JP2008544951A - イソアルカン混合物ならびにその調製および使用 - Google Patents
イソアルカン混合物ならびにその調製および使用 Download PDFInfo
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- JP2008544951A JP2008544951A JP2008510500A JP2008510500A JP2008544951A JP 2008544951 A JP2008544951 A JP 2008544951A JP 2008510500 A JP2008510500 A JP 2008510500A JP 2008510500 A JP2008510500 A JP 2008510500A JP 2008544951 A JP2008544951 A JP 2008544951A
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- Prior art keywords
- isoalkane
- weight
- isoalkane mixture
- application examples
- application
- Prior art date
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- Granted
Links
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- 238000002360 preparation method Methods 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 85
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- 239000004480 active ingredient Substances 0.000 claims description 52
- 238000006243 chemical reaction Methods 0.000 claims description 50
- 150000001336 alkenes Chemical class 0.000 claims description 49
- 238000005984 hydrogenation reaction Methods 0.000 claims description 47
- 229920000642 polymer Polymers 0.000 claims description 43
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 41
- 238000006384 oligomerization reaction Methods 0.000 claims description 38
- 125000004432 carbon atom Chemical group C* 0.000 claims description 37
- 150000001875 compounds Chemical class 0.000 claims description 36
- 239000004215 Carbon black (E152) Substances 0.000 claims description 35
- 239000000499 gel Substances 0.000 claims description 35
- 210000004209 hair Anatomy 0.000 claims description 35
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 35
- 229930195733 hydrocarbon Natural products 0.000 claims description 32
- 239000000126 substance Substances 0.000 claims description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims description 31
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 150000002430 hydrocarbons Chemical class 0.000 claims description 30
- 239000001257 hydrogen Substances 0.000 claims description 30
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- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- 238000007334 copolymerization reaction Methods 0.000 claims description 24
- 239000006071 cream Substances 0.000 claims description 23
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- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 18
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- 229910052759 nickel Inorganic materials 0.000 claims description 17
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- 229920001296 polysiloxane Polymers 0.000 claims description 15
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
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- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 12
