JP4683928B2 - クレイの剥離方法、該方法から得られた組成物、及び該組成物を含む変性ゴム - Google Patents
クレイの剥離方法、該方法から得られた組成物、及び該組成物を含む変性ゴム Download PDFInfo
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Description
(式中、Xはハロゲン化物であり、R1、R2、R3及びR4は、水素及び炭素数1〜30の直線状又は分岐状のアルキル鎖であり、さらに、該アルキル鎖は任意に芳香族部分を含んでも良い。R1〜R4のうち少なくとも1つは炭素数4〜30の前述のアルキル鎖であるべきである)
を有する有機塩が挙げられる。
(式中、R1は結合、又は炭素数1〜18の直線状又は分岐状のアルキレン基、炭素数3〜20のシクロアルキレン基、及び炭素数6〜24のアリーレン基から選択されるアルキレン基であり、R1は、エーテル基又は第3級アミン基を含んでも良い。R2及びR3の基は、炭素数1〜18の直線状又は分岐状のアルキル基、炭素数3〜炭素数20のシクロアルキル基、及び炭素数6〜24の芳香族基から独立して選択され、R2及びR3の基は、エーテル基又は第3級アミン基を含んでも良い)
を有する化合物とを共重合させることを伴う。
a)溶媒システムにイソブチレンを混合する工程と、
b)イソブチレン/溶媒混合物を冷却する工程と、
c)N,N−ジメチルビニルベンジルアミンを、開始剤及び調整剤と共に混合物に添加する工程と、
d)四塩化チタンを添加することによって重合反応を開始する工程と、
e)メタノールで重合を停止する工程と、
f)いかなる残存溶媒も蒸発させる工程とを有し、結果として生じたイソブチレンとN,N−ジメチルビニルベンジルアミンとの共重合体の生成物が得られる。
a)ポリイソブチレン無水コハク酸(PIBSA)と、例えば、3−(ジメチルアミノ)プロピルアミン、テトラエチレンペンタミン、3,3’−ジアミノ−N−メチルジプロピルアミン、1−(2−アミノエチル)ピペラジン、4−アミノ−1−ベンジルピペリジン、ジメチルアミノビニルベンジルアミン、ポリエチレンイミン、3−アミノピロリジン、3−(ジメチルアミノ)ピロリジン、及びN,N’−ビス(3−アミノプロピル)エチレンジアミンから選択される多価アミン化合物とを混合する工程と、
b)混合物を約150℃に加熱する工程と、
c)加熱した混合物を約150℃で約5分間維持する工程と、
d)混合物を冷却する工程と、
e)HClと水を、工程d)の冷却した混合物に添加する工程とを有し、その結果、PIBASが形成される。
400mLのジクロロメタン及び41.68g(0.215mol)のα,α,α’,α’−テトラメチル−1,4−ベンゼンジメタノール(99%,Aldrich)を、還流冷却器を備え付けた窒素パージした3首の1000mL丸底フラスコに攪拌しながら添加した。この溶液に、31.3mL(0.215mol)の塩化チオニル(99+%,Aldrich)を15分間に渡ってゆっくりと添加した。12時間後、溶液をロータリーエバポレーターで蒸発させ、α,α,α’,α’−テトラメチル−1,4−ベンゼンジメチル塩化物の白色の結晶を得た。生成物をヘキサンから2回再結晶させ、使用するまで−20℃で貯蔵した。使用する直前に、結晶をもう一度ヘキサンから再結晶させて、α,α,α’,α’−テトラメチル−1,4−ベンゼンジメチル塩化物を得た:mp=69〜70℃、1H-NMR(CDCl3):7.56ppm,4H,s;1.99ppm,12H,s。
