ポリビニルピロリドン 化学特性,用途語,生産方法
外観
白色〜わずかにうすい黄色, 結晶性粉末〜粉末
定義
本品は、1-ビニル-2-ピロリドン(VP)の重合体であり、次の化学式で表される。
性質
N-ビニル-2-ピロリドン (C6H9NO) が直鎖状に重合した、吸湿性の非結晶性の高分子です。無臭またはわずかな特異臭があります。密度は1.2g/cm3、融点 (ガラス転移温度) は150~180℃、分解温度は約400℃です。
水、アルコールに可溶で、ピリジン、クロロホルムなど、ほとんどの極性溶媒に溶解します。また、他の高分子との相溶性も高い性質があります。反面、アセトンには溶けにくく、エステル、エーテル、炭化水素系の溶媒にはほとんど溶けません。
人体や環境への安全性が高いことから、幅広い用途で用いられています。また、非イオン性ポリマーであるため、電気伝導性が低く、絶縁性にも優れています。
溶解性
水及びエタノールに溶けやすく、アセトンに溶けにくい。
解説
ポリビニルピロリドン，N-ビニル-2-ピロリドンの重合体。水に可溶であり，水溶液は染料の溶解度を著しく増加させるので，染料の脱色剤として用いられる。
化粧品の成分用途
ヘアスタイリング剤、非活性剤系分散剤、結合剤、皮膜形成剤、乳化安定剤
用途
代用血漿として第2次世界大戦中ドイツで使用された。そのほか香粧品，ビールなどの添加剤として，また口紅型接着剤に用いられている。
効能
撒布剤, 懸濁剤
主な用途／役割
1,4-ブタンジオールとアンモニアを原料として生成したn-ビニル-2-ピロリドンを重合させたもの。紙用接着剤原料、エマルション系接着剤の増粘剤として使用される。
化学的特性
Hygroscopic, white or yellowish-white powder or flakes.
使用
Polyvinylpyrrolidone is used as an adhesive in glue sticks; an emulsifier and a disintegrant for solution polymerization; an additive to Doro's RNA extraction buffer; as a liquid-phase dispersion enhancing agent in diffusion-ordered spectroscopy (DOSY) NMR and as a thickening agent in tooth whitening gels. It finds use in personal care products like shampoos and toothpastes, in ink for inkjet printers as well as in contact lens solutions. It is used as a food additive and in the wine industry as a fining agent for white wine. It is used as a capping agent to synthesize silver nanowires through a polyol process.
製造方法
N-Vinylpyrrolidone is prepared from 1,4-butanediol as follows:
N -Vinylpyrrolidone is water-soluble and is usually polymerized in aqueous solution at about 50??C with ammonia and hydrogen peroxide. The polymer
is also water-soluble and is isolated by spray-drying. Commercial grades of
polyvinylpyrrolidone (PVP) have average molecular weights (Mv) ranging
from about 10000 up to 360000.
The largest use of polyvinylpyrrolidone is in cosmetic formulations, especially hair lacquers. In the latter applications, polyvinylpyrrolidone is the
preferred film-former on account of good adhesion to hair, lustre of the film
and ease of removal on washing. The polymer is also used as a binder in
pharmaceutical tablets. Polyvinylpyrrolidone also finds use in the textile
industry, particularly in colour stripping operations, where the great affinity
of the polymer for dyestuffs is utilized. An interesting application of polyvinylpyrrolidone is in aqueous solution as a blood plasma substitute; such
material was extensively used in Germany during the Second World War.
調製方法
Povidone is manufactured by the Reppe process. Acetylene and
formaldehyde are reacted in the presence of a highly active copper
acetylide catalyst to form butynediol, which is hydrogenated to
butanediol and then cyclodehydrogenated to form butyrolactone.
Pyrrolidone is produced by reacting butyrolactone with ammonia.
This is followed by a vinylation reaction in which pyrrolidone and
acetylene are reacted under pressure. The monomer, vinylpyrrolidone,
is then polymerized in the presence of a combination of
catalysts to produce povidone.