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- 239000006210 lotion Substances 0.000 claims description 12
- 238000011282 treatment Methods 0.000 claims description 12
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- 239000004094 surface-active agent Substances 0.000 claims description 9
- 239000000975 dye Substances 0.000 claims description 8
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 8
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- 239000002304 perfume Substances 0.000 claims description 8
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- 230000003606 oligomerizing effect Effects 0.000 claims description 7
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 claims description 7
- 239000011541 reaction mixture Substances 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 7
- 239000013543 active substance Substances 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003750 conditioning effect Effects 0.000 claims description 6
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- 102000008186 Collagen Human genes 0.000 claims description 4
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- 239000000446 fuel Substances 0.000 claims description 4
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- 230000003711 photoprotective effect Effects 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
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- 239000003974 emollient agent Substances 0.000 claims description 3
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- 239000000725 suspension Substances 0.000 claims description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 239000002216 antistatic agent Substances 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims description 2
- 239000003086 colorant Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
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- 230000035939 shock Effects 0.000 claims description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 claims description 2
- OMOVVBIIQSXZSZ-UHFFFAOYSA-N [6-(4-acetyloxy-5,9a-dimethyl-2,7-dioxo-4,5a,6,9-tetrahydro-3h-pyrano[3,4-b]oxepin-5-yl)-5-formyloxy-3-(furan-3-yl)-3a-methyl-7-methylidene-1a,2,3,4,5,6-hexahydroindeno[1,7a-b]oxiren-4-yl] 2-hydroxy-3-methylpentanoate Chemical compound CC12C(OC(=O)C(O)C(C)CC)C(OC=O)C(C3(C)C(CC(=O)OC4(C)COC(=O)CC43)OC(C)=O)C(=C)C32OC3CC1C=1C=COC=1 OMOVVBIIQSXZSZ-UHFFFAOYSA-N 0.000 claims 1
- 150000001991 dicarboxylic acids Chemical class 0.000 claims 1
- 239000013529 heat transfer fluid Substances 0.000 claims 1
- 230000003472 neutralizing effect Effects 0.000 claims 1
- 238000009736 wetting Methods 0.000 claims 1
- 239000012071 phase Substances 0.000 description 110