1Lの窒素パージした瓶に、173.2gの23重量%イソブチレン・ヘキサン溶液と、272.6gの塩化メチルを攪拌しながら添加した。瓶を−78℃に冷却し、1.5mLのジメチルアセトアミド(Aldrich)、0.8mLのジ−t−ブチルピリジン(Aldrich)、1.98gのα,α,α’,α’−テトラメチル−1,4−ベンゼンジメチル塩化物(上記の合成法に従って製造したもの)、及び1.38gのN,N−ジメチルビニルベンジルアミン(Aldrich)を添加した。4mLの四塩化チタン(Aldrich)を添加することにより重合を開始し、温度を−60.7℃に上昇させた。43分後、さらに2mLの四塩化チタンを添加した。90分後、反応を20mLのメタノールで停止させた。塩化メチルを蒸発させ、生じたヘキサン溶液を300mLのメタノールで抽出した。溶媒を蒸発させることによって、下記の特性を有するイソブチレンとN,N−ジメチルビニルベンジルアミンとの共重合体を得た:Mn=9.4x103g/mol、Mw=1.34x104g/mol。1H-NMRスペクトルにおけるN−(CH3)2のピークの積分及びポリイソブチレンのメチル基との比較によって、鎖当たり1.67のN,N−ジメチルビニルベンジルアミンが挿入されていることが明らかとなった。
層状の珪酸塩は、約98mequiv/100gの電荷交換容量を有するモントモリロナイト(Southern Clay Products,Gonzales,TX 天然ベントナイト・クレイ)であった。クレイを、塩化ベンズアルコニウム(Aldrich,Milwaukee,WI)で陽イオン交換反応によって有機変性した。この反応では、200mLの塩化ベンズアルコニウム水溶液(30重量%)を用いて、50gのクレイを処理した。反応を密封したフラスコ内で行い、反応物質を23℃で20時間振盪した。次に、混合物を濾紙によって濾過した。その後、クレイを、別の200mLの塩化ベンズアルコニウム水溶液内で分散させた。工程を3回繰り返した。最後に、過剰な塩化ベンズアルコニウムをイソプロパノールを用いて除去して、生成物を洗浄した。真空乾燥後、熱重量分析(TGA)によって測定したところ、変性したモントモリロナイトは、約45%の有機物(すなわち、ベンズアルコニウム)を含有していた。中でも、TA Instruments及びPerkin Elmerによって製造された装置でTGAを行った。
トルエン、ブチルゴム(MH-11)、処理した珪酸塩(実施例2)、及び10重量%のイソブチレンとN,N−ジメチルビニルベンジルアミンとの共重合体(実施例1)のトルエン溶液の必要量(下記の表1より)を950mLの瓶に装入した。次に、瓶を機械式シェーカー上に24時間置き、ポリマーと処理した珪酸塩をトルエンに溶解した。次に、過剰な界面活性剤をエタノールで抽出し、その後、生じた物質をドラム乾燥した。小角X線散乱(SAXS)によって、イソブチレンとN,N−ジメチルビニルベンジルアミンとの共重合体を添加することで、ブチルゴム中へのクレイの剥離が向上したことが示された(図1)。特に、実施例5では、モントモリロナイトの層状のピークが全く観察されず、このことは、クレイが完全に剥離したことを示している。
ポリイソブチレン無水コハク酸(PIBSA)を用いて合成を開始した。PIBSAは、Chevron Chemical Companyから得られ、熱処理によって製造される。使用したPIBSAは、ORONITE(登録商標)OL15500であり、〜1,000のMnと〜1,900のMwを有する。PIBSAは粘性の液体である。
300gのPIBSAをビーカーに量り取った。15.9gのジメチルアミノプロピルアミンをPIBSAに添加した。混合物を沸騰水の浴槽内で約1時間加熱した。161.4gのこの生成物を、ビーカー内で、13.5gのα,α’−ジブロモキシレンと完全に混合し、90℃のオーブン内で16時間加熱した。生成物はPIBQSだった。
