メタクリル酸メチル 化学特性,用途語,生産方法
外観
無色澄明の液体
定義
本品は、次の化学式で表される有機化合物である。
溶解性
水にわずかに可溶 (0.1～1g/100ml水, 17℃), アルコール, エーテル混和。エタノール及びアセトンに溶け、水にやや溶けにくい。
製造法
メタクリル酸メチルは，略称MMA．不飽和脂肪酸エステルの一つ。工業的には、アセトンシアノヒドリン法）によりアセトンとシアン化水素から製造されていた。現在では、モリブデン系触媒を用いてイソブチレンを空気中の酸素により酸化する方法）が主流になっている。製造法としては，(1)アセトンと青酸を出発原料にしたアセトンシアノヒドリン法，(2)イソブテンを出発原料にしたエスカンビア法，(3)メタクリルアルデヒド法，(4)メタクリル酸法(直接法)，(5)メタクリロニトリル法，(6)メチルアセチレンのカルボニル化によるメチルアセチレン法，(7)プロペンのオキソ化の際に得られるイソブチルアルデヒドを出発原料にしたイソ酪酸法，などがある．特臭のある無色の液体．融点－48.2 ℃，沸点100.3 ℃．d20 0.936．森北出版「化学辞典（第2版）
解説
通常の有機溶剤に可溶で，水にかなり溶けるほか、エタノール（エチルアルコール）、エーテルなどの有機溶媒と任意の割合で混じり合う。光，熱，放射線などにより単独または共重合する．単独重合体のガラス転移点 Tg82～102 ℃．メタクリル酸メチルの重合により得られるメタクリル樹脂は透明性に優れ加工しやすいので、有機ガラスなどに広く使われている。ほかのビニル化合物との共重合体の原料としても重要である。重合しやすいので、保存の際には0.01％程度のヒドロキノンを添加し褐色瓶に入れておく。
用途
透明性や耐候性に優れ、リサイクル性の高さから環境にやさしい素材として注目されているアクリル樹脂をはじめ、各種化学品の原料となります。
- 板、棒、パイプ等の製造
- 成形材料
- 塗料
- 歯科材料
- 接着剤
- 繊維処理剤
- 皮革処理剤
- その他
用途
成型用アクリル樹脂合成原料(建築材料,照明器具,歯科材料,化粧品原料等)、塗料樹脂合成原料(自動車用塗料,家電用塗料,建築用塗料等)、透明ABS樹脂合成原料、紙?樹脂の改質剤合成原料、繊維処理剤合成原料、ポリメタクリル酸メチルシート(水族館浴槽用等の大型プラスチックガラス)製造用、アクリル樹脂?塗料?接着剤原料
化粧品の成分用途
不透明化剤、非活性剤系分散剤、抗ケーキング剤、人工爪剤
主な用途／役割
アクリル樹脂原料、反応性アクリル樹脂系接着剤に使用される。
説明
Methyl methacrylate is an organic compound with the formula CH
2=C(CH
3)COOCH
3. This colourless liquid, the methyl ester of methacrylic acid (MAA) is a monomer produced on a large scale for the production of poly(methyl methacrylate) (PMMA).
化学的特性
Methyl methacrylate is a methyl ester of methacrylic acid. It is a colourless, volatile liquid with an acrid fruity odour. It has a relatively high vapour pressure (4 kPa at 20°C), moderate water solubility (15.8 g/litre), and a low log octanol/water partition coefficient (Kow = 1.38) . Methyl methacrylate is typically 99.9% pure and contains small amounts of inhibitor to retard polymerization.
物理的性質
Clear, colorless liquid with a penetrating, fruity odor. An experimentally determined odor
threshold concentration of 210 ppb
v was reported by Leonardos et al. (1969). Experimentally
determined detection and recognition odor threshold concentrations were 200 μg/m
3 (49 ppb
v) and
1.4 mg/m
3 (340 ppb
v), respectively (Hellman and Small, 1974).
使用
The principal application, consuming approximately 80% of the MMA, is the manufacture of poly methyl methacrylate acrylic plastics (PMMA). Methyl methacrylate is also used for the production of the co-polymer methyl methacrylate-butadiene-styrene (MBS), used as a modifier for PVC. Another application is as cement used in total hip replacements as well as total knee replacements. Used as the "grout" by orthopedic surgeons to make the bone inserts fix into bone, it greatly reduces post-operative pain from the insertions but has a finite lifespan. Typically the lifespan of methyl methacrylate as bone cement is 20 years before revision surgery is required. Cemented implants are usually only done in elderly populations that require more immediate short term replacements. In younger populations, cementless implants are used because their lifespan is considerably longer. Also used in fracture repair in small exotic animal species using internal fixation.