定義
ChEBI: A vinyl polymer composed of repeating -CH2-CR- units where R is a 2-oxopyrrolidin-1-yl group.
世界保健機関（WHO）
Polyvidone, a polymer of vinylpyrrolidinone, is an excipient used
as a suspending and dispersing agent. Injectable preparations containing polymers
with a molecular weight in the order of 12,000 have caused painful local granulomatous lesions. This has led to the withdrawal of polyvidone from such
preparations in some countries. Polyvidone was formerly also used as a plasma
expander but, because it was sequestered within the liver and spleen, this use has
been discontinued. However, it remains widely used as a vehicle for ophthalmic
preparations, and as the major component of artificial tears.
一般的な説明
White powder. Compatible with a wide range of hydrophilic and hydrophobic resins.
空気と水の反応
Hygroscopic. Water soluble.
反応プロフィール
Polyvinylpyrrolidone is a polymeric material and probably has low reactivity. Polyvinylpyrrolidone reacts as a weak base.
危険性
Questionable carcinogen.
健康ハザード
SYMPTOMS: Polyvinylpyrrolidone may cause interstitial fibrosis in the lungs. Lesions regress when patient is no longer being exposed to the compound.
火災危険
Flash point data for Polyvinylpyrrolidone are not available, but Polyvinylpyrrolidone is probably non-flammable.
使用用途
ポリビニルピロリドンは、多くの合成高分子化合物と異なり水によく溶けるので、この性質を利用して様々な用途に用いられます。さらに、高吸湿性、成膜性、接着性、分散性などの特徴のほか、人体や環境への安全性の高さから医薬品や食品添加物へも使用されています。
1. 医薬品
日本薬局方第二部に収載され、消毒薬のポピドンヨードの原料、錠剤やカプセルを製造する際のバインダー、懸濁液やエマルションの安定化剤、軟膏やクリームの基剤などに用いられています。また、人口腎臓に用いられる中空糸の血液適合性を向上させるために、中空糸の素材にポリビニルピロリドンがブレンドされています。
2. 食品添加物
ビタミン、ミネラル製品の安定剤、バインダ、分散剤として使用されています。また、ポリビニルピロリドンのピロリドン部分を架橋したポリビニルポリピロリドン (PVPP) と名称の高分子があり、ビール、ワインなどの清澄剤、茶系飲料の渋味低減剤などに用いられています。ポロビニルピロリドンが水溶性に対して、PVPPは非水溶性です。
応用例（製薬）
Although povidone is used in a variety of pharmaceutical
formulations, it is primarily used in solid-dosage forms. In tableting,
povidone solutions are used as binders in wet-granulation
processes.Povidone is also added to powder blends in the dry
form and granulated in situ by the addition of water, alcohol, or
hydroalcoholic solutions. Povidone is used as a solubilizer in oral
and parenteral formulations, and has been shown to enhance
dissolution of poorly soluble drugs from solid-dosage forms.
Povidone solutions may also be used as coating agents or as binders
when coating active pharmaceutical ingredients on a support such
as sugar beads.
Povidone is additionally used as a suspending, stabilizing, or
viscosity-increasing agent in a number of topical and oral
suspensions and solutions. The solubility of a number of poorly soluble active drugs may be increased by mixing with povidone.
Special grades of pyrogen-free povidone are available and have
been used in parenteral formulations;
接触アレルゲン
Polyvinylpyrrolidone is widely used as is in cosmetics
such as hair care products and in medical products. It
acts as iodophor in iodine-polyvinylpyrrolidone. PVP
is an irritant and has been claimed as the allergen in
some cases of dermatitis from iodine-polyvinylpyrrolidone
(although iodine is more likely the hapten). It
may cause type I contact urticaria or anaphylaxis.
安全性プロファイル
Mtldly toxic by
intraperitoneal and intravenous routes.
Questionable carcinogen. When heated to
decomposition it emits toxic fumes of NOx.