- 235000019198 oils Nutrition 0.000 description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 35
- 239000011575 calcium Substances 0.000 description 32
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 27
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 23
- 239000007788 liquid Substances 0.000 description 23
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- 238000009472 formulation Methods 0.000 description 22
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- 239000002184 metal Substances 0.000 description 21
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 19
- 239000000194 fatty acid Substances 0.000 description 19
- 235000014113 dietary fatty acids Nutrition 0.000 description 18
- 229930195729 fatty acid Natural products 0.000 description 18
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 16
- 229910019142 PO4 Inorganic materials 0.000 description 16
- 239000000443 aerosol Substances 0.000 description 16
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- FMRHJJZUHUTGKE-UHFFFAOYSA-N Ethylhexyl salicylate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1O FMRHJJZUHUTGKE-UHFFFAOYSA-N 0.000 description 15
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- 239000002453 shampoo Substances 0.000 description 14
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 13
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- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 239000008266 hair spray Substances 0.000 description 12
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 12
- 150000003254 radicals Chemical class 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 11
- 150000004665 fatty acids Chemical class 0.000 description 11
- 235000019645 odor Nutrition 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 10
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- 125000000217 alkyl group Chemical group 0.000 description 10
- 125000002091 cationic group Chemical group 0.000 description 10
- 239000003814 drug Substances 0.000 description 10
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 10
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 10
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Abstract
【選択図】なし
Description
1.フリーデル・クラフツ触媒の存在下、イソブテンまたはイソブテン含有C4-オレフィン混合物の重合、
2.蒸留、
3.水素化、および
4.脱臭のための蒸気蒸留
によって得ることができる化粧品用の油が記載されている。
a) 2〜6の炭素原子を有する少なくとも1種のオレフィンを含む炭化水素供給材料を準備する、
b) 該炭化水素供給材料を遷移金属含有触媒上でオリゴマー化する、
c) ステップb)で得られたオリゴマー化生成物を完全に水素化する、
によって得ることができる。
ステップa)のための適切なオレフィン供給材料は原則として、2〜6の炭素原子および少なくとも1つのエチレン性不飽和二重結合を含む全ての化合物である。
・モレキュラーシーブ分離、
・分留、
・可逆的水和反応によるtert-ブタノールへの変換、
・酸触媒的アルコール付加による3級エーテルへの変換、例えばメタノール付加によるメチルtert-ブチルエーテル(MTBE)への変換、
・不可逆的触媒的オリゴマー化によるジ-、またはトリイソブテンへの変換、
・不可逆的重合によるポリイソブテンへの変換。
0.5〜5重量%のイソブタン、
5〜20重量%のn-ブタン、
20〜40重量%のトランス-2-ブテン、
10〜20重量%のシス-2-ブテン、
25〜55重量%の1-ブテン、
0.5〜5重量%のイソブテン、および