定義
ChEBI: Methyl methacrylate is an enoate ester having methacrylic acid as the carboxylic acid component and methanol as the alcohol component. It has a role as an allergen and a polymerisation monomer. It is an enoate ester and a methyl ester. It is functionally related to a methacrylic acid.
調製方法
The compound is manufactured by several methods, the principal one being the acetone cyanohydrin (ACH) route, using acetone and hydrogen cyanide as raw materials. The intermediate cyanohydrin is converted with sulfuric acid to a sulfate ester of the methacrylamide, methanolysis of which gives ammonium bisulfate and MMA. Although widely used, the ACH route coproduces substantial amounts of ammonium sulfate. Some producers start with an isobutylene or, equivalently, tert-butanol, which is sequentially oxidized first to methacrolein and then to methacrylic acid, which is then esterified with methanol. Propene can be carbonylated in the presence of acids to iso butyric acid, which undergoes subsequent dehydrogenation . The combined technologies afford more than 3 billion kilograms per year. MMA can also be prepared from methyl propionate and formaldehyde.
製造方法
Prepared by the esterification of methacrylamide sulfate with methanol.
一般的な説明
A clear colorless liquid. Slightly soluble in water and floats on water. Vapors heavier than air. Vapors irritate the eyes and respiratory system. Containers must be heavily insulated or shipped under refrigeration. An inhibitor such as hydroquinone, hydroquinone methyl ester and dimethyl t-butylphenol is added to keep the chemical from initiating polymerization. The chemical may polymerize exothermically if heated or contaminated with strong acid or base. If the polymerization takes place inside a container, the container may rupture violently. Used to make plastics.
空気と水の反応
Highly flammable. Very slightly soluble in water.
反応プロフィール
Methyl methacrylate, may polymerize if contaminated or subjected to heat. If polymerization takes place in a container, the container is subject to violent rupture. Oxidizes readily in air to form unstable peroxides that may explode spontaneously [Bretherick 1979. p.151-154, 164]. Peroxides may also initiate exothermic polymierization of the bulk material [Bretherick 1979. p. 160]. Benzoyl peroxide was weighed into a beaker that had previously been rinsed with methyl methacrylate. The peroxide catalyzed polymerization of the methyl methacrylate and the build-up of heat ignited the remaining peroxide [MCA Case History 996. 1964].
危険性
Flammable, dangerous fire risk, explosivelimits in air 2.1–12.5%. Eye and upper respiratorytract irritant, body weight effects, and pulmonaryedema. Questionable carcinogen.
健康ハザード
- Methyl methacrylate may cause slight eye irritation or moderate skin irritation. It is considered a skin sensitizer; allergic reactions may result from contact. Inhalation of vapor or mist can cause irritation of the nose, throat, and lungs and can be fatal in high concentrations. Prolonged or repeated overexposure has been reported to affect the kidneys, liver, gastrointestinal tract, nervous system and lung.
- Methyl methacrylate is moderately toxic to aquatic organisms on an acute basis. The bioconcentration potential (tendency to accumulate in the food chain) is low. If released to surface water, methyl methacrylate will readily biodegrade. A portion may evaporate to the air. It will not persist in the environment.
- Irritation of eyes, nose, and throat. Nausea and vomiting. Liquid may cause skin irritation.
火災危険
Behavior in Fire: Vapor is heavier than air and may travel a considerable distance to a source of ignition and flash back. Containers may explode in fire or when heated because of polymerization.
使用用途
メタクリル酸メチルは、主に吹き付けアクリル板、押し型成形樹脂の製造に用いられています。
重合体、および共重合体はメタクリル樹脂と呼ばれ、塗料用樹脂の原料、樹脂改質剤、塗料、紙のコーティング剤、、繊維加工材、歯科補填物、外科用セメント、合成指爪、義肢装具などに使用されています。
また、メタクリル樹脂は透明性、耐候性、リサイクルが可能な環境対応性などの優れた特性があるため、近年はIT向けや自動車向けなどの用途が拡大しています。
最近では、の成形材の１つとして使われています。装置も安価になり、硬くて精細な形成ができるようになりました。中でも医療分野では術前検討において形態の確認、術式検討に用いるなど、非常に有用です。ただし、かなり硬い素材ですので、成形後の切断はかなり難しい場合があります。
工業用途
Initiators for methyl methacrylate polymerization include AIBN, dilauroyl peroxide (LPO), and 2,2'-Azobis[2-(2-imidazolin-2- yl)propane].