3つの1リットル瓶を製造に用いた。量と構成成分を下記表3に記載する。トルエン、ブチルゴム(MH-11)、処理した珪酸塩(実施例2)、及びPIBAS(実施例6)を瓶内に装入した。次に、瓶を機械式シェーカー上に置いた。約24時間後、ポリマーと処理した珪酸塩はトルエン溶媒に溶解した。次に、溶液をエタノール溶媒中へ注いで、過剰な界面活性剤を抽出した。次に、凝結したストックをドラム乾燥した。生成物を、小角X線散乱(SAXS)を用いてチェックした。X線散乱の結果より、PIBASを添加することによって、ブチルゴム中へのクレイの剥離が大きく向上することが示された(図2)。適量のPIBASを用いて、ストック内におけるモントモリロナイトの層のX線散乱のピークを低角度にシフトすることができ、該ピークは徐々に消え、このことは、クレイが最終的に剥離することを示す。しかしながら、PIBASの濃度は重要な役割を果たす。散乱チャートから分かるように、過剰のPIBASを添加した場合、低角度にて別のピークが現れる。
実施例6に従い製造したPIBASポリマー界面活性剤の一部45gに、100mlのTHFと30mlのアルコールを添加した。次に、この混合物を、室温で30分間、ポリマー界面活性剤が溶解するまで振盪した。これとは別に、15gのモントモリロナイト−クレイ(Southern Clay Products(Gonzales,Texas)のCloisite Na)を15mlの水と混合した。クレイと水の混合物を室温で約1時間置いて、クレイを膨潤させた。その後、膨潤したクレイとポリマー界面活性剤組成物を混合し、約24時間、振盪した。次に、最終生成物を得るために、クレイを濾過し、乾燥した。
ブチルゴムの40gのサンプルを、16gの実施例13の有機クレイと、60gのブラベンダー・ミキサー内で、70℃、60rpmで3分間混合した。X線散乱を用いて、ゴム配合物中のクレイが完全に剥離しているかどうか決定した(図3参照)。
層状の珪酸塩は、約98mequiv/100gの電荷交換容量(CEC)を有するモントモリロナイト(Southern Clay Products(Gonzales、TX)の天然のベントナイトのクレイ)であった。陽イオン交換反応を用いて、クレイを塩化ベンズアルコニウム(Aldrich(Milwaukee,WI))で有機変性した。この反応において、200mLの塩化ベンズアルコニウム水溶液(30重量%)を使用して50gのクレイを処理した。反応を密封したフラスコ内で行い、反応物質を23℃で20時間振盪した。次に、混合物を濾紙によって濾過した。その後、別の200mLの塩化ベンズアルコニウム水溶液内でクレイを処理した。工程を3回繰り返した。最後に、過剰な塩化ベンズアルコニウムをイソプロパノールで除去して生成物を洗浄した。真空乾燥後、熱重量分析(TGA)によって測定したところ、変性したモントモリロナイトは約45%の有機物(すなわち、ベンズアルコニウム)を含有していた。中でも、TA Instruments及びPerkin Elmerによって製造された装置でTGAを行った。
3つの4L瓶を製造に使用した。各実施例における量と構成成分を下記の表6に記載する。トルエン(Aldrich(Milwaukee,WI))、Exxpro(商標)(Exxon(Houston,TX))ゴム、及び実施例16の有機変性クレイを瓶に装入した。次に、瓶を約30rpmのボトル・ローラー上に置いた。約48時間後、ゴムと処理したクレイはトルエン溶媒に溶解した。次に、溶液をドラム乾燥し、生じた生成物を小角X線散乱(SAXS)及び透過型電子顕微鏡(TEM)で分析した。X線散乱によって、材料中にモントモリロナイトの層のピークが全くないことが示された(すなわち、完全な剥離が生じた)。TEMの写真により、約1,000nmのモントモリロナイトのプレートと、約1000のアスペクト比が示された。
11種類のゴム配合物を、表7及び表8に示す処方にしたがって、実施例17〜19の剥離したクレイを配合処方に選択して用いることで製造した。各実施例において、材料の混合物を表9に記載されている方法によって混練した。最終のストックを、シート状にし、160℃で25分間、加硫成形した。実施例20〜30において、引張り強度の測定は、22℃でのASTM-D 412の条件を基にした。試験片の幾何学を、幅0.127cm(0.05インチ)、厚さ0.191cm(0,075インチ)のリングを用いて測定した。空気透過試験を、ASTM Standard D1434に従って、厚さ1mmのシート上で行った。実施例20〜30の組成物の物理特性を表10に示す。