それぞれ1重量%以下の範囲の微量のガス、例えば1,3-ブタジエン、プロペン、プロパン、シクロプロパン、プロパジエン、メチルシクロプロパン、ビニルアセチレン、ペンテン、ペンタンなど。
イソ-、n-ブタン 26重量%
イソブテン 1重量%
1-ブテン 26重量%
トランス-2-ブテン 31重量%
シス-2-ブテン 16重量%
本発明の目的において、用語「オリゴマー」はダイマー、トリマー、テトラマーおよび使用するオレフィンの合成反応由来の高分子生成物を含む。好ましくは、ステップb)において得られるオリゴマーはダイマー、トリマーおよびテトラマーから選択される。該オリゴマーはその一部がオレフィン性不飽和である。所望のイソアルカンは、炭化水素供給材料および以下に記載するようなオリゴマー化に使用するオリゴマー化触媒を適当に選択することにより得ることができる。
ステップc)において、使用することができる水素化触媒は通常、オレフィンの対応するアルカンへの水素化を触媒する従来技術の全ての触媒である。該触媒は不均一相で使用すること、または均一系触媒として使用することができる。好ましくは、水素化触媒はVIII族のうちの少なくとも1種の金属を含む。
・アダムス触媒:該金属酸化物、特に白金およびパラジウムの酸化物は水素化に使用される水素によってそのまま還元される。
・骨格触媒またはラネー触媒:該触媒は金属(特に、ニッケルまたはコバルト)とアルミニウムまたはケイ素との二元合金から酸またはアルカリを用いて一方のパートナーを溶出させることにより、「金属スポンジ」として調製される。残りの元の合金のパートナーは相乗効果を有することが多い。
・担持触媒:ブラック触媒を担持物質の表面に沈着させることもできる。適切な担持および担持物質は以下に記載されている。
a) 全ブテンの合計に基づいて、5質量%未満のイソブテンを有するブテン含有C4-炭化水素蒸気をニッケル含有触媒の存在下でオリゴマー化する、
b) C16-オレフィン留分を反応混合物から分離する、
c) C16留分を水素化する。
A) 上記で定義したような少なくとも1種のイソアルカン混合物、
B) 少なくとも1種の化粧品上または製薬上許容される活性成分または有効物質、
C) 適切であれば、B)とは異なる少なくとも1種の別の化粧品上または製薬上許容される助剤、
を含む化粧品または医薬組成物をさらに提供する。
i) 成分A)と異なるオイル、脂質、ワックス、
ii) C6-C30-モノカルボン酸と一価、二価または多価アルコールとのエステル、
iii) 成分A)と異なる飽和の非環式および環式炭化水素、
iv) 脂肪酸、
v) 脂肪アルコール、
vi) 噴射ガス、
およびそれらの混合物から選択される。
R13は場合により1つ以上のC1-C4-アルキル基で置換された分岐もしくは非分岐のC1-C18-アルキル基またはC5-C12-シクロアルキル基であり、
Zは酸素原子またはNH基であり、
R14は場合により1つ以上のC1-C4-アルキル基で置換された分岐または非分岐のC1-C18-アルキル基、C5-C12-シクロアルキル基、または水素原子、アルカリ金属原子、アンモニウム基または以下の式
Aは場合により1つ以上のC1-C4-アルキル基で置換された分岐または非分岐のC1-C18-アルキル基、C5-C12-シクロアルキル基またはアリール基であり、
R16は水素原子またはメチル基であり、
nは1〜10の数である)
の基であり、
R15は、XがNH基である場合、場合により1つ以上のC1-C4-アルキル基で置換された分岐または非分岐のC1-C18-アルキル基またはC5-C12-シクロアルキル基であり、Xが酸素原子である場合、場合により1つ以上のC1-C4-アルキル基で置換された分岐または非分岐のC1-C18-アルキル基またはC5-C12-シクロアルキル基、または水素原子、アルカリ金属原子、アンモニウム基または以下の式
Aは場合により1つ以上のC1-C4-アルキル基で置換された分岐または非分岐のC1-C18-アルキル基、C5-C12-シクロアルキル基またはアリール基であり、
R16は水素原子またはメチル基であり、
nは1〜10の数である)
の基である]
で表わされる。
で表わされる。
3-ベンジリデンカンファー誘導体、好ましくは3-(4-メチルベンジリデン)カンファーまたは3-ベンジリデンカンファー;
4-アミノ安息香酸誘導体、好ましくは
4-(ジメチルアミノ)安息香酸(2-エチルヘキシル)エステルまたは
4-(ジメチルアミノ)安息香酸アミルエステル;
ベンゾフェノン誘導体、好ましくは2-ヒドロキシ-4-メトキシベンゾフェノン(Uvinul(登録商標)M40の商品名でBASFから市販)、
2-ヒドロキシ-4-メトキシ-4’-メチルベンゾフェノン、2,2’-ジヒドロキシ-4-メトキシベンゾフェノンまたは2,2‘,4,4‘-テトラヒドロキシベンゾフェノン (Uvinul(登録商標)D 50の商品名でBASFから市販)である。
を特徴とする。
a) 0.05〜20重量%の少なくとも1種の毛髪用ポリマー、
b) 本発明のイソアルカン混合物または高C16-含有イソアルカン混合物に基づいて、20〜99.95重量%の担体物質ならびに水および/またはアルコール、
c) 0〜50重量%の少なくとも1種の噴射ガス、
d) 0〜5重量%の少なくとも1種の乳化剤、
e) 0〜3重量%の少なくとも1種の増粘剤、および
f) 25重量%以下の別の構成成分
を含む。
a) 0.1〜10重量%の少なくとも1種の毛髪用ポリマー、
b) 20〜99.9重量%の水および/またはアルコール、
c) 0〜70重量%の少なくとも1種の噴射剤、
d) 0〜20重量%の別の構成成分、
e) 0.01〜10重量%の本発明のイソアルカン混合物または高C16-含有イソアルカン混合物
を含む。
a) 0.1〜10重量%の少なくとも1種の毛髪用ポリマー、
b) 55〜99.8重量%の水および/またはアルコール、
c) 5〜20重量%の噴射剤、
d) 0.1〜5重量%の乳化剤
e) 0〜10重量%の別の構成成分、
f) 0.01〜10重量%の本発明のイソアルカン混合物または高C16-含有イソアルカン混合物
を含む。
a) 0.1〜10重量%の少なくとも1種の毛髪用ポリマー、
b) 80〜99.85重量%の水および/またはアルコール、
c) 0〜3重量%、好ましくは0.05〜2重量%の本発明のイソアルカン混合物または高C16-含有イソアルカン混合物、
d) 0〜20重量%の別の構成成分、
を有することができる。