安全性プロファイル
Moderately toxic by
inhalation and intraperitoneal routes. Mildly
toxic by ingestion. Human systemic effects
by inhalation: sleep effects, excitement,
anorexia, and blood pressure decrease.
Experimental teratogenic and reproductive
effects. Mutation data reported. A skin and
eye irritant. Questionable carcinogen with
experimental tumorigenic data. A common
air contaminant.
A very dangerous fire hazard when
exposed to heat or flame; can react with
oxidizing materials. Explosive in the form of
vapor when exposed to heat or flame. The
monomer may undergo spontaneous,
explosive polymerization. Reacts in air to
form a heat-sensitive explosive product
(explodes on evaporation at 6OOC). May
ignite on contact with benzoyl peroxide.
Potentially violent reaction with the
polymerization initiators azoisobutyronitrile,
dibenzoyl peroxide, di-tert-butyl peroxide,
propionaldehyde. To fight fire, use foam,
CO2, dry chemical. When heated to
decomposition it emits acrid smoke and
irritating fumes.
職業ばく露
Virtually all of the methyl methacrylate monomer produced is used in the production of
polymers, such as surface coating resins; plastics (Plexiglas
and Lucite); ion exchange resins; and plastic dentures.
発がん性
In several lifetime animal studies,
there was no evidence that methyl methacrylate is
carcinogenic.
環境運命予測
Chemical/Physical. Polymerizes easily (Windholz et al., 1983). Methyl methacrylate undergoes
nucleophilic attack by OH ions in water (hydrolysis) resulting in the formation of methacrylic acid
and methanol (Kollig, 1993). Hydrolysis occurs at a rate of 171/M?h at 25 °C (Sharma and
Sharma, 1970). No measurable hydrolysis was observed at 85.0 °C (pH 7) and 25 °C (pH 7.07).
Hydrolysis half-lives of 9 and 134 min were observed at 66.0 °C (pH 9.86) and 25.0 °C (pH 11.3),
respectively (Ellington et al., 1987).
貯蔵
Methyl methacrylate is a reactive chemical that must be stored and handled with care. It is stable under recommended storage conditions. Heat can cause polymerization. Inhibitor is added to methyl methacrylate monomer to prevent polymerization. For the inhibitor to be effective, the oxygen concentration in the vapor space must be at least 5%. Store material in containers made of stainless steel, carbon steel, glass, or aluminum. Avoid contact with acids, bases, oxidizing agents, reducing agents, UV light (ultraviolet light, which is found in sunlight), free-radical initiators, and organic peroxides.
輸送方法
UN1247 Methyl methacrylate monomer,
stabilized, Hazard Class: 3; Labels: 3-Flammable liquid.
純化方法
Wash the ester twice with aqueous 5% NaOH (to remove inhibitors such as hydroquinone) and twice with water. Dry it with CaCl2, Na2CO3, Na2SO4 or MgSO4, then with CaH2 under nitrogen under reduced pressure. The distillate is stored at low temperatures and redistilled before use. Prior to distilling, inhibitors such as hydroquinone (0,004%), .-naphthylamine (0.2%) or di--naphthol are sometimes added. Also purify it by boiling with aqueous H3PO4 solution and finally with saturated NaCl solution. It is dried for 24hours over anhydrous CaSO4, distilled at 0.1mm Hg at room temperature and stored at -30o [Albeck et al. J Chem Soc, Faraday Trans 1 1 1488 1978]. [Beilstein 2 II 398, 2 III 1279, 2 IV 1519.]
不和合性
Vapor may form explosive mixture
with air. Reacts in air to form a heat-sensitive explosive
product @ 60C. Incompatible with nitrates, oxidizers,
peroxides, strong acids; strong alkalis; oxidizers,
reducing agents; amines, moisture. Contact with benzoyl
peroxide may cause ignition, fire and explosion. May
polymerize if subjected to heat, polymerization catalysts
e. g., azoisobutyronitrile, dibenzoyl peroxide; di-tert-butyl
peroxide, propionaldehyde); strong oxidizers; or ultraviolet light. May contain an inhibitor, such as hydroquinone.
廃棄物の処理
Consult with environmental
regulatory agencies for guidance on acceptable disposal
practices. Generators of waste containing this contaminant
(≥100 kg/mo) must conform to EPA regulations governing
storage, transportation, treatment, and waste disposal.
Incineration may be allowed.
メタクリル酸メチル 上流と下流の製品情報
原材料
準備製品