105.5gのポリイソブチレン無水コハク酸と、5.12gの3−(ジメチルアミノ)プロピルアミンを室温で混合し、次に、95〜100℃の間で3時間加熱した。混合物に、4.1mlの12.1N 塩酸を添加し、混合した。混合物を95〜100℃の間で3時間加熱した。水を除去するために、混合物を100℃の真空オーブン内に1日置いた。
400gのポリイソブチレン無水コハク酸と20.1gの3−(ジメチルアミノ)プロピルアミンを室温で混合し、次に、95〜100℃の間で1時間加熱した。混合物に、25.9gのα,α’−p−ジブロモ−キシレンを添加し、混合した。混合物を95〜100℃の間で1時間加熱した。混合物を100℃の真空オーブン内に4時間置いて水を除去した。
表11に従って、少量の実施例31又は32のポリマー剥離剤と、6.7gのTHFとを混合した。次に、混合物を、室温で30分間、ポリマー剥離剤が溶解するまで振盪した。1gの(Cloisite Na)クレイと、表11に従う少量のジオクタデシルジメチルアンモニウム(低分子量の界面活性剤)とを混合した。クレイと低分子量の界面活性剤との混合物に、ポリマー剥離剤の混合物を添加し、次に、1分間振盪した。2gのアルコールを混合物に添加し、次に、1gの水を添加した。混合物を1日間以上振盪した。最終生成物を得るために、混合物を濾過し、真空下で乾燥した。
Claims (4)
- 低ガス透過性のブチルゴム組成物であって、該組成物は、a)有機変性クレイと、b)ブチルゴムと、c)エチレンとプロピレンとブロモ−p−メチルスチレンとの共重合体;ポリイソブチレンアミン塩(PIBAS);ポリイソブチレン・第4級アンモニウム塩(PIBQS);多価の第4級塩を有するポリイソブチレン(PIB2QS2);イソブチレンと、下記式:
- 前記有機変性クレイは、塩化ベンズアルコニウムで変性されたモントモリロナイト、又はジオクタデシルジメチルアンモニウムで変性されたCloisite Naクレイを含むことを特徴とする請求項1に記載の組成物。
- R 1 がメチレンであり、R 2 及びR 3 がメチルであるか、又は前記PIBASは、ポリイソブチレン無水コハク酸(PIBSA)と、3−(ジメチルアミノ)プロピルアミン、テトラエチレンペンタミン、3,3’−ジアミノ−N−メチルジプロピルアミン、1−(2−アミノエチル)ピペラジン、4−アミノ−1−ベンジルピペリジン、ジメチルアミノビニルベンジルアミン、ポリエチレンイミン、3−アミノピロリジン、3−(ジメチルアミノ)ピロリジン、及びN,N’−ビス(3−アミノプロピル)エチレンジアミン及びそれらの混合物から成る群より選択される多価アミン化合物と、任意にHCl又はα,α’−ジブロモ−p−キシレンとの反応産物を含むことを特徴とする請求項1記載の組成物。
- クレイを剥離する方法であって、有機変性クレイと、エチレンとプロピレンとブロモ−p−メチルスチレンとの共重合体;ポリイソブチレンアミン塩(PIBAS);ポリイソブチレン・第4級アンモニウム塩(PIBQS);多価の第4級塩を有するポリイソブチレン(PIB 2 QS 2 );イソブチレンと、下記式:
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EP1583780B1 (en) | 2013-09-04 |
JP2006511648A (ja) | 2006-04-06 |
AU2003301053A1 (en) | 2004-07-22 |
US20060235128A1 (en) | 2006-10-19 |
WO2004058874A1 (en) | 2004-07-15 |
US7576155B2 (en) | 2009-08-18 |
EP1583780A1 (en) | 2005-10-12 |
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