安全性
Povidone has been used in pharmaceutical formulations for many
years, being first used in the 1940s as a plasma expander, although it
has now been superseded for this purpose by dextran.
Povidone is widely used as an excipient, particularly in oral
tablets and solutions. When consumed orally, povidone may be
regarded as essentially nontoxic since it is not absorbed from the
gastrointestinal tract or mucous membranes.Povidone additionally
has no irritant effect on the skin and causes no sensitization.
exists that povidone may accumulate in the organs of the body
following intramuscular injection.
A temporary acceptable daily intake for povidone has been set
by the WHO at up to 25 mg/kg body-weight.
(mouse, IP): 12 g/kg
製造方法
ポリビニルピロリドンの製造方法
ポリビニルピロリドンは、アセチレンとホルムアルデヒドを原料にして、以下の工程を経て生産されます。
1. γ-ブチロラクトンの合成
アセチレンとホルムアルデヒドを加圧下で反応させた後、接触還元することで1,4-ブタンジオールが得られます。これを銅触媒下で200℃に加熱すると分子内で脱水反応が起こり、γ-ブチロラクトンが得られます。
C2H2 + HCHO → HOCH2CH2CH2CH2OH (1,4-ブタンジオール) → C4H6O2 (γ-ブチロラクトン)
2. N-ビニル-2-ピロリドンの合成
γ-ブチロラクトンをアンモニア処理して、2-ピロリドンとし、これに加圧アセチレンを作用させることで、N-ビニル-2-ピロリドンが得られます。
C4H6O2 + NH3 → C4H7NO (2-ピロリドン)
C4H7NO + C2H2→ C6H9NO
γ-ブチロラクトンからN-ビニル-2-ピロリドンを合成する方法は上記の他にもモノエタノールアミンと反応させて合成する方法もあります。こちらは、γ-ブチロラクトンとモノエタノールアミンからN-ヒドロキシエチルピロリドンを生成します。これを気相脱水させることで、N-ビニル-2-ピロリドンが得られます。
C4H6O2 + HOCH2CH2NH2 → C6H11O3 (N-ヒドロキシエチルピロリドン)
C6H11O3 → C6H9NO + H2O
3. N-ビニル-2-ピロリドンの重合
N-ビニル-2-ピロリドンを過酸化水素存在下で加熱して重合してビニルピロリドンが得られます。
貯蔵
Povidone darkens to some extent on heating at 150°C, with a
reduction in aqueous solubility. It is stable to a short cycle of heat
exposure around 110–130°C; steam sterilization of an aqueous
solution does not alter its properties. Aqueous solutions are susceptible to mold growth and consequently require the addition of
suitable preservatives.
Povidone may be stored under ordinary conditions without
undergoing decomposition or degradation. However, since the
powder is hygroscopic, it should be stored in an airtight container in
a cool, dry place.
純化方法
Purify it by dialysis, and freeze-drying. Also by precipitation from CHCl3 solution by pouring into ether. Dry it in a vacuum over P2O5. For the crosslinked polymer purification is by boiling for 10minutes in 10% HCl and then washing with glass-distilled water until free from Cl ions. Finally, Cl ions are removed more readily by neutralising with KOH and continued washing.
不和合性
Povidone is compatible in solution with a wide range of inorganic
salts, natural and synthetic resins, and other chemicals. It forms
molecular adducts in solution with sulfathiazole, sodium salicylate,
salicylic acid, phenobarbital, tannin, and other compounds; see
Section 18. The efficacy of some preservatives, e.g. thimerosal, may
be adversely affected by the formation of complexes with povidone.
規制状況(Regulatory Status)
Accepted for use in Europe as a food additive. Included in the FDA
Inactive Ingredients Database (IM and IV injections; ophthalmic
preparations; oral capsules, drops, granules, suspensions, and
tablets; sublingual tablets; topical and vaginal preparations).
Included in nonparenteral medicines licensed in the UK. Included
in the Canadian List of Acceptable Non-medicinal Ingredients.
ポリビニルピロリドン 上流と下流の製品情報
原材料
準備製品