a) 0.05〜10重量%の少なくとも1種の本発明のイソアルカン混合物または高C16-含有イソアルカン混合物、
b) 25〜94.95重量%の水、
c) 5〜50重量%の界面活性剤、
c) 0〜5重量%の別のコンディショナー、
d) 0〜10重量%の別の化粧成分、
を含む。
(A) 4〜8の炭素原子を有する少なくとも1種のジカルボン酸から誘導される少なくとも1種のエチレン性不飽和ジカルボン酸無水物、
(B) 少なくとも1種の分岐または非分岐のC3-C10-アルケン由来の少なくとも1種のオリゴマー(該オリゴマーは300〜5000g/mol、好ましくは1200g/mol以下の範囲の平均分子量Mnを有するか、または少なくとも3等量のC3-C10-アルケンのオリゴマー化によって得ることができる)、
(C) 場合により、24以下、好ましくは16以下の炭素原子を有する少なくとも1種のα‐オレフィン、
(D) 場合により、(A)、(B)および(C)とは異なる少なくとも1種の別のエチレン性不飽和コモノマー、
の共重合、適切であれば
(E) 一般式Ia、Ib、IcまたはId
A1は同一または異なるC2-C20-アルキレンであり、
R1は直鎖もしくは分岐鎖のC1-C30-アルキル、フェニルまたは水素であり、
nは1〜200の整数である]
の少なくとも1種の化合物との反応、および
適切であればそれに続く水との接触より得ることができる。
A) 4〜8の炭素原子を有する少なくとも1種のジカルボン酸から誘導される少なくとも1種のエチレン性不飽和ジカルボン酸無水物、例えばマレイン酸無水物、イタコン酸無水物、シトラコン酸無水物、メチレンマロン酸無水物、好ましくはイタコン酸無水物およびマレイン酸無水物、非常に好ましくは、マレイン酸無水物、
B) 少なくとも1種の分岐または非分岐C3-C10-アルケンのオリゴマー(少なくとも1種のオリゴマーは300〜5000g/mol、好ましくは1200g/mol以下の範囲の平均分子量Mnを有するか、または少なくとも3等量のC3-C10-アルケンのオリゴマー化によって得ることができる)、
C) 場合により、24以下、好ましくは16以下の炭素原子を有する少なくとも1種のα‐オレフィン、
D) 場合により、A)、B)およびC)とは異なる少なくとも1種の別のエチレン性不飽和コモノマー、
のフリーラジカル共重合、適切であれば
E) 一般式Ia、Ib、IcまたはId
A1は同一または異なるC2-C20-アルキレンであり、
R1は直鎖もしくは分岐鎖のC1-C30-アルキル、フェニルまたは水素であり、
nは1〜200の整数である]
の少なくとも1種の化合物との反応(コポリマーa)のカルボキシル基は少なくとも部分的にエステル化またはアミド化されていてもよい)、および
適切であればそれに続く水との接触よって得ることができる。
コモノマーC)として使用する16以下の炭素原子を有するα‐オレフィンはプロピレン、1-ブテン、イソブテン、1-ペンテン、4-メチルブタ-1-エン、1-ヘキセン、ジイソブテン(2,4,4-トリメチル-1-ペンテンおよび2,4,4-トリメチル-2-ペンテンの混合物)、1-ヘプテン、1-オクテン、1-デセン、1-ドデセン、1-テトラデセンおよび1-ヘキサデセンから選択される;イソブテン、ジイソブテンおよび1-ドデセンが特に好ましい。
A1はC2-C20-アルキレン、例えば-(CH2)2-、-CH2-CH(CH3)-、-(CH2)3-、-CH2-CH(C2H5)-、-(CH2)4-、-(CH2)5-、-(CH2)6-、好ましくはC2-C4-アルキレン、特に-(CH2)2-、-CH2-CH(CH3)-および-CH2-CH(C2H5)-であり;
R1はフェニル、水素、または好ましくは直鎖もしくは分岐鎖のC1-C30-アルキル、例えばメチル、エチル、n-プロピル、イソプロピル、n-ブチル、イソブチル、sec-ブチル、tert-ブチル、n-ペンチル、イソペンチル、sec-ペンチル、neo-ペンチル、1,2-ジメチルプロピル、イソアミル、n-ヘキシル、イソヘキシル、sec-ヘキシル、n-ヘプチル、n-オクチル、n-ノニル、n-デシル、n-ドデシル、n-ヘキサデシル、n-オクタデシル、n-エイコシル、特に好ましくはC1-C4-アルキル、例えばメチル、エチル、n-プロピル、イソプロピル、n-ブチル、イソブチル、sec-ブチルおよびtert-ブチル、とりわけ好ましくはメチルであり;
nは1〜200、好ましくは4〜20の範囲の整数である]
・式HO-(CH2CH2O)m-CH3のメチル末端キャップポリエチレングリコール(式中、mは1〜200、好ましくは4〜100、特に好ましくは4〜50である);
・300〜5000g/molの分子量Mnを有する、エチレンオキシド、プロピレンオキシドおよび/またはブチレンオキシドのメチル末端キャップブロックコポリマー;
・300〜5000g/molの分子量Mnを有する、エチレンオキシド、プロピレンオキシドおよび/またはブチレンオキシドのメチル末端キャップランダムコポリマー;
・アルコキシル化C2-C30-アルコール、特に脂肪アルコールアルコキレート、オキソアルコールアルコキシレートまたはGuerbetアルコールアルコキシレート(アルコキシル化はエチレンオキシド、プロピレンオキシドおよび/またはブチレンオキシドを用いて行うことができる)、
例としては:
・3〜30のエチレンオキシド単位を有するC13-C15-オキソアルコールエトキシレート;
・3〜30のエチレンオキシド単位を有するC13-オキソアルコールエトキシレート;
・3〜30のエチレンオキシド単位を有するC12C14-脂肪アルコールエトキシレート;
・3〜30のエチレンオキシド単位を有するC10-オキソアルコールエトキシレート;
・3〜30のエチレンオキシド単位を有するC10-Guerbetアルコールエトキシレート;
・2〜20のエチレンオキシド単位、2〜20のプロピレンオキシド単位および/または1〜5のブチレンオキシド単位を有するC9-C11-オキソアルコールアルコキシレート;
・2〜20のエチレンオキシド単位、2〜20のプロピレンオキシド単位および/または1〜5のブチレンオキシド単位を有するC13-C15-オキソアルコールアルコキシレート;
・2〜20のエチレンオキシド単位を有するC4-C20-アルコールエトキシレート、
がある。
上記モノマー、つまり場合により本発明に従って使用されるコポリマーCa)の調製のために使用できるモノマーD)はA)、B)およびC)とは異なっている。記載する好ましいモノマーD)は:
