and 20 mg of hydroquinone monomethyl ether were added, and benzene was distilled off under reduced pressure at room temperature to obtain 80 g of solid. The solid substance was dissolved in 400 c.c. of methylene chloride, 100 c.c. of water was added, and the mixture was vigorously stirred at 35° C. for one day and night. The methylene chloride layer was separated from the aqueous layer, washed four times with 100 c.c. of water, and then dehydrated by adding anhydrous magnesium sulfate. After standing overnight, remove the magnesium sulfate and add 2.6-
20 mg of di-t-butyl-p-cresol and 20 mg of hydroquinone monomethyl ether were added, and methylene chloride was distilled off under reduced pressure at room temperature, and 73 g of solid was taken out. When the structure of this product was determined as described above, it was confirmed to be compound (A).
Claims (1)
水トリメリツト酸ハライドとの脱ハロゲン化水
素反応によりグリセリン−１・３−ジメタクリ
レートの無水トリメリツト酸エステルを合成
し、しかる後該化合物の酸無水物基を加水分解
することを特微とする化学構造式 で表わされる化合物の製造法。[Claims] 1 (1) Chemical structural formula Compound (2) The trimellitic anhydride ester of glycerin-1,3-dimethacrylate is synthesized by a dehydrohalogenation reaction between glycerin-1,3-dimethacrylate and trimellitic anhydride halide, and then the compound is Chemical structural formula characterized by hydrolysis of acid anhydride groups A method for producing a compound represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11360980A JPS5738749A (en) | 1980-08-18 | 1980-08-18 | 2- 3,4-dicarboxybenzoyloxy -1,3-dimethacryloyloxypropane and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11360980A JPS5738749A (en) | 1980-08-18 | 1980-08-18 | 2- 3,4-dicarboxybenzoyloxy -1,3-dimethacryloyloxypropane and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5738749A JPS5738749A (en) | 1982-03-03 |
| JPS6236512B2 true JPS6236512B2 (en) | 1987-08-07 |
Family
ID=14616549
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11360980A Granted JPS5738749A (en) | 1980-08-18 | 1980-08-18 | 2- 3,4-dicarboxybenzoyloxy -1,3-dimethacryloyloxypropane and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5738749A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58173175A (en) * | 1982-04-05 | 1983-10-12 | Kuraray Co Ltd | Dental adhesive |
| JPS6236476A (en) * | 1985-08-12 | 1987-02-17 | Semedain Kk | Electromagnetic wave curable non-solvent adhesive composition |
| US5260476A (en) * | 1990-12-14 | 1993-11-09 | Tokuyama Soda Kabushiki Kaisha | Diacrylate compounds |
| JP6529428B2 (en) * | 2015-12-18 | 2019-06-12 | 株式会社トクヤマデンタル | Adhesive composition for polyaryl ether ketone resin material |
-
1980
- 1980-08-18 JP JP11360980A patent/JPS5738749A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5738749A (en) | 1982-03-03 |
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