一般式II
窒素含有芳香族化合物のN-ビニル誘導体、好ましくはN-ビニルイミダゾール、2-メチル-1-ビニルイミダゾール、N-ビニルオキサゾリドン、N-ビニルトリアゾール、2-ビニルピリジン、4-ビニルピリジン、4-ビニルピリジンN-オキシド、N-ビニルイミダゾリン、N-ビニル-2-メチルイミダゾリン;
α,β‐不飽和ニトリル、例えばアクリロニトリル、メタクリロニトリル;
一般式V
ホスフェート-、ホスホネート-、スルフェート-およびスルホネート含有コモノマー、例えば[2-{(メタ)アクリロイルオキシ}エチル]ホスフェート、2-(メタ)アクリルアミド-2-メチル-1-プロパンスルホン酸;
直鎖または分岐鎖で18〜40の炭素原子、好ましくは24以下の炭素原子を有するα‐オレフィン、例えば1-オクタデセン、1-エイコセン、α‐C22H44、α‐C24H48、および上記α‐オレフィンの混合物である。
R2およびR3は同一であるか、または異なり、非分岐または分岐のC1-C5-アルキル、例えばメチル、エチル、n-プロピル、イソプロピル、n-ブチル、イソブチル、sec-ブチル、tert-ブチル、n-ペンチル、イソペンチル、sec-ペンチル、ネオペンチル、1,2-ジメチルプロピル、イソアミル、特に好ましくはC1-C4-アルキル、例えばメチル、エチル、n-プロピル、イソプロピル、n-ブチル、イソブチル、sec-ブチルおよびtert-ブチルから選択され;特に水素であり;
R4は同一であるか、または異なり、分岐または非分岐のC1-C22-アルキル、例えばメチル、エチル、n-プロピル、イソプロピル、n-ブチル、イソブチル、sec-ブチル、tert-ブチル、n-ペンチル、イソペンチル、sec-ペンチル、ネオペンチル、1,2-ジメチルプロピル、イソアミル、n-ヘキシル、イソヘキシル、sec-ヘキシル、n-ヘプチル、n-オクチル、n-ノニル、n-デシル、n-ドデシル、n-エイコシル;得に好ましくはC1-C4-アルキル、例えばメチル、エチル、n-プロピル、イソプロピル、n-ブチル、イソブチル、sec-ブチルおよびtert-ブチルから選択され;または特に好ましくは水素であり;
R5は水素またはメチルであり;
xは2〜6、好ましくは3〜5の範囲の整数であり;
yは0または1から選択される整数、好ましくは1であり;
aは0〜6の範囲、好ましくは0〜2の範囲の整数であり;
R6およびR7は同一であるか、または異なり、水素、非分岐または分岐のC1-C10-アルキル、例えばメチル、エチル、n-プロピル、イソプロピル、n-ブチル、イソブチル、sec-ブチル、tert-ブチル、n-ペンチル、イソペンチル、sec-ペンチル、ネオペンチル、1,2-ジメチルプロピル、イソアミル、n-ヘキシル、イソヘキシル、sec-ヘキシル、n-ヘプチル、n-オクチル、n-ノニル、n-デシル、好ましくはC1-C4-アルキル、例えばメチル、エチル、n-プロピル、イソプロピル、n-ブチル、イソブチル、sec-ブチルおよびtert-ブチルから選択され、とりわけ好ましくはメチルであり;
Xは酸素またはN-R4であり;
R8は[A3-O]n-R4であり;
R9は非分岐または分岐のC1-C20-アルキル、例えばメチル、エチル、n-プロピル、イソプロピル、n-ブチル、イソブチル、sec-ブチル、tert-ブチル、n-ペンチル、イソペンチル、sec-ペンチル、ネオペンチル、1,2-ジメチルプロピル、イソアミル、n-ヘキシル、イソヘキシル、sec-ヘキシル、n-ヘプチル、n-オクチル、n-ノニル、n-デシル、n-ドデシル、n-テトラデシル、n-ヘキサデシル、n-オクタデシル、n-エイコシルから選択され;好ましくはC1-C14-アルキル、例えばメチル、エチル、n-プロピル、イソプロピル、n-ブチル、イソブチル、sec-ブチル、tert-ブチル、n-ペンチル、イソペンチル、sec-ペンチル、ネオペンチル、1,2-ジメチルプロピル、イソアミル、n-ヘキシル、イソヘキシル、sec-ヘキシル、n-ヘプチル、n-オクチル、n-ノニル、n-デシル、n-ドデシル、n-テトラデシル、特に水素またはメチルであり;
R10およびR11は互いに独立してそれぞれ水素、メチルまたはエチルであり、好ましくはR10およびR11はそれぞれ水素であり;
R12はメチルまたはエチルであり;
kは0〜2の範囲の整数であり、好ましくはkは0であり;
A2およびA3は同一であるか、または異なり、C2-C20-アルキレン、例えば-(CH2)2-、-CH2-CH(CH3)-、-(CH2)3-、-CH2-CH(C2H5)-、-(CH2)4-、-(CH2)5-、-(CH2)6-、好ましくはC2-C4-アルキレン;特に-(CH2)2-、-CH2-CH(CH3)-および-(CH2)3-であり;
A4はC1-C20-アルキレン、例えば-CH2-、-CH(CH3)-、-CH(C6H5)-、-C(CH3)2-、-(CH2)2-、-CH2-CH(CH3)-、-(CH2)3-、-CH2-CH(C2H5)-、-(CH2)4-、-(CH2)5-、-(CH2)6-、好ましくはC2-C4-アルキレン;特に-(CH2)2-、-CH2-CH(CH3)-および-(CH2)3-であるか、または特に単結合である。
A) 5〜60mol%、好ましくは10〜55mol%の範囲、
B) 1〜95mol%、好ましくは5〜70mol%の範囲、
C) 0〜60mol%、好ましくは10〜55mol%の範囲、
D) 0〜70mol%、好ましくは1〜50mol%であり、
ここでA)、B)、C)およびD)の合計は100mol%を与え、ならびにコポリマー中の全てのカルボキシル基に基づいて
E) 0〜50mol%、好ましくは1〜30mol%、特に好ましくは2〜20mol%の範囲である。
A) 上記で定義したような少なくとも1種のイソアルカン混合物、
B) 少なくとも1種の製薬上許容される活性成分、
C) 適切であれば少なくとも1種の別の製薬上許容される活性成分、またはB)とは異なる助剤、
を含む医薬組成物をさらに提供する。
実施例1:イソアルケン混合物の調製
WO95/14647の実施例3に記載されているオリゴマーを、該文献に記載されているC4炭化水素混合物からWO95/14647の実施例1に記載されている触媒を用いて調製した。このオリゴマー2kgを80cm充填カラム(ワイヤーメッシュコイル)を用い、還流比1:5で分留した。これにより以下のようなものが得られた:
実施例1で得られたブテンテトラマー1c 6リットルとPd/活性炭(10%Pd)50gとを9リットルの攪拌加圧型容器に入れた。最初に、水素を50bar(5MPa)の最大値まで、温度が50℃を超えないように注入した。次に、50℃で、水素圧を200bar(20MPa)まで上げて、その後2時間かけて混合物を水素化した。水素化が終了した際、まずひだ付濾紙で、次いでAl2O3を含む短いカラムで触媒を分離した。透明で淡色、無臭の液体を4.4kg得た。
実施例1で得られたブタンダイマー1a 2リットルとPd/活性炭(10%Pd)20gとを3.5リットルの攪拌加圧型容器に入れた。最初に、水素を20bar(2MPa)の最大値まで、温度が50℃を超えないように注入した。次に、50℃で、水素圧を200bar(20MPa)まで上げて、その後2時間かけて混合物を水素化した。水素化が終了した際、まずひだ付濾紙で、次いでAl2O3を含む短いカラムで触媒を分離除去した。透明で淡色、無臭の液体を1.2kg得た。
実施例1で得られたブテントリマー1b 2リットルとPd/活性炭(10%Pd)20gとを3.5リットルの加圧攪拌容器に入れた。最初に、水素を20bar(2MPa)の最大値まで、温度が50℃を超えないように注入した。次に、50℃で、水素圧を200bar(20MPa)まで上げて、その後2時間かけて混合物を水素化した。水素化が終了した際、まずひだ付濾紙で、次いでAl2O3を含む短いカラムで触媒を分離した。透明で淡色、無臭の液体を1.2kg得た。
イソブテン800gと1-ブテン200gとを、最初に3リットルの攪拌加圧容器に入れ、100gのLewatit(登録商標)SPC 112も加えた。(WO2004/091555とは対照的に、イオン交換樹脂は事前に10%H2SO4で活性H+型に変換し、H2Oで完全に洗浄し乾燥させた。この触媒の活性化なしには変換は進行しなかった。)混合物を100℃で3時間攪拌し、20bar(2MPa)の最大圧とした。反応器の内容物を取り出し、触媒と分離し、ロータリーエバポレータを用いて40℃/100mbar(0.02MPa)で脱気した。水様で淡色、低粘性のオレフィン臭がする液体を815g得た。
以下の記載した拡散値は次のような方法で測定した:ろ紙の小片(ろ紙グレード1243/90、白、500×500mmシート、製造業者:Porringer、約200×200mm)を時計皿またはペトリ皿の上に自由に浮いた状態で置き、測定する脂質10μlをその中央に配置した。10分後、脂質に浸った領域をマークし、切り抜いて秤量した。同じ方法を、内部標準(流動パラフィン)にも用いた。相対拡散値を以下の式によって得られた値から計算した:
相対拡散値=(被測定物質の領域×100)/流動パラフィンの領域
Claims (33)
- テトラメチルシランを基準として、0.6〜1.0ppmの化学シフトδの範囲における1H NMRスペクトルが、総積分面に基づいて、25〜70%の積分面を有するイソアルカン混合物。
- 0.6〜1.0ppmの化学シフトδの範囲における1H NMRスペクトルが、総積分面に基づいて、30〜60%、好ましくは35〜55%の積分面を有する、請求項1に記載のイソアルカン混合物。
- 0.1〜0.35、好ましくは0.12〜0.3、特に好ましくは0.15〜0.27、とりわけ0.17〜0.23の範囲の分岐度Bを有する、請求項1または2に記載のイソアルカン混合物。
- 本質的にtert-ブチル基を有しない、請求項1〜3のいずれか1項に記載のイソアルカン混合物。
- 少なくとも70重量%、好ましくは少なくとも85重量%、特には少なくとも95重量%の8〜20の炭素原子を有するアルカンを含む、請求項1〜4のいずれか1項に記載のイソアルカン混合物。
- 少なくとも70重量%、好ましくは少なくとも80重量%、特には少なくとも90重量%の12〜20の炭素原子を有するアルカンを含む、請求項1〜5のいずれか1項に記載のイソアルカン混合物。
- 本質的に、8、12または16の炭素原子を有するアルカンからなる、請求項1〜6のいずれか1項に記載のイソアルカン混合物。
- 請求項1〜7のいずれか1項に記載のイソアルカン混合物であって、その全重量を基準として、95重量%未満、好ましくは90重量%以下の同一の分子量のアルカンを含む、上記イソアルカン混合物。
- Paraffinum perliquidumを基準として、少なくとも130%、好ましくは少なくとも140%、特には少なくとも150%の拡散性を有する、請求項1〜8のいずれか1項に記載のイソアルカン混合物。
- Brookfieldに従って測定したときに、2〜10mPasの範囲、好ましくは4〜8mPasの範囲における粘度を有する、請求項1〜9のいずれか1項に記載のイソアルカン混合物。
- 5〜25cStの範囲、好ましくは10〜20cStの範囲における動粘度を有する、請求項1〜10のいずれか1項に記載のイソアルカン混合物。
- 0.7〜0.82g/cm3の範囲、特に好ましくは0.75〜0.8g/cm3の範囲における密度を有する、請求項1〜11のいずれか1項に記載のイソアルカン混合物。
- 1.4〜1.5の範囲における屈折率を有する、請求項1〜12のいずれか1項に記載のイソアルカン混合物。
- 以下の方法:
a) 2〜6の炭素原子を有する少なくとも1種のオレフィンを含む炭化水素供給材料を準備する、
b) 該炭化水素供給材料を遷移金属含有触媒上でオリゴマー化する、
c) ステップb)で得られるオリゴマー化生成物を完全に水素化する、
によって得ることができるイソアルカン混合物。 - ステップb)で得られるオリゴマー化生成物および/またはステップc)で得られる水素化生成物が分離される、請求項14に記載のイソアルカン混合物。
- ステップa)において、全オレフィン含有量を基準として、直鎖オレフィンの含有量が少なくとも80重量%、特に好ましくは少なくとも90重量%、特には少なくとも95重量%である炭化水素混合物を準備する、請求項14または15に記載のイソアルカン混合物。
- ステップa)において、C4-炭化水素混合物を準備する、請求項14〜16のいずれか1項に記載のイソアルカン混合物。
- ステップb)で使用される触媒がニッケルを含む不均一系触媒である、請求項14〜17のいずれか1項に記載のイソアルカン混合物。
- ステップc)において得られる水素化オリゴマー生成物を少なくとも1種の吸着剤に接触させることにより後処理する方法によって得ることができる、請求項14〜18のいずれか1項に記載のイソアルカン混合物。
- a) 2〜6の炭素原子を有する少なくとも1種のオレフィンを含む炭化水素供給材料を準備する、
b) 該炭化水素供給材料を遷移金属含有触媒上でオリゴマー化する、
c) ステップb)で得られるオリゴマー化生成物を完全に水素化する、
イソアルカン混合物の調製法。 - 少なくとも95重量%の同じ分子量のアルカンを有する少なくとも1種のイソアルカン混合物を含む化粧品または医薬組成物。
- C16-イソアルカンを有する混合物を含み、存在する分子が平均して1分子当たり1.0未満の4級炭素原子を含む組成であり、該混合物のC16-アルカンの割合が95質量%以上であり、該混合物のn-ヘキサデカンの割合が5質量%未満である、請求項21に記載の組成物。
- a) 全ブテンの合計を基準として、5質量%未満のイソブテンを有するブテン含有C4-炭化水素蒸気をニッケル含有触媒の存在下でオリゴマー化する、
b) C16-オレフィン留分を該反応混合物から分離する、
c) C16留分を水素化する、
方法によって得ることができるC16-イソアルカンを有する混合物を含む、請求項21または22に記載の組成物。 - A) 少なくとも1種のイソアルカン混合物、好ましくはC16-イソアルカンを有する少なくとも1種の混合物、
B) 少なくとも1種の化粧品上または製薬上許容される活性成分または有効物質、
C) 適切であれば、B)とは異なる少なくとも1種の別の化粧品上または製薬上許容される助剤、
を含む、請求項21〜23のいずれか1項に記載の組成物。 - A) 請求項1〜19のいずれか1項に記載の少なくとも1種のイソアルカン混合物、
B) 少なくとも1種の化粧品上または製薬上許容される活性成分または有効物質、
C) 適切であれば、B)とは異なる少なくとも1種の別の化粧品上または製薬上許容される助剤、
を含む、化粧品または医薬組成物。 - 軟膏、クリーム、乳液、懸濁液、ローション、ミルク、ペースト、ゲル、フォームまたはスプレーの形態である、請求項21〜25のいずれか1項に記載の組成物。
- 組成物の全重量を基準として、成分A)が0.01〜99.9重量%、好ましくは0.1〜75重量%、特に1〜50重量%の割合である、請求項21〜26のいずれか1項に記載の組成物。
- 成分B)およびC)が担体、賦形剤、乳化剤、界面活性剤、防腐剤、香料、香油、増粘剤、ポリマー、ゲル形成剤、染料、顔料、光保護剤、稠度調整剤、酸化防止剤、消泡剤、帯電防止剤、樹脂、溶媒、溶解促進剤、中和剤、安定剤、滅菌剤、噴射剤、乾燥剤、乳白剤、化粧品活性成分、毛髪用ポリマー、髪および皮膚のコンディショナー、グラフトポリマー、水溶性または分散性シリコーン含有ポリマー、漂白剤、ケア剤、染色剤、着色剤、タンニング剤、保湿剤、脂化剤、コラーゲン、タンパク質加水分解物、脂質、皮膚軟化剤および柔軟剤ならびにそれらの混合物から選択される、請求項21〜27のいずれか1項に記載の組成物。
- a) 0.05〜20重量%の少なくとも1種の毛髪用ポリマー、
b) 請求項1〜19のいずれか1項に記載の少なくとも1種のイソアルカン混合物または請求項21〜23のいずれか1項に記載のC16-アルカンを有する混合物を含む、20〜99.95重量%の担体、
c) 0〜50重量%の少なくとも1種の噴射ガス、
d) 0〜5重量%の少なくとも1種の乳化剤、
e) 0〜3重量%の少なくとも1種の増粘剤、および
f) 25重量%以下の別の構成成分、
を含む、毛髪用化粧品組成物。 - 活性成分もしくは有効物質B)または助剤C)として、
A) 4〜8の炭素原子を有する少なくとも1種のジカルボン酸から誘導される少なくとも1種のエチレン性不飽和ジカルボン酸無水物、
B) 分岐または非分岐のC3-C10-アルケンの少なくとも1種のオリゴマーであって、300〜5000g/molの範囲、好ましくは1200g/mol以下の平均分子量Mnを有するか、または少なくとも3等量のC3-C10-アルケンのオリゴマー化によって得ることができる、上記少なくとも1種のオリゴマー、
C) 場合により、24以下、好ましくは16以下の炭素原子を有する少なくとも1種のα‐オレフィン、
D) 場合により、A)、B)およびC)とは異なる少なくとも1種の別のエチレン性不飽和コモノマー、
の共重合、適切であれば
E) 一般式Ia、Ib、IcまたはId
A1は同一または異なるC2-C20-アルキレンであり、
R1は直鎖もしくは分岐鎖のC1-C30-アルキル、フェニルまたは水素であり、
nは1〜200の整数である]
の少なくとも1種の化合物との反応、および
適切であればそれに続く水との接触よって得ることができる少なくとも1種のコポリマーCa)を含み、
適切であれば、該コポリマーCa)が分岐または非分岐のC3-C10-アルケンの少なくとも1種の付加的なオリゴマーZ)と混合され、少なくとも1種のオリゴマーZ)が300〜5000g/molの範囲、好ましくは1200g/mol以下の平均分子量Mnを有するか、あるいは少なくとも3等量のC3-C10-アルケンのオリゴマー化によって得ることができ、
コポリマー成分B)および/またはオリゴマーZ)が請求項1〜23のいずれか1項に記載のイソアルカン混合物を含むか、あるいはそのようなイソアルカン混合物からなる、
請求項21または29に記載の組成物。 - 均一系または不均一系の化粧品または医薬組成物の疎水性成分としてのまたは疎水性成分中における請求項1〜19のいずれか1項に記載のイソアルカン混合物の使用。
- 皮膚の治療および保護のための組成物、皮膚洗浄組成物、装飾化粧製剤、毛髪処理組成物、皮膚保湿組成物、皮膚または髪のコンディショニング組成物、レオロジー特性を修正するための組成物、皮膚適合性を改善するための組成物および/または良好な湿潤を生じるための組成物における請求項1〜19のいずれか1項に記載のイソアルカン混合物の使用。
- 熱媒液、燃料添加剤用溶媒、低温燃料または衝撃吸収オイルとしての請求項1〜19のいずれか1項に記載のイソアルカン混合物の使用。
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CA2607229A1 (en) | 2006-11-16 |
BRPI0609765A8 (pt) | 2018-04-17